Fluorine atom-containing silane compound

Abstract

Provided is a fluorine-atom-containing silane compound having further improved friction resistance durability and weather resistance. A fluorine-atom-containing silane compound represented by formula (A1) or formula (A2) [wherein the meaning of each symbol is the same as in the description]. RF1-CH2CH2-RSi... (A1), RSi-CH2CH2-RF2-CH2CH2-RSi... (A2), and a method for manufacturing the same.

Description

Technical Field

[0001] This invention relates to silane compounds containing fluorine atoms, compositions containing the fluorine-containing silane compounds, and methods for manufacturing the same. Background Technology

[0002] It is known that silane compounds having fluorine atoms in their molecules (hereinafter, sometimes referred to as "fluorine-containing silane compounds") can help, for example, form layers (hereinafter, sometimes referred to as "surface treatment layers") with properties such as water repellency and oil repellency (e.g., Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-80448 Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] This invention aims to further improve friction durability compared to existing technologies. The objective of this invention is to provide a fluorine-containing silane compound with further improved friction durability and weather resistance.

[0008] Technical solutions for solving technical problems

[0009] The present invention provides the following [1] to [9]. [1]

[0011] A silane compound containing fluorine atoms as shown in formula (A1) or (A2).

[0012] R F1 -CH2CH2-R Si …(A1)

[0013] R Si -CH2CH2-R F2 -CH2CH2-R Si …(A2)

[0014] [In the formula:]

[0015] R F1 For Rf 1 -R F -O q -;

[0016] R F2 -Rf 2 p -R F -O q -;

[0017] Rf 1 C atoms that can be substituted by more than one fluorine atom 1－16 alkyl;

[0018] Rf 2 C atoms that can be substituted by more than one fluorine atom 1－6 Alkylene;

[0019] R F Each of the following groups is independently a divalent fluorine atom;

[0020] p is 0 or 1;

[0021] q can be 0 or 1 independently;

[0022] R Si Each of these is independently a monovalent group comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; and,

[0023] At least 1 R Si It contains Si atoms bonded with hydroxyl groups or hydrolyzable groups. [2]

[0025] As described in [1], silane compounds containing fluorine atoms, wherein,

[0026] R F Each of the following groups can be independently represented by formula (f1) or formula (f2).

[0027] -(OC) j R e 2j ) j1 -(OC) h R e 2h－2 ) h1 - (f1)

[0028] [In the formula:]

[0029] -OC j R e 2j - Each is an independent repeating unit with a straight chain or branches;

[0030] -OC h R e 2h－2 - Each is an independent repeating unit with a ring structure;

[0031] R e Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom;

[0032] Among them, in R F In, at least one R eIt is a fluorine atom;

[0033] j are each an independent integer from 1 to 6;

[0034] h are independent integers from 1 to 7;

[0035] j1 is an integer greater than or equal to 0;

[0036] h1 is an integer greater than or equal to 0;

[0037] The sum of j1 and h1 is 1 or more;

[0038] The order of repeated units with j1 or h1 enclosed in parentheses is arbitrary in the formula.

[0039] -(C s R e1 2s ) s1 -(R) d ) s2 - (f2)

[0040] [In the formula:]

[0041] s are each an independent integer from 1 to 10;

[0042] R e1 Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom;

[0043] R d Each is an arylene group that can be substituted by a fluorine atom;

[0044] Among them, R d Substituents or R e1 At least one of them is a fluorine atom;

[0045] s1 is an integer greater than or equal to 0;

[0046] s2 is an integer greater than or equal to 0;

[0047] The sum of s1 and s2 is 1 or more;

[0048] The order of repeated units with s1 or s2 enclosed in parentheses is arbitrary in the formula. [3]

[0050] Silane compounds containing fluorine atoms as described in [1] or [2], wherein,

[0051] R F Each of the following groups can be independently represented:

[0052] -(OC6F 12 ) a1 -(OC5F)10 ) b1 -(OC4F8) c1 -(OC3R) Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 -

[0053] [In the formula:]

[0054] a1, b1, c1, d1, e1, and f1 are each independent integers from 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 1 or more;

[0055] The order of repeated units with a1, b1, c1, d1, e1, or f1 enclosed in parentheses is arbitrary in the formula;

[0056] R Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom. [4]

[0058] The silane compound containing fluorine atoms as described in any one of [1] to [3], wherein,

[0059] R F Each of the following groups can be independently represented by one of the following formulas: (f11), (f12), (f13), (f14), (f15), or (f16).

[0060] -(OC3F6) d1 -(OC2F4) e1 - (f11)

[0061] [In the formula:]

[0062] d1 is an integer from 1 to 200;

[0063] e1 is either 0 or 1.

[0064] -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 -(f12)

[0065] [In the formula:]

[0066] c1 and d1 are independent integers above 0 and below 30;

[0067] e1 and f1 are each an independent integer greater than 1 and less than 200;

[0068] The sum of c1, d1, e1, and f1 is 2 or more;

[0069] The order of repeated units marked with subscripts c1, d1, e1, or f1 and enclosed in parentheses is arbitrary in the formula.

[0070] -(R) 71 -R 72 ) g1 -R 73 - (f13)

[0071] [In the formula:]

[0072] R 71 It is either OCF2 or OC2F4;

[0073] R 72 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups independently selected from these groups;

[0074] R 73 It is a single bond, or selected from OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups selected from these groups;

[0075] g1 is an integer from 2 to 100.

[0076] -(R) 71 -R 72 ) g1 -R r -(R) 72’ -R 71’ ) g1’ - (f14)

[0077] [In the formula:]

[0078] R 71 It is either OCF2 or OC2F4;

[0079] R 72 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups independently selected from these groups;

[0080] R 71’ It is either OCF2 or OC2F4;

[0081] R 72’ Selected from OC2F4, OC3F6, OC4F8, OC5F10 and OC6F 12 The group, or a combination of two or three groups independently selected from these groups;

[0082] g1 is an integer from 2 to 100;

[0083] g1' is an integer from 2 to 100;

[0084] R r It can be any one of the following groups.

[0085]

[0086] (In the formula, * indicates the bonding position.)

[0087] -(OC6F 12 ) a1 -(OC5F) 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f15)

[0088] [In the formula:]

[0089] e1 is an integer greater than 1 and less than 200, a1, b1, c1, d1, and f1 are each independently an integer greater than 0 and less than 200, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units with a1, b1, c1, d1, e1, or f1 enclosed in parentheses is arbitrary in the formula.

[0090] -(OC6F 12 ) a1 -(OC5F) 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f16)

[0091] [In the formula:]

[0092] f1 is an integer greater than 1 and less than 200, a1, b1, c1, d1, and e1 are each independently an integer greater than 0 and less than 200, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units with a1, b1, c1, d1, e1, or f1 enclosed in parentheses is arbitrary in the formula. [5]

[0094] The silane compound containing fluorine atoms as described in any one of [1] to [4], wherein,

[0095] R Si It is represented by the following formula (S1),

[0096] -SiR a1 k1 R b1 l1 R c1 m1 …(S1)

[0097] [In the formula:]

[0098] R a1 Each independently is -Z 1 -SiR 41 r1 R 42 r2 R 43 r3 ;

[0099] Z 1 Each can be an oxygen atom or a divalent organic group independently;

[0100] R 41 Each independently is -Z 1’ -SiR 41’ r1’ R 42’ r2’ R 43’ r3’ ;

[0101] Z 1’ Each can be an oxygen atom or a divalent organic group independently;

[0102] R 41’ Each independently is -Z 1” -SiR 41” r1” R 42” r2” ;

[0103] Z 1” Each can be an oxygen atom or a divalent organic group independently;

[0104] R 41” Each is independently a hydroxyl group or a hydrolyzable group;

[0105] R 42” Each can be independently a hydrogen atom or a monovalent organic group;

[0106] r1” can be an integer from 0 to 3, respectively;

[0107] r2” are independent integers from 0 to 3;

[0108] R 42’ Each is independently a hydroxyl group or a hydrolyzable group;

[0109] R 43’ Each can be independently a hydrogen atom or a monovalent organic group;

[0110] r1' are independent integers from 0 to 3;

[0111] r2' are independent integers from 0 to 3;

[0112] r3' are each an independent integer from 0 to 3;

[0113] R 42 Each is independently a hydroxyl group or a hydrolyzable group;

[0114] R 43 Each can be independently a hydrogen atom or a monovalent organic group;

[0115] r1 can be an integer from 0 to 3 independently;

[0116] r2 are independent integers from 0 to 3;

[0117] r3 are independent integers from 0 to 3;

[0118] R b1 Each is independently a hydroxyl group or a hydrolyzable group;

[0119] R c1 Each can be independently a hydrogen atom or a monovalent organic group;

[0120] k1 are independent integers from 0 to 3;

[0121] l1 can be an integer from 0 to 3 independently;

[0122] m1 are independent integers from 0 to 3;

[0123] In formula (S1), there exists at least one Si atom bonded to a hydroxyl group or a hydrolyzable group. [6]

[0125] As described in [5], silane compounds containing fluorine atoms, wherein,

[0126] Z 1 C, each independently 1－6 Alkylene, -(CH2) z1 -O-(CH2) z2 - or - (CH2) z3-Phenylidene-(CH2) z4 -;

[0127] z1 to z4 are independent integers from 0 to 6. [7]

[0129] A composition comprising the silane compound containing fluorine atoms as described in [1] to [6]. [8]

[0131] An article having a substrate and a layer formed on the surface of the substrate by the composition described in [7]. [9]

[0133] A method for manufacturing a compound, comprising a formation step of adding a methyleneizing agent to a compound of formula (B31) or (B41) to form a compound of formula (B1) or (B2).

[0134]

[0135] R F1 -CH=CH2…(B1)

[0136] CH2=CH-R F2 -CH=CH2…(B2)

[0137] [In the formula:]

[0138] R F1 For Rf 1 -R F -O q -;

[0139] R F2 -Rf 2 p -R F -O q -;

[0140] Rf 1 C atoms that can be substituted by more than one fluorine atom 1－16 alkyl;

[0141] Rf 2 C atoms that can be substituted by more than one fluorine atom 1－6 Alkylene;

[0142] R F Each of the following groups is independently a divalent fluorine atom;

[0143] p is 0 or 1;

[0144] q can be 0 or 1 independently.

[10]

[0146] The silane compound containing fluorine atoms as described in any one of [1] to [6], which is any one of the following compounds.

[0147]

[0148] Invention Effects

[0149] According to the present invention, fluorine-containing silane compounds can provide further improved friction resistance, durability, and weather resistance. Detailed Implementation

[0150] When used in this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, specifically a group obtained by removing one hydrogen atom from a hydrocarbon. There is no particular limitation on the type of hydrocarbon group; examples include hydrocarbon groups with 1 to 20 carbon atoms that can be substituted by one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon group" can be linear, branched, or cyclic, and can be saturated or unsaturated. Furthermore, the hydrocarbon group can contain one or more ring structures. Additionally, the hydrocarbon group can have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, or carbonyloxy groups at its terminal or in the molecular chain.

[0151] When used in this specification, the term "hydrocarbon group" is not particularly limited, and examples include: halogen atoms; groups selected from those that can be substituted by one or more halogen atoms, C 1－6 Alkyl, C 2－6 alkenyl, C 2－6 alkynyl group, C 3－10 cycloalkyl, C 3－10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclic groups, 5-10 membered unsaturated heterocyclic groups, C 6－10 One or more groups selected from aryl and 5- to 10-membered heteroaryl groups.

[0152] When used in this specification, "organic group" refers to a group containing a carbon atom. For example, a divalent organic group refers to a divalent group containing carbon. There is no particular limitation on divalent organic groups; examples include divalent groups obtained by further removing 1 to 9 hydrogen atoms from a hydrocarbon group. There is also no particular limitation on divalent organic groups; examples include divalent groups obtained by further removing 1 hydrogen atom from a hydrocarbon group.

[0153] In this specification, "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, that is, a group that can be removed from the main skeleton of a compound through a hydrolysis reaction. Examples of hydrolyzable groups include -OR h1 -OCOR h1 -O-N=CRh1 2. -NR h1 2. -NHR h1 halogens (in these formulas, R) h1 The alkyl group (with 1 to 4 carbon atoms, either substituted or unsubstituted) is preferred, especially -OR. h1 (i.e., alkoxy group). R h1 Examples include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl.

[0154] (Silane compounds containing fluorine atoms)

[0155] Silane compounds containing fluorine atoms are represented by formula (A1) or (A2).

[0156] R F1 -CH2CH2-R Si …(A1)

[0157] R Si -CH2CH2-R F2 -CH2CH2-R Si …(A2).

[0158] R F1 For Rf 1 -R F -O q -.

[0159] R F2 -Rf 2 p -R F -O q -.

[0160] p is either 0 or 1. In one mode, p is 0. In another mode, p is 1.

[0161] q can be 0 or 1 independently. In one mode, q is 0. In another mode, q is 1.

[0162] Rf 1 C atoms that can be substituted by more than one fluorine atom 1－16 Alkyl group. The above "C" 1－16 "alkyl" can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Alkyl groups, especially straight-chain or branched C4 groups 1－3 Alkyl groups, more preferably straight-chain C4 groups 1－6 Alkyl groups, especially straight-chain C4 groups 1－3 alkyl.

[0163] The above Rf 1Preferably, C atoms are substituted with one or more fluorine atoms. 1－16 Alkyl, more preferably C 1－16 Perfluoroalkyl. The above C 1－16 Perfluoroalkyl groups can be straight-chain or branched, preferably straight-chain or branched C14 groups. 1－6 Perfluoroalkyl, especially straight-chain or branched C 1－3 Perfluoroalkyl, more preferably straight-chain C 1－6 Perfluoroalkyl, especially straight-chain C 1－3 Perfluoroalkyl.

[0164] In one approach, Rf 1 C atoms that can be substituted by more than one fluorine atom 1－6 Alkyl group. The above "C" 1－6 "alkyl" can be straight-chain or branched, preferably straight-chain or branched C. 1－3 alkyl.

[0165] As a way, the above C 1－6 Alkyl groups are straight-chain C 1－6 Alkyl group, preferably C 1－3 Alkyl group. Rf 1 In one mode, it is CF3-; in another mode, it is CF3CF2-; and in yet another mode, it is CF3CF2CF2-.

[0166] In the above method, Rf 1 Preferably, C atoms are substituted with one or more fluorine atoms. 1－6 Alkyl, more preferably C 1－6 Perfluoroalkyl. In this embodiment, the above C 1－6 Perfluoroalkyl groups can be straight-chain or branched, preferably straight-chain C12. 1－6 Perfluoroalkyl, especially straight-chain C 1－3 Perfluoroalkyl.

[0167] Rf 2 C atoms that can be substituted by more than one fluorine atom 1－6 Alkylene. The "C" 1－6 "alkylene" can be straight-chain or branched, preferably straight-chain or branched C 1－3 Alkylene, more preferably straight-chain C 1－3 Alkylene.

[0168] The above Rf 2 Preferably, C atoms are substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene groups.

[0169] The above C1－6 Perfluoroalkylene groups can be straight-chain or branched, preferably straight-chain or branched C. 1－3 Perfluoroalkylene, more preferably straight-chain C 1－3 Perfluoroalkylene compounds, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0170] R F Each is independently a divalent fluorinated polyether group (PFPE group). A divalent fluorinated group is a divalent organic group in which at least a portion of the hydrogen atoms are replaced by fluorine atoms.

[0171] Preferred R F Each independently consists of the group R represented by the following formula (f1). F11 Or the group R shown in the following formula (f2) F12 express.

[0172] -(OC) j R e 2j ) j1 -(OC) h R e 2h－2 ) h1 - (f1)

[0173] -(C s R e1 2s ) s1 -(R) d ) s2 - (f2)

[0174] Furthermore, in this specification, the left side of equations (f1) and (f2) is related to Rf 1 - or - Rf 2 p - Bonding, right side with -O q - Bonding.

[0175] ·R F11

[0176] -(OC) j R e 2j ) j1 -(OC) h R e 2h－2 ) h1 - (f1)

[0177] -OC j R e 2j - Each is an independent repeating unit with a straight chain or a branched chain.

[0178] -OC h R e 2h－2 - Each is an independent repeating unit with a ring structure.

[0179] R e Each can be independently a hydrogen atom, a fluorine atom, or a chlorine atom, wherein, in R F11 In, at least one R e It is a fluorine atom.

[0180] R e The preferred atom is fluorine.

[0181] j can be an integer from 1 to 6, each independently.

[0182] h can be an integer from 1 to 7, each independently.

[0183] j1 is an integer greater than or equal to 0.

[0184] h1 is an integer greater than or equal to 0.

[0185] Wherein, the sum of j1 and h1 is 1 or more, preferably 2 or more. The order of the repeating units with j1 or h1 enclosed in parentheses is arbitrary in the formula.

[0186] In one approach, -(OC) j R e 2j ) j1 - Expressed by the following formula,

[0187] -(OC6F 12 ) a1 -(OC5F) 10 ) b1 -(OC4F8) c1 -(OC3R) Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 -.

[0188] a1, b1, c1, d1, e1, and f1 are each independent integers from 0 to 200. The sum of a1, b1, c1, d1, e1, and f1 is 1 or more. The order of the repeating units enclosed in parentheses and containing a1, b1, c1, d1, e1, or f1 is arbitrary in the formula.

[0189] By having the groups described above, it is possible to form a surface treatment layer with properties such as water repellency, oil repellency, chemical resistance, friction durability, and weather resistance (e.g., ultraviolet (UV) durability).

[0190] R FaEach can be independently a hydrogen atom, a chlorine atom, or a fluorine atom.

[0191] The above R Fa Preferably, it is a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0192] a1, b1, c1, d1, e1, and f1 can each be an integer from 0 to 100 independently.

[0193] The sum of a1, b1, c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, for example, it can be 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, and even more preferably 60 or less, for example, it can be 50 or less or 30 or less.

[0194] As (OC) j R e 2j For example, repeating units as described below can be listed. —(OC6F) 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 )- can be any of -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(that is, in the above formula, R Fa The fluorine atom can be any of the following: -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- can be any of the following: -(OCF2CF2)- and -(OCF(CF3))-.

[0195] In one embodiment, the repeating units described above are in a linear chain.

[0196] In one embodiment, the aforementioned repeating unit is branched.

[0197] In one approach, (OC) j R e 2j It can be expressed by the following formula:

[0198] -(OC6F 12 ) a1 -(OC5F) 10 ) b1 -(OC4F8) c1 -(OC3R) Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 -.

[0199] The symbols are as described above.

[0200] -(OC) h R e 2h－2 )- of C h R e 2h－2 It can be a ternary ring, quaternary ring, quinary ring, or hexaternary ring.

[0201]

[0202] [In the formula, * indicates the bond position.]

[0203] In one approach, R F11 Each time it appears, it is independently represented by any one of the groups shown in the following formulas (f11) to (f16).

[0204] -(OC3F6) d1 -(OC2F4) e1 - (f11)

[0205] [In the formula, d1 is an integer from 1 to 200; e1 is 0 or 1, preferably 1.]

[0206] -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 -(f12)

[0207] [In the formula, c1 and d1 are independent integers above 0 and below 30, and e1 and f1 are independent integers above 1 and below 200;

[0208] The sum of c1, d1, e1, and f1 is 2 or more;

[0209] The order of repeated units marked with subscripts c1, d1, e1, or f1 and enclosed in parentheses is arbitrary in the formula.

[0210] -(R) 71 -R 72 ) g1 -R 73 - (f13)

[0211] [In the formula, R] 71 It is either OCF2 or OC2F4;

[0212] R 72 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or a combination of two or three groups independently selected from these groups;

[0213] R 73 It is a single bond or selected from OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or a combination of two or three groups selected from these groups;

[0214] g1 is an integer from 2 to 100.

[0215] -(R) 71 -R 72 ) g1 -R r -(R) 72’ -R 71’ ) g1’ - (f14)

[0216] [In the formula, R] 71 It is either OCF2 or OC2F4;

[0217] R 72 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or a combination of two or three groups independently selected from these groups;

[0218] R 71’ It is either OCF2 or OC2F4;

[0219] R 72’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10and OC6F 12 The groups in the group, or a combination of two or three groups independently selected from these groups;

[0220] g1 is an integer from 2 to 100;

[0221] g1' is an integer from 2 to 100;

[0222] R r For any of the groups shown in the following formula:

[0223]

[0224] (In the formula, * indicates the bonding position.)

[0225] -(OC6F 12 ) a1 -(OC5F) 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f15)

[0226] [In the formula, e1 is an integer greater than 1 and less than 200, a1, b1, c1, d1, and f1 are each independently an integer greater than 0 and less than 200, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units with a1, b1, c1, d1, e1, or f1 enclosed in parentheses is arbitrary in the formula.]

[0227] -(OC6F 12 ) a1 -(OC5F) 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f16)

[0228] [In the formula, f1 is an integer greater than 1 and less than 200, a1, b1, c1, d1, and e1 are each independently an integer greater than 0 and less than 200, 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.]

[0229] In the above formula (f11), d1 is preferably 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, for example, an integer from 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).

[0230] In the above formula (f12), e1 and f1 are each preferably 5 or more and 200 or less, more preferably integers from 10 to 200. Furthermore, the sum of c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f12) is preferably -(OCF2CF2CF2CF2) c1 -(OCF2CF2CF2) d1 -(OCF2CF2) e1 -(OCF2) f1 - The group shown. In another embodiment, formula (f12) can be -(OC2F4). e1 -(OCF2) f1 - The group shown.

[0231] In the above equation (f13), R 71 Preferably, it is OC2F4. In the above (f13), R 72Preferably, the group is 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. There is no particular limitation on the combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8; examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F 4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4- etc. In the above formula (f13), g1 is preferably 3 or more, more preferably an integer of 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 It can be any type of straight chain or branched chain, preferably a straight chain. In this method, the above formula (f13) is preferably -(OC2F4-OC3F6). g1 - or - (OC2F4 - OC4F8) g1 - In one approach, R 73 It is a single bond. In another way, R 73 Selected from OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group in R, or a combination of two or three groups selected from these groups. 73 Preferably, the group is selected from OCF2, OC2F4, OC3F6 and OC4F8, or a combination of two or three groups selected from these groups, more preferably -OC2F4OC3F6-.

[0232] In the above equation (f14), R 71 R 72 The meaning of g1 is the same as that of the above formula (f13), and they have the same manner. R 71’ R 72’ The meanings of g1 and g1' are respectively the same as those of R described in the above equation (f13). 71 R 72 Similar to g1, it follows the same method.r Preferably, any one of the groups shown in the following formula is preferred:

[0233]

[0234] [In the formula, * indicates the bond position.]

[0235] More preferably

[0236]

[0237] [In the formula, * indicates the bonding position.]

[0238] In the above formula (f15), e1 is preferably an integer of 1 to 100, more preferably an integer of 5 to 100. The sum of a1, b1, c1, d1, e1 and f1 is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0239] In the above equation (f15), R F11 The repeating unit at the end of the can be -(OCF2CF2OCF2CF2CF2)-.

[0240] In the above formula (f16), f1 is preferably an integer of 1 to 100, more preferably an integer of 5 to 100. The sum of a1, b1, c1, d1, e1 and f1 is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0241] In one approach, the aforementioned R F11 The group is represented by the formula (f11) above.

[0242] In one approach, the aforementioned R F11 The group is represented by the formula (f12) above.

[0243] In one approach, the aforementioned R F11 The group is represented by formula (f13) or (f14) above.

[0244] In one approach, the aforementioned R F11 The group is represented by the formula (f13) above.

[0245] In one approach, the aforementioned R F11 The group is represented by the formula (f14) above.

[0246] In one approach, the aforementioned R F11 The group is represented by the formula (f15) above.

[0247] In one approach, the aforementioned R F11 The group is represented by the formula (f16) above.

[0248] In one approach, the aforementioned R F11 The group is represented by formula (f11), (f12), (f15) or (f16) above.

[0249] In one approach, the aforementioned R F11 The group is represented by formula (f11), (f12) or (f16) above.

[0250] In the above R F11 In this ratio, the ratio of e1 to f1 (hereinafter referred to as the "e / f ratio") is, for example, 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, further preferably 0.2 to 1.5, even more preferably 0.2 or more and less than 0.9, and particularly preferably 0.2 to 0.85 or less. By keeping the e / f ratio within the above range, the stability of the obtained fluorinated compound is improved. Here, f1 is an integer of 1 or more.

[0251] In one approach, in R F11 In this context, the e / f ratio is preferably 1.0 or higher, for example, it can be 1.1 or higher, or 1.3 or higher. In R... F11 In this process, 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. In R F11 In this context, the e / f ratio can be listed as 1.0 to 10.0, more specifically as 1.0 to 5.0, more specifically as 1.0 to 2.0, and even more specifically as 1.0 to 1.5.

[0252] In one approach, in R F11 In this case, the e / f ratio can be in the range of 1.0 to 1.2.

[0253] In one approach, in R F11 In this context, the e / f ratio is below 1.0; for example, it can be below 0.9, below 0.8, or below 0.7. In R... F11 In this process, the e / f ratio is preferably 0.2 or higher, more preferably 0.3 or higher, even more preferably 0.4 or higher, and particularly preferably 0.5 or higher. In R F11 In this context, the e / f ratio can be listed as being greater than 0.2 and less than 0.9, specifically 0.4 and less than 0.8, and more specifically 0.5 and less than 0.7.

[0254] In one approach, in R F11In this embodiment, d1 is preferably an integer of 1 or more, more preferably 3 or more, even more preferably 6 or more, and can be 200 or less, 120 or less, 60 or less, or 54 or less. In this embodiment, d1 can be 1 to 200, 3 to 120, 3 to 60, or 6 to 60.

[0255] In one approach, R F11 The group represented by formula (f11):

[0256] -(OC3F6) d1 -(OC2F4) e1 - (f11)

[0257] [In the formula, d1 is an integer from 3 to 60, preferably an integer from 6 to 54; e1 is 1; OC3F6 and OC2F4 are linear chains.]

[0258] In one approach, R F11 The group represented by formula (f11):

[0259] -(OC3F6) d1 -(OC2F4) e1 - (f11)

[0260] [In the formula, d1 is an integer from 3 to 120, preferably an integer from 6 to 60; e1 is 1; each OC3F6 and OC2F4 has a branch.]

[0261] For example, in equation (f11), the repeating unit is represented by -OCF(CF3)CF2-.

[0262] The above R F11 The number-average molecular weight of the fraction is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In this specification, R... F11 The number average molecular weight is obtained through 19 The value measured by F-NMR.

[0263] In another way, R F11 The number average molecular weight of the fraction is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000, for example, 3,000 to 6,000.

[0264] In another way, R F11 The number average molecular weight of the fraction is 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0265] ·R F12

[0266] -(C s R e1 2s ) s1 -(R) d ) s2 - (f2)

[0267] R e1 Each can be independently a hydrogen atom, a fluorine atom, or a chlorine atom.

[0268] R d Each is an arylene group that can be substituted by a fluorine atom.

[0269] Among them, R d Substituents or R e1 At least one of them is a fluorine atom.

[0270] The aforementioned arylene group refers to a divalent organic group obtained by removing two hydrogen atoms from the ring structure of an aromatic hydrocarbon group. For example, phenylene can be listed as an arylene group.

[0271] In one approach, R e1 It is a fluorine atom.

[0272] In one approach, in -C s R e1 2s - In the middle, all R e1 It is replaced by a fluorine atom. That is, -C s R e1 2s - is a perfluoroalkylene group, i.e. -(C s F 2s )-.

[0273] In one approach, R d (Specifically, R) d At least a portion of the hydrogen atoms in R are replaced by fluorine atoms. That is, R d It is an arylene group substituted with a fluorine atom.

[0274] In one approach, in R d In this case, all hydrogen atoms are replaced by fluorine atoms.

[0275] In one approach, in R F12 In this context, the arylene group is a phenylene group. This phenylene group can 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.

[0276] In one approach, in R F12 In this case, all the hydrogen atoms of the phenylene group are replaced by fluorine atoms.

[0277] s is an integer from 1 to 10.

[0278] s1 is an integer greater than or equal to 0, and s2 is an integer greater than or equal to 0. The sum of s1 and s2 is greater than or equal to 1. The order of repeated units with s1 or s2 enclosed in parentheses is arbitrary in the formula.

[0279] In one method, s1 is an integer from 0 to 20, and s2 is an integer from 0 to 10. The sum of s1 and s2 is 1 or more.

[0280] R Si Each of the following is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group. At least one R... Si It contains Si atoms bonded with hydroxyl groups or hydrolyzable groups.

[0281] R Si Preferably, it contains the group represented by the following formula (S1).

[0282] -SiR a1 k1 R b1 l1 R c1 m1 …(S1)

[0283] R a1 Each independently is -Z 1 -SiR 41 r1 R 42 r2 R 43 r3 .

[0284] Z 1 Each can be an oxygen atom or a divalent organic group, independently. Furthermore, the following are considered as Z. 1 The recorded structure is the right side and (SiR) 41 r1 R 42 r2 R 43 r3 ) bond.

[0285] In the preferred method, Z 1 It is a divalent organic group.

[0286] In the preferred method, Z 1 Excluding Z 1 The bonded Si atoms form a siloxane bond structure. That is, in formula (S1), (Si-Z 1 -Si) does not contain siloxane bonds.

[0287] The above Z 1 C is preferred 1－6 Alkylene, -(CH2) z1 -O-(CH2) z2 -(where z1 is an integer from 0 to 6, for example, an integer from 1 to 6, and z2 is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z3 -Phenylidene-(CH2) z4 —(In the formula, z3 is an integer from 0 to 6, for example, an integer from 1 to 6; z4 is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be, for example, fluorine atoms, selected from C... 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted.

[0288] In the preferred method, Z 1 C 1－6 Alkylene or (CH2) z3 -Phenylidene-(CH2) z4 -, preferably -phenylene-(CH2) z4 -. Z 1 When such a group is used, light resistance, especially UV resistance, can be further improved.

[0289] In another preferred embodiment, Z 1 C 1－6 Alkylene or (CH2) z1 -O-(CH2) z2 -.

[0290] In another preferred embodiment, Z 1 C 1－6 Alkylene, preferably C 1－3 Alkylene. In one manner, Z 1 It can be -CH2CH2CH2-. In another way, Z 1 It can be -CH2CH2-.

[0291] The above R 41 Each occurrence is independently -Z 1’ -SiR 41’ r1’ R 42’ r2’ R 43’ r3’ .

[0292] The above Z1’ Each time it appears, it is independently either an oxygen atom or a divalent organic group. Furthermore, the following is referred to as Z. 1’ The recorded structure is the right side and (SiR) 41’ r1’ R 42’ r2’ R 43’ r3’ ) bond.

[0293] In the preferred method, Z 1’ It is a divalent organic group.

[0294] In the preferred method, Z 1’ Excluding Z 1’ The bonded Si atoms form a siloxane bond structure. That is, in formula (S1), (Si-Z 1’ -Si) does not contain siloxane bonds.

[0295] The above Z 1’ C is preferred 1－6 Alkylene, -(CH2) z1’ -O-(CH2) z2’ -(where z1' is an integer from 0 to 6, for example, an integer from 1 to 6, and z2' is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z3’ -Phenylidene-(CH2) z4’ —(In the formula, z3' is an integer from 0 to 6, for example, an integer from 1 to 6; z4' is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be, for example, fluorine atoms, selected from C... 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted. For example, the total of z1' and z2' can be 1 or more, and the total of z3' and z4' can be 1 or more.

[0296] In the preferred method, Z 1’ C 1－6 Alkylene or (CH2) z3’ -Phenylidene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ -. Z 1’ When such a group is used, light resistance, especially UV resistance, can be further improved.

[0297] In another preferred embodiment, the above Z 1’ C 1－6 Alkylene, preferably C 1－3Alkylene. In one manner, Z 1’ It can be -CH2CH2CH2-. In another way, Z 1’ It can be -CH2CH2-.

[0298] The above R 41’ Each occurrence is independently -Z 1” -SiR 41” r1” R 42” r2” .

[0299] The above Z 1” Each time it appears, it is either an oxygen atom or a divalent organic group.

[0300] Z 1” Each time it appears, it is independently either an oxygen atom or a divalent organic group. Furthermore, the following is referred to as Z. 1” The recorded structure is the right side and (SiR) 41” r1” R 42” r2” ) bond.

[0301] In the preferred method, Z 1” It is a divalent organic group.

[0302] In the preferred method, Z 1” Excluding Z 1” The bonded Si atoms form a siloxane bond structure. That is, in formula (S1), (Si-Z 1” -Si) does not contain siloxane bonds.

[0303] The above Z 1” C is preferred 1－6 Alkylene, -(CH2) z1” -O-(CH2) z2” -(where z1” is an integer from 0 to 6, for example, an integer from 1 to 6, and z2” is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z3” -Phenylidene-(CH2) z4” —(In the formula, z3” is an integer from 0 to 6, for example, an integer from 1 to 6, and z4” is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be, for example, fluorine atoms, selected from C... 1－6 Alkyl, C 2－6 alkenyl and C 2－6One or more substituents in the alkynyl group are substituted, preferably unsubstituted. For example, the total of z1” and z2” can be 1 or more, and the total of z3” and z4” can be 1 or more.

[0304] In the preferred method, Z 1” C 1－6 Alkylene or (CH2) z3” -Phenylidene-(CH2) z4” -, preferably -phenylene-(CH2) z4” -. Z 1” When such a group is used, light resistance, especially UV resistance, can be further improved.

[0305] In another preferred embodiment, the above Z 1” C 1－6 Alkylene, preferably C 1－3 Alkylene. In one manner, Z 1” It can be -CH2CH2CH2-. In another way, Z 1” It can be -CH2CH2-.

[0306] R 41” Each can be a hydroxyl group or a hydrolyzable group, independently.

[0307] The above R 41” Preferably, each group is a hydrolyzable group. The meaning of a hydrolyzable group is the same as described above.

[0308] R 42” Each can be an independent hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the groups mentioned above that can be hydrolyzed.

[0309] In the above R 42” In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0310] The aforementioned r1” are each an independent integer from 0 to 3; the aforementioned r2” are each an independent integer from 0 to 3. Furthermore, the sum of r1” and r2” is within (SiR). 41” r1” R 42” r2” The value in unit ) is 3.

[0311] r1” in each (SiR 41” r1” R 42” r2” The units are preferably integers of 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0312] The above R 42’ Each can be a hydroxyl group or a hydrolyzable group, independently.

[0313] R 42’ Preferably, each group is a hydrolyzable group. The meaning of a hydrolyzable group is the same as described above.

[0314] The above R 43’ Each can be an independent hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the groups mentioned above that can be hydrolyzed.

[0315] In the above R 43’ In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0316] Each of the above r1' is an independent integer from 0 to 3; each of the above r2's is an independent integer from 0 to 3; and each of the above r3's is an independent integer from 0 to 3. Furthermore, the sum of r1', r2', and r3' is within the range of (SiR). 41’ r1’ R 42’ r2’ R 43’ r3’ The value in unit ) is 3.

[0317] In one mode, r1' is 0.

[0318] In one manner, r1' in each (SiR 41’ r1’ R 42’ r2’ R 43’ r3’ Each of the units can be an integer from 1 to 3, an integer from 2 to 3, or 3. In the preferred embodiment, r1' is 3.

[0319] In one manner, r2' in each (SiR 41’ r1’ R 42’ r2’ R 43’ r3’ Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0320] In one mode, r2' is 0, and r3' is in each (SiR 41’ r1’ R 42’ r2’ R 43’ r3’Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0321] The above R 42 Each can be a hydroxyl group or a hydrolyzable group, independently.

[0322] R 42 Preferably, each group is a hydrolyzable group. The meaning of a hydrolyzable group is the same as described above.

[0323] The above R 43 Each can be an independent hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the groups mentioned above that can be hydrolyzed.

[0324] In the above R 43 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0325] Each of the above r1 values ​​is an independent integer from 0 to 3; each of the above r2 values ​​is an independent integer from 0 to 3; and each of the above r3 values ​​is an independent integer from 0 to 3. Furthermore, the sum of r1, r2, and r3 is within the range of (SiR). 41 r1 R 42 r2 R 43 r3 The value in unit ) is 3.

[0326] In one mode, r1 is 0.

[0327] In one manner, r1 in each (SiR) 41 r1 R 42 r2 R 43 r3 Each of the units can be an integer from 1 to 3, an integer from 2 to 3, or 3. In the preferred embodiment, r1 is 3.

[0328] In one manner, r2 in each (SiR) 41 r1 R 42 r2 R 43 r3 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0329] In one mode, r1 is 0, and r2 is in each (SiR) 41 r1 R 42 r2 R43 r3 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0330] The above R b1 Each can be a hydroxyl group or a hydrolyzable group, independently.

[0331] The above R b1 Preferably, each group is a hydrolyzable group. The meaning of a hydrolyzable group is the same as described above.

[0332] The above R c1 Each can be an independent hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the groups mentioned above that can be hydrolyzed.

[0333] In the above R c1 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0334] The above k1 are each an independent integer from 0 to 3; the above l1 are each an independent integer from 0 to 3; the above m1 are each an independent integer from 0 to 3. Furthermore, the sum of k1, l1, and m1 is within (SiR). a1 k1 R b1 l1 R c1 m1 The value in unit ) is 3.

[0335] In one approach, k1 is in each (SiR) a1 k1 R b1 l1 R c1 m1 Each of the units is an independent integer from 1 to 3, preferably 2 or 3, more preferably 3. In the preferred embodiment, k1 is 3.

[0336] In one approach, in each (SiR) a1 k1 R b1 l1 R c1 m1 Each cell is independent, with k1 being 1 or 2, l1 being 2 or 1, and m1 being 0.

[0337] In one approach, in each (SiR) a1 k1 R b1 l1 R c1 m1Each cell is independent, with k1 being 1 or 2, l1 being 0, and m1 being 2 or 1.

[0338] In one mode, k1 is 0. In other words, -SiR a1 k1 R b1 l1 R c1 m1 The group shown is -SiR b1 l1 R c1 m1 The sum of l1 and m1 is 3. In this method, at least one Si atom bonded to a hydroxyl group or a hydrolyzable group exists in the terminal portion of formulas (A1) and (A2).

[0339] The number l1 mentioned above is preferably an integer from 1 to 3 each time it appears, more preferably 2 or 3, and even more preferably 3.

[0340] In one embodiment, k1 is 0, and l1 is preferably 2 or 3, more preferably k1 is 0 and l1 is 3.

[0341] In formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group. That is, the group shown in formula (S1) has a -SiR group. b1 l1 R c1 m1 (In the formula, l1 is an integer from 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 (In the formula, r2 is an integer from 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’ (In the formula, r2' is an integer from 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” (In the formula, r1” is any one of an integer from 1 to 3, preferably 2 or 3, more preferably 3, and the sum of r1” and r2” is 3.)

[0342] In a preferred embodiment, at least two Si atoms bonded to hydroxyl groups or hydrolyzable groups are present in the terminal portions of formulas (A1) and (A2).

[0343] In the preferred embodiment, R exists in equation (S1). a1 At that time, in at least one, preferably all R a1 In this context, r2 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0344] In the preferred embodiment, R exists in equation (S1). 41 At that time, in at least one, preferably all R 41 In this context, r2' is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0345] In the preferred embodiment, R exists in equation (S1). 41’ At that time, in at least one, preferably all R 41’ In this context, r1” is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0346] In the preferred embodiment, in formula (S1), k1 is 2 or 3, preferably 3, r1 is 0, and r2 is 2 or 3, preferably 3.

[0347] In one embodiment, the fluorine-containing silane compound is the compound represented by formula (A1).

[0348] In one embodiment, the fluorine-containing silane compound is the compound shown in formula (A2).

[0349] The silane compounds containing fluorine atoms shown in formula (A1) or formula (A2) above are not particularly limited and may have a concentration of 5 × 10⁻⁶. 2 ~1×10 5 The average molecular weight. Within this range, from the viewpoint of friction durability, an average molecular weight of 2,000 to 32,000 is preferred, and more preferably 2,500 to 12,000 is preferred. Furthermore, this "average molecular weight" is the exponential average molecular weight, and the "average molecular weight" is determined by... 19 The value measured by F-NMR.

[0350] (Method for manufacturing silane compounds containing fluorine atoms)

[0351] The aforementioned fluorine-containing silane compounds can be manufactured by a method including the following steps. Furthermore, the aforementioned fluorine-containing silane compounds are not limited to the following steps and can also be obtained by other methods.

[0352] Provide methods including process (A), process (B), and process (C):

[0353] Process (A):

[0354] Make the compound represented by formula (B1) or formula (B2) (where R) F1 R F2The meaning is the same as above) and HSiM3 (where M is a halogen atom or C independently). 1－6 The process of reacting alkoxy groups to obtain compounds of formula (B13) or (B23)

[0355] R F1 -CH=CH2…(B1)

[0356] CH2=CH-R F2 -CH=CH2…(B2)

[0357] R F1 -CH2CH2-SiM3…(B13)

[0358] M3Si-CH2CH2-R F2 -CH2CH2-SiM3…(B23);

[0359] Process (B):

[0360] Make the compound represented by formula (B13) or formula (B23) and the compound represented by formula: Hal-J-Z'-CH=CH2 (where Z' represents a valence bond or a divalent organic group, J represents Mg, Cu, Pd or Zn, and Hal represents a halogen atom) and according to the desired formula: Y h L (where Y has the same meaning as R) b1 or R c1 Similarly, L represents a group that can bond with Y, and h is an integer from 1 to 3. The process of reacting the compound shown in formula (B14) to obtain the compound shown in formula (B24) is as follows:

[0361] R F1 -CH2CH2-Si(Y 3-k’ (-Z'-CH=CH2) k’ …(B14)

[0362] (CH2=CH-Z'-)(Y 3-k’ )Si-CH2CH2-*

[0363] *R F2 -CH2CH2-Si(Y 3-k' (-Z'-CH=CH2) k’ …(B24)

[0364] (where R is in the formula) F1 and R F2 The meanings of are the same as above, and the meanings of Y and Z' are the same as above, where k' is an integer from 1 to 3.

[0365] Process (C):

[0366] Make the compound represented by formula (B14) or formula (B24) and formula: HSiM3 (where M has the same meaning as above) and / or formula: R 1 i L'(where R is in the formula) 1 The meaning and R 42 or R 43 Similarly, L' indicates that it can interact with R. 1 The bonded groups, i being an integer from 1 to 3. The compound shown and according to the desired formula: R 2’ j L (where R is in the formula) 2’ Indicates C 1－22 Alkyl, "L" indicates that it can react with R 2’ The bonded groups, where j is an integer from 1 to 3. The reaction steps of the compound shown.

[0367] The above-mentioned processes (A) to (C) can be carried out, for example, based on Japanese Patent Application Publication No. 2014-218639.

[0368] The compound represented by formula (B1) or formula (B2) can be manufactured by a method including the following step (D).

[0369] Process (D):

[0370] The formation process of compounds of formula (B1) or (B2) involves adding a methyleneizing agent to the compounds shown in formula (B31) or (B41).

[0371]

[0372] R F1 -CH=CH2…(B1)

[0373] CH2=CH-R F2 -CH=CH2…(B2).

[0374] Furthermore, the compounds shown in formula (B31) and formula (B41) can be represented as hydrates of the following compounds, respectively.

[0375] R F1 -C(=O)-H…(B32)

[0376] H-(O=)CR F2 -C(=O)-H…(B42)

[0377] R F1 and R F2 The meanings are the same as those mentioned above.

[0378] Examples of methyleneizing reagents include Wittig, Horner-Wadsworth-Emmons, Peterson, Tebbe, Petasis, and Julia-Koclenski, with Wittig being the preferred choice.

[0379] Wittig reagent can be used to react Ph3PR with a base. 12 Hal is obtained by processing and dehydrohalogenating, thus forming the ylidene Ph3P. + C － R 12 Phosphine Ph3P=CR 12 The resonance structure. In the formula, Ph is phenyl; R 12 It can contain alkyl groups with heteroatoms, divalent organic groups with carbon-carbon double bonds at the ends, etc.; Hal is a halogen atom (e.g., F, Cl, Br, I). R 12 For example, being able to list C 1－3 Alkyl or C 2－3 Alkylene.

[0380] As Ph3PR 12 Examples of Hal include Ph3PCH3Br, Ph3PCH3Cl, Ph3PCH2CH3Br, Ph3PCH2CH2CH3Br, and Ph3PCH2CH=CH2Br.

[0381] Examples of alkalis include potassium tert-butoxide, butyllithium, phenyllithium, and potassium hexamethyldisilazane.

[0382] The concentration of the methylene methylating agent can be adjusted appropriately; for example, 1 to 10 times can be added for 1 mol of carbonyl groups in formulas (B32) and (B42).

[0383] Process (D) can be carried out at temperatures ranging from 0 to 80°C as needed. There is no particular limitation on the reaction time, for example, from 0.5 to 48 hours.

[0384] Step (D) can be carried out at room temperature. The reaction time is not particularly limited, for example, from 0.5 to 48 hours. Furthermore, heating may be performed as needed.

[0385] In step (D), at least one of the compounds shown in formula (B31) and formula (B41) can be appropriately added to the solution, for example, 1 to 1,000 g / L can be added relative to the overall solution.

[0386] Step (D) is preferably carried out in solution, and solvents such as dichloromethane, tetrahydrofuran, toluene, NovecHFE7200, NovecHFE7300, and 1,3-bis(trifluoromethyl)benzene can be used.

[0387] In step (D), at least one of the compounds shown in formula (B31) and formula (B41) can be appropriately added to the solution, for example, 1 to 1,000 g / L can be added relative to the overall solution.

[0388] The compounds represented by formula (B31) or formula (B41) can be manufactured, for example, based on the following process (E) or process (F).

[0389] Process (E)

[0390] Process (E1):

[0391] The reaction process involves the formation of ester bonds through the dehydration condensation reaction of the compound shown in formula (B11) or formula (B21) with an alcohol.

[0392]

[0393] and

[0394] Process (E2):

[0395] The reaction process that uses a metal hydride reagent to reduce ester bonds.

[0396] Process (E1) in orthoformate HCR 11 This is performed in the presence of 3. Here, R 11 Each is an alkoxy group (e.g., methoxy group).

[0397] Process (E1) can be carried out at 0–100°C as needed. There is no particular limitation on the reaction time, for example, 1–20 hours.

[0398] Process (E2) can be carried out using hydride metal reagents, such as diisobutylaluminum hydride.

[0399] Process (E2) can be carried out at room temperature. Here, room temperature refers to the range of 0–30°C. The reaction time is not particularly limited, for example, 1–48 hours. Furthermore, heating may be performed as needed.

[0400] Process (F)

[0401] Process (F1):

[0402] The reduction reaction process involves adding a reducing agent to the compound shown in formula (B11) or formula (B21) to reduce the above-mentioned compound.

[0403]

[0404] Process (F2):

[0405] An oxidation process in which an oxidizing agent is added to the compound represented by formula (B12) or formula (B22) obtained in the above process to oxidize the compound.

[0406] R F1 -CH2-OH…(B12)

[0407] HO-CH2-R F2 -CH2-OH…(B22).

[0408] A reducing agent can be used in the reduction reaction of process (F1). Examples of reducing agents include hydride metal reagents such as NaBH4 and LiAlH4, and hydrogen addition in the presence of a Pd catalyst.

[0409] The reduction reaction in process (F1) can be carried out, for example, using NaBH4.

[0410] In process (F2), as an oxidant, a superatomic iodine compound, such as Des Martin oxidant (1,1,1-triacetoxy-1,1-dihydro-1,2-benzyl-3-(1H)-one), can be used.

[0411] (Composition)

[0412] The silane compounds containing fluorine atoms shown in formula (A1) or formula (A2) can be used as compositions.

[0413] The content of the fluorine-containing silane compound relative to the composition may, for example, be less than 10% by mass, or less than 3% by mass. The aforementioned content may, for example, be more than 0.5% by mass, or more than 0.01% by mass.

[0414] The above composition can impart water-repellent, oil-repellent, anti-fouling, surface lubrication, and friction durability to the substrate. Without particular limitation, it can be used as a surface treatment agent, anti-fouling coating, or waterproof coating for surface treatment of the substrate.

[0415] The above composition may contain silane compounds with fluorine atoms as shown in formula (A1) and silane compounds with fluorine atoms as shown in formula (A2).

[0416] In one embodiment, the lower limit of the molar ratio (of the fluorine-containing silane compound represented by formula (A2) to the total of the fluorine-containing silane compounds represented by formulas (A1) and (A2) is preferably 0.001, more preferably 0.002, further preferably 0.005, even more preferably 0.01, particularly preferably 0.02, especially 0.05. The upper limit of the molar ratio (of the fluorine-containing silane compound represented by formula (A2) to the total of the fluorine-containing silane compounds represented by formulas (A1) and (A2) is preferably 0.70, more preferably 0.60, more preferably 0.50, further preferably 0.40, even more preferably 0.20 or 0.10. The ratio (molar ratio) of the fluorine-containing silane compound shown in formula (A2) to the total of the fluorine-containing silane compounds shown in formulas (A1) and (A2) can be 0.001 to 0.70 or less, 0.001 to 0.60 or less, 0.001 to 0.50 or less, 0.002 to 0.40 or less, 0.005 to 0.30 or less, 0.01 to 0.20 or less, for example, 0.02 to 0.20 or less (specifically 0.15 or less) or 0.05 to 0.20 or less (specifically 0.15 or less).

[0417] In one embodiment, the lower limit of the molar ratio (of the fluorine-containing silane compound represented by formula (A1) to the total of the fluorine-containing silane compounds represented by formulas (A1) and (A2) is preferably 0.001, more preferably 0.002, further preferably 0.005, even more preferably 0.01, particularly preferably 0.02, especially 0.05. The upper limit of the molar ratio (of the fluorine-containing silane compound represented by formula (A1) to the total of the fluorine-containing silane compounds represented by formulas (A1) and (A2) is preferably 0.70, more preferably 0.60, more preferably 0.50, further preferably 0.40, even more preferably 0.20 or 0.10. The ratio (molar ratio) of the fluorine-containing silane compound shown in formula (A1) to the total of the fluorine-containing silane compounds shown in formulas (A1) and (A2) can be 0.001 to 0.70 or less, 0.001 to 0.60 or less, 0.001 to 0.50 or less, 0.002 to 0.40 or less, 0.005 to 0.30 or less, 0.01 to 0.20 or less, for example, 0.02 to 0.20 or less (specifically 0.15 or less) or 0.05 to 0.20 or less (specifically 0.15 or less).

[0418] The above composition may further include a solvent, a (non-reactive) fluorinated polyether compound which can be understood as a fluorinated oil, preferably a PFPE compound (hereinafter collectively referred to as "fluorinated oil"), a (non-reactive) organosilicon compound which can be understood as an organosilicon oil (hereinafter referred to as "organosilicon oil"), a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, etc.

[0419] Examples of solvents mentioned above include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral oil; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and naphthol; and methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, acetic acid cellosol, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl-2-hydroxybutyric acid. Esters such as ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether. Diol ethers such as 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, octanol, 3-methyl-3-methoxybutanol, and tert-pentanol; diols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydrofuran, and dioxane; N,N-dimethyl... Amides such as formamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; fluorinated 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, etc. Alternatively, two or more of these mixed solvents can be listed.

[0420] There are no particular limitations on the fluorinated oils mentioned above. For example, compounds represented by the following general formula (3) (PFPE compounds) can be listed.

[0421] Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’-Rf 6 ···(3)

[0422] In the formula, Rf 5 The alkyl group (preferably C16) represents a carbon atom that can be replaced by one or more fluorine atoms. 1―16 perfluoroalkyl), Rf 6 The alkyl group (preferably C16) represents a carbon atom that can be replaced by one or more fluorine atoms. 1－16 perfluoroalkyl), fluorine atom or hydrogen atom, Rf 5 and Rf 6 More preferably, each independently is C 1－3 Perfluoroalkyl.

[0423] a', b', c', and d' represent the number of four repeating units of the perfluoro(poly)ether constituting the main backbone of the polymer, and are independent integers ranging from 0 to 300. 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 the repeating units with subscripts a', b', c', or d' and enclosed in parentheses is arbitrary in the formula. Among these repeating units, -(OC4F8)- can be any one of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, preferably -(OCF2CF2CF2)-. -(OC2F4)- can be either -(OCF2CF2)- or (OCF(CF3))-, preferably -(OCF2CF2)-.

[0424] As an example of the PFPE compound shown in the above general formula (3), the following compounds shown in either general formula (3a) and (3b) can be listed (which may be one or a mixture of two or more).

[0425] Rf 5 -(OCF2CF2CF2) b” -Rf 6 ···(3a)

[0426] Rf 5 -(OCF2CF2CF2CF2)a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 ···(3b)

[0427] In these formulas, Rf 5 and Rf 6 As described above; in equation (3a), b” is an integer greater than 1 and less than 100; in equation (3b), a” and b” are each independently an integer greater than 0 and less than 30, and c” and d” are each independently an integer greater than 1 and less than 300. The order of the repeated units with subscripts a”, b”, c”, and d” and enclosed in parentheses is arbitrary in the equation.

[0428] Alternatively, from another perspective, fluorinated oils can be classified as having the general formula Rf. 3 -F(where Rf) 3 C 5－16 The compound shown is a perfluoroalkyl group. Alternatively, it can be a trichlorofluoroethylene oligomer.

[0429] The aforementioned fluorinated oils can have an average molecular weight of 500 to 10,000. The molecular weight of fluorinated oils can be determined using gel permeation chromatography (GPC).

[0430] The fluorinated oil may contain, for example, 0 to 50% by mass relative to the composition of the present invention (e.g., a surface treatment agent), preferably 0 to 30% by mass, more preferably 0 to 5% by mass. In one embodiment, the composition of the present invention is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means completely free of fluorinated oil, or may contain trace amounts of fluorinated oil.

[0431] Fluorinated oils help improve the surface slip properties of layers formed from the compositions of the present invention (e.g., surface treatment agents).

[0432] In one embodiment, relative to the total of the fluorine-containing silane compound shown in formula (A1), the fluorine-containing silane compound shown in formula (A2), and the fluorinated oil, the compound shown in formula (A2) may contain, 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. Relative to the total of the fluorine-containing silane compound shown in formula (A1), the fluorine-containing silane compound shown in formula (A2), and the fluorinated oil, the fluorine-containing silane compound shown in formula (A2) may contain, for example, 1 to 70 mol%, or 5 to 50 mol%.

[0433] In one embodiment, relative to the total of the fluorinated silane compound with fluorine atoms shown in formula (A1), the fluorinated silane compound with fluorine atoms shown in formula (A2), and the fluorinated oil, the fluorinated oil may, for example, contain 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. Relative to the total of the fluorinated silane compound with fluorine atoms shown in formula (A1), the fluorinated silane compound with fluorine atoms shown in formula (A2), and the fluorinated oil, the fluorinated oil may, for example, contain 0.001 to 50 mol%, or 0.01 to 40 mol%.

[0434] In one embodiment, relative to the total of the fluorine-containing silane compound of formula (A1), the fluorine-containing silane compound of formula (A2), and the fluorinated oil, it is preferable to contain 0.001 to 70 mol% of the fluorine-containing silane compound of formula (A2) and 0.001 to 50 mol% of the fluorine-containing oil; more preferably, it contains 0.01 to 60 mol% of the fluorine-containing silane compound of formula (A2) and 0.01 to 40 mol% of the fluorinated oil; even more preferably, it contains 0.1 to 50 mol% of the fluorine-containing silane compound of formula (A2) and 0.1 to 30 mol% of the fluorinated oil.

[0435] As the aforementioned silicone oil, for example, linear or cyclic silicone oils with siloxane bonds of 2,000 or less can be used. Linear silicone oils can be so-called ordinary silicone oils and modified silicone oils. Examples of ordinary silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrosilicone oil. Examples of modified silicone oils include silicone oils formed by modifying ordinary silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, or alcohol groups. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0436] In the composition of the present invention, the organosilicon oil may be contained, for example, in 0 to 300 parts by mass, preferably in 50 to 200 parts by mass, relative to the total of 100 parts by mass of the fluorine-containing silane compounds of the present invention (or the total of two or more, and so on below).

[0437] Organosilicon oil helps to improve the surface slip properties of the layer formed by the composition of the present invention.

[0438] Examples of catalysts mentioned above include acids (such as acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), and transition metals (such as Ti, Ni, Sn, etc.).

[0439] The catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compounds of the present invention, and promotes the formation of layers formed by the compositions of the present invention (e.g., surface treatment agents).

[0440] Other components, besides those mentioned above, include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, methyltriacetoxysilane, etc.

[0441] (granular material)

[0442] The compositions of the present invention can be impregnated in porous materials, such as porous ceramic materials, or materials in which metal fibers, such as steel wool, are fixed in a cotton-like form to form granules. These granules can be used, for example, in vacuum evaporation.

[0443] In one embodiment, the composition of the present invention is used for wet covering.

[0444] (thing)

[0445] The items of the present invention will now be described.

[0446] The articles of the present invention include a substrate and a layer (surface treatment layer) formed on the surface of the substrate by a composition (surface treatment agent) comprising a silane compound containing fluorine atoms of the present invention.

[0447] The substrate that can be used in this invention can be made of any suitable material, such as glass, resin (natural or synthetic resin, for example, a general plastic material, which can be in sheet, film, or other form), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building components, etc.

[0448] For example, if the desired product is an optical component, the material constituting the surface of the substrate can be a material used for optical components, such as glass or transparent plastic. Additionally, if the desired product is an optical component, certain layers (or films), such as a hard coating or an anti-reflective layer, can be formed on the surface (outermost layer) of the substrate. The anti-reflective layer can be either a single-layer anti-reflective layer or a multi-layer anti-reflective layer. Examples of inorganic materials that can be used for anti-reflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic materials can be used alone or in combination of two or more (e.g., in the form of a mixture). In the case of a multi-layer anti-reflective layer, the outermost layer is preferably made of SiO2 and / or SiO. When the desired product is an optical glass component for a touch panel, a portion of the surface of the substrate (glass) can have a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide. Additionally, the substrate can have insulating layers, adhesive layers, protective layers, decorative frame layers (I-CON), atomizing film layers, hard coating layers, polarizing films, retardation films, and liquid crystal display components, depending on its specific specifications.

[0449] There are no particular limitations on the shape of the substrate. In addition, the surface area of ​​the substrate to which the surface treatment layer is to be formed only needs to be at least a portion of the substrate surface, and can be appropriately determined according to the intended use and specific specifications of the item to be manufactured.

[0450] As the substrate, at least its surface portion can be composed of a material that originally possesses hydroxyl groups. Examples of such materials include glass, as well as metals (especially base metals), ceramics, semiconductors, etc., whose surfaces have naturally formed or thermally formed oxide films. Alternatively, in cases where the substrate, such as resin, possesses hydroxyl groups but not enough, or where it originally lacks hydroxyl groups, certain pretreatments can be performed on the substrate to introduce or increase hydroxyl groups on its surface. Examples of such pretreatments include plasma treatment (e.g., corona discharge) or ion beam irradiation. Plasma treatment is also suitable for introducing or increasing hydroxyl groups on the substrate surface and for cleaning the substrate surface (removing foreign matter, etc.). Another example of such pretreatment is the method of pre-forming a surface adsorbent with carbon-carbon unsaturated bonds on the substrate surface in the form of a monolayer using the LB method (Langmuir-Blodgett method) or chemisorption, followed by breaking the unsaturated bonds in an atmosphere containing oxygen or nitrogen.

[0451] Alternatively, as the substrate, at least its surface portion may be formed of a material containing an organosilicon compound having one or more other reactive groups such as Si-H groups, and / or an alkoxysilane.

[0452] Next, a layer of the composition of the present invention (e.g., a surface treatment agent) described above is formed on the surface of the substrate, and the layer is post-treated as needed, thereby forming a layer from the composition of the present invention.

[0453] The surface treatment agent of the present invention can be layered by applying the above-described composition to the surface of a substrate in a manner that covers the surface. The covering method is not particularly limited. For example, a wet covering method and a dry covering method can be used.

[0454] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, gravure coating, and similar methods.

[0455] Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum vapor deposition) 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.

[0456] Alternatively, atmospheric pressure plasma method can be used to achieve coverage.

[0457] When using the wet coating method, the compositions of the present invention can be diluted with a solvent and then applied to the substrate surface. From the viewpoint of the stability of the compositions of the present invention and the volatility of the solvent, solvents with the following characteristics are preferred: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluorinated aromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluorinated aliphatic hydrocarbons (e.g., C6F...). 13CH2CH3 (e.g., Asahiklin AC-6000 manufactured by Asahi Glass Co., Ltd., registered trademark); 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora H manufactured by Zeon Corporation, registered trademark); hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Co., Ltd., registered trademark); perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Co., Ltd., registered trademark). Alkyl perfluoroalkyl ethers such as 7100), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Corporation), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec (trademark) 7300 manufactured by Sumitomo 3M Corporation) (the perfluoroalkyl and alkyl groups can be linear or branched), or CF3CH2OCF2CHF2 (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) etc. These solvents can be used alone or in mixtures of two or more. Among them, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0458] As the solvent used for the wet covering method, it is preferable to use the same solvent as the solvent of the composition of the present invention.

[0459] When using the drying and covering method, the composition of the present invention can be used directly in the drying and covering method or diluted with the solvent described above before being used in the drying and covering method.

[0460] From the viewpoint of achieving good dispersibility, the compositions of the present invention can be used effectively in wet coating methods, particularly in spraying applications.

[0461] The layer formation of the composition is preferably carried out in such a manner that the composition of the present invention is present in the layer together with a catalyst for hydrolysis and dehydration condensation. For simplicity, when using the wet coating method, the composition of the present invention can be diluted with a solvent, and the catalyst can be added to the diluted solution of the composition of the present invention before it is applied to the substrate surface. When using the dry coating method, the composition of the present invention with the catalyst added can be used directly for vapor deposition (usually vacuum vapor deposition), or vapor deposition (usually vacuum vapor deposition) can be performed using granular material of the surface treatment agent of the present invention impregnated with the catalyst added in a porous metal such as iron or copper.

[0462] The catalyst can be any suitable acid or base. As an acid catalyst, examples include acetic acid, formic acid, and trifluoroacetic acid. As a base catalyst, examples include ammonia and organic amines.

[0463] As described above, a layer derived from the composition of the present invention is formed on the surface of a substrate to manufacture the article of the present invention. The resulting layer exhibits both high surface slip properties and high frictional durability. In addition to high frictional durability, depending on the composition of the surface treatment agent used, the layer may also possess properties such as water repellency, oil repellency, stain resistance (preventing the adhesion of dirt such as fingerprints), water resistance (preventing water from penetrating electronic components, etc.), and surface slip properties (or lubrication, the ability to wipe away dirt such as fingerprints, and excellent tactile feel for fingers), making it suitable for use as a functional film.

[0464] That is, the present invention also relates to optical materials having the above-described composition (e.g., a surface treatment layer) in the outermost layer.

[0465] In addition to optical materials related to displays, as exemplified below, a wide variety of optical materials are preferred as optical materials, such as cathode ray tubes (CRTs, such as personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent tubes (VFDs), field emission displays (FEDs), and other displays or protective plates for these displays, or materials on which anti-reflective coatings have been applied to their surfaces.

[0466] Articles having the layer obtained by the present invention are not particularly limited and can be optical components. Examples of optical components include the following: lenses for eyeglasses, etc.; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as portable telephones and portable information terminals; disc surfaces for Blu-ray discs, DVD discs, CD-Rs, MO discs, etc.; optical fibers; and the display surface of clocks, etc.

[0467] In addition, articles having the layer obtained by the present invention can also be medical devices or medical materials.

[0468] Furthermore, articles having the layer obtained by the present invention can be automotive interior and exterior parts. Examples of exterior parts include: windows, lamp covers, and exterior camera covers. Examples of interior parts include: dashboard covers, navigation system touchscreens, and interior trim.

[0469] The thickness of the above-mentioned layer is not particularly limited. When it is an optical component, from the viewpoint of optical performance, surface lubricity, friction durability and anti-fouling properties, the thickness of the above-mentioned layer is in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm.

[0470] The foregoing has described in detail the fluorine-containing silane compounds, compositions containing the fluorine-containing silane compounds, articles having a substrate and a layer formed from the composition, and methods for manufacturing the fluorine-containing silane compounds of the present invention. Furthermore, the fluorine-containing silane compounds, compositions containing the fluorine-containing silane compounds, substrates, and compositions of the present invention are not limited to the examples exemplified above, and various modifications are possible in their manner and details as long as they do not depart from the essential points and scope of the claimed protection.

[0471] Example

[0472] The present invention will be described below with reference to embodiments, but the present invention is not limited to the following embodiments.

[0473] (Synthesis example 1)

[0474] Dissolve 2.5 g of methyltriphenylphosphonium bromide in 5.0 g of tetrahydrofuran and chill. Add 6.7 ml of potassium tert-butoxide (1.0 M / L tetrahydrofuran solution) and stir for 20 minutes. Slowly add this solution to chilled CF3O-(CF2CF2O). m -(CF2O) n 10.0 g of CF₂CH(OH)₂ (m≈25, n≈23) was dissolved in 20.0 g of 1,3-bis(trifluoromethyl)benzene, and the solution was stirred at room temperature for 20 hours. The endpoint of the reaction was determined by... 19 F-NMR confirmed the presence of CF3O (CF2CF2O). m -(CF2O) n The chemical shift of the -CF2- group at the β-position of the aldehyde group in CF2CH(OH)2 moves to the low magnetic field side, and through... 1 H-NMR confirmed the peak of vinyl formation. Water was added to the reaction solution to separate the lower phase. The upper phase was extracted with 1,3-bis(trifluoromethyl)benzene and combined with the lower phase. The mixture was washed twice with water, dried with magnesium sulfate, and concentrated. The concentrate was purified by rapid column chromatography to give 7.8 g of compound (A) containing polyether groups.

[0475] Compound (A) containing polyether groups:

[0476]

[0477] (Synthesis example 2)

[0478] 3.0 g of the polyether-containing compound (A) obtained in Synthesis Example 1 was dissolved in 6 g of 1,3-bis(trifluoromethyl)benzene. 0.04 ml of a 2% xylene solution containing 0.02 g of triacetoxymethylsilane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane Pt complex was added, followed by 0.8 g of trichlorosilane. The mixture was stirred at 10°C for 30 minutes. Then, it was heated to 80°C and stirred for 5 hours. The reaction endpoint was reached via... 1 ¹H-NMR confirmed the disappearance of protons in the vinyl group. After removing volatile components by distillation under reduced pressure, the mixture was chilled, and 3.7 ml of allyl magnesium chloride (1.0 M / L tetrahydrofuran solution) was slowly added. The reaction mixture was brought to room temperature and stirred overnight. 3.0 ml of dehydrated methanol was added to the reaction mixture, and the mixture was filtered through diatomaceous earth. The lower phase was concentrated to give 3.0 g of compound (B) containing polyether groups.

[0479] Compounds containing polyether groups (B):

[0480]

[0481] (Synthesis example 3)

[0482] 3.0 g of the polyether-containing compound (B) obtained in Synthesis Example 2 was dissolved in 6 g of 1,3-bis(trifluoromethyl)benzene. 0.04 ml of a xylene solution containing 0.02 g of triacetoxymethylsilane and 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, followed by 0.8 g of trichlorosilane. The mixture was stirred at 10°C for 30 minutes. Then, the mixture was heated to 65°C and stirred for 4 hours. Afterward, volatile components were removed by distillation 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. Subsequently, by purification, 2.9 g of a silane compound (C) with a fluorine atom at the terminal trimethoxysilyl group was obtained.

[0483] Silane compounds containing fluorine atoms (C):

[0484]

[0485] (Synthesis Example 4)

[0486] In addition to using CF3CF2CF2O-(CF2CF2CF2O) m Except for 10.0 g of -CF2CF2CH(OH)2(m≈27), the same operation as in Synthetic Examples 1 to 3 was performed to obtain 3.0 g of silane compound (D) containing fluorine atoms.

[0487] Silane compounds containing fluorine atoms (D):

[0488]

[0489] (Synthesis Example 5)

[0490] 3.0 g of the polyether-containing compound (A) obtained in Synthesis Example 1 was dissolved in 6 g of 1,3-bis(trifluoromethyl)benzene. 0.04 ml of a 2% xylene solution containing 0.02 g of triacetoxymethylsilane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane Pt complex was added, followed by 0.8 g of trichlorosilane. The mixture was stirred at 10°C for 30 minutes. Then, it was heated to 80°C and stirred for 5 hours. The reaction endpoint was reached via... 1 ¹H-NMR confirmed the disappearance of protons in the vinyl group. After removing volatile components by distillation under reduced pressure, the mixture was chilled and 3.7 ml of vinyl magnesium chloride (1.0 M / L tetrahydrofuran solution) was slowly added. The reaction mixture was brought to room temperature and stirred overnight. 3.0 ml of dehydrated methanol was added to the reaction mixture, and the mixture was filtered through diatomaceous earth. The lower phase was concentrated to give 2.9 g of the polyether-containing compound (E).

[0491] Compounds containing polyether groups (E):

[0492]

[0493] (Synthesis Example 6)

[0494] 2.0 g of the polyether-containing compound (E) obtained in Synthesis Example 5 was dissolved in 4 g of 1,3-bis(trifluoromethyl)benzene. 0.03 ml of a xylene solution containing 0.02 g of triacetoxymethylsilane and 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, followed by 0.6 g of trichlorosilane. The mixture was stirred at 10°C for 30 minutes. Then, the mixture was heated to 65°C and stirred for 4 hours. After removing volatile components by distillation 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. Subsequently, by purification, 2.0 g of a silane compound (F) with a fluorine atom at the terminal trimethoxysilyl group was obtained.

[0495] Silane compounds containing fluorine atoms (F):

[0496]

[0497] (Example 1)

[0498] The fluorine-containing silane compound (C) obtained in the above synthesis example 3 was dissolved in hydrofluoroether (3M Corporation, Novec HFE-7200) at a concentration of 0.1% by mass to prepare a surface treatment agent (1).

[0499] (Example 2)

[0500] The fluorine-containing silane compound (D) obtained in the above synthesis example 4 was dissolved in hydrofluoroether (3M Corporation, Novec HFE-7200) at a concentration of 0.1% by mass to prepare surface treatment agent (2).

[0501] (Example 3)

[0502] The fluorine-containing silane compound (F) obtained in the above synthesis example 6 was dissolved in hydrofluoroether (3M Corporation, Novec HFE-7200) at a concentration of 0.1% by mass to prepare a surface treatment agent (3).

[0503] (Comparative Example 1)

[0504] Instead of the polyether-containing compound (D), the following control compound (1) was used, and the comparative surface treatment agent (1) was prepared in the same manner as in Example 2.

[0505] Control compound (1):

[0506]

[0507] (Formation of the cured film)

[0508] A cured film was formed using surface treatment agents (1) to (3) and comparative surface treatment agent (1) as described below.

[0509] The surface treatment agent or a comparative surface treatment agent is applied to the chemically strengthened glass (Corning, "Gorilla" glass, 0.7 mm thick) using a spin coater.

[0510] The spin coating conditions are: 300 rpm for 3 seconds; 2000 rpm for 30 seconds.

[0511] The coated glass is heated at 150°C for 30 minutes in a constant temperature bath under atmospheric conditions to form a cured film.

[0512] (Static contact angle)

[0513] The static contact angle was measured using a DropMaster 700 fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) as follows.

[0514] <Methods for determining static contact angle>

[0515] The static contact angle is calculated as follows: 2 μL of water or n-hexadecane is added dropwise to a horizontally placed substrate using a micro-syringe, and a still image is captured using a video microscope 1 second after the addition.

[0516] (Evaluation of the abrasion resistance of the cured film)

[0517] The wear resistance of the obtained cured film is evaluated as follows.

[0518] <Rubber Friction Resistance Test>

[0519] Using a friction testing machine (manufactured by Shin-Tung Science & Technology Co., Ltd.), the water contact angle was measured every 2,500 wiping cycles under the following conditions, and the test was continued until 10,000 cycles or below 100 degrees. The test environment conditions were 25°C and 40% RH.

[0520] Eraser: Raber Eraser (Made by Minoan)

[0521] Grounding area:

[0522] Travel distance (one way): 30mm

[0523] Movement speed: 3,600 mm / min

[0524] Load:

[0525] The evaluation results are shown in Table 1 below.

[0526] [Table 1]

[0527] 0 times 2500 times 5000 times 7500 times 10,000 times Surface treatment agent (1) 115° 111° 108° 106° 100° Surface treatment agent (2) 115° 113° 110° 109° 102° Surface treatment agent (3) 115° 109° 108° 101° 85° Comparison of surface treatment agents (1) 113° 102° 86° － －

[0528] (Evaluation of the weather resistance of the cured film)

[0529] The weather resistance of the obtained cured film is evaluated as follows.

[0530] <Promoting Weather Resistance Test>

[0531] UV irradiation was conducted as follows: A UVB-313 lamp (manufactured by Q-Lab) was used, emitting an illuminance of 0.63 W / m² at 310 nm. 2 The distance between the lamp and the surface treatment layer of the substrate was set to 5 cm, and the temperature of the board 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 five times back and forth using wiping paper (Kimwipes) (trade name, manufactured by Kimberly-Clark). The static contact angle of water was then measured immediately thereafter.

[0532] The evaluation results are shown in Table 2 below.

[0533] [Table 2]

[0534] 0 hours 72 hours 144 hours 240 hours 312 hours 360 hours 480 hours 648 hours Surface treatment agent (1) 116° 115° 115° 114° 114° 113° 112° 111° Surface treatment agent (2) 115° 115° 114° 113° 113° 113° 111° 110° Surface treatment agent (3) 115° 114° 114° 113° 113° 113° 112° 111° Comparison of surface treatment agents (1) 113° 114° 110° 96° － － － －

[0535] As shown in Tables 1 and 2, it can be seen that by using CH2CH2 as the first joint, a surface treatment layer with good friction durability and weather resistance is formed. This is presumably because the length and volume of the first joint are very short, thus, on the outermost surface side of the surface treatment layer (the side opposite to the substrate), R... F The dense substrate results in increased resistance of the surface treatment layer to friction and UV irradiation.

[0536] Industrial availability

[0537] This invention can be appropriately used to form a surface treatment layer with better friction durability and weather resistance on a wide variety of substrates, especially optical components that require transparency.

Claims

1. A silane compound containing fluorine atoms, as shown in formula (A1) or (A2), wherein, R F1 -CH2CH2-R Si …(A1) R Si -CH2CH2-R F2 -CH2CH2-R Si …(A2) In the formula: R F1 is Rf 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 C atoms that can be substituted by more than one fluorine atom 1－16 alkyl; Rf 2 C atoms that can be substituted by more than one fluorine atom 1－6 Alkylene; R F Each of the following groups is independently a divalent fluorine atom; p is 0 or 1; q can be 0 or 1 independently; R Si Each of these is independently a monovalent group comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; and, At least 1 R Si It contains Si atoms bonded with hydroxyl groups or hydrolyzable groups.

2. The fluorine-containing silane compound as described in claim 1, characterized in that: R F Each of the following groups can be independently represented by formula (f1) or formula (f2). -(OC j R e 2j ) j1 -(OC h R e 2h－2 ) h1 - (f1) In equation (f1): -OC j R e 2j - Each is an independent repeating unit with a straight chain or branches; -OC h R e 2h－2 - Each is an independent repeating unit with a ring structure; R e Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom; Among them, in R F In, at least one R e It is a fluorine atom; j are each an independent integer from 1 to 6; h are independent integers 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 1 or more; The order of repeated units with j1 or h1 enclosed in parentheses is arbitrary in the formula. -(C s R e1 2s ) s1 -(R d ) s2 -(f2) In equation (f2): s are each an independent integer from 1 to 10; R e1 Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom; R d Each is an arylene group that can be substituted by a fluorine atom; Among them, R d Substituents or R e1 At least one of them 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 1 or more; The order of the repeating units with s1 or s2 enclosed in parentheses is arbitrary in the formula.

3. The fluorine-containing silane compound as described in claim 1 or 2, characterized in that: R F Each of the following groups can be independently represented: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - In the formula: a1, b1, c1, d1, e1, and f1 are each independent integers from 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 1 or more; The order of repeated units with a1, b1, c1, d1, e1, or f1 enclosed in parentheses is arbitrary in the formula; R Fa Each time it appears, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom.

4. The fluorine-containing silane compound as described in claim 1 or 2, characterized in that: R F Each of the following groups can be independently represented by one of the following formulas: (f11), (f12), (f13), (f14), (f15), or (f16). -(OC3F6) d1 -(OC2F4) e1 -(f11) In equation (f11): d1 is an integer from 1 to 200; e1 is either 0 or 1; -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 -(f12) In equation (f12): c1 and d1 are independent integers above 0 and below 30; e1 and f1 are each an independent integer greater than 1 and less than 200; The sum of c1, d1, e1, and f1 is 2 or more; The order of repeated units with subscripts c1, d1, e1 or f1 and enclosed in parentheses is arbitrary in the formula; -(R 71 -R 72 ) g1 -R 73 -(f13) In equation (f13): R 71 It is either OCF2 or OC2F4; R 72 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups independently selected from these groups; R 73 It is a single bond, or selected from OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, 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 equation (f14): R 71 It is either OCF2 or OC2F4; R 72 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups independently selected from these groups; R 71’ It is either OCF2 or OC2F4; R 72’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, 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 It is any one of the following groups: In the formula, * indicates the bonding position; -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 -(f15) In equation (f15): e1 is an integer greater than 1 and less than 200, a1, b1, c1, d1 and f1 are each an integer greater than 0 and less than 200, the sum of a1, b1, c1, d1, e1 and f1 is at least 1, and the order of the repeating units with a1, b1, c1, d1, e1 or f1 enclosed in parentheses is arbitrary in the formula; -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 -(f16) In equation (f16): f1 is an integer greater than 1 and less than 200, a1, b1, c1, d1 and e1 are each an integer greater than 0 and less than 200, the sum of a1, b1, c1, d1, e1 and f1 is at least 1, and the order of the repeating units with a1, b1, c1, d1, e1 or f1 and enclosed in parentheses is arbitrary in the formula.

5. The fluorine-containing silane compound as described in claim 1 or 2, characterized in that: R Si It is represented by the following formula (S1), -SiR a1 k1 R b1 11 R c1 m1 …(S1) In the formula: R a1 Each independently is -Z 1 -SiR 41 r1 R 42 r2 R 43 r3 ; Z 1 Each can be an oxygen atom or a divalent organic group independently; R 41 Each independently is -Z 1’ -SiR 41’ r1’ R 42’ r2’ R 43’ r3’ ; Z 1’ Each can be an oxygen atom or a divalent organic group independently; R 41’ Each independently is -Z 1” -SiR 41” r1” R 42” r2” ; Z 1” Each can be an oxygen atom or a divalent organic group independently; R 41” Each is independently a hydroxyl group or a hydrolyzable group; R 42” Each can be independently a hydrogen atom or a monovalent organic group; r1” can be an integer from 0 to 3, respectively; r2” are independent integers from 0 to 3; R 42’ Each is independently a hydroxyl group or a hydrolyzable group; R 43’ Each can be independently a hydrogen atom or a monovalent organic group; r1' are independent integers from 0 to 3; r2' are independent integers from 0 to 3; r3' are each an independent integer from 0 to 3; R 42 Each is independently a hydroxyl group or a hydrolyzable group; R 43 Each can be independently a hydrogen atom or a monovalent organic group; r1 can be an integer from 0 to 3 independently; r2 are independent integers from 0 to 3; r3 are independent integers from 0 to 3; R b1 Each is independently a hydroxyl group or a hydrolyzable group; R c1 Each can be independently a hydrogen atom or a monovalent organic group; k1 are independent integers from 0 to 3; l1 can be an integer from 0 to 3 independently; m1 are independent integers from 0 to 3; In formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group.

6. The fluorine-containing silane compound as described in claim 5, characterized in that: Z 1 C independently 1－6 Alkylene, -(CH2) z1 -O-(CH2) z2 - or - (CH2) z3 -Phenylidene-(CH2) z4 -; z1 to z4 are independent integers from 0 to 6.

7. A composition, characterized in that: A silane compound comprising the fluorine-containing atoms as described in claim 1 or 2.

8. An article characterized by: It has a substrate and a layer formed on the surface of the substrate by the composition of claim 7.

9. A method for manufacturing a compound, characterized in that: This includes a formation step of adding a methyleneizing agent to a compound of formula (B31) or formula (B41) to form a compound of formula (B1) or formula (B2). R F1 -CH=CH2…(B1) CH2=CH-R F2 -CH=CH2…(B2) In the formula: R F1 is Rf 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 C atoms that can be substituted by more than one fluorine atom 1－16 alkyl; Rf 2 C atoms that can be substituted by more than one fluorine atom 1－6 Alkylene; R F Each of the following groups is independently a divalent fluorine atom; p is 0 or 1; q can be 0 or 1 independently.

10. The fluorine-containing silane compound as described in claim 1 or 2, characterized in that: It is any one of the following compounds, m≈25, n≈23; m≈27； m≈25, n≈23.

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