Fluoro (poly) ether group-containing silane compound

Abstract

A fluoro (poly) ether group-containing silane compound represented by any of formulae (A1), (A2), (B1), (B2), (C1) or (C2). In the formula, PFPE is independently, at each occurrence, a group represented by the formula:-(OC6F12) a-(OC5F10) b-(OC4F8) c-(OC3XF6) d-(OC2F4) e-(OCF2) f-and having at least one branched chain structure. The meaning of each symbol is the same as that described in the description.

Description

[0001] This case is filed on January 31, 2019 、Application No. 201980011172.X(PCT / JP2019 / 003488) 、The name of the invention is Silane compounds containing fluorinated (poly)ether groups Divisional application. Technical Field

[0002] The present invention relates to silane compounds containing fluorinated (poly)ether groups. Background Art

[0003] It is known that certain types of fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties, etc. when used for surface treatment of substrates. For example, Patent Document 1 discloses a surface treatment composition containing a substance sometimes referred to as a perfluoro(poly)ether-containing silane compound, which has a perfluoro(poly)ether group in the main chain of the molecule and a hydrolyzable group bonded to a Si atom at the molecular end or end portion.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2015-221888 Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] The layer formed of the surface treatment composition (surface treatment agent) as described above (sometimes referred to as a surface treatment layer) is sometimes required to have durability against ultraviolet rays (UV) (sometimes referred to as "ultraviolet durability" or "UV durability").

[0009] The present invention relates to a silane compound having a fluoropolyether group (hereinafter sometimes referred to as a "PFPE-containing silane compound") which contributes to the formation of a surface-treated layer having excellent ultraviolet durability.

[0010] Technical solutions for solving technical problems

[0011] According to the present invention, the following aspects are provided.

[0012] [Method 1]

[0013] A silane compound containing a fluorinated (poly)ether group represented by any one of formulas (A1), (A2), (B1), (B2), (C1) or (C2).

[0014]

[0015] (Rf-PFPE) β’ -X 3 -(SiR ak1 R b l1 R c m1 ) β …(B1)

[0016] (R c m1 R b l1 R a k1 Si) β -X 3 -PFPE-X 3 -(SiR a k1 R b l1 R c m1 ) β …(B2)

[0017] (Rf-PFPE) γ’ -X 5 -(CR d k2 R e l2 R f m2 ) γ …(C1)

[0018] (R f m2 R e l2 R d k2 C) γ -X 5 -PFPE-X 5 -(CR d k2 R e l2 R f m2 ) γ …(C2)

[0019] [Wherein,

[0020] PFPE is independently represented at each occurrence by the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3X F 6) d -(OC2F4) e -(OCF2)f - represents a group having at least one branched structure (wherein a, b, c, d, e and f are each independently an integer from 0 to 200, the sum of a, b, c, d, e and f is at least 1, the order of existence of the repeating units marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary, X F is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence);

[0021] Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0022] X 1 Each occurrence independently represents a single bond or a 2- to 10-valent organic group;

[0023] α is independently an integer from 1 to 9 at each occurrence;

[0024] α′ is independently an integer from 1 to 9;

[0025] R 11 represents independently at each occurrence a hydrogen atom or a halogen atom;

[0026] R 12 represents independently at each occurrence a hydrogen atom or a lower alkyl group;

[0027] X 2 Each occurrence independently represents a single bond or a divalent organic group;

[0028] R 13 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0029] R 14 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

[0030] n in each (-SiR 13 n R 14 3－n ) units independently represent an integer of 0 to 3 or more;

[0031] t is independently an integer from 2 to 10 at each occurrence;

[0032] Wherein, in formula (A1) and (A2), there are at least 2 SiR 13 ;

[0033] X 3 Each occurrence independently represents a single bond or a 2- to 10-valent organic group;

[0034] β is independently an integer from 1 to 9 at each occurrence;

[0035] β' is independently an integer from 1 to 9;

[0036] R a Each occurrence represents -Z independently 3 -SiR 71 p1 R 72 q1 R 73 r1 ;

[0037] Z 3 Each occurrence independently represents an oxygen atom or a divalent organic group;

[0038] R 71 Each occurrence represents R independently a′ ;

[0039] R a′ The meaning of R a same;

[0040] R a Via Z 3 The maximum number of Si groups connected in a straight chain is 5;

[0041] R 72 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0042] R 73 represents independently at each occurrence a hydrogen atom or a lower alkyl group;

[0043] p1 is independently an integer from 0 to 3 at each occurrence;

[0044] q1 is independently an integer from 0 to 3 each time it appears;

[0045] r1 is independently an integer from 0 to 3 at each occurrence;

[0046] Among them, in each (-Z 3 -SiR 71 p1 R 72 q1 R 73 r1 ), the sum of p1, q1 and r1 is 3;

[0047] R b Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0048] Rc represents independently at each occurrence a hydrogen atom or a lower alkyl group;

[0049] k1 is independently an integer from 0 to 3 at each occurrence;

[0050] l1 is independently an integer from 0 to 3 each time it appears;

[0051] m1 is independently an integer from 0 to 3 at each occurrence;

[0052] Among them, in each (SiR a k1 R b l1 R c m1 ), the sum of k1, l1 and m1 is 3, and in formulas (B1) and (B2), there are at least 2 Si groups bonded to hydroxyl groups or hydrolyzable groups;

[0053] X 5 Each independently represents a single bond or a 2- to 10-valent organic group;

[0054] γ is independently an integer from 1 to 9;

[0055] γ′ is independently an integer from 1 to 9;

[0056] R d Each occurrence represents -Z independently 4 -CR 81 p2 R 82 q2 R 83 r2 ;

[0057] Z 4 Each occurrence independently represents an oxygen atom or a divalent organic group;

[0058] R 81 Each occurrence represents R independently d′ ;

[0059] R d′ The meaning of R d same;

[0060] R d Via Z 4 The maximum number of carbon atoms connected in a straight chain is 5.

[0061] R 82 Each occurrence represents -Y-SiR independently 85 n2 R 863－n2 ;

[0062] Y, at each occurrence, independently represents a divalent organic group;

[0063] R 85 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0064] R 86 represents independently at each occurrence a hydrogen atom or a lower alkyl group;

[0065] n2 in each (-Y-SiR 85 n2 R 86 3－n2 ) units independently represent an integer from 0 to 3;

[0066] R 83 represents independently at each occurrence a hydrogen atom, a hydroxyl group or a lower alkyl group;

[0067] p2 is independently an integer from 0 to 3 at each occurrence;

[0068] q2 is independently an integer from 0 to 3 at each occurrence;

[0069] r2 is independently an integer from 0 to 3 at each occurrence;

[0070] Among them, in each (-Z 4 -CR 81 p2 R 82 q2 R 83 r2 ), the sum of p2, q2 and r2 is 3;

[0071] R e Each occurrence represents -Y-SiR independently 85 n2 R 86 3－n2 ;

[0072] R f represents independently at each occurrence a hydrogen atom, a hydroxyl group or a lower alkyl group;

[0073] k2 is independently an integer from 0 to 3 at each occurrence;

[0074] l2 is independently an integer from 0 to 3 at each occurrence;

[0075] m2 is independently an integer from 0 to 3 at each occurrence;

[0076] Among them, in each (CRd k2 R e l2 R f m2 ), the sum of k2, l2 and m2 is 3, and in formulas (C1) and (C2), there are two or more -Y-SiR 85 The groups shown.]

[0077] [Method 2]

[0078] The fluorinated (poly)ether group-containing silane compound according to [Embodiment 1], wherein X F A fluorine atom.

[0079] [Method 3]

[0080] The fluorinated (poly)ether group-containing silane compound as described in [Embodiment 1] or [Embodiment 2], wherein the PFPE is represented by the formula: -(OC3F6) d - indicates that the repeating unit OC3F6 of the above formula includes a branched structure, and d is an integer of 2 to 200.

[0081] [Method 4]

[0082] The fluorinated (poly)ether group-containing silane compound according to any one of [Formula 1] to [Formula 3], wherein the PFPE is represented by the formula: -(OC3F6) d - indicates that the repeating unit OC3F6 of the above formula is represented by OCF(CF3)CF2, and d is an integer of 2 to 200.

[0083] [Method 5]

[0084] The fluorinated (poly)ether group-containing silane compound according to any one of [Embodiment 1] to [Embodiment 4], wherein α, α′, β, β′, γ, and γ′ are 1.

[0085] [Method 6]

[0086] The fluorinated (poly)ether group-containing silane compound according to any one of [Embodiment 1] to [Embodiment 5], wherein X 1 , X 3 and X 5 Each time it occurs, it is independently -X 10 -CON(R 34 )-X 11 -, -X 10 -(OR 35 ) n4 -X 11 - or C 1－6 Any of alkylene groups.

[0087] [Wherein,

[0088] X 10 Each occurrence is independently a single bond or a divalent organic group;

[0089] X 11 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group;

[0090] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 alkyl;

[0091] R 35 Each time it occurs, it is independently C 1－6 of alkylene;

[0092] n4 is independently an integer from 1 to 5 at each occurrence.]

[0093] [Method 7]

[0094] The fluorinated (poly)ether group-containing silane compound according to any one of [Embodiment 1] to [Embodiment 6], wherein k1 is 2 or 3, and q1 is 2 or 3.

[0095] [Method 8]

[0096] The fluorinated (poly)ether group-containing silane compound according to any one of [Form 1] to [Form 7], wherein l2 is 2 or 3, and n2 is 2 or 3.

[0097] [Method 9]

[0098] The fluorinated (poly)ether group-containing silane compound according to any one of [Formula 1] to [Formula 8], which is represented by formula (B1), (B2), (C1) or (C2).

[0099] [Method 10]

[0100] The fluorinated (poly)ether group-containing silane compound according to any one of [Embodiment 1] to [Embodiment 9], which is represented by formula (B1).

[0101] [Method 11]

[0102] The fluorinated (poly)ether group-containing silane compound according to any one of [Embodiment 1] to [Embodiment 9], which is represented by formula (C1) or (C2).

[0103] [Method 12]

[0104] The fluorinated (poly)ether group-containing silane compound according to any one of [Embodiment 1] to [Embodiment 9] or [Embodiment 11], which is represented by formula (C1).

[0105] [Method 13]

[0106] The fluorinated (poly)ether group-containing silane compound according to any one of [Embodiment 1] to [Embodiment 12], wherein R 83 and R f Each occurrence is independently a hydrogen atom or a lower alkyl group.

[0107] [Method 14]

[0108] A surface treatment agent containing the fluorinated (poly)ether group-containing silane compound according to any one of [Aspect 1] to [Aspect 13].

[0109] [Method 15]

[0110] The surface treatment agent according to [Aspect 14] further comprises a solvent.

[0111] [Method 16]

[0112] The surface treatment agent as described in [Mode 14] or [Mode 15], further comprising one or more other components selected from the group consisting of fluorinated oil, silicone oil, alcohol, catalyst, transition metal, halide ion and a compound containing an atom having an unshared electron pair in its molecular structure.

[0113] [Method 17]

[0114] The surface treatment agent according to any one of [Aspect 14] to [Aspect 16], which is used as an antifouling coating agent or a water-repellent coating agent.

[0115] [Method 18]

[0116] A pellet containing the surface treatment agent according to any one of [Aspect 14] to [Aspect 17].

[0117] [Method 19]

[0118] An article comprising a substrate and a layer formed on a surface of the substrate using the surface treatment agent according to any one of [Aspect 14] to [Aspect 18].

[0119] [Method 20]

[0120] An article having a surface water contact angle of 100 degrees or more, and an irradiation intensity of 0.63 W / m 2 The ratio of the water contact angle of the surface after irradiation with ultraviolet rays of 310 nm for 96 hours was 83% or more.

[0121] [Method 21]

[0122] A method for producing a fluorinated (poly)ether group-containing silane compound represented by formula (C1) or (C2) according to [Embodiment 1], comprising the following step (3): reacting a compound represented by formula (c1-3) or formula (c2-3) with HSiM ′ The compound shown in 3 and the formula as required: R 85 i L' represents a compound and / or a compound of the formula: R 86′ j The compound shown in L″ reacts

[0123]

[0124] [Wherein,

[0125] Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0126] PFPE is composed of (-OCF(CF3)CF2-) d express;

[0127] d is an integer greater than 2 and less than 200;

[0128] X 10 Each occurrence is independently a single bond or a divalent organic group;

[0129] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 alkyl;

[0130] X 11 Each occurrence is independently a single bond or a divalent organic group;

[0131] Y 11 Each occurrence is independently a single bond or a divalent organic group.]

[0132] HSiM′3

[0133] [wherein, M' is independently a halogen atom or C 1－6 Alkoxy.]

[0134] Formula: R 85 i L′

[0135] [Wherein,

[0136] R 85 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0137] L′ indicates that it can be 85 Bonded groups;

[0138] i is an integer from 1 to 3.]

[0139] Formula: R 86′ j L ″

[0140] [Wherein,

[0141] R 86′ Each occurrence represents C independently 1～22 alkyl;

[0142] L″ indicates that it can be connected with R 86′ Bonded groups;

[0143] j is an integer from 1 to 3.]

[0144] [Method 22]

[0145] The method according to [Embodiment 21] is a method for producing a fluorinated (poly)ether group-containing silane compound represented by formula (C1) or (C2) according to [Embodiment 1], further comprising the following steps (1) and (2):

[0146] Step (1): a step of reacting a compound represented by formula (c1-1) or formula (c2-1) with SOM2 to obtain a compound represented by formula (c1-2) or formula (c2-2),

[0147] Rf-PFPE-X 10 -C(O)OH…(c1-1)

[0148] HOC(O)-X 10 PFPE-X 10 -C(O)OH…(c2-1)

[0149] [Wherein, Rf, PFPE and X 10 The meaning is the same as that of [Method 21].

[0150] SOM2

[0151] [In the formula, M is independently a chlorine atom or a fluorine atom at each occurrence.]

[0152]

[0153] [Wherein,

[0154] Rf, PFPE and X 10 The meaning is the same as that of [Method 21];

[0155] M has the same meaning as above.]

[0156] Step (2): reacting the compound represented by the above formula (c1-2) or formula (c2-2) with a compound represented by the formula: HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3 to obtain a compound represented by formula (c1-3) or formula (c2-3),

[0157] Formula: HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3

[0158] [Where R 34 , X 11 and Y 11 The meaning is the same as that of [Method 21].

[0159]

[0160] [Wherein, Rf, PFPE, X 10 , R 34 and X 11 The meaning is the same as that of [Method 21].

[0161] [Method 23]

[0162] A compound represented by formula (c1-2) or (c2-2).

[0163]

[0164] [Wherein,

[0165] Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0166] PFPE is composed of (-OCF(CF3)CF2-) d express;

[0167] d is an integer greater than 2 and less than 200;

[0168] X 10 Each occurrence is independently a single bond or a divalent organic group;

[0169] M is independently a chlorine atom or a fluorine atom at each occurrence.]

[0170] [Method 24]

[0171] A compound represented by formula (c1-3) or (c2-3).

[0172]

[0173] [Wherein,

[0174] Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0175] PFPE is composed of (-OCF(CF3)CF2-) d express;

[0176] d is an integer greater than 2 and less than 200;

[0177] X 10 Each occurrence is independently a single bond or a divalent organic group;

[0178] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 alkyl;

[0179] X 11 Each occurrence is independently a single bond or a divalent organic group;

[0180] Y 11 Each occurrence is independently a single bond or a divalent organic group.]

[0181] Effects of the Invention

[0182] According to the present invention, a PFPE-containing silane compound that contributes to the formation of a surface-treated layer having excellent ultraviolet durability can be provided. DETAILED DESCRIPTION

[0183] As used in this specification, "a 2- to 10-valent organic group" refers to a 2- to 10-valent group containing carbon. The 2- to 10-valent organic group is not particularly limited, and examples thereof include 2- to 10-valent groups obtained by removing 1 to 9 hydrogen atoms from a hydrocarbon group. The divalent organic group is not particularly limited, and examples thereof include divalent groups obtained by removing one hydrogen atom from a hydrocarbon group.

[0184] When used in this specification, "hydrocarbon group" is a group containing carbon and hydrogen, and refers to a group obtained by removing one hydrogen atom from a molecule. The hydrocarbon group is not particularly limited, and examples include hydrocarbon groups with 1 to 20 carbon atoms that can be substituted with one or more substituents, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc. The above-mentioned "aliphatic hydrocarbon group" can be any of linear, branched or cyclic, and can be any of saturated or unsaturated. In addition, the hydrocarbon group can contain one or more ring structures. In addition, the hydrocarbon group can have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at its end or in the molecular chain.

[0185] As used in this specification, the substituent of the "hydrocarbon group" is not particularly limited, and examples thereof include halogen atoms; 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 unsaturated cycloalkyl, 5- to 10-membered heterocyclic group, 5- to 10-membered unsaturated heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0186] In the present specification, unless otherwise specified, alkyl and phenyl groups may be unsubstituted or substituted. Substituents for these groups are not particularly limited, and examples thereof include halogen atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more groups in an alkynyl group.

[0187] In this specification, an alkylene group is a group having -(C δ H 2δ The group having a )- structure may be substituted or unsubstituted, and may be linear or branched, unless otherwise specified.

[0188] Hereinafter, the PFPE-containing silane compound of the present invention will be described.

[0189] Formula (A1) and (A2):

[0190]

[0191] In the above formula, Rf, at each occurrence, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

[0192] The "alkyl group having 1 to 16 carbon atoms" in the above-mentioned alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be a linear or branched chain, and is preferably a linear or branched chain alkyl group having 1 to 6 carbon atoms, particularly a linear chain alkyl group having 1 to 3 carbon atoms, and is more preferably a linear chain alkyl group having 1 to 3 carbon atoms.

[0193] The above Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, and more preferably CF2H—C 1－15 Fluorinated alkylene or C 1－16 Perfluoroalkyl, more preferably C 1－16 Perfluoroalkyl.

[0194] The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, particularly a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0195] In the above formula, PFPE is independently -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3X F 6) d -(OC2F4) e -(OCF2) f -, and the PFPE has at least one branched structure. That is, the PFPE has at least one CF3 terminal (specifically -CF3, -C2F5, etc., more specifically -CF3). In formula (A1), in the PFPE, the oxygen atom at the left terminal of the above formula is bonded to the Rf group, and the carbon atom at the right terminal is bonded to the X 1 By using PFPE having such a structure, the layer (e.g., surface treatment layer) formed using a PFPE-containing silane compound (or a surface treatment agent containing a PFPE-containing silane compound) has better UV durability, water repellency, oil repellency, antifouling properties (preventing adhesion of dirt such as fingerprints), chemical resistance, hydrolysis resistance, anti-slip effect, high friction durability, heat resistance, moisture resistance, etc.

[0196] X F Each occurrence of is independently a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0197] In the above formula, a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer from 0 to 100. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e and f is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, more specifically 10 or more and 100 or less. In addition, the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary.

[0198] The PFPE structure preferably has at least 5 branched structures, more preferably 10 branched structures, and particularly preferably 20 branched structures.

[0199] In the PFPE structure, the number of repeating units having a branched structure is preferably 40 or more, more preferably 60 or more, and particularly preferably 80 or more, relative to the total number of repeating units (e.g., the sum of a, b, c, d, e, and f) of 100. In the PFPE structure, the number of repeating units having a branched structure may be 100 or less, for example, 90 or less, relative to the total number of repeating units of 100.

[0200] In the PFPE structure, the number of repeating units having a branched structure is preferably in the range of 40 to 100, more preferably in the range of 60 to 100, and particularly preferably in the range of 80 to 100, relative to 100 of the total number of repeating units.

[0201] As the branch chain in the branched structure, for example, CF3 can be mentioned.

[0202] As a repeating unit having a branched structure, for example, -(OC6F 12 )-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10 )-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. As -(OC4F8)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. As -(OC3F6)- (that is, in the above formula, X F As -(OC2F4)-, -(OCF(CF3))- can be mentioned.

[0203] The PFPE may include a repeating unit having a branched structure and a linear repeating unit. Examples of the linear repeating unit include -(OCF2CF2CF2CF2CF2CF2)-, -(OCF2CF2CF2CF2CF2)-, -(OCF2CF2CF2CF2)-, -(OCF2CF2CF2CF2)-, -(OCF2CF2CF2)-, and -(OCF2CF2CF2)-.

[0204] Preferably, in the above PFPE, the repeating unit -(OC6F 12 )-、-(OC5F 10 )-, -(OC4F8)- and -(OC3F6)- have branched structures.

[0205] More preferably, the PFPE is composed of branched repeating units OC6F 12 、OC5F 10 , OC4F8 and OC3F6.

[0206] In one embodiment, the PFPE is -(OC3F6) d - (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200), and PFPE has at least one branched structure.

[0207] In this embodiment, PFPE may further include a linear repeating unit -(OCF2CF2CF2)-.

[0208] In the above embodiment, the PFPE is preferably composed of a branched repeating unit OC3F6. More preferably, the PFPE is of the formula: -(OCF2CF(CF3)) d In the above formula, d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200.

[0209] In another embodiment, PFPE is -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (wherein, c and d are each independently an integer of 0 to 30, e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, the sum of c, d, e and f is at least 5, preferably 10, and the order of existence of the repeating units marked with subscripts c, d, e or f and enclosed in parentheses is arbitrary in the formula), the PFPE has at least one branched structure.

[0210] In yet another embodiment, PFPE is -(R 6-R 7 ) j -, the PFPE has at least one branched structure. 6 is OCF2 or OC2F4, preferably OC2F4. Wherein, R 7 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups. 7 is a group selected from OC2F4, OC3F6 and OC4F8 or selected from OC3F6, OC4F8, OC5F 10 and OC6F 12 The group is a group, or a combination of two or three groups independently selected from these groups, more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4-. The above j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less. In the above formula, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It has a branched chain structure.

[0211] More preferably, in the above method, PFPE is composed of branched repeating units OC6F 12 、OC5F 10 , OC4F8 and OC3F6.

[0212] In the above formula, R 13 Each occurrence independently represents a hydroxyl group or a hydrolyzable group.

[0213] When used in this specification, "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, that is, a group that can be separated from the main skeleton of the compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR, -OCOR, -O-N=CR2, -NR2, -NHR, halogen (in these formulas, R represents a substituted or unsubstituted alkyl group with 1 to 4 carbon atoms), etc., preferably -OR (i.e., alkoxy). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl. Among these, alkyl groups, especially unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. The hydroxyl group is not particularly limited and may also be produced by hydrolysis of a hydrolyzable group.

[0214] In the above formula, R 14 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.

[0215] In the above formula, R 11 Each occurrence of is independently a hydrogen atom or a halogen atom. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.

[0216] In the above formula, R 12 Each occurrence of is independently a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, and propyl.

[0217] In the above formula, n is in each (-SiR 13 n R 14 3－n ) units are independently an integer of 0 to 3, preferably 1 to 3, and more preferably 3. However, in formula (A1) or (A2), at least two n are 1 or more. In other words, in formula (A1) and (A2), at least two SiR 13 .

[0218] Preferably, in formula (A1) and (A2), n is 2 or 3, and more preferably n is 3. In other words, in formula (A1) and (A2), the Si atom is preferably in the form of -SiR 13 2R 14 or -SiR 13 3 exists, preferably in the form of -SiR 13 3Existence.

[0219] In the above formula, X 1 Each occurrence of X independently represents a single bond or a divalent to devalent organic group. 1It can be understood that in the compounds represented by formula (A1) and (A2), the fluoropolyether part (i.e., the Rf-PFPE part or -PFPE- part) which mainly provides water repellency and surface slip, and the silane part (i.e., the group marked with α and enclosed in brackets) which provides the ability to bind to the substrate are connected to the linking group. 1 As long as the compounds represented by formula (A1) and (A2) can exist stably, they may be single bonds or any organic groups. 1 Among the groups, the left side is bonded to the group shown by PFPE, and the right side is bonded to the group marked with α and enclosed in parentheses.

[0220] In the above formula, α is an integer of 1 to 9, and α′ is an integer of 1 to 9. These α and α′ may correspond to X 1 In formula (A1), the sum of α and α′ and X 1 The valences are equal. For example, in X 1 When X is a devalent organic group, the sum of α and α′ is 10, for example, α is 9 and α′ is 1, α is 5 and α′ is 5, or α is 1 and α′ is 9. 1 When X is a divalent organic group, α and α′ are 1. In formula (A2), α is X 1 The value obtained by subtracting 1 from the value of the valence.

[0221] In one approach, X 1 Each time it occurs, it is independently -CON(R 34 )-、C 1－6 Alkylene, or containing OR 35 A 2- to 10-valent organic group.

[0222] The above R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably a hydrogen atom or a C 1－6 The alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

[0223] The above R 35 C 1－6 Alkylene, preferably C 1－3 Alkylene.

[0224] In one embodiment, the above X 1 For example, the following formula can be cited: 31 ) p′ -(X a ) q′ - is a divalent group.

[0225] [Wherein,

[0226] R 31 -(CH2) represents a single bond which may be substituted by one or more fluorine atoms s′ - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH2) which may be substituted with one or more fluorine atoms s′ -

[0227] s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and further preferably 1 or 2.

[0228] X a Indicates - (X b ) l′ -

[0229] X b Each occurrence independently represents a group selected from -O-, -(OR 35 ) n4 -, -S-, o-phenylene, m-phenylene or p-phenylene, -C(O)O-, -Si(R 33 )2-、-(Si(R 33 )2O) m′ -Si(R 33 )2-,-CON(R 34 )-、-O-CON(R 34 )-、-N(R 34 )- and -(CH2) n′ - in the group,

[0230] R 33 Each occurrence independently represents phenyl, C 1－6 Alkyl or C 1－6 Alkoxy, preferably phenyl or C 1－6 Alkyl, more preferably methyl,

[0231] R 34 Each occurrence independently represents a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably represents a hydrogen atom or a C 1－6 Alkyl, more preferably represents a hydrogen atom or a methyl group, further preferably represents a hydrogen atom,

[0232] R 35 Each time it occurs, it is independently C 1－6 The alkylene group is preferably C 1－3 The alkylene group,

[0233] n4 is independently an integer of 1 to 5 at each occurrence, preferably an integer of 1 to 3, more preferably 1,

[0234] m' is independently an integer of 1 to 100 at each occurrence, preferably an integer of 1 to 20,

[0235] n' is independently an integer of 1 to 20 at each occurrence, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,

[0236] l' is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3,

[0237] p′ is 0 or 1,

[0238] q′ is 0 or 1,

[0239] Here, at least one of p' and q' is 1, and the order of existence of each repeating unit indicated by p' or q' and enclosed in parentheses is arbitrary].

[0240] Here, R 31 and X a (Typically R 31 and X a The hydrogen atoms) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents.

[0241] In one embodiment, l' is 1.

[0242] Preferably the above X 1 For - (R 31 ) p′ -(X a ) q′ -R 32 -. R 32 Represents a single bond, -(CH2) t′ - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH2) t′ -. t' is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. Here, R 32 (Typically R 32 The hydrogen atoms) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents.

[0243] As the above X 1 Examples are not particularly limited, and the following structures can be cited.

[0244] -X 10 -CON(R 34 )-X 11 -

[0245] -X10 -(OR 35 ) n4 -X 11 -

[0246] C 1－6 Alkylene (preferably propylene).

[0247] Due to X 1 With such a structure, the layer formed of the PFPE-containing silane compound has better hydrolysis resistance, friction durability, chemical resistance, moisture resistance, and the like.

[0248] The above X 10 Each occurrence is independently a single bond or a divalent organic group, preferably a single bond, -O-R 36 -O-, -R 36 - or o-phenylene, m-phenylene or p-phenylene, more preferably a single bond, -O-R 36 -O- or -R 36 -

[0249] In one embodiment, the above X 10 is a single bond or -R 36 -, more preferably a single bond.

[0250] The above R 36 is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3 Alkylene is more preferably C 1－2 Alkylene. The above-mentioned alkylene may be linear or branched.

[0251] In one embodiment, the above X 10 The alkylene group in which one or more fluorine atoms may be substituted is, for example, C 1－3 Perfluoroalkylene, C substituted with one or more fluorine atoms 1－3 Fluorinated alkylene or unsubstituted C 1－3 Alkylene, more specifically C 1－2 Perfluoroalkylene, C substituted with one or more fluorine atoms 1－2 Fluorinated alkylene or unsubstituted C 1－2 Alkylene.

[0252] The above X 11 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group, preferably a single bond, an oxygen atom or a C which may be substituted with one or more fluorine atoms. 1－20 Alkylene.

[0253] In one approach, X11 Preferably, the C 1－20 Alkylene is more preferably a single bond or an unsubstituted C 1－6 Alkylene, more preferably a single bond or unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene.

[0254] The above X 11 The alkylene group which may be substituted with one or more fluorine atoms is preferably a C 1－6 Alkylene is more preferably C 1－3 Alkylene. The above-mentioned alkylene may be linear or branched.

[0255] More preferably, the above X 11 The alkylene group which may be substituted with one or more fluorine atoms is preferably C 1－6 Alkylene, more preferably C 1－3 Alkylene.

[0256] The above R 34 Each occurrence independently represents a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably represents a hydrogen atom or a C 1－6 Alkyl, more preferably represents a hydrogen atom or a methyl group, further preferably represents a hydrogen atom,

[0257] The above R 35 Each time it occurs, it is independently C 1－6 Alkylene, preferably C 1－3 Alkylene.

[0258] The above n4 is independently an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1, at each occurrence.

[0259] In one approach, X 1 For -X 10 -CON(R 34 )-X 11 - or C 1－6 Alkylene (preferably propylene).

[0260] In the above formula,

[0261] R 34 The meaning is the same as above, preferably a hydrogen atom or C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0262] X 10The meanings are the same as above, preferably a single bond, -R 36 - or o-phenylene, m-phenylene or p-phenylene, more preferably a single bond or -R 36 -, more preferably a single bond;

[0263] R 36 The meaning is the same as above, preferably C which may be substituted by one or more fluorine atoms 1－20 Alkylene is more preferably C 1－3 Alkylene, more preferably C 1－2 Alkylene;

[0264] X 11 The meaning is the same as above, preferably a single bond or C which may be substituted by one or more fluorine atoms 1－20 Alkylene, more preferably a single bond or an unsubstituted C 1－6 Alkylene, more preferably a single bond or unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene.

[0265] In the above embodiment, X is particularly preferred 1 For -X 10 -CON(R 34 )-X 11 -. In the above formula, R 34 , X 10 and X 11 Same meaning as above.

[0266] In the above embodiment, it is particularly preferred that the above X 10 is a single bond, and the above X 11 C 1－3 Alkylene, more preferably X 11 C without a substituent 1－3 Alkylene.

[0267] In one embodiment, the above X 10 is a single bond, and the above X 11 C 1－3 Alkylene, preferably X 11 C without a substituent 1－3 Alkylene.

[0268] In one way, as X 1 Examples, without particular limitation, include the following structures:

[0269] -X f -X 10 -CON(R 34 )-X 11-

[0270] -X f -X 10 -(OR 35 ) n4 -X 11 -

[0271] -X f -C 1－6 Alkylene (preferably propylene).

[0272] Where, X 10 , R 34 , X 11 , R 35 Same meaning as n4.

[0273] Where, X f Each occurrence of X is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 4 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 2 carbon atoms (eg, methylene). f The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted. f It may be either linear or branched, but is preferably linear.

[0274] As the above X 1 Specific examples include:

[0275] -CH2OCH2-,

[0276] -CH2O(CH2)2-,

[0277] -CH2O(CH2)3-,

[0278] -CH2O(CH2)6-,

[0279] -CF2-CH2OCH2-,

[0280] -CF2-CH2O(CH2)2-,

[0281] -CF2-CH2O(CH2)3-,

[0282] -CF2-CH2O(CH2)6-,

[0283] -O-CFHCF2-O-CH2OCH2-,

[0284] -O-CFHCF2-O-CH2O(CH2)2-,

[0285] -O-CFHCF2-O-CH2O(CH2)3-、

[0286] -O-CFHCF2-O-CH2O(CH2)6-、

[0287] -CH2OCF2CHFOCF2-、

[0288] -CH2OCF2CHFOCF2CF2-、

[0289] -CH2OCF2CHFOCF2CF2CF2-、

[0290] -CH2OCH2CF2CF2OCF2-、

[0291] -CH2OCH2CF2CF2OCF2CF2-、

[0292] -CH2OCH2CF2CF2OCF2CF2CF2-、

[0293] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[0294] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[0295] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[0296] -CH2OCH2CHFCF2OCF2-、

[0297] -CH2OCH2CHFCF2OCF2CF2-、

[0298] -CH2OCH2CHFCF2OCF2CF2CF2-、

[0299] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[0300] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[0301] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[0302] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[0303] -CH2-、

[0304] -(CH2)2-、

[0305] -(CH2)3-、

[0306] -(CH2)4-、

[0307] -(CH2)5-、

[0308] -(CH2)6-、

[0309] -CF2-、

[0310] -(CF2)2-、

[0311] -CF2-CH2-、

[0312] -CF2-(CH2)2-、

[0313] -CF2-(CH2)3-、

[0314] -CF2-(CH2)4-、

[0315] -CF2-(CH2)5-、

[0316] -CF2-(CH2)6-、

[0317] -CONH-、

[0318] -CONH-CH2-、

[0319] -CONH-(CH2)2-、

[0320] -CONH-(CH2)3-、

[0321] -CONH-(CH2)6-、

[0322] -CF2-CONH-、

[0323] -CF2-CONH-CH2-、

[0324] -CF2-CONH-(CH2)2-、

[0325] -CF2-CONH-(CH2)3-、

[0326] -CF2-CONH-(CH2)6-、

[0327] -O-CFHCF2-O-CONH-、

[0328] -O-CFHCF2-O-CONH-CH2-、

[0329] -O-CFHCF2-O-CONH-(CH2)2-、

[0330] -O-CFHCF2-O-CONH-(CH2)3-,

[0331] -O-CFHCF2-O-CONH-(CH2)6-,

[0332] -CON(CH3)-

[0333] -CON(CH3)-CH2-,

[0334] -CON(CH3)-(CH2)2-,

[0335] -CON(CH3)-(CH2)3-,

[0336] -CON(CH3)-(CH2)6-,

[0337] -CON(CH3)-C6H4-、

[0338] -CON(Ph)-(CH2)3- (where Ph represents phenyl),

[0339] -CON(Ph)-(CH2)6- (wherein Ph represents phenyl),

[0340] -CF2-CON(CH3)-,

[0341] -CF2-CON(CH3)-CH2-,

[0342] -CF2-CON(CH3)-(CH2)2-,

[0343] -CF2-CON(CH3)-(CH2)3-,

[0344] -CF2-CON(CH3)-(CH2)6-,

[0345] -CF2-CON(CH3)-C6H4-,

[0346] -CF2-CON(Ph)-(CH2)3- (where Ph represents phenyl),

[0347] -CF2-CON(Ph)-(CH2)6- (where Ph represents phenyl),

[0348] -CH2-CON(CH3)-CH2-,

[0349] -CH2-CON(CH3)-(CH2)2-,

[0350] -CH2-CON(CH3)-(CH2)3-,

[0351] -CH2O-CONH-(CH2)3-、

[0352] -CH2O-CONH-(CH2)6-、

[0353] -OCH2-,

[0354] -O(CH2)3-,

[0355] -OCFHCF2-,

[0356] -O-CFHCF2-O-,

[0357] -O-CFHCF2-O-CH2-,

[0358] -O-CFHCF2-O-(CH2)2-,

[0359] -O-CFHCF2-O-(CH2)3-,

[0360] -O-CFHCF2-O-(CH2)6-,

[0361] -O-CFHCF2-O-C6H4- or wait.

[0362] As a more preferred X 1 , we can list:

[0363] -O-CFHCF2-O-CONH-,

[0364] -O-CFHCF2-O-CONH-CH2-,

[0365] -O-CFHCF2-O-CONH-(CH2)2-,

[0366] -O-CFHCF2-O-CONH-(CH2)3-,

[0367] -O-CFHCF2-O-CONH-(CH2)6-,

[0368] -CONH-,

[0369] -CONH-CH2-,

[0370] -CONH-(CH2)2-,

[0371] -CONH-(CH2)3-,

[0372] -CONH-(CH2)6-,

[0373] -CF2-CONH-,

[0374] -CF2-CONH-CH2-、

[0375] -CF2-CONH-(CH2)2-、

[0376] -CF2-CONH-(CH2)3-、

[0377] -CF2-CONH-(CH2)6-、

[0378] -O-CFHCF2-O-CH2OCH2-、

[0379] -O-CFHCF2-O-CH2O(CH2)2-、

[0380] -O-CFHCF2-O-CH2O(CH2)3-、

[0381] -O-CFHCF2-O-CH2O(CH2)6-、

[0382] -CH2OCH2-、

[0383] -CH2O(CH2)2-、

[0384] -CH2O(CH2)3-、

[0385] -CH2O(CH2)6-、

[0386] -CF2-CH2OCH2-、

[0387] -CF2-CH2O(CH2)2-、

[0388] -CF2-CH2O(CH2)3-、

[0389] -CF2-CH2O(CH2)6-、

[0390] -O-CFHCF2-O-、

[0391] -O-CFHCF2-O-(CH2)2-、

[0392] -O-CFHCF2-O-(CH2)3-、

[0393] -O-CFHCF2-O-(CH2)6-、

[0394] -CH2-、

[0395] -(CH2)2-、

[0396] -(CH2)3-、

[0397] -(CH2)6-

[0398] -CF2-,

[0399] -(CF2)2-,

[0400] -CF2-CH2-,

[0401] -CF2-(CH2)2-,

[0402] -CF2-(CH2)3-,

[0403] -CF2-(CH2)6-, etc.

[0404] In yet another embodiment, as X 1 Examples of the group include the following groups:

[0405]

[0406] [Wherein,

[0407] R 41 are independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1－6 Alkoxy, preferably methyl;

[0408] Each X 1 In the group, any of T is the following group bonded to the PFPE of the main chain of the molecule:

[0409] -CH2O(CH2)2-,

[0410] -CH2O(CH2)3-,

[0411] -CF2O(CH2)3-,

[0412] -CH2-,

[0413] -(CH2)2-,

[0414] -(CH2)3-,

[0415] -(CH2)4-,

[0416] -CONH-(CH2)3-,

[0417] -CON(CH3)-(CH2)3-,

[0418] -CON(Ph)-(CH2)3- (wherein Ph represents phenyl) or

[0419]

[0420] [Where R 42 Each independently represents a hydrogen atom, a C 1－6Alkyl or C 1－6 alkoxy, preferably methyl or methoxy, more preferably methyl],

[0421] The other T's are -(CH2) bonded to the opposite groups of PFPE in the main chain of the molecule. n″ - (n" is an integer from 2 to 6), when present, the remaining T are each independently methyl, phenyl, C 1－6 Alkoxy groups or free radical scavenging groups or ultraviolet absorbing groups.

[0422] The radical scavenging group is not particularly limited as long as it is a group that can scavenges free radicals generated by light irradiation, and examples thereof include residues of benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organic acrylates, hindered amines, hindered phenols, or triazines.

[0423] The ultraviolet absorbing group is not particularly limited as long as it is a group that can absorb ultraviolet rays, and examples thereof include residues of benzotriazoles, hydroxybenzophenones, substituted and unsubstituted esters of benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.

[0424] In a preferred embodiment, preferred free radical scavenging groups or ultraviolet absorbing groups include:

[0425]

[0426] In this method, X 1 (and the following X 3 and X 5 ) may be a tri- to decavalent organic group.

[0427] In the above formula, X 2 Each occurrence of X independently represents a single bond or a divalent organic group. 2 It is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably -(CH2) u -(where u is an integer from 0 to 2).

[0428] In the above formula, t is independently an integer of 2 to 10. In a preferred embodiment, t is an integer of 2 to 6.

[0429] In a preferred embodiment, in formula (A1) and (A2),

[0430] PFPE are independently of each other and are of the formula: -(OCF(CF3)CF2) d- a group represented by (wherein, regarding d, d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200);

[0431] X 1 Each time it occurs, it is independently -X f -X 10 -CON(R 34 )-X 11 -, -X f -X 10 -(OR 35 ) n4 -X 11 -, or -X f -C 1－6 A group represented by an alkylene group (preferably a propylene group);

[0432] X f Each occurrence is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 2 carbon atoms (e.g., methylene), X f The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted;

[0433] X 10 Each occurrence is independently a single bond, -O-R 36 -O-, -R 36 -, or o-phenylene, m-phenylene or p-phenylene, preferably a single bond, -O-R 36 -O- or -R 36 -, more preferably a single bond or -R 36 -, more preferably a single bond;

[0434] R 36 is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3 Alkylene is more preferably C 1－2 Alkylene, R 36 The above alkylene group may be linear or branched;

[0435] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably a hydrogen atom or a C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0436] R 35 Each time it occurs, it is independently C 1－6 Alkylene, preferably C 1－3 Alkylene;

[0437] n4 is independently an integer of 1 to 5 at each occurrence, preferably an integer of 1 to 3, more preferably 1;

[0438] X 11 Each occurrence is independently a single bond, an oxygen atom, or a C which may be substituted with one or more fluorine atoms. 1－20 Alkylene, preferably a single bond or unsubstituted C 1－6 Alkylene, more preferably a single bond or an unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene;

[0439] X 2 For -(CH2) u -;

[0440] u is independently an integer from 0 to 2 at each occurrence.

[0441] In a preferred embodiment, the compounds represented by formulae (A1) and (A2) are compounds represented by the following formulae (A1′) and (A2′).

[0442]

[0443] [Wherein,

[0444] PFPE are independently of each other and are of the formula: -(OCF(CF3)CF2) d - a group represented by (wherein d is an integer from 0 to 200);

[0445] Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0446] R 13 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0447] R 14 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

[0448] R 11 represents independently at each occurrence a hydrogen atom or a halogen atom;

[0449] R 12 represents independently at each occurrence a hydrogen atom or a lower alkyl group;

[0450] n is 2 or 3, preferably 3;

[0451] X 1 Each time it occurs, it is independently -X 10 -CONH-X 11 -, -X 10 -(OR 35 ) n4 -X 11 -(R 35 C 1－3 Alkylene; n4 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1) or C 1－6 Alkylene (preferably propylene);

[0452] X 10 Each occurrence is independently a single bond, -O-R 36 -O- or -R 36 -;

[0453] R 36 is C which may be substituted with one or more fluorine atoms 1－3 Alkylene;

[0454] X 11 is independently a single bond, an oxygen atom or a C 1－3 Alkylene;

[0455] X 2 For -(CH2) u -;

[0456] u is independently an integer from 0 to 2 at each occurrence;

[0457] t is independently an integer from 2 to 10 at each occurrence.]

[0458] The number average molecular weight of the compounds represented by the above formulae (A1) and (A2) is not particularly limited, and may be, for example, 1,000 to 40,000, preferably 1,000 to 32,000, more preferably 1,000 to 20,000, and even more preferably 1,000 to 12,000. 19 F-NMR and 1 The value measured by H-NMR.

[0459] In one embodiment, the number average molecular weight of the compounds represented by the above formulae (A1) and (A2) is 1,000 to 8,000, preferably 1,000 to 4,000. By having such a number average molecular weight, a layer (e.g., a surface treatment layer) formed using the above compounds (or a surface treatment agent containing the above compounds) has particularly good sliding suppression effect, wear resistance, etc.

[0460] In one embodiment, the weight average molecular weight Mw of the compounds represented by the formulae (A1) and (A2) is 3,000 or more and less than 6,000, and the molecular weight distribution (Mw / Mn) of the compounds is 1.2 or less. The weight average molecular weight and molecular weight distribution are determined, for example, by GPC (gel permeation chromatography) measurement.

[0461] In a preferred embodiment, the compounds represented by formula (A1) and (A2) are the compounds represented by formula (A1), and more preferably are the compounds represented by formula (A1′).

[0462] In one embodiment, the compounds represented by the above formulae (A1) and (A2) can be obtained, for example, by using a fluoropolyether derivative corresponding to the Rf-PFPE- portion as a raw material, introducing a hydroxyl group at the terminal, and subjecting it to a Williamson reaction together with, for example, a compound having a halogenated alkyl group at the terminal.

[0463] Formula (B1) and (B2):

[0464] (Rf-PFPE) β’ -X 3 -(SiR a k1 R b l1 R c m1 ) β …(B1)

[0465] (R c m1 R b l1 R a k1 Si) β -X 3 -PFPE-X 3 -(SiR a k1 R b l1 R c m1 ) β …(B2)

[0466] In the above formulas (B1) and (B2), Rf and PFPE have the same meanings as those in the above formulas (A1) and (A2). 1 "Base" is replaced by "X 3 base".

[0467] In the above formula, X 3Each independently represents a single bond or a di- to decavalent organic group. 3 It can be understood that the compounds represented by formulas (B1) and (B2) mainly provide good UV durability, water repellency, oil repellency, antifouling properties (preventing adhesion of dirt such as fingerprints), chemical resistance, hydrolysis resistance, anti-slip effect, high friction durability, heat resistance, moisture resistance, etc. The fluoropolyether part (i.e., the Rf-PFPE part or the -PFPE- part) and the silane part (specifically -SiR a k1 R b l1 R c m1 Therefore, the X 3 As long as the compounds represented by formula (B1) and (B2) can exist stably, they may be single bonds or any organic groups. 3 In the structure of , the left side of the description is bonded to the group represented by PFPE, and the right side is bonded to the group marked with β and enclosed in parentheses.

[0468] In the above formula, β is an integer of 1 to 9, and β' is an integer of 1 to 9. These β and β' may correspond to X 3 In formula (B1), the sum of β and β′ and X 3 The valences are equal. For example, in X 3 When X is a devalent organic group, the sum of β and β' is 10, for example, β is 9 and β' is 1, β is 5 and β' is 5, or β is 1 and β' is 9. 3 When X is a divalent organic group, β and β' are 1. In formula (B2), β is X 3 The value obtained by subtracting 1 from the value of the valence.

[0469] The above X 3 The organic group is preferably a di- to hepta-valent group, more preferably a di- to tetra-valent group, and still more preferably a divalent group.

[0470] In one approach, X 3 It is a divalent to tetravalent organic group, β is 1 to 3, and β' is 1.

[0471] In another way, X 3 is a divalent organic group, β is 1, and β' is 1. In this case, formulae (B1) and (B2) are represented by the following formulae (B1') and (B2').

[0472] Rf-PFPE-X 3 -SiR a k1 R b l1R c m1 …(B1′)

[0473] R c m1 R b l1 R a k1 Si-X 3 -PFPE-X 3 -SiR a k1 R b l1 R c m1 …(B2′)

[0474] As the above X 3 Examples of X are not particularly limited, for example, 1 The same groups as those described above.

[0475] Among them, as the preferred X 3 , we can list: -X 10 -CON(R 34 )-X 11 -, -X 10 -(OR 35 ) n4 -X 11 - C 1－6 In the above formula, R 34 , R 35 , X 10 , X 11 Same meaning as n4.

[0476] As a particularly preferred 3 , specifically:

[0477] -O-CFHCF2-O-CONH-,

[0478] -O-CFHCF2-O-CONH-CH2-,

[0479] -O-CFHCF2-O-CONH-(CH2)2-,

[0480] -O-CFHCF2-O-CONH-(CH2)3-,

[0481] -O-CFHCF2-O-CONH-(CH2)6-,

[0482] -CONH-,

[0483] -CONH-CH2-,

[0484] -CONH-(CH2)2-、

[0485] -CONH-(CH2)3-、

[0486] -CONH-(CH2)6-、

[0487] -CF2CONH-、

[0488] -CF2CONHCH2-、

[0489] -CF2CONH(CH2)2-、

[0490] -CF2CONH(CH2)3-、

[0491] -CF2CONH(CH2)6-、

[0492] -O-CFHCF2-O-CH2OCH2-、

[0493] -O-CFHCF2-O-CH2O(CH2)2-、

[0494] -O-CFHCF2-O-CH2O(CH2)3-、

[0495] -O-CFHCF2-O-CH2O(CH2)6-、

[0496] -CH2OCH2-、

[0497] -CH2O(CH2)2-、

[0498] -CH2O(CH2)3-、

[0499] -CH2O(CH2)6-、

[0500] -CF2-CH2-O-CH2-、

[0501] -CF2-CH2-O-(CH2)2-、

[0502] -CF2-CH2-O-(CH2)3-、

[0503] -CF2-CH2-O-(CH2)6-、

[0504] -O-CFHCF2-O-、

[0505] -O-CFHCF2-O-(CH2)2-、

[0506] -O-CFHCF2-O-(CH2)3-、

[0507] -O-CFHCF2-O-(CH2)6-,

[0508] -CH2-,

[0509] -(CH2)2-,

[0510] -(CH2)3-,

[0511] -(CH2)6-,

[0512] -CF2-,

[0513] -(CF2)2-,

[0514] -CF2-CH2-,

[0515] -CF2-(CH2)2-,

[0516] -CF2-(CH2)3-,

[0517] -CF2-(CH2)4-,

[0518] -CF2-(CH2)5-,

[0519] -CF2-(CH2)6-, etc.

[0520] In a preferred embodiment, X 3 For -X 10 -CON(R 34 )-X 11 - or C 1－6 Alkylene (preferably propylene).

[0521] In the above formula,

[0522] R 34 The meaning is the same as above, preferably a hydrogen atom or C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0523] X 10 The meanings are the same as above, preferably a single bond, -R 36 -, or o-phenylene, m-phenylene or p-phenylene, more preferably a single bond or -R 36 -, more preferably a single bond;

[0524] R 36 The meaning is the same as above, preferably C which may be substituted by one or more fluorine atoms 1－20 Alkylene is more preferably C 1－3 Alkylene, more preferably C 1－2 Alkylene;

[0525] X 11 The meaning is the same as above, preferably a single bond or C which may be substituted by one or more fluorine atoms 1－20 Alkylene, more preferably a single bond or an unsubstituted C 1－6 Alkylene, more preferably a single bond or unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene.

[0526] In the above embodiment, X is particularly preferred 3 For -X 10 -CON(R 34 )-X 11 -. In the above formula, R 34 , X 10 and X 11 Same meaning as above.

[0527] In the above embodiment, it is particularly preferred that the above X 10 is a single bond, and the above X 11 C 1－3 Alkylene, more preferably X 11 C without a substituent 1－3 Alkylene.

[0528] In one approach, as X 3 Examples, without particular limitation, include the following structures:

[0529] -X f -X 10 -CON(R 34 )-X 11 -

[0530] -X f -X 10 -(OR 35 ) n4 -X 11 -

[0531] -X f -C 1－6 Alkylene (preferably propylene),

[0532] Where, X f , X 10 , R 34 , X 11 , R 35 Same meaning as n4.

[0533] In the above formula, R a Each occurrence represents -Z independently 3 -SiR 71p1 R 72 q1 R 73 r1 .

[0534] In the formula, Z 3 Each occurrence independently represents an oxygen atom or a divalent organic group.

[0535] The above Z 3 Preferably, it is a divalent organic group, excluding the Si atom at the end of the molecular main chain in formula (B1) or formula (B2) (with R a The case where the bonded Si atoms) form a siloxane bond.

[0536] The above Z 3 Preferably C 1－6 Alkylene, -(CH2) g -O-(CH2) h -(wherein, g is an integer of 1 to 6, and h is an integer of 1 to 6) or -phenylene-(CH2) i - (wherein i is an integer from 0 to 6), more preferably C 1－6 Alkylene, particularly preferably C 1－3 These groups can be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 From the viewpoint of particularly good ultraviolet durability, the Z 3 More preferably, it is a linear or branched alkylene group, and even more preferably a linear alkylene group. 3 The number of carbon atoms in the alkylene group is preferably in the range of 1 to 6, and more preferably in the range of 1 to 3. The alkylene group is as described above.

[0537] In one approach, Z 3 Can be C 1－6 Alkylene or -phenylene-(CH2) i -. In Z 3 When it is the above group, the light resistance, especially the ultraviolet resistance is further improved.

[0538] In the above embodiment, it is preferred that the above Z 3 C 1－6 Alkylene, more preferably C 1－3 Alkylene.

[0539] In one way,

[0540] The above X 3 Preferably -X 10 -CON(R34 )-X 11 - or C 1－6 Alkylene (preferably propylene), more preferably -X 10 -CON(R 34 )-X 11 -;in addition,

[0541] The above Z 3 Preferably C 1－6 Alkylene or -phenylene-(CH2) i -, more preferably C 1－6 Alkylene, more preferably C 1－3 Alkylene,

[0542] R 34 , X 10 , X 11 Same meaning as i.

[0543] In one way,

[0544] The above X 3 Preferably -X 10 -CON(R 34 )-X 11 - or C 1－6 Alkylene (preferably propylene), more preferably -X 10 -CON(R 34 )-X 11 -;in addition,

[0545] The above Z 3 Preferably C 1－6 Alkylene or -phenylene-(CH2) i -, more preferably C 1－6 Alkylene, more preferably C 1－3 Alkylene.

[0546] In the above formula,

[0547] R 34 A hydrogen atom or C 1－6 An alkyl group is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom;

[0548] X 10 is a single bond, -R 36 - or o-phenylene, m-phenylene or p-phenylene, preferably a single bond or -R 36 -, more preferably a single bond;

[0549] R 36 is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3Alkylene is more preferably C 1－2 Alkylene;

[0550] X 11 is a single bond or may be substituted with one or more fluorine atoms. 1－20 Alkylene, preferably a single bond or unsubstituted C 1－6 Alkylene, more preferably a single bond or an unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene;

[0551] i is an integer from 0 to 6.

[0552] In the above embodiment, it is particularly preferred that the above X 10 is a single bond, and the above X 11 C 1－3 Alkylene, more preferably X 11 C without a substituent 1－3 The above X 3 More preferably -X 10 -CON(R 34 )-X 11 -

[0553] In one way,

[0554] X 3 For -X f -X 10 -(OR 35 ) n4 -X 11 - the group shown;

[0555] Z 3 C 1－6 Alkylene, more preferably C 1－3 Alkylene. In the formula, X f , X 10 , X 11 , R 35 Same meaning as n4.

[0556] In the formula, R 71 Each occurrence represents R independently a′ . R a′ The meaning of R a same.

[0557] R a In, through Z 3 The maximum number of Si groups connected in a straight chain is 5. a In the case of at least one R 71 In the case of Ra Via Z 3 There are two or more Si atoms connected in a straight chain via the above Z 3 The maximum number of Si atoms connected in a straight chain is 5. a Via Z 3 The number of Si atoms connected in a straight chain is equal to the number of Si atoms in R a -Z connected in a straight chain 3 The number of repeating units of -Si-.

[0558] For example, the following represents R a Si atoms in Z 3 An example of base connection.

[0559]

[0560] In the above formula, * indicates the site of the main chain bonded to Si, ... indicates the site of the main chain bonded to Z 3 The prescribed group other than Si, that is, when all the three valence bonds of Si atom are ..., indicates Z 3 The position where the repeating unit of Si ends. In addition, the number on the upper right corner of Si indicates the number of Z starting from *. 3 The number of occurrences of Si groups connected in a straight chain. 3 Si repeating unit is Si 2 The chain ends with "R a Via Z 3 The number of Si atoms connected in a straight chain is 2. Similarly, Z 3 Si repeating unit is Si 3 、Si 4 and Si 5 The chain ends with "R a Via Z 3 The number of Si atoms connected in a straight chain is 3, 4 and 5 respectively. And, according to the above formula, R a There are multiple Z 3 Si chains, however, do not necessarily all have to be the same length and each may be any length.

[0561] In a preferred embodiment, as described below, "R a Via Z 3 The number of Si atoms connected in a straight chain by the groups is 1 (left-hand formula) or 2 (right-hand formula) in all chains.

[0562]

[0563] In one approach, R a Via Z 3The number of Si atoms connected in a straight chain is 1 or 2, preferably 1.

[0564] In the formula, R 72 Each occurrence independently represents a hydroxyl group or a hydrolyzable group. "Hydrolyzable group" has the same meaning as above.

[0565] Preferred R 72 is a hydrolyzable group, more preferably -OR (wherein R represents a substituted or unsubstituted C 1－3 Alkyl, more preferably means methyl).

[0566] In the formula, R 73 Each occurrence of is independently a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

[0567] In one approach, R 73 The meaning of lower alkyl is the same as above.

[0568] In the formula, p1 is an integer from 0 to 3 independently at each occurrence; q1 is an integer from 0 to 3 independently at each occurrence; r1 is an integer from 0 to 3 independently at each occurrence. 3 -SiR 71 p1 R 72 q1 R 73 r1 ), the sum of p1, q1 and r1 is 3, and in formulas (B1) and (B2), there are at least 2 Si atoms bonded to hydroxyl groups or hydrolyzable groups. That is, in formulas (B1) and (B2), -SiR 72 and / or -SiR b At least two are present. By having such a structure, the PFPE-containing silane compound of the present invention can form a surface-treated layer that can be well bonded to the surface of a substrate or the like.

[0569] Preferably, in formula (B1) and (B2) there is -SiR 72 2 (Specifically -SiR 72 2R 73 or -SiR 72 3) or -SiR b 2 (Specifically -SiR a R b 2. -SiR b 2R c or -SiR b 3).

[0570] In a preferred embodiment, in Ra The R at the end of a′ (There is no R a′ When R a ) in which q1 is preferably 2 or 3, more preferably 3.

[0571] In a preferred embodiment, R a At least one of the terminal portions is -Si(-Z 3 -SiR 72 q1 R 73 r1 )2(Specifically -Si(-Z 3 -SiR 72 q1 R 73 r1 )2R 73 ) or -Si(-Z 3 -SiR 72 q1 R 73 r1 )3, preferably -Si(-Z 3 -SiR 72 q1 R 73 r1 )3. Here, q1 is an integer greater than 1, preferably q1 is 2 or 3. Here, the sum of q1 and r1 is 3. In the formula, (-Z 3 -SiR 72 q1 R 73 r1 ) unit is preferably (-Z 3 -SiR 72 3) In a more preferred embodiment, R a The terminal parts are all -Si(-Z 3 -SiR 72 q1 R 73 r1 )3. Preferably -Si(-Z 3 -SiR 72 3)3.

[0572] In the above formula, R b Each occurrence independently represents a hydroxyl group or a hydrolyzable group.

[0573] The above R bPreferred are hydroxyl, -OR, -OCOR, -O-N=C(R)2, -N(R)2, -NHR, halogen (in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), and more preferably -OR. R includes: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl. Among these, alkyl groups, especially unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. The hydroxyl group is not particularly limited, and may be generated by hydrolysis of a hydrolyzable group. More preferably, R b -OR (where R represents a substituted or unsubstituted C 1－3 Alkyl, more preferably means methyl).

[0574] In the above formula, R c Each occurrence of is independently a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

[0575] In the formula, k1 is independently an integer of 0 to 3 at each occurrence; l1 is independently an integer of 0 to 3 at each occurrence; m1 is independently an integer of 0 to 3 at each occurrence. a k1 R b l1 R c m1 ), the sum of k1, l1 and m1 is 3.

[0576] In one embodiment, k1 is preferably 1 to 3, more preferably 2 or 3, and particularly preferably 3. In this embodiment, q1 is 1 to 3, preferably 2 or 3, and more preferably 3.

[0577] In one embodiment, k1 is preferably an integer of 1 to 3 and q1 is 2 or 3, more preferably k1 is 2 or 3 and q1 is 2 or 3, and even more preferably k1 is 3 and q1 is 2 or 3.

[0578] In one embodiment, k1 is preferably an integer of 1 to 3 and q1 is 3, k1 is more preferably 2 or 3 and q1 is 3, and k1 is further preferably 3 and q1 is 3.

[0579] In one embodiment, k1 is an integer from 1 to 3, and Z 3 It is a divalent organic group. 3 The Si atom at the end of the main chain of the molecule in formula (B1) or formula (B2) (bonded with R a The above Z is more preferably 3 Preferably C 1－6 Alkylene, -(CH2)g -O-(CH2) h -(wherein, g is an integer of 1 to 6, and h is an integer of 1 to 6) or -phenylene-(CH2) i - (wherein i is an integer from 0 to 6), more preferably C 1－3 Alkylene.

[0580] Preferred PFPE-containing silane compounds represented by formula (B1) include the following compounds. Hereinafter, Rf has the same meaning as above, and d is 5 to 40.

[0581] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CH2CH2CH2-Si(CH2CH2SiCH3(OCH3)2)3,

[0582] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CH2CH2CH2-Si(CH2CH2CH2 SiCH3(OCH3)2)3,

[0583] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CH2OCH2CH2CH2-Si(CH2CH2SiCH3(OCH3)2)3,

[0584] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CH2OCH2CH2CH2-Si(CH2CH2CH2SiCH3(OCH3)2)3,

[0585] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CONH-CH2-Si(CH2CH2SiCH3(OCH3)2)3,

[0586] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CONH-CH2-Si(CH2CH2CH2SiCH3(OCH3)2)3,

[0587] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CONH-CH2CH2CH2-Si(CH2CH2SiCH3(OCH3)2)3,

[0588] Rf-(OCF(CF3)CF2) d-OCF(CF3)-CONH-CH2CH2CH2-Si(CH2CH2CH2SiCH3(OCH3)2)3,

[0589] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CH2CH2CH2-Si(CH2CH2Si(OCH3)3,

[0590] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CH2CH2CH2-Si(CH2CH2CH2Si(OCH3)3)3,

[0591] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CH2OCH2CH2CH2-Si(CH2CH2Si(OCH3)3)3,

[0592] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CH2OCH2CH2CH2-Si(CH2CH2CH2Si(OCH3)3)3,

[0593] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CONH-CH2-Si(CH2CH2Si(OCH3)3)3,

[0594] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CONH-CH2-Si(CH2CH2CH2Si(OCH3)3) 3、

[0595] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CONH-CH2CH2CH2-Si(CH2CH2Si(OCH3)3)3,

[0596] Rf-(OCF(CF3)CF2) d -OCF(CF3)-CONH-CH2CH2CH2-Si(CH2CH2CH2Si(OCH3)3)3

[0597] The number average molecular weight of the compounds represented by the above formulae (B1) and (B2) is not particularly limited, and may be, for example, 5×10 2 ~1×10 5In this range, the number average molecular weight is preferably 1,000 to 30,000, more preferably 1,000 to 12,000, and further preferably 1,000 to 6,000. In the present invention, the number average molecular weight is 19 The value measured by F-NMR.

[0598] In a preferred embodiment, in formula (B1) and (B2),

[0599] PFPE are independently of each other and are of the formula: -(OCF(CF3)CF2) d - a group represented by (wherein, regarding d, d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200);

[0600] X 3 Each time it occurs, it is independently -X f -X 10 -CON(R 34 )-X 11 -, -X f -X 10 -(OR 35 ) n4 -X 11 -or-X f -C 1－6 Alkylene (preferably propylene), preferably -X f -X 10 -CON(R 34 )-X 11 -;

[0601] X f Each occurrence is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 2 carbon atoms (e.g., methylene), X f The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted;

[0602] X 10 Each occurrence is independently a single bond, -O-R 36 -O-, -R 36 -, or o-phenylene, m-phenylene or p-phenylene, preferably a single bond, -O-R 36 -O- or -R 36 -, more preferably a single bond or -R 36 -, more preferably a single bond;

[0603] R 36is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3 Alkylene is more preferably C 1－2 Alkylene, R 36 The above alkylene group may be linear or branched;

[0604] X 11 Each occurrence is independently a single bond, an oxygen atom, or a C which may be substituted with one or more fluorine atoms. 1－20 Alkylene, preferably a single bond or unsubstituted C 1－6 Alkylene, more preferably a single bond or an unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene;

[0605] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably a hydrogen atom or a C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0606] R 35 Each time it occurs, it is independently C 1－6 Alkylene, preferably C 1－3 Alkylene;

[0607] n4 is independently an integer of 1 to 5 at each occurrence, preferably an integer of 1 to 3, more preferably 1;

[0608] Z 3 Preferably C 1－6 Alkylene or -phenylene-(CH2) i -, more preferably C 1－6 Alkylene, more preferably C 1－3 Alkylene;

[0609] i is an integer from 0 to 6.

[0610] In one embodiment, the number average molecular weight of the compounds represented by the above formulae (B1) and (B2) is 1,000 to 8,000, preferably 1,000 to 4,000. By having such a number average molecular weight, the layer (e.g., surface treatment layer) formed using the above compounds (or a surface treatment agent containing the above compounds) has better anti-slip effect, friction durability, etc.

[0611] In a preferred embodiment, the compounds represented by formula (B1) and (B2) are the compound represented by formula (B1).

[0612] In one embodiment, the compounds represented by the above formulae (B1) and (B2) can be obtained, for example, by the following method: using a fluoropolyether derivative corresponding to the Rf-PFPE- portion as a raw material, introducing a hydroxyl group at the terminal, introducing a group having an unsaturated bond at the terminal, reacting the group having an unsaturated bond with a silyl derivative having a halogen atom, then introducing a hydroxyl group at the terminal of the silyl group, then introducing a group having an unsaturated bond, and finally reacting the introduced group having an unsaturated bond with a silyl derivative. For example, the synthesis can be performed according to the description of International Publication No. 2014 / 069592.

[0613] Formula (C1) and (C2):

[0614] (Rf-PFPE) γ’ -X 5 -(CR d k2 R e l2 R f m2 ) γ …(C1)

[0615] (R f m2 R e l2 R d k2 C) γ -X 5 -PFPE-X 5 -(CR d k2 R e l2 R f m2 ) γ …(C2)

[0616] In the above formulas (C1) and (C2), Rf and PFPE have the same meanings as those in the above formulas (A1) and (A2). However, "Formula (A1)" is replaced by "Formula (C1)", "X 1 "Base" is replaced by "X 5 base".

[0617] In the above formula, X 5 Each independently represents a single bond or a di- to decavalent organic group. 5 It can be understood that in the compounds represented by formula (C1) and (C2), the fluoropolyether part (i.e., the Rf-PFPE part or the -PFPE- part) that mainly provides water repellency and surface slip, etc., and the part that provides the ability to bind to the substrate (i.e., the group marked with γ and enclosed in brackets) are connected to the linking group.5 As long as the compounds represented by formula (C1) and (C2) can exist stably, they may be single bonds or any organic groups. 5 In the group, the left side is bonded to the group shown by PFPE, and the right side is bonded to the group marked with γ and enclosed in parentheses.

[0618] In the above formula, γ is an integer of 1 to 9, and γ′ is an integer of 1 to 9. These γ and γ′ may correspond to X 5 In formula (C1), the sum of γ and γ′ and X 5 The valences are equal. For example, in X 5 When X is a devalent organic group, the sum of γ and γ′ is 10, for example, γ is 9 and γ′ is 1, γ is 5 and γ′ is 5, or γ is 1 and γ′ is 9. 5 When X is a divalent organic group, γ and γ' are 1. In formula (C2), γ is X 5 The value obtained by subtracting 1 from the value of the valence.

[0619] The above X 5 The organic group is preferably a di- to hepta-valent group, more preferably a di- to tetra-valent group, and still more preferably a divalent group.

[0620] In one approach, X 5 It is a divalent to tetravalent organic group, γ is 1 to 3, and γ' is 1.

[0621] In another way, X 5 is a divalent organic group, γ is 1, and γ' is 1. In this case, formulae (C1) and (C2) are represented by the following formulae (C1') and (C2').

[0622] Rf-PFPE-X 5 -CR d k2 R e l2 R f m2 …(C1′)

[0623] R f m2 R e l2 R d k2 CX 5 -PFPE-X 5 -CR d k2 R e l2 R f m2 …(C2′)

[0624] As the above X 5 Examples of X are not particularly limited, for example, 1 The same groups as those described above.

[0625] Among them, the preferred X 5 Can be listed: -X 10 -CON(R 34 )-X 11 -, -X 10 -(OR 35 ) n4 -X 11 - C 1－6 In the above formula, R 34 , R 35 , X 10 , X 11 Same meaning as n4.

[0626] In one approach, X 5 For a single key.

[0627] In one approach, as X 5 Examples, without particular limitation, include the following structures:

[0628] -X f -X 10 -CON(R 34 )-X 11 -

[0629] -X f -X 10 -(OR 35 ) n4 -X 11 -

[0630] -X f -C 1－6 Alkylene (preferably propylene).

[0631] In the formula, X f , X 10 , R 34 , X 11 , R 35 Same meaning as n4.

[0632] Among the above, X is particularly preferably 5 , we can list:

[0633] single bond,

[0634] -O-CFHCF2-O-CONH-,

[0635] -O-CFHCF2-O-CONH-CH2-、

[0636] -O-CFHCF2-O-CONH-(CH2)2-、

[0637] -O-CFHCF2-O-CONH-(CH2)3-、

[0638] -O-CFHCF2-O-CONH-(CH2)6-、

[0639] -CONH-、

[0640] -CONH-CH2-、

[0641] -CONH-(CH2)2-、

[0642] -CONH-(CH2)3-、

[0643] -CONH-(CH2)6-、

[0644] -CF2-CONH-、

[0645] -CF2-CONH-CH2-、

[0646] -CF2-CONH-(CH2)2-、

[0647] -CF2-CONH-(CH2)3-、

[0648] -CF2-CONH-(CH2)6-、

[0649] -O-CFHCF2-O-CH2OCH2-、

[0650] -O-CFHCF2-O-CH2O(CH2)2-、

[0651] -O-CFHCF2-O-CH2O(CH2)3-、

[0652] -O-CFHCF2-O-CH2O(CH2)6-、

[0653] -CH2OCH2-、

[0654] -CH2O(CH2)2-、

[0655] -CH2O(CH2)3-、

[0656] -CH2O(CH2)6-、

[0657] -CF2-CH2OCH2-、

[0658] -CF2-CH2O(CH2)2-,

[0659] -CF2-CH2O(CH2)3-,

[0660] -CF2-CH2O(CH2)6-,

[0661] -O-CFHCF2-O-,

[0662] -O-CFHCF2-O-(CH2)2-,

[0663] -O-CFHCF2-O-(CH2)3-,

[0664] -O-CFHCF2-O-(CH2)6-,

[0665] -CH2-,

[0666] -(CH2)2-,

[0667] -(CH2)3-,

[0668] -(CH2)6-

[0669] -CF2-,

[0670] -(CF2)2-,

[0671] -CF2-CH2-,

[0672] -CF2-(CH2)2-,

[0673] -CF2-(CH2)3-,

[0674] -CF2-(CH2)4-,

[0675] -CF2-(CH2)5-,

[0676] -CF2-(CH2)6-, etc.

[0677] In a preferred embodiment, X 5 For -X 10 -CON(R 34 )-X 11 - or C 1－6 Alkylene (preferably propylene).

[0678] In the above formula,

[0679] R 34 The meaning is the same as above, preferably a hydrogen atom or C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0680] X 10The meanings are the same as above, preferably a single bond, -R 36 - or o-phenylene, m-phenylene or p-phenylene, more preferably a single bond or -R 36 -, more preferably a single bond;

[0681] R 36 The meaning is the same as above, preferably C which may be substituted by one or more fluorine atoms 1－20 Alkylene is more preferably C 1－3 Alkylene, more preferably C 1－2 Alkylene;

[0682] X 11 The meaning is the same as above, preferably a single bond or C which may be substituted by one or more fluorine atoms 1－20 Alkylene, more preferably a single bond or an unsubstituted C 1－6 Alkylene, more preferably a single bond or unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene.

[0683] In the above embodiment, X is particularly preferred 5 For -X 10 -CON(R 34 )-X 11 -. In the above formula, R 34 , X 10 and X 11 Same meaning as above.

[0684] In the above embodiment, it is particularly preferred that the above X 10 is a single bond, and the above X 11 C 1－3 Alkylene, more preferably X 11 C without a substituent 1－3 Alkylene.

[0685] In the above formula, R d Each occurrence represents -Z independently 4 -CR 81 p2 R 82 q2 R 83 r2 .

[0686] In the formula, Z 4 Each occurrence independently represents an oxygen atom or a divalent organic group.

[0687] The above Z 4 Preferably C 1－6Alkylene, -(CH2) g -O-(CH2) h -(wherein, g is an integer of 0 to 6, for example, an integer of 1 to 6, and h is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene-(CH2) i - (wherein i is an integer from 0 to 6), more preferably C 1－3 These groups can be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 The alkynyl group is substituted by one or more substituents.

[0688] In the formula, R 81 Each occurrence represents R independently d′ . R d′ The meaning of R d same.

[0689] R d In, through Z 4 The maximum number of carbon atoms connected in a straight chain is 5. d In the case of at least one R 81 In the case of R d Via Z 4 There are two or more C atoms connected in a straight chain via the above Z 4 The maximum number of carbon atoms connected in a straight chain is 5. d Via Z 4 The number of carbon atoms connected to form a straight chain is equal to the number of carbon atoms in R d -Z connected in a straight chain 4 -C- repeating units.

[0690] In a preferred embodiment, as shown below, "R d Via Z 4 The "number of carbon atoms connected in a straight chain" is 1 (left-hand formula) or 2 (right-hand formula) in all chains.

[0691]

[0692] In one approach, R d Via Z 4 The number of carbon atoms connected in a straight chain is 1 or 2, preferably 1.

[0693] In the formula, R 82 Each occurrence represents -Y-SiR independently 85 n2 R 86 3－n2 .

[0694] Y, at each occurrence, independently represents a divalent organic group.

[0695] In a preferred embodiment, Y is C 1－6 Alkylene, -(CH2) g′ -O-(CH2) h′ -(wherein, g' is an integer of 0 to 6, for example, an integer of 1 to 6, and h' is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene-(CH2) i′ - (wherein i' is an integer from 0 to 6). These groups can be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 The alkynyl group is substituted by one or more substituents.

[0696] In one embodiment, Y can be C 1－6 Alkylene or -phenylene-(CH2) i′ When Y is the above group, light resistance, especially ultraviolet resistance, is further improved. In the formula, i' is an integer of 0-6.

[0697] Preferably, the above Y is C 1－6 Alkylene, more preferably C 2－3 Alkylene.

[0698] In one way,

[0699] The above X 5 Preferably -X 10 -CON(R 34 )-X 11 - or C 1－6 Alkylene (preferably propylene), more preferably -X 10 -CON(R 34 )-X 11 -;and,

[0700] The above Y is preferably C 1－6 Alkylene or -phenylene-(CH2) i′ -, more preferably C 1－6 Alkylene.

[0701] R 34 , X 10 , X 11 and i′ have the same meaning as above.

[0702] In one way,

[0703] The above X 5 Preferably -X 10 -CON(R 34 )-X 11- or C 1－6 Alkylene (preferably propylene), more preferably -X 10 -CON(R 34 )-X 11 -;and,

[0704] The above Y is preferably C 1－6 Alkylene or -phenylene-(CH2) i′ -, more preferably C 1－6 Alkylene, more preferably C 2－3 Alkylene.

[0705] In the above formula,

[0706] R 34 A hydrogen atom or C 1－6 An alkyl group is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom;

[0707] X 10 is a single bond, -R 36 - or o-phenylene, m-phenylene or p-phenylene, preferably a single bond or -R 36 -, more preferably a single bond;

[0708] R 36 is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3 Alkylene is more preferably C 1－2 Alkylene;

[0709] X 11 is a single bond or may be substituted with one or more fluorine atoms. 1－20 Alkylene, preferably a single bond or unsubstituted C 1－6 Alkylene, more preferably a single bond or an unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene;

[0710] i' is an integer from 0 to 6.

[0711] In the above embodiment, it is particularly preferred that the above X 10 is a single bond, and the above X 11 C 1－3 Alkylene, more preferably X 11 C without a substituent 1－3 It is further preferred that the above X 5 For -X 10 -CON(R 34 )-X 11 -

[0712] The above R 85 Each occurrence independently represents a hydroxyl group or a hydrolyzable group. "Hydrolyzable group" has the same meaning as above.

[0713] Preferred R 85 -OR (where R represents a substituted or unsubstituted C 1－3 Alkyl, more preferably means ethyl or methyl, especially means methyl).

[0714] The above R 86 Each occurrence of is independently a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

[0715] The above n2 is in each (-Y-SiR 85 n2 R 86 3－n2 ) units independently represent an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 3.

[0716] The above R 83 Each occurrence independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group, preferably a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

[0717] In the formula, p2 is an integer from 0 to 3 independently at each occurrence; q2 is an integer from 0 to 3 independently at each occurrence; r2 is an integer from 0 to 3 independently at each occurrence. 4 -CR 81 p2 R 82 q2 R 83 r2 ), the sum of p2, q2 and r2 is 3.

[0718] In the above formula, R e Each occurrence represents -Y-SiR independently 85 n2 R 86 3－n2 Here, Y, R 85 , R 86 The meanings of n2 and R are the same as those mentioned above. 82 The records in are the same.

[0719] In the above formula, R fEach occurrence independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group, preferably a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

[0720] In the formula, k2 is independently an integer of 0 to 3 at each occurrence; l2 is independently an integer of 0 to 3 at each occurrence; m2 is independently an integer of 0 to 3 at each occurrence. The sum of k2, l2 and m2 is 3.

[0721] In the above formulas (C1) and (C2), there are two or more -Y-SiR 85 Specifically, there are two or more -Y-SiR 85 n2 R 86 3－n2 Preferably, in the above formulae (C1) and (C2), at least two -Y-SiR groups with n2 being 2 or more are present. 85 n2 R 86 3－n2 That is, preferably, in the above formulas (C1) and (C2), at least two -Y-SiR 85 2R 86 The group shown or -Y-SiR 85 3 shown in the group.

[0722] In the above formulas (C1) and (C2), (-Y-SiR 85 n2 R 86 3－n2 ) unit is preferably (-Y-SiR 85 2R 86 ) or (-Y-SiR 85 3), more preferably (-Y-SiR 85 3).

[0723] In a preferred embodiment, in R d The R at the end of d′ (There is no R d′ When R d ), the above q2 is preferably 2 or more, for example, 2 or 3, and more preferably 3. In this embodiment, it is more preferred that q2 is 2 or more, for example, 2 or 3, and n2 is an integer of 2 or 3; it is further preferred that q2 is 2 or more, for example, 2 or 3, and n2 is 3; it is particularly preferred that q2 is 3 and n2 is 3.

[0724] In a preferred embodiment, R d At least one of the terminal parts is -C(-Y-SiR85 n2 R 86 3－n2 )2(Specifically -C(-Y-SiR 85 n2 R 86 3－n2 )2R 83 ) or -C(-Y-SiR 85 n2 R 86 3－n2 )3, preferably -C(-Y-SiR 85 n2 R 86 3－n2 )3. In the formula, (-Y-SiR 85 n2 R 86 3－n2 ) unit is (-Y-SiR 85 2R 86 ) or (-Y-SiR 85 3), preferably (-Y-SiR 85 3) In a more preferred embodiment, R d The end parts are all -C(-Y-SiR 85 n2 R 86 3－n2 )3, and n2 is an integer of 2 or 3, preferably -C(-Y-SiR 85 3)3.

[0725] In a more preferred embodiment, (CR d k2 R e l2 R f m2 The terminal of the group represented by ) is C(-Y-SiR 85 n2 R 86 3－n2 )2R 83 、C(-Y-SiR 85 n2 R 86 3－n2 )2R f or C(-Y-SiR 85 n2 R 86 3－n2 )3, preferably C(-Y-SiR 85 n2 R 86 3－n2 )2R f or C(-Y-SiR85 n2 R 86 3－n2 )3, more preferably C(-Y-SiR 85 n2 R 86 3－n2 )3. Here, n2 is an integer from 1 to 3. In the formula, (-Y-SiR 85 n2 R 86 3－n2 ) unit is preferably (-Y-SiR 85 3). In a further preferred embodiment, the terminal parts of the above groups are all -C(-Y-SiR 85 n2 R 86 3－n2 )3, preferably -C(-Y-SiR 85 3)3.

[0726] In one approach, R e There are 1 to 3 (i.e. l2 is an integer from 1 to 3), preferably R e There are 2 or 3 (i.e. l2 is 2 or 3), preferably R e There are 3 (i.e., l2 is 3). In this embodiment, n2 is 2 or 3, preferably 3. More preferably, l2 is 2 or 3, and n2 is 2 or 3, and further preferably, l2 is 3, and n2 is 3.

[0727] In one approach, R e There are 1 to 3 (i.e. l2 is an integer from 1 to 3), preferably R e There are 2 or 3 (i.e. l2 is 2 or 3), preferably R e There are 3 (i.e. l2 is 3). In this method, the R e (-Y-SiR 85 2R 86 ) or (-Y-SiR 85 3), preferably (-Y-SiR 85 3) More preferably, l2 is 2 or 3, and R e (-Y-SiR 85 2R 86 ) or (-Y-SiR 85 3), further preferably l2 is 3, and R e (-Y-SiR 85 3).

[0728] In one embodiment, at least one k2 is 2 or 3, preferably 3. In this embodiment, in R d The R at the end of d′ (There is no R d′When R d ), there are two or more R 82 (i.e. q2 is greater than 2), for example, there are 2 or 3 R 82 (i.e. q2 is 2 or 3), and the R 82 (-Y-SiR 85 2R 86 ) or (-Y-SiR 85 3), preferably (-Y-SiR 85 3) More preferably, there are 3 R 82 (i.e. q2 is 3), and the R 82 (-Y-SiR 85 2R 86 ) or (-Y-SiR 85 3), particularly preferably there are 3 R 82 (i.e. q2 is 3), and the R 82 (-Y-SiR 85 3).

[0729] In one embodiment, k2 is 2 or 3, preferably 3. In this embodiment, in R d The R at the end of d′ (There is no R d′ When R d ), R 82 There are 2 or 3, and the R 82 (-Y-SiR 85 2R 86 ) or (-Y-SiR 85 3) More preferably R 82 There are 2 or 3, and the R 82 (-Y-SiR 85 3), particularly preferably R 82 There are 3, and the R 82 (-Y-SiR 85 3).

[0730] Preferred PFPE-containing silane compounds represented by formula (C1) include the following compounds: Hereinafter, Rf has the same meaning as above (e.g., CF3CF2CF2), and d is 5 to 40.

[0731] Rf-(OCF(CF3)CF2) d OCF(CF3)CONHCH2C(CH3)(CH2CH2CH2Si(OCH3)3)2,

[0732] Rf-(OCF(CF3)CF2) d OCF(CF3)CONHCH2C(CH2CH2CH2Si(OCH3)3)3,

[0733] Rf-(OCF(CF3)CF2) d OCF(CF3)CH2OCH2C(CH3)(CH2CH2CH2Si(OCH3)3)2,

[0734] Rf-(OCF(CF3)CF2) d OCF(CF3)CH2OCH2C(CH2CH2CH2Si(OCH3)3)3,

[0735] Rf-(OCF(CF3)CF2) d OCF(CF3)CH2OCH2C(CH3)(CH2OCH2CH2CH2Si(OCH3)3)2,

[0736] Rf-(OCF(CF3)CF2) d OCF(CF3)CH2OCH2C(CH2OCH2CH2CH2Si(OCH3)3)3,

[0737] Rf-(OCF(CF3)CF2) d OCF(CF3)-CH2CH2CH2-C(CH3)(CH2CH2CH2Si(OCH3)3)2,

[0738] Rf-(OCF(CF3)CF2) d OCF(CF3)-CH2CH2CH2-C(CH2CH2CH2Si(OCH3)3)3

[0739] The number average molecular weight of the compounds represented by the above formulae (C1) and (C2) is not particularly limited, and may be, for example, 5×10 2 ~1×10 5 In this range, the number average molecular weight is preferably 1,000 to 30,000, more preferably 1,000 to 12,000, and further preferably 1,000 to 6,000. In the present invention, the number average molecular weight is 19 The value measured by F-NMR.

[0740] In one embodiment, the number average molecular weight of the compounds represented by the above formulae (C1) and (C2) is 1,000 to 8,000, preferably 1,000 to 4,000. By having such a number average molecular weight, the layer (e.g., surface treatment layer) formed using the above compounds (or a surface treatment agent containing the above compounds) has better anti-slip effect, wear resistance, etc.

[0741] In one way,

[0742] PFPE are independently of each other and are of the formula: -(OCF(CF3)CF2) d - a group represented by (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200);

[0743] X 5 For a single bond, -X f -X 10 -CON(R 34 )-X 11 -, -X f -X 10 -(OR 35 ) n4 -X 11 -or-X f -C 1－6 Alkylene (preferably propylene);

[0744] X f Each occurrence is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 2 carbon atoms (e.g., methylene), X f The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted;

[0745] X 10 Each occurrence is independently a single bond, -O-R 36 -O-, -R 36 -, or o-phenylene, m-phenylene or p-phenylene, preferably a single bond, -O-R 36 -O- or -R 36 -, more preferably a single bond or -R 36 -, more preferably a single bond;

[0746] R 36 is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3 Alkylene is more preferably C 1－2 Alkylene, R 36 The above alkylene group may be linear or branched;

[0747] X 11 Each occurrence is independently a single bond, an oxygen atom, or a C which may be substituted with one or more fluorine atoms. 1－20 Alkylene, preferably a single bond or unsubstituted C1－6 Alkylene, more preferably a single bond or an unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene;

[0748] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably a hydrogen atom or a C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0749] R 35 Each time it occurs, it is independently C 1－6 Alkylene, preferably C 1－3 Alkylene;

[0750] n4 is independently an integer of 1 to 5 at each occurrence, preferably an integer of 1 to 3, more preferably 1;

[0751] Y is independently -(CH2) at each occurrence g′ -O-(CH2) h′ - (wherein, g' is an integer of 0 to 6, h' is an integer of 0 to 6, for example, an integer of 1 to 6) or C 1－6 Alkylene (preferably C 2－3 Alkylene);

[0752] l2 is 3;

[0753] n2 is 3.

[0754] In the above method, g′ can be zero.

[0755] In one way,

[0756] PFPE are independently of each other and are of the formula: -(OCF(CF3)CF2) d - a group represented by (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200);

[0757] X 5 is a single bond;

[0758] Y is independently -(CH2) at each occurrence g′ -O-(CH2) h′ - (wherein, g' is an integer of 0 to 6, for example, g' is 0, and h' is an integer of 0 to 6, for example, an integer of 1 to 6) or C 1－6 Alkylene (preferably C 2－3 Alkylene);

[0759] l2 is 3;

[0760] n2 is 3.

[0761] In a preferred embodiment, in formula (C1) and (C2),

[0762] PFPE are independently of each other and are of the formula: -(OCF(CF3)CF2) d - a group represented by (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200);

[0763] X 5 Each time it occurs, it is independently -X f -X 10 -CON(R 34 )-X 11 -, -X f -X 10 -(OR 35 ) n4 -X 11 -or-X f -C 1－6 Alkylene (preferably propylene), preferably -X f -X 10 -CON(R 34 )-X 11 -;

[0764] X f Each occurrence is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 2 carbon atoms (e.g., methylene), X f The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted;

[0765] X 10 Each occurrence is independently a single bond, -O-R 36 -O-, -R 36 - or o-phenylene, m-phenylene or p-phenylene, preferably a single bond, -O-R 36 -O- or -R 36 -, more preferably a single bond or -R 36 -, more preferably a single bond;

[0766] R 36 is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3 Alkylene is more preferably C1－2 Alkylene, R 36 The above alkylene group may be linear or branched;

[0767] X 11 Each occurrence is independently a single bond, an oxygen atom, or a C which may be substituted with one or more fluorine atoms. 1－20 Alkylene, preferably a single bond or unsubstituted C 1－6 Alkylene, more preferably a single bond or an unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene;

[0768] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably a hydrogen atom or a C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0769] R 35 Each time it occurs, it is independently C 1－6 Alkylene, preferably C 1－3 Alkylene;

[0770] n4 is independently an integer of 1 to 5 at each occurrence, preferably an integer of 1 to 3, more preferably 1;

[0771] Y is C 1－6 Alkylene, preferably C 2－3 Alkylene.

[0772] In a preferred embodiment, the compounds represented by formula (C1) and (C2) are the compound represented by formula (C1).

[0773] In one embodiment, the PFPE-containing silane compound represented by formula (C1) or formula (C2) can be produced by combining known methods.

[0774] In one embodiment, the PFPE-containing silane compound of the present invention is a compound represented by formula (B1), formula (B2), formula (C1), or formula (C2).

[0775] In the above embodiment, the formula (B1) is preferably represented by the following formula (B1″).

[0776] Rf-PFPE-X 3 -SiR a k1 R b l1 R c m1 …(B1″)

[0777] In formula (B1″),

[0778] Rf is independently CF2H-C 1－15 Fluorinated alkylene or C 1－16 Perfluoroalkyl, preferably C 1－16 Perfluoroalkyl;

[0779] PFPE is -(OC3F6) d -, and PFPE has at least one branched structure, preferably -(OCF2CF(CF3)) d ;

[0780] d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200;

[0781] X 3 For -X f -X 10 -CON(R 34 )-X 11 -, -X f -X 10 -(OR 35 ) n4 -X 11 -or-X f -C 1－6 Alkylene (preferably propylene), preferably -X f -X 10 -CON(R 34 )-X 11 -;

[0782] X f Each occurrence is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 2 carbon atoms (e.g., methylene), X f The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted;

[0783] X 10 Each occurrence is independently a single bond, -O-R 36 -O-, -R 36 - or o-phenylene, m-phenylene or p-phenylene, preferably a single bond, -O-R 36 -O- or -R 36 -, more preferably a single bond or -R 36 -, more preferably a single bond;

[0784] R36 is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3 Alkylene is more preferably C 1－2 Alkylene, R 36 The above alkylene group may be linear or branched;

[0785] X 11 Each occurrence is independently a single bond, an oxygen atom, or a C which may be substituted with one or more fluorine atoms. 1－20 Alkylene, preferably a single bond or unsubstituted C 1－6 Alkylene, more preferably a single bond or an unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene;

[0786] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably a hydrogen atom or a C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0787] R 35 Each time it occurs, it is independently C 1－6 Alkylene, preferably C 1－3 Alkylene;

[0788] n4 is independently an integer of 1 to 5 at each occurrence, preferably an integer of 1 to 3, more preferably 1;

[0789] R a Each occurrence represents -Z independently 3 -SiR 71 p1 R 72 q1 R 73 r1 ;

[0790] Z 3 Preferably C 1－6 Alkylene or -phenylene-(CH2) i -, more preferably C 1－6 Alkylene, more preferably C 1－3 Alkylene;

[0791] R 72 is a hydrolyzable group, more preferably -OR (wherein R represents a substituted or unsubstituted C 1－3 Alkyl, more preferably methyl);

[0792] p1 is 0, q1 is 3, r1 is 0;

[0793] k1 is 3, l1 and m1 are 0.

[0794] In the above method, X 3 Can be -X f -X 10 -(OR 35 ) n4 -X 11 - shown in the formula. f , X 10 , X 11 , R 35 Same meaning as n4.

[0795] In the above embodiment, the formula (B2) is preferably represented by the following formula (B2″).

[0796] R c m1 R b l1 R a k1 Si-X 3 -PFPE-X 3 -SiR a k1 R b l1 R c m1 …(B2″)

[0797] In formula (B2"), the meanings of the symbols are the same as those in formula (B1")

[0798] In the above embodiment, the formula (C1) is preferably represented by the following formula (C1″).

[0799] Rf-PFPE-X 5 -CR d k2 R e l2 R f m2 …(C1″)

[0800] In formula (C1″),

[0801] Rf is independently CF2H-C 1－15 Fluorinated alkylene or C 1－16 Perfluoroalkyl, preferably C 1－16 Perfluoroalkyl;

[0802] PFPE is -(OC3F6)d-, and PFPE has at least one branched structure, preferably -(OCF2CF(CF3)) d ;

[0803] d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200;

[0804] X 5 For -X f -X 10 -CON(R 34 )-X 11 -, -X f -X 10 -(OR 35 ) n4 -X 11 -or-X f -C 1－6 Alkylene (preferably propylene), preferably -X f -X 10 -CON(R 34 )-X 11 -;

[0805] X f Each occurrence is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 2 carbon atoms (e.g., methylene), X f The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted;

[0806] X 10 Each occurrence is independently a single bond, -O-R 36 -O-, -R 36 - or o-phenylene, m-phenylene or p-phenylene, preferably a single bond, -O-R 36 -O- or -R 36 -, more preferably a single bond or -R 36 -, more preferably a single bond;

[0807] R 36 is C which may be substituted with one or more fluorine atoms 1－20 The alkylene group is preferably a C 1－3 Alkylene is more preferably C 1－2 Alkylene, R 36 The above alkylene group may be linear or branched;

[0808] X 11 Each occurrence is independently a single bond, an oxygen atom, or a C which may be substituted with one or more fluorine atoms. 1－20 Alkylene, preferably a single bond or unsubstituted C 1－6 Alkylene, more preferably a single bond or an unsubstituted C 1－3 Alkylene, particularly preferably C 1－3 Alkylene;

[0809] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably a hydrogen atom or a C 1－6 An alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;

[0810] R 35 Each time it occurs, it is independently C 1－6 Alkylene, preferably C 1－3 Alkylene;

[0811] n4 is independently an integer of 1 to 5 at each occurrence, preferably an integer of 1 to 3, more preferably 1;

[0812] k2 is 0, l2 is 3, m2 is 0;

[0813] R e By -Y-SiR 85 n2 R 86 3－n2 express;

[0814] Y is C 1－6 Alkylene, preferably C 2－3 Alkylene;

[0815] R 85 Each occurrence independently represents a hydroxyl group or a hydrolyzable group, preferably -OR (wherein R represents a substituted or unsubstituted C 1－3 Alkyl, more preferably ethyl or methyl, particularly preferably methyl);

[0816] n2 is 3.

[0817] In the above embodiment, the formula (C2) is preferably represented by the following formula (C2″).

[0818] R f m2 R e l2 R d k2 CX 5 -PFPE-X 5-CR d k2 R e l2 R f m2 …(C2″)

[0819] In formula (C2"), the meanings of the symbols are the same as those in formula (C1")

[0820] In one embodiment, the PFPE-containing silane compound of the present invention is a compound represented by formula (C1) or formula (C2).

[0821] In the above embodiment, it is preferred that the compound represented by formula (C1) is the compound represented by formula (C1″) and the compound represented by formula (C2) is the compound represented by formula (C2″).

[0822] In a preferred embodiment, the PFPE-containing silane compound of the present invention is a compound represented by formula (B1) or (C1).

[0823] More preferably, the PFPE-containing silane compound of the present invention is a compound represented by formula (C1).

[0824] In the above embodiment, the compound represented by formula (C1) is preferably a compound represented by formula (C1″) above.

[0825] Hereinafter, a method suitable for producing the PFPE-containing silane compound of the present invention will be described by giving an example, but the method of the present invention is not limited to the following method.

[0826] In one embodiment, a method suitable for producing a PFPE-containing silane compound represented by formula (C1) or (C2) is described. The method includes the following steps.

[0827] Step (3): a compound represented by formula (c1-3) or formula (c2-3) and HSiM′3 and, if necessary, a compound represented by formula: R 85 i L', and / or the formula: R 86′ j A step for reacting a compound represented by L″.

[0828]

[0829] [Wherein,

[0830] Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0831] PFPE is composed of (-OCF(CF3)CF2-) d express;

[0832] d is an integer greater than 2 and less than 200;

[0833] X 10 Each occurrence is independently a single bond or a divalent organic group;

[0834] R 34 Each occurrence is independently a hydrogen atom or a C 1－6 alkyl;

[0835] X 11 Each occurrence is independently a single bond or a divalent organic group;

[0836] Y 11 Each occurrence is independently a single bond or a divalent organic group.]

[0837] HSiM′3

[0838] [Wherein,

[0839] M' is independently a halogen atom or C 1－6 Alkoxy.]

[0840] Formula: R 85 i L′

[0841] [Wherein,

[0842] R 85 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0843] L′ indicates that it can be 85 Bonded groups;

[0844] i is an integer from 1 to 3.]

[0845] Formula: R 86′ j L″

[0846] [Wherein,

[0847] R 86′ Represents C 1－22 alkyl;

[0848] L″ indicates that it can be connected with R 86′ Bonded groups;

[0849] j is an integer from 1 to 3.]

[0850] Among them, -X 10 -C(O)N(R 34 )-X 11 - X corresponding to formula (C1) and (C2) 5 , -Y11 -CH2CH2- corresponds to Y in formulas (C1) and (C2).

[0851] In the above embodiment, it is preferred that the compound represented by the above formula (c1-3) or formula (c2-3) is produced by a method including the following steps (1) and (2).

[0852] Step (1): a step of reacting a compound represented by formula (c1-1) or formula (c2-1) with SOM2 to obtain a compound represented by formula (c1-2) or formula (c2-2).

[0853] Rf-PFPE-X 10 -C(O)OH…(c1-1)

[0854] HOC(O)-X 10 PFPE-X 10 -C(O)OH…(c2-1)

[0855] [Wherein, Rf, PFPE and X 10 has the same meaning as above.]

[0856] SOM2

[0857] [In the formula, M is independently a chlorine atom or a fluorine atom at each occurrence.]

[0858]

[0859] [Wherein, Rf, PFPE, X 10 Same meaning as above for M.]

[0860] Step (2): reacting the compound represented by the above formula (c1-2) or formula (c2-2) with a compound represented by the formula: HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3 to obtain a compound represented by formula (c1-3) or formula (c2-3).

[0861] Formula: HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3

[0862] [Where R 34 , X 11 and Y 11 has the same meaning as above.]

[0863]

[0864] [Wherein, Rf, PFPE, X 10 , R34 and X 11 has the same meaning as above.]

[0865] Hereinafter, the above-mentioned production method will be described in detail.

[0866] Process (1):

[0867] In formula (c1-1) or formula (c2-1), Rf has the same meaning as above.

[0868] In formula (c1-1) or formula (c2-1), PFPE has the same meaning as above, and is preferably of the formula: -(OC3F6) d -, more preferably a group represented by the formula: -(OCF(CF3)CF2) d In the above formula, d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200.

[0869] In formula (c1-1) or formula (c2-1), X 10 Each occurrence is independently a single bond or a divalent organic group, preferably a single bond or a C 1－6 Alkylene is more preferably C 1－3 Alkylene.

[0870] The compound represented by formula (c1-1) or formula (c2-1) may be a commercially available product, or may be produced from a commercially available compound using a common technique in the technical field.

[0871] In SOM2 used in step (1), M is independently a chlorine atom or a fluorine atom at each occurrence, preferably a chlorine atom. The compound may be a commercially available product, or may be prepared from a commercially available compound using a common technique in the art.

[0872] The amount of SOM2 used in step (1) is preferably 1 mol or more relative to 1 mol of the terminal COOH group of the compound represented by the above formula (c1-1) and / or formula (c2-1) (the total of these compounds when two or more compounds are used, the same below).

[0873] The reaction in step (1) is preferably carried out in the presence of a suitable catalyst in a suitable solvent.

[0874] Examples of suitable catalysts include N,N-dimethylformamide (DMF) and the like.

[0875] The suitable solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include 1,3-bis(trifluoromethyl)benzene, perfluorobutyl ethyl ether, and perfluorohexyl methyl ether.

[0876] The reaction temperature of the reaction is not particularly limited, and is usually 0 to 150°C, preferably 80 to 100°C; the reaction time is not particularly limited, and is usually 30 to 600 minutes, preferably 60 to 120 minutes; the reaction pressure is not particularly limited, and is -0.2 to 1 MPa (gauge pressure), and is normal pressure for simplicity.

[0877] Step (2):

[0878] Compound used in step (2): HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3, X 11 is a single bond or a divalent organic group, preferably a single bond, a C 1－6 Alkylene, more preferably C 1－3 Alkylene.

[0879] In the above formula, R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 Alkyl, preferably a hydrogen atom or a C 1－6 The alkyl group is more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

[0880] In the above formula, Y 11 Each occurrence of Y is independently a single bond or a divalent organic group. 11 An alkylene group having 1 to 6 carbon atoms is preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred.

[0881] Compound used in step (2): HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3, specifically H2NCH2C(CH2-CH=CH2)3, H2NCH2CH2C(CH2-CH=CH2)3, H2NCH2CH2CH2C(CH2-CH=CH2)3, etc. can be listed.

[0882] About formula: HN(R 34 )-X 11 -C(Y 11 The amount of the compound represented by -CH=CH2)3 is preferably 1 mol or more per 1 mol of the terminal -C(O)M group of the compound represented by the above formula (c1-2) and / or formula (c2-2).

[0883] The reaction in step (2) is preferably carried out in the presence of a suitable catalyst in a suitable solvent.

[0884] Examples of suitable catalysts include triethylamine and diisopropylethylamine.

[0885] The suitable solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include 1,3-bis(trifluoromethyl)benzene, perfluorobutyl ethyl ether, and perfluorohexyl methyl ether.

[0886] The reaction temperature in the reaction is not particularly limited, and is usually 0 to 100°C, preferably 0 to 40°C; the reaction time is not particularly limited, and is usually 30 to 600 minutes, preferably 60 to 120 minutes; the reaction pressure is not particularly limited, and is -0.2 to 1 MPa (gauge pressure), and is normal pressure for simplicity.

[0887] Step (3):

[0888] In step (3), the compound represented by formula (c1-3) or formula (c2-3) is reacted with HSiM′3 and, if necessary, a compound represented by formula: R 85 i L' represents a compound and / or a compound of the formula: R 86′ j The compound shown by L" reacts.

[0889] The compound represented by the above formula (c1-3) or formula (c2-3) is preferably obtained in step (2).

[0890] The compound used in step (3): HSiM′3, M′ is independently a halogen atom or C 1－6 The alkoxy group is preferably a halogen atom, more preferably a chlorine atom.

[0891] Formula used in step (3): R 85 i In the compound represented by L′, R 85 The meanings are the same as those in formulas (C1) and (C2); L′ represents a 85 Bonding group; i is an integer from 1 to 3.

[0892] Formula used in step (3): R 86′ j In the compound represented by L″, R 86′ C 1－22 Alkyl; L" indicates that it can be combined with R 86′ Bonding group; j is an integer from 1 to 3.

[0893] The above L' and L" are "capable of being combined with R 85 Bonding group" and "capable of bonding with R 86′ The bonding groups are able to 85 and R 86′bonding, as long as R 85 and R 86′ There is no particular limitation on the number of atoms that can be separated from R, and examples thereof include hydrogen atoms, lithium, sodium, etc. 85 Bonding group" and "capable of bonding with R 86′ The "bonded group" may have multiple R 85 or R 86′ For those skilled in the art, appropriate groups that can react with R can be selected according to the type of the compound to be reacted, the solvent, the temperature and other conditions. 85 The bonding group and the R 86′ Bonded groups.

[0894] The amount of HSiM'3 used in step (3) may be 1 mol or more, and preferably 2 mol, relative to 1 mol of the terminal -CH=CH2 groups of the compounds represented by the above formula (c1-3) and / or formula (c2-3).

[0895] Use R in step (3) 85 i In the case of a compound represented by L′, the amount used may be in accordance with the amount of R to be introduced. 85 Such amount may be appropriately determined by those skilled in the art.

[0896] Use R in step (3) 86′ j In the case of a compound represented by L″, the amount used may be in accordance with the amount of R to be introduced. 86′ Such amount may be appropriately determined by those skilled in the art.

[0897] In the reaction of step (3), first, the terminal -CH=CH2 group of the compound represented by the above formula (c1-3) and / or formula (c2-3) reacts with HSiM'3 to convert the terminal into a -CH2CH2SiM'3 group. 85 i The compound represented by L' and / or R 86′ j The compound represented by L″ reacts, and M′ is replaced by R 85 or R 86′ Replace. Among them, R 85 i The compound represented by L′ and R 86′ j The compounds represented by L" may be reacted simultaneously or individually.

[0898] However, in one embodiment of the present invention, HSiM′3, R 85 i The compound represented by L′ and R 86′ j The compound represented by L″ is used as HSi(R 85 i )(R 86′ j ) (where i+j is 3). 85 i )(R 86′ j ) can be prepared by a person skilled in the art using common techniques in the art.

[0899] In another embodiment, R in step (3) is reacted with 1 mol of terminal -CH=CH2 groups of the compound represented by the above formula (c1-3) and / or formula (c2-3). 85 i The compound represented by L' and / or R 86′ j The total amount of the compound represented by L″ used is set to 3 mol or more. According to this embodiment, the M′ of the terminal -CH2CH2SiM′3 generated in the reaction of step (3) can be substantially completely replaced by R 85 or R 86′ replace.

[0900] The reaction in step (3) is preferably carried out in the presence of a suitable catalyst in a suitable solvent.

[0901] As suitable catalysts, Pt, Pd, Rh, etc. can be mentioned. The above catalyst is preferably Pt. Such a catalyst can be in any form, for example, it can be in the form of a coordination compound.

[0902] The suitable solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include 1,3-bis(trifluoromethyl)benzene, perfluorobutyl ethyl ether, and perfluorohexyl methyl ether.

[0903] The reaction temperature of the reaction is not particularly limited, and is usually 0 to 100°C, preferably 50 to 80°C; the reaction time is not particularly limited, and is usually 30 to 600 minutes, preferably 60 to 240 minutes; the reaction pressure is not particularly limited, and is -0.2 to 1 MPa (gauge pressure), and is normal pressure for simplicity.

[0904] The reaction of step (3) is preferably carried out in the presence of an appropriate anti-rearrangement agent.

[0905] Suitable anti-rearrangement agents are not particularly limited, and examples thereof include carboxylic acid compounds. The carboxylic acid compounds include (a) carboxylic acids, (b) carboxylic anhydrides, (c) silylated carboxylic acids, and / or (d) substances that generate the above carboxylic acid compounds (i.e., (a), (b) or (c)) in the reaction of step (3). These carboxylic acid compounds may be used alone or in combination of two or more.

[0906] In the case where the rearrangement prevention agent contains (a) a carboxylic acid, any carboxylic acid having a carboxyl group can be used. Examples of suitable carboxylic acids are not particularly limited, and saturated carboxylic acids, unsaturated carboxylic acids, monocarboxylic acids, and dicarboxylic acids can be cited. Specific examples of suitable carboxylic acids are not particularly limited, and include: saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, caproic acid, cyclohexanoic acid, lauric acid, and stearic acid; saturated dicarboxylic acids such as oxalic acid and adipic acid; aromatic carboxylic acids such as benzoic acid and terephthalic acid; carboxylic acids in which the hydrogen atoms on the carbon of the hydrocarbon group of these carboxylic acids such as chloroacetic acid, dichloroacetic acid, trifluoroacetic acid, p-chlorobenzoic acid, and trimethylsilylacetic acid are substituted with halogen atoms or organic silyl groups; unsaturated fatty acids such as acrylic acid, methacrylic acid, and oleic acid; compounds having a hydroxyl group, a carbonyl group, or an amino group in addition to a carboxyl group, i.e., hydroxy acids such as lactic acid, keto acids such as acetoacetic acid, aldehyde acids such as glyoxylic acid, and amino acids such as glutamic acid.

[0907] Examples of (b) carboxylic anhydrides are not particularly limited, and include acetic anhydride, propionic anhydride, and benzoic anhydride. These carboxylic anhydrides may be those generated in the reaction system of step (3), and include: acetyl chloride, butyryl chloride, benzoyl chloride, and other carboxylic acid halides; carboxylic acid metal salts such as zinc acetate and thallium acetate; and carboxylic acid esters decomposed by light or heat such as (2-nitrophenyl) propionate.

[0908] Examples of (c) silylated carboxylic acids are not particularly limited, and examples thereof include trialkylsilylated carboxylic acids such as trimethylsilylformate, trimethylsilylacetate, triethylsilylpropionate, trimethylsilylbenzoic acid, and trimethylsilyltrifluoroacetic acid; and di-, tri-, or tetracarboxy silicates such as dimethyldiacetoxysilane, diphenyldiacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, di-tert-butoxydiacetoxysilane, and tetrabenzoic acid silicon salts.

[0909] The anti-rearrangement agent is not particularly limited and can be used in an amount of 0.001 to 20% by weight, for example, 0.01 to 5% by weight or 0.01 to 1% by weight. Regarding the amount of the anti-rearrangement agent used, those skilled in the art can appropriately select it according to the reaction compound, reagent, solvent, and other conditions. The anti-rearrangement agent can be, for example, DOW CORNING (registered trademark) ETS900 sold by Dow Corning Corporation (Midland, MI) or commercially available as XIAMETER (registered trademark) OFS-1579 Silane.

[0910] In a preferred embodiment, the PFPE is -(OCF(CF3)CF2) d - (wherein d is an integer from 1 to 200, preferably from 5 to 200, more preferably from 10 to 200), in the above production method, the compound represented by formula (c1-3) is reacted in step (3). More preferably, in the above production method, the compound represented by formula (c1-2) is produced from the compound represented by formula (c1-1) in step (1); the compound represented by formula (c1-3) is produced from the compound represented by formula (c1-2) in step (2), and the compound represented by formula (c1-3) is reacted in step (3). The operations in each step are as described above.

[0911] In one embodiment, the present invention provides a method for producing a fluorinated (poly)ether group-containing silane compound comprising the following steps (1) to (3).

[0912] Step (1): a step of reacting a compound represented by the following formula (c1-1) or formula (c2-1) with SOM2 to obtain a compound represented by the following formula (c1-2) or formula (c2-2);

[0913] Rf-PFPE-X 10 -C(O)OH…(c1-1)

[0914] HOC(O)-X 10 PFPE-X 10 -C(O)OH…(c2-1)

[0915] [Wherein, Rf, PFPE and X 10 has the same meaning as above.]

[0916] SOM2

[0917] [Wherein, M has the same meaning as above.]

[0918]

[0919] [Wherein, Rf, PFPE, X 10Same meaning as above for M.]

[0920] Step (2): reacting the compound represented by the above formula (c1-2) or formula (c2-2) with a compound represented by the formula: HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3 to obtain a compound represented by the following formula (c1-3) or formula (c2-3);

[0921] Formula: HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3

[0922] [Where R 34 , X 11 and Y 11 has the same meaning as above.]

[0923]

[0924] [Wherein, Rf, PFPE, X 10 , R 34 and X 11 has the same meaning as above.]

[0925] Step (3): a compound represented by the following formula (c1-3) or formula (c2-3) is reacted with HSiM′3 and, if necessary, a compound represented by the formula: R 85 i L' represents a compound and / or a compound of the formula: R 86′ j A step for reacting a compound represented by L″.

[0926]

[0927] [Formula HSiM′3, Formula: R 85 i L', formula: R 86′ In L″, M′, R 85 ,L′,i,R 86′ , L″ and j have the same meanings as above.]

[0928] The present invention also provides a compound represented by formula (c1-2) or (c2-2), which is an intermediate in the above production method.

[0929]

[0930] In the above formula, Rf, PFPE, X 10 Same meaning as M.

[0931] The intermediate is preferably a compound represented by formula (c1-2).

[0932] The present invention also provides a compound represented by formula (c1-3) or (c2-3), which is an intermediate in the above production method.

[0933]

[0934] In the above formula, Rf, PFPE, X 10 , R 34 , X 11 and Y 11 Same meaning as above.

[0935] The intermediate is preferably a compound represented by formula (c1-3).

[0936] (Surface treatment agent)

[0937] The surface treatment agent of the present invention contains a PFPE-containing silane compound represented by formula (A1), (A2), (B1), (B2), (C1) or (C2).

[0938] The above-mentioned surface treatment agent helps to form a surface treatment layer having good UV durability, water repellency, oil repellency, antifouling properties (preventing the adhesion of dirt such as fingerprints), chemical resistance, hydrolysis resistance, anti-slip effect, high friction durability, heat resistance, moisture resistance, etc.

[0939] The surface treatment agent can be diluted with a solvent. Such a solvent is not particularly limited, and examples thereof include solvents selected from the following fluorine-containing solvents, etc.:

[0940] Perfluorohexane, CF3CF2CHCl2, CF3CH2CF2CH3, CF3CHFCHFC2F5, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane (Zeorora H (trade name) etc.), C4F9OCH3, C4F9OC2H5, CF3CH2OCF2CHF2, C6F 13 CH=CH2、C6F 13 OCH3, hexafluoroxylene, perfluorobenzene, methyl pentafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF2CF2CH2OH, methyl trifluoromethanesulfonate, trifluoroacetic acid and CF3O (CF2CF2O) m1 (CF2O) n1CF2CF3 [wherein, m1 and n1 are each independently an integer of 0 to 1000, the order of existence of each repeating unit marked with m1 or n1 and enclosed in parentheses is arbitrary in the formula, and the sum of m1 and n1 is 1 or more], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene. These solvents can be used alone or in the form of a mixture of two or more.

[0941] The water content contained in the above solvent is preferably 20 mass ppm or less. The above water content can be measured by Karl Fischer method. By setting it to such a water content, the storage stability of the surface treatment agent can be improved.

[0942] The surface treatment agent may contain other components in addition to the PFPE-containing silane compound represented by formula (A1), (A2), (B1), (B2), (C1) or (C2). Such other components are not particularly limited, and examples thereof include: (non-reactive) fluoropolyether compounds that can be understood as fluorine-containing oils, preferably perfluoro(poly)ether compounds (hereinafter referred to as "fluorine-containing oils"), (non-reactive) organosilicon compounds that can be understood as silicone oils (hereinafter referred to as "silicone oils"), catalysts, lower alcohols, transition metals, halide ions, compounds containing atoms having non-shared electron pairs in their molecular structures, and the like.

[0943] The fluorine-containing oil is not particularly limited, and examples thereof include compounds represented by the following general formula (1) (perfluoro (poly) ether compound).

[0944] R 5 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 6 …(1)

[0945] In the formula, Rf 5 represents an alkyl group having 1 to 16 carbon atoms (preferably C 1－16 perfluoroalkyl), Rf 6 represents an alkyl group having 1 to 16 carbon atoms (preferably C 1－16 perfluoroalkyl), fluorine atom or hydrogen atom, Rf 5 and Rf 6More preferably, each independently is C 1－3 Perfluoroalkyl.

[0946] a', b', c' and d' respectively represent the number of four repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 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 existence of each repeating unit marked with a', b', c' or d' and enclosed in brackets is arbitrary in the formula. The above repeating unit has at least one branched structure. That is, the above repeating unit has at least one CF3 end (specifically -CF3, -C2F5, etc., more specifically -CF3). As repeating units having a branched structure, as -(OC4F8)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and -(OCF2CF(C2F5))- can be listed; as -(OC3F6)-, -(OCF(CF3)CF2)- and -(OCF2CF(CF3))- can be listed; as -(OC2F4)-, -(OCF(CF3))- can be listed.

[0947] Examples of the perfluoro(poly)ether compound represented by the general formula (1) include compounds represented by any one of the following general formulas (1a) and (1b) (the compounds may be one or a mixture of two or more).

[0948] R 5 -(OCF(CF3)CF2) b″ -Rf 6 …(1a)

[0949] R 5 -(OC4F8) a″ -(OC3F6) b″ -(OCF(CF3)) c″ -(OCF2) d″ -Rf 6 …(1b)

[0950] In these formulas, Rf 5 and Rf 6As described above; in formula (1a), b″ is an integer greater than 1 and less than 100; in formula (1b), a″ and b″ are each independently an integer greater than 1 and less than 30, and c″ and d″ are each independently an integer greater than 1 and less than 300. The order of existence of each repeating unit marked with subscripts a″, b″, c″, d″ and enclosed in parentheses is arbitrary in the formula. -(OC4F8)-, -(OC3F6)- have a branched structure.

[0951] The above-mentioned fluorinated oil may have a number average molecular weight of 1,000 to 30,000. It is particularly preferred that the number average molecular weight of the compound represented by formula (1a) is 2,000 to 8,000. By having such a number average molecular weight, good friction durability can be obtained. In one embodiment, the number average molecular weight of the compound represented by formula (1b) is 3,000 to 8,000. In another embodiment, the number average molecular weight of the compound represented by formula (1b) is 8,000 to 30,000.

[0952] In the surface treatment agent, the content of the fluorinated oil is, for example, 0 to 500 parts by mass, preferably 0 to 100 parts by mass, more preferably 1 to 50 parts by mass, and further preferably 1 to 5 parts by mass, based on 100 parts by mass of the PFPE-containing silane compound.

[0953] From another viewpoint, the fluorinated oil may be of the general formula Rf′-F (wherein Rf′ is C 5－16 The compound represented by Rf′-F and the chlorotrifluoroethylene oligomer can obtain the same compound represented by Rf as C 1－16 From this point of view, perfluoroalkyl groups are preferred because of their high affinity for the above-mentioned fluorinated (poly)ether group-containing silane compounds.

[0954] Fluorine-containing oil helps to improve the surface slip properties of the surface treatment layer.

[0955] As the above-mentioned silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be a so-called ordinary silicone oil and a modified silicone oil. As ordinary silicone oil, dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil can be mentioned. As modified silicone oil, silicone oil formed by modifying ordinary silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. can be mentioned. As cyclic silicone oil, for example, cyclic dimethylsiloxane oil can be mentioned.

[0956] In the surface treatment agent, the content of the silicone oil is, for example, 0 to 50 parts by mass, preferably 0 to 5 parts by mass, relative to 100 parts by mass of the PFPE-containing silane compound (or the total of the compounds when there are two or more types, the same below).

[0957] Silicone oil helps to improve the surface slip properties of the surface treatment layer.

[0958] Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), and transition metals (eg, Ti, Ni, Sn, etc.).

[0959] The catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound, thereby promoting the formation of the surface treatment layer.

[0960] Examples of the lower alcohol as the other component include alcohol compounds having 1 to 6 carbon atoms.

[0961] Examples of the transition metal include platinum, ruthenium, and rhodium.

[0962] Examples of the halide ions include chloride ions and the like.

[0963] Examples of the compound containing an atom having an unshared electron pair in the molecular structure include diethylamine, triethylamine, aniline, pyridine, hexamethylphosphoramide, N,N-diethylacetamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylformamide, N,N-dimethylformamide, N-methylpyrrolidone, tetramethylurea, dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide, etc. Among these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.

[0964] Examples of other components include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane in addition to the above.

[0965] As other components, in addition to the above, for example, compounds (E) having fluoro (poly) ether groups and carboxylic acid groups in the molecular structure can also be cited. In the above-mentioned compound (E), the fluoro (poly) ether group at least contains 1 fluorine atom. By containing such a compound (E), the reaction with the glass can be promoted, thereby the surface treatment layer can be formed in a shorter time.

[0966] Examples of the compound (E) include compounds represented by the following formula (E1) or (E2), and specifically, compounds represented by formula (E1).

[0967] R 1 -PFPE 1 -X f1 -COOH…(E1)

[0968] HOOC-X f1 -PFPE1 -X f1 -COOH…(E2)

[0969] In formulas (E1) and (E2),

[0970] R 1 Each occurrence independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

[0971] The "alkyl group having 1 to 16 carbon atoms" in the above-mentioned alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be a linear or branched chain, and is preferably a linear or branched chain alkyl group having 1 to 6 carbon atoms, particularly a linear chain alkyl group having 1 to 3 carbon atoms, and is more preferably a linear chain alkyl group having 1 to 3 carbon atoms.

[0972] The above Rf 1 Preferably, it is an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, more preferably CF2H—C 1－15 Fluorinated alkylene or C 1－16 Perfluoroalkyl, more preferably C 1－16 Perfluoroalkyl.

[0973] The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, particularly a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0974] In formulas (E1) and (E2),

[0975] PFPE 1 Independently at each occurrence is -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3X F 6) d1 -(OC2F4) e1 -(OCF2) f1 - shown groups, and PFPE 1 There is at least one branched structure in the PFPE 1 At least one CF3 terminal (specifically -CF3, -C2F5, etc., more specifically -CF3) is present. 1 The oxygen atom at the left end of the above formula is 1 The carbon atom at the right end is bonded to the X f1 Base bonding.

[0976] X F Each occurrence of is independently a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0977] In the above formula, a1, b1, c1, d1, e1 and f1 are each independently an integer from 0 to 200, and the sum of a1, b1, c1, d1, e1 and f1 is at least 1. Preferably, a1, b1, c1, d1, e1 and f1 are each independently an integer from 0 to 100. Preferably, the sum of a1, b1, c1, d1, e1 and f1 is 5 or more, more preferably 10 or more. Preferably, the sum of a1, b1, c1, d1, e1 and f1 is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, more specifically 10 or more and 100 or less. In addition, the order of existence of each repeating unit marked with a1, b1, c1, d1, e1 or f1 and enclosed in parentheses is arbitrary in the formula.

[0978] PFPE 1 It preferably has at least 5 branched structures, more preferably 10 branched structures, and particularly preferably 20 branched structures.

[0979] PFPE 1 In the structure, the number of repeating units having a branched structure is preferably 40 or more, more preferably 60 or more, and particularly preferably 80 or more, relative to the total number of repeating units (e.g., the sum of a1, b1, c1, d1, e1, and f1) of 100. PFPE 1 In the structure, the number of repeating units having a branched structure may be 100 or less, for example, 90 or less, relative to the total number of repeating units being 100.

[0980] PFPE 1 In the structure, the number of repeating units having a branched structure is preferably in the range of 40 to 100, more preferably in the range of 60 to 100, and particularly preferably in the range of 80 to 100, relative to the total number of repeating units of 100.

[0981] As the branch chain in the branched structure, for example, CF3 can be mentioned.

[0982] As a repeating unit having a branched structure, for example, as -(OC6F 12)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10 )-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. As -(OC4F8)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. As -(OC3F6)- (i.e., X in the above formula) F As -(OC2F4)-, -(OCF(CF3))- can be mentioned.

[0983] The above PFPE 1 The repeating unit may include a branched structure and a linear repeating unit. Examples of the linear repeating unit include -(OCF2CF2CF2CF2CF2CF2)-, -(OCF2CF2CF2CF2CF2)-, -(OCF2CF2CF2CF2)-, -(OCF2CF2CF2CF2)-, -(OCF2CF2CF2)-, and -(OCF2CF2)-.

[0984] The above PFPE is preferably 1 In the repeating unit - (OC6F 12 )-、-(OC5F 10 )-, -(OC4F8)- and -(OC3F6)- have branched structures.

[0985] More preferably, the above PFPE 1 The branched repeating unit OC6F 12 、OC5F 10 , OC4F8 and OC3F6.

[0986] In one embodiment, the PFPE 1 For - (OC3F6) d1- (wherein d1 is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200), PFPE 1 There is at least one branched structure.

[0987] In this method, PFPE 1 It may further contain a linear repeating unit -(OCF2CF2CF2)-.

[0988] In the above method, it is preferred that the above PFPE 1 It is composed of a branched structure repeating unit OC3F6. More preferably, the above PFPE 1 From the formula: -(OCF2CF(CF3)) d1 In the above formula, d1 is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200.

[0989] In another embodiment, PFPE 1 For - (OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (wherein, c1 and d1 are each independently an integer of 0 to 30, e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, the sum of c1, d1, e1 and f1 is at least 5, preferably 10, and the order of existence of the repeating units marked with subscript c1, d1, e1 or f1 and enclosed in parentheses is arbitrary in the formula), PFPE 1 There is at least one branched structure.

[0990] In yet another embodiment, PFPE 1 For - (R 61 -R 62 ) j1 -, the PFPE has at least one branched structure. 61 is OCF2 or OC2F4, preferably OC2F4. Wherein, R 62 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups. 62 is a group selected from OC2F4, OC3F6 and OC4F8, is a group selected from OC3F6, OC4F8, OC5F 10 and OC6F 12A group or a combination of two or three groups independently selected from these groups. More preferably, it is 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. For example, -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4-. The above j1 is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less. In the above formula, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It preferably has a branched structure.

[0991] More preferably, in the above method, PFPE 1 The branched repeating unit OC6F 12 、OC5F 10 , OC4F8 and OC3F6.

[0992] In formulas (E1) and (E2),

[0993] X f1 Each occurrence of X is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 4 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 2 carbon atoms (eg, methylene). f1 The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted. f1 It may be linear or branched, and is preferably linear.

[0994] Preferred Rf 1 and PFPE 1 Each of them has the same structure as Rf or PFPE in the PFPE-containing silane compound contained in the surface treatment agent.

[0995] The compound (E) is preferably a compound represented by formula (E1).

[0996] In the above-mentioned surface treatment agent, the ratio of the PFPE-containing silane compound of the present invention to the compound represented by the above-mentioned formula (E) can be, for example, in terms of molar ratio, PFPE-containing silane compound:compound represented by the above-mentioned formula (E) = 99.9:0.1 to 85.0:15.0, 99.9:0.1 to 90.0:10.0, or 99.9:0.1 to 95.0:5.0.

[0997] In one embodiment, the surface treatment agent does not contain the above-mentioned other components such as fluorinated oil, silicone oil, catalyst, lower alcohol, transition metal, halide ion, and compound containing an atom having an unshared electron pair in its molecular structure.

[0998] In one embodiment, the surface treatment agent contains a PFPE-containing silane compound represented by formula (B1), formula (B2), formula (C1), or formula (C2).

[0999] In one embodiment, the surface treatment agent contains a PFPE-containing silane compound represented by formula (C1) or formula (C2).

[1000] In one embodiment, the surface treatment agent contains a PFPE-containing silane compound represented by formula (C1).

[1001] In one embodiment, the surface treatment agent contains a PFPE-containing silane compound represented by formula (B1) or (C1), and preferably contains a PFPE-containing silane compound represented by formula (C1).

[1002] In one embodiment, the surface treatment agent contains the PFPE-containing silane compound represented by formula (C1) and does not contain the fluorinated oil as another component (for example, the content of the fluorinated oil is 1 part by mass or less, more specifically 0 part by mass, relative to 100 parts by mass of the surface treatment agent).

[1003] The surface treatment agent can be impregnated into a porous material such as a porous ceramic material or a material in which metal fibers such as steel wool are fixed in a cotton-like state to form a granular material, which can be used for vacuum evaporation, for example.

[1004] (thing)

[1005] The article of the present invention comprises a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the PFPE-containing silane compound of the present invention (or a surface treatment agent containing the PFPE-containing silane compound).

[1006] The surface treatment layer of the present invention has not only good ultraviolet durability, but also has the effect of inhibiting slippage, antifouling properties (preventing adhesion of dirt such as fingerprints), chemical resistance, high friction durability, water repellency, oil repellency, heat resistance, hydrolysis resistance, moisture resistance, etc.

[1007] The surface treatment layer preferably has a water contact angle of 100 degrees or more.

[1008] The water contact angle refers to the static contact angle of water on the surface of an article, and is a value measured using 2 μL of water at 21° C. and 65% humidity. The water contact angle is preferably 100 degrees or more, and more preferably 110 degrees or more.

[1009] The contact angle of n-hexadecane on the surface of the surface treatment layer is preferably 50 degrees or more, more preferably 60 degrees or more. The contact angle of n-hexadecane refers to the static contact angle of n-hexadecane on the surface of the article, and is a value measured using 2 μL of water at 21° C. and 65% humidity.

[1010] The surface of the surface treatment layer is irradiated with an illumination of 0.63 W / m 2 The ratio of the water contact angle of the surface after 96 hours of irradiation with 310 nm ultraviolet rays to the water contact angle (the water contact angle of the surface before ultraviolet irradiation) (the value of the contact angle after 96 hours of cumulative UV irradiation time / the value of the contact angle of UV irradiation time 0 hours) is preferably 83% or more, more preferably 85% or more. The method for measuring the water contact angle is as described above.

[1011] In one embodiment, the water contact angle of the surface of the surface treatment layer is 100 degrees or more, preferably 110 degrees or more; and

[1012] With respect to the water contact angle, the irradiation intensity is 0.63 W / m 2 The ratio of the water contact angle of the surface after irradiation with ultraviolet rays of 310 nm for 96 hours is preferably 83% or more, more preferably 85% or more.

[1013] The above-mentioned dynamic friction coefficient is a value measured according to ASTM D4917. The above-mentioned dynamic friction coefficient is preferably 0.1 or more, more preferably 0.2 or more, preferably 0.5 or less, more preferably 0.4 or less. The above-mentioned dynamic friction coefficient can be, for example, in the range of 0.1 to 0.5, or in the range of 0.15 to 0.35.

[1014] It is particularly preferred that the water contact angle of the surface of the article of the present invention is 100 degrees or more, preferably 110 degrees or more;

[1015] The contact angle value after the cumulative UV irradiation time of 96 hours / the contact angle value after the UV irradiation time of 0 hours) is preferably 83% or more, more preferably 85% or more;

[1016] Furthermore, the dynamic friction coefficient of the surface is in the range of 0.15 to 0.35. It is particularly preferred that the contact angle of n-hexadecane on the surface of the article of the present invention is 60 degrees or more.

[1017] The above-mentioned article can be manufactured, for example, by the following operations.

[1018] First, prepare a substrate. The substrate that can be used in the present invention can be composed of any appropriate material such as glass, resin (natural or synthetic resin, such as a general plastic material, in the form of a plate, film, or other form), metal (a metal single substance such as aluminum, copper, iron, or a composite of an alloy, etc.), ceramic, semiconductor (silicon, germanium, etc.), fiber (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc., building components, etc.

[1019] As the above-mentioned glass, sapphire glass, soda-lime glass, alkali-aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferred, and chemically strengthened soda-lime glass, chemically strengthened alkali-aluminosilicate glass, and chemically bonded borosilicate glass are particularly preferred.

[1020] As the resin, acrylic resin and polycarbonate are preferred.

[1021] For example, when the article to be manufactured is an optical component, the material constituting the surface of the substrate can be a material for optical components, such as glass or transparent plastic. In addition, when the article to be manufactured is an optical component, certain layers (or films), such as a hard coating or an anti-reflection layer, can be formed on the surface (outermost layer) of the substrate. The anti-reflection layer can use any of a single-layer anti-reflection layer and a multi-layer anti-reflection layer. Examples of inorganic substances that can be used in the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances can be used alone or in combination of two or more (for example, in the form of a mixture). In the case of a multi-layer anti-reflection layer, SiO2 and / or SiO are preferably used in its outermost layer. When the desired article is an optical glass part for a touch panel, a portion of the surface of the substrate (glass) may have a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide. In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, a polarizing film, a phase difference film, and a liquid crystal display component, etc., depending on its specific specifications.

[1022] The shape of the substrate is not particularly limited. In addition, the surface area of ​​the substrate where 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 purpose and specific specifications of the article to be manufactured.

[1023] As such a substrate, at least part of its surface may be composed of a material that originally has hydroxyl groups. As such a material, glass may be cited, and metals (especially base metals), ceramics, semiconductors, etc., with natural oxide films or thermal oxide films formed on the surface may also be cited. Alternatively, in the case where there are not enough hydroxyl groups, such as resins, or in the case where there are no hydroxyl groups originally, hydroxyl groups may be introduced or increased on the surface of the substrate by subjecting the substrate to certain pretreatments. As examples of such pretreatments, plasma treatment (such as corona discharge) or ion beam irradiation may be cited. Plasma treatment may also be suitable for introducing or increasing hydroxyl groups on the surface of the substrate and for cleaning the surface of the substrate (removing foreign matter, etc.). In addition, as other examples of such pretreatments, a surface adsorbent having a carbon-carbon unsaturated bond may be exemplified by using the LB method (Langmuir-Blodgett method) or chemical adsorption method to form a monomolecular film on the surface of the substrate in advance, and then disconnecting the unsaturated bonds in an atmosphere containing oxygen or nitrogen.

[1024] Alternatively, at least the surface portion of such a substrate may be formed of a material containing an organic silicon compound having one or more other reactive groups such as Si—H groups, or an alkoxysilane.

[1025] Next, a film of the surface treatment composition of the present invention is formed on the surface of the substrate, and the film is post-treated as necessary, thereby forming a surface treatment layer using the surface treatment composition of the present invention.

[1026] The film formation of the surface treatment composition of the present invention can be implemented by applying the surface treatment composition of the present invention to the surface of the substrate in a manner of covering the surface. There is no particular limitation on the covering method. For example, a wet covering method and a dry covering method can be used.

[1027] As examples of the wet coating method, there can be cited dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and the like.

[1028] Examples of dry coating methods include evaporation (usually vacuum evaporation), sputtering, CVD, and similar methods. Specific examples of evaporation methods (usually vacuum evaporation) include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[1029] Alternatively, the coating may be achieved using a normal pressure plasma method.

[1030] Film formation is preferably implemented in a manner that the surface treatment composition of the present invention is present in the film together with a catalyst for hydrolysis and dehydration condensation. For simplicity, in the case of a wet covering method, a catalyst can be added to the diluent of the surface treatment composition of the present invention after the surface treatment composition of the present invention is diluted with a solvent and before it is applied to the substrate surface. In the case of a dry covering method, the surface treatment composition of the present invention to which a catalyst is added can be directly subjected to vapor deposition (usually vacuum deposition) treatment, or a granular material in which the surface treatment composition of the present invention to which a catalyst is added is impregnated in a metal porous body such as iron or copper for vapor deposition (usually vacuum deposition) treatment.

[1031] Any suitable acid or base can be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid, etc. can be used. In addition, as the base catalyst, for example, ammonia, organic amines, etc. can be used.

[1032] Next, the film is subjected to post-treatment as necessary. The post-treatment is not particularly limited, and for example, water supply and drying and heating may be performed sequentially or simultaneously.

[1033] After forming a film of the surface treatment composition of the present invention on the surface of the substrate as described above, water is supplied to the film (hereinafter also referred to as "precursor film"). The method for supplying water is not particularly limited, and for example, a method of condensation using the temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or a method of spraying water vapor (steam), etc. can be used.

[1034] The supply of water can be carried out, for example, in an atmosphere of 0 to 250° C., preferably 60° C. or higher, more preferably 100° C. or higher, and preferably 180° C. or lower, more preferably 150° C. or lower. By supplying water within such a temperature range, hydrolysis can be advanced. The pressure at this time is not particularly limited, and can be set to normal pressure for simplicity.

[1035] Next, the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60° C. The dry heating method is not particularly limited, and the precursor film and the substrate may be placed together in an atmosphere having an unsaturated water vapor pressure at a temperature exceeding 60° C., preferably exceeding 100° C., and for example, at a temperature below 250° C., preferably below 180° C. The pressure at this time is not particularly limited, and may be set to normal pressure for simplicity.

[1036] In such an atmosphere, the hydrolyzed Si-bonded groups between the PFPE-containing silane compounds rapidly undergo dehydration condensation. Also, between such a compound and a substrate, the hydrolyzed Si-bonded groups of the compound rapidly react with reactive groups present on the substrate surface, and dehydration condensation occurs when the reactive groups present on the substrate surface are hydroxyl groups. As a result, a bond is formed between the PFPE-containing silane compound and the substrate.

[1037] The above-mentioned water supply and drying heating can be continuously performed by using superheated water vapor.

[1038] The post-treatment can be performed as described above. The post-treatment is performed to further improve the friction durability, but it should be noted that this is not necessary for manufacturing the article. For example, the surface treatment composition of the present invention can be applied to the substrate surface and then simply left to stand.

[1039] By operating as described above, a layer of a film derived from the surface treatment composition of the present invention is formed on the surface of the substrate to manufacture an article. The layer derived from the surface treatment composition thus obtained can have good ultraviolet durability, water repellency, oil repellency, antifouling (preventing dirt such as fingerprints from adhering), chemical resistance, hydrolysis resistance, sliding inhibition effect, high friction durability, heat resistance, moisture resistance, etc. In addition, the layer can also have surface sliding (or lubricity, wipeability of dirt such as fingerprints, and excellent touch of fingers), high friction durability, etc. according to the composition of the composition used, and is suitable for use as a functional film.

[1040] That is, the surface treatment composition of the present invention can also be used to form an optical material having the above-mentioned cured product as the outermost layer.

[1041] As optical materials, in addition to optical materials related to displays, etc. as exemplified below, a variety of optical materials are preferably listed: for example, cathode ray tubes (CRT, such as TV, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED: Field Emission Display) and other displays or protective plates of these displays, or materials with anti-reflection film treated on their surfaces.

[1042] The article having the surface treatment composition obtained by the present invention is not particularly limited, and may be an optical component. Examples of optical components include the following components: lenses of glasses, etc.; front surface protection plates, anti-reflection plates, polarizing plates, anti-glare plates of displays such as PDP and LCD; touch panel sheets of devices such as mobile phones and portable information terminals; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-R, MO, etc.; optical fibers, etc.

[1043] In one embodiment, the article having the surface treatment composition obtained by the present invention may be, for example, an outer shell of an electronic device or office equipment, such as a portable electronic device (portable information terminals such as mobile phones, smart phones, and tablet terminals; electronic dictionaries, portable music recorders, recorders, and players), a clock, a charging stand (such as the charging stand for the above-mentioned portable devices), etc. Specifically, a layer containing a PFPE silane compound is formed on the outer shell (preferably the outermost layer) of the outer shell of these devices.

[1044] Furthermore, the article having the surface-treated layer obtained by the present invention may be a medical device or a medical material.

[1045] The thickness of the surface treatment composition layer is not particularly limited. In the case of optical parts, the thickness of the layer is 1 to 50 nm, more preferably 1 to 30 nm, and particularly preferably 1 to 15 nm from the viewpoint of good anti-slip effect, optical performance, good UV durability, water repellency, oil repellency, antifouling (preventing adhesion of dirt such as fingerprints), chemical resistance, hydrolysis resistance, high friction durability, heat resistance and moisture resistance.

[1046] As another embodiment, after another layer is formed on the surface of the substrate, a film of the surface treatment layer obtained by the present invention may be formed on the surface of the other layer.

[1047] In another embodiment, the article of the present invention preferably has a surface water contact angle of 100 degrees or more, and the article is irradiated with an illuminance of 0.63 W / m 2 The ratio of the water contact angle of the surface after irradiation with ultraviolet rays of 310 nm for 96 hours was 83% or more. The method for measuring the water contact angle is as described above.

[1048] In the above aspect, the water contact angle of the article of the present invention is more preferably 110 degrees or more.

[1049] In the above aspect, the dynamic friction coefficient of the surface of the article of the present invention is more preferably in the range of 0.1 to 0.5, and further preferably in the range of 0.15 to 0.35. The method for measuring the dynamic friction coefficient is as described above.

[1050] In the above aspect, the article of the present invention preferably has a contact angle of n-hexadecane on the surface of 50 degrees or more. The method for measuring the contact angle of n-hexadecane is as described above.

[1051] In the above-mentioned manner, the article of the present invention has good UV durability, water repellency, oil repellency, antifouling property (preventing the adhesion of dirt such as fingerprints), chemical resistance, hydrolysis resistance, anti-slip effect, high friction durability, heat resistance, and moisture resistance.

[1052] The articles obtained by using the surface treatment composition of the present invention have been described in detail above, but the uses, methods of use, and methods of producing articles of the surface treatment composition of the present invention are not limited to the above examples.

[1053] Example

[1054] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[1055] (Synthesis example 1)

[1056] In a 200 mL four-necked flask equipped with a reflux cooler, a thermometer and a stirrer, a mixture of CF3CF2CF2O [CF(CF3)CF2O] with an average composition of 22 32g of perfluoropolyether-modified carboxylic acid represented by CF(CF3)COOH, 16g of 1,3-bis(trifluoromethyl)benzene, 0.13g of N,N-dimethylformamide and 2.17g of thionyl chloride were stirred at 90°C for 1 hour under nitrogen flow. Then, after distilling off the volatile components under reduced pressure, 16g of 1,3-bis(trifluoromethyl)benzene, 1.35g of triethylamine and 1.73g of NH2CH2C(CH2CH=CH2)3 were added and stirred at room temperature for 6 hours under nitrogen flow. Then, 30g of perfluorohexane, 10g of acetone and 20g of 3mol / L hydrochloric acid were added and stirred for 30 minutes, and then the perfluorohexane phase was separated using a separatory funnel. Thereafter, the separated perfluorohexane phase was filtered, and then the volatile components were distilled off under reduced pressure to obtain 29.6 g of a perfluoropolyether group-containing allyl compound (A) having an allyl group at the terminal and represented by the following formula.

[1057] ·Perfluoropolyether-containing allyl compound (A):

[1058] CF3CF2CF2O[CF(CF3)CF2O] 22 CF(CF3)CONHCH2C(CH2CH=CH2)3

[1059] (Synthesis example 2)

[1060] In a 200 mL four-necked flask equipped with a reflux cooler, a thermometer and a stirrer, 29 g of the allyl compound (A) containing a terminal allyl group synthesized in Synthesis Example 1, 35 ml of 1,3-bis(trifluoromethyl)benzene and 6.7 g of trichlorosilane were added, and stirred at 5°C for 30 minutes under a nitrogen stream. Next, 0.3 ml of a 2% xylene solution of a Pt coordination compound containing 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the temperature was raised to 60°C and stirred at this temperature for 6 hours. Thereafter, the volatile components were distilled off under reduced pressure. Next, 30 ml of 1,3-bis(trifluoromethyl)benzene was added, and after stirring at 55°C for 10 minutes, a mixed solution of 0.73 g of methanol and 16.8 g of trimethyl orthoformate was added, and stirred at this temperature for 2 hours. Thereafter, volatile components were distilled off under reduced pressure to obtain 30.1 g of the following perfluoropolyether group-containing silane compound (B) having a trimethylsilyl group at the terminal.

[1061] ·Perfluoropolyether-containing silane compound (B)

[1062] CF3CF2CF2O[CF(CF3)CF2O] 22 CF(CF3)CONHCH2C[CH2CH2CH2Si(OCH3)3]3

[1063] (Synthesis example 3)

[1064] In a 200 mL four-necked flask equipped with a reflux cooler, a thermometer and a stirrer, a mixture of CF3CF2CF2O [CF(CF3)CF2O] with an average composition of 28 32g of perfluoropolyether-modified carboxylic acid represented by CF(CF3)COOH, 16g of 1,3-bis(trifluoromethyl)benzene, 0.10g of N,N-dimethylformamide and 1.69g of thionyl chloride were stirred at 90°C for 1 hour under nitrogen flow. Then, after distilling off the volatile components under reduced pressure, 16g of 1,3-bis(trifluoromethyl)benzene, 1.05g of triethylamine and 1.36g of NH2CH2C(CH2CH=CH2)3 were added, and stirred at room temperature for 6 hours under nitrogen flow. Then, 30g of perfluorohexane, 10g of acetone and 20g of 3mol / L hydrochloric acid were added, and stirred for 30 minutes, and then the perfluorohexane phase was separated using a separatory funnel. Thereafter, the separated perfluorohexane phase was filtered, and then the volatile components were distilled off under reduced pressure to obtain 29.2 g of a perfluoropolyether group-containing allyl compound (C) having an allyl group at the terminal and having the following formula.

[1065] CF3CF2CF2O[CF(CF3)CF2O] 28 CF(CF3)CONHCH2C(CH2CH=CH2)3 (Synthesis Example 4)

[1066] In a 200 mL four-necked flask equipped with a reflux cooler, a thermometer and a stirrer, 29 g of the allyl compound (C) containing a terminal allyl group synthesized in Synthesis Example 3, 35 ml of 1,3-bis(trifluoromethyl)benzene and 5.2 g of trichlorosilane were added, and stirred at 5°C for 30 minutes under a nitrogen stream. Next, 0.23 ml of a 2% xylene solution of a Pt coordination compound containing 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the temperature was raised to 60°C and stirred at this temperature for 6 hours. Thereafter, the volatile components were distilled off under reduced pressure. Next, 30 ml of 1,3-bis(trifluoromethyl)benzene was added, and after stirring at 55°C for 10 minutes, a mixed solution of 0.57 g of methanol and 13.1 g of trimethyl orthoformate was added, and stirred at this temperature for 2 hours. Thereafter, volatile components were distilled off under reduced pressure to obtain 29.6 g of the following perfluoropolyether group-containing silane compound (D) having a trimethylsilyl group at the terminal.

[1067] ·Perfluoropolyether-containing silane compound (D)

[1068] CF3CF2CF2O[CF(CF3)CF2O] 28 CF(CF3)CONHCH2C[CH2CH2CH2Si(OCH3)3]3

[1069] (Synthesis Example 5)

[1070] In a 200 mL four-necked flask equipped with a reflux cooler, a thermometer and a stirrer, a mixture of CF3CF2CF2O [CF(CF3)CF2O] with an average composition of 11 32g of perfluoropolyether-modified carboxylic acid represented by CF(CF3)COOH, 16g of 1,3-bis(trifluoromethyl)benzene, 0.23g of N,N-dimethylformamide and 3.81g of thionyl chloride were stirred at 90°C for 1 hour under nitrogen flow. Then, after distilling off the volatile components under reduced pressure, 16g of 1,3-bis(trifluoromethyl)benzene, 2.43g of triethylamine and 3.04g of NH2CH2C(CH2CH=CH2)3 were added, and stirred at room temperature for 6 hours under nitrogen flow. Then, 30g of perfluorohexane, 10g of acetone and 20g of 3mol / L hydrochloric acid were added, stirred for 30 minutes, and then the perfluorohexane phase was separated using a separatory funnel. Thereafter, the separated perfluorohexane phase was filtered, and then the volatile components were distilled off under reduced pressure to obtain 29.4 g of a perfluoropolyether group-containing allyl compound (E) having an allyl group at the terminal and having the following formula.

[1071] CF3CF2CF2O[CF(CF3)CF2O] 11CF(CF3)CONHCH2C(CH2CH=CH2)3

[1072] (Synthesis Example 6)

[1073] In a 200 mL four-necked flask equipped with a reflux cooler, a thermometer, and a stirrer, 29 g of the perfluoropolyether group-containing allyl compound (E) synthesized in Synthesis Example 5, 29.0 ml of 1,3-bis(trifluoromethyl)benzene, and 11.8 g of trichlorosilane were added, and stirred at 5°C for 30 minutes under a nitrogen stream. Next, 0.8 ml of a 2% xylene solution of a Pt coordination compound containing 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the temperature was raised to 60°C and stirred at this temperature for 6 hours. Thereafter, the volatile components were distilled off under reduced pressure. Next, 29.0 ml of 1,3-bis(trifluoromethyl)benzene was added, and after stirring at 55°C for 10 minutes, a mixed solution of 1.30 g of methanol and 29.2 g of trimethyl orthoformate was added, and stirred at this temperature for 2 hours. Thereafter, volatile components were distilled off under reduced pressure to obtain 30.0 g of the following perfluoropolyether group-containing silane compound (F) having a trimethylsilyl group at the terminal.

[1074] ·Perfluoropolyether-containing silane compound (F)

[1075] CF3CF2CF2O[CF(CF3)CF2O] 11 CF(CF3)CONHCH2C[CH2CH2CH2Si(OCH3)3]3

[1076] (Example 1)

[1077] The compound (B) obtained in the above Synthesis Example 2 was dissolved in hydrofluoroether (Novec HFE7200 produced by 3M Company) at a concentration of 20 wt % to prepare a surface treatment agent.

[1078] (Example 2)

[1079] A surface treating agent was prepared in the same manner as in Example 1 except that the compound (D) obtained in Synthesis Example 4 was used instead of the compound (B).

[1080] (Example 3)

[1081] A surface treating agent was prepared in the same manner as in Example 1 except that the compound (F) obtained in the above Synthesis Example 6 was used instead of the compound (B).

[1082] (Example 4)

[1083] A surface treating agent was prepared in the same manner as in Example 1 except that the compound (G) was used instead of the compound (B).

[1084] Compound (G)

[1085] CF3CF2CF2O[CF(CF3)CF2O] 22 CF(CF3)CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3

[1086] (Example 5)

[1087] A surface treating agent was prepared in the same manner as in Example 1 except that the compound (H) was used instead of the compound (B).

[1088] Compound (H)

[1089] CF3CF2CF2O[CF(CF3)CF2O] 22 CF(CF3)C[OCH2CH2CH2Si(OCH3)3][CH2CH2CH2Si(OCH3)3]2

[1090] (Comparative Examples 1 to 3)

[1091] Surface treatment agents were prepared in the same manner as in Example 1 except that the following reference compounds 1 to 3 were used instead of compound (B).

[1092] ·Comparative compound 1

[1093] CF3CF2CF2O(CF2CF2CF2O) 30 CF2CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3

[1094] ·Comparative compound 2

[1095] CF3O(CF2CF2O) 22 (CF2O) 23 CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3

[1096] ·Comparative compound 3

[1097] CF3CF2CF2O[CF(CF3)CF2O] 28 CF(CF3)CONHCH2CH2CH2Si(OCH3)3

[1098] <Evaluation>

[1099] The surface treatment agents prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were vacuum-deposited onto chemically strengthened glass ("gorilla" glass produced by Corning, thickness 0.7 mm). The vacuum deposition process conditions were set at a pressure of 3.0 × 10－3 Pa, a 5 nm silicon dioxide film was formed on the surface of the chemically strengthened glass, and then 4 mg of a surface treatment agent (i.e., containing 0.8 mg of compound (B), compound (D) or reference compounds 1 to 3) was vapor-deposited on one sheet of chemically strengthened glass (55 mm × 100 mm). Then, the chemically strengthened glass with the vapor-deposited film was left to stand for 30 minutes in an atmosphere at a temperature of 150°C, and then cooled to room temperature to form a surface treatment layer.

[1100] (UV resistance evaluation)

[1101] The static contact angle of water was measured before and after UV irradiation for the surface treatment layer formed above. UV irradiation was performed using a UVB-313 lamp (produced by Q-Lab, with an irradiance of 0.63 W / m at 310 nm). 2 ), the blackboard temperature of the substrate was set to 63 degrees, and the distance between the lamp and the surface treatment layer was set to 5 cm for measurement. The static contact angle of water was measured using a contact angle measuring device (produced by Kyowa Interface Science Co., Ltd.) using 2 μL of water.

[1102] First, as an initial evaluation, the static contact angle of water is measured after the surface treatment layer is formed and before UV irradiation (UV irradiation time 0 hours). Afterwards, the static contact angle of water is measured for the surface treatment layer after UV irradiation for a predetermined time. The evaluation is performed until the cumulative irradiation time is 96 hours. The results are shown in Table 1. In addition, the ratio of the value of the contact angle after the cumulative UV irradiation time of 96 hours to the value of the contact angle after the UV irradiation time of 0 hours (the value of the contact angle after the cumulative UV irradiation time of 96 hours / the value of the contact angle after the UV irradiation time of 0 hours) is shown in Table 2.

[1103] [Table 1]

[1104]

[1105] [Table 2]

[1106]

[1107] (Determination of static contact angle of n-hexadecane)

[1108] The static contact angle of n-hexadecane was measured for the surface treatment layer formed as described above. The static contact angle of n-hexadecane was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) using 2 μL of n-hexadecane. The results are shown in the following table.

[1109] [Table 3]

[1110] Contact angle of n-hexadecane (degrees) Example 1 70 Example 2 70 Example 3 70 Example 4 68 Example 5 66

[1111] · Surface sliding property evaluation (determination of dynamic friction coefficient)

[1112] The base material having the surface treatment layer formed above was measured for dynamic friction coefficient (-) using a surface property measuring instrument (FPT-1 manufactured by Labthink) and paper as a friction material in accordance with ASTM D4917.

[1113] Specifically, a substrate with a surface treatment layer was placed horizontally, and a friction piece of paper (2 cm x 2 cm) was brought into contact with the exposed upper surface of the surface treatment layer, and a load of 200 gf was applied thereto. Thereafter, the friction piece of paper was moved parallel to the substrate at a speed of 200 mm / s under the applied load, and the dynamic friction coefficient was measured. The results are shown in the following table.

[1114] [Table 4]

[1115] Dynamic friction coefficient (I) Example 1 0.26 Example 2 0.23 Example 3 0.28 Example 4 0.24 Example 5 0.23 Comparative Example 1 0.07 Comparative Example 2 0.03 Comparative Example 3 0.22

[1116] Friction durability evaluation

[1117] The surface treatment layers formed using the surface treatment agents of Examples 1 to 5 and Comparative Example 3 were evaluated for friction durability by a rubber friction durability test.

[1118] First, as an initial evaluation, the static contact angle of water in the rubber friction durability test (friction number 0) was measured.

[1119] Afterwards, the substrate formed with the surface treatment layer was arranged horizontally, and a rubber (produced by Minoan, model: MB006004, diameter 0.6 cm) was brought into contact with the surface of the surface treatment layer, and a load of 1000 gf was applied thereto. Afterwards, the rubber was reciprocated at a speed of 20 mm / sec under the applied load. The static contact angle (degree) of water was measured every time the reciprocating number reached 1000 times. The results are shown in the following table. "-" in the table means not measured.

[1120] [Table 5]

[1121]

[1122] Industrial Applicability

[1123] The present invention is suitable for forming a surface treatment layer on the surface of various substrates, particularly articles (eg, electronic devices) that require UV durability, anti-slip effects, and the like.

Claims

1. A silane compound containing a fluorinated (poly)ether group, characterized in that: is represented by any one of formula (A1), (A2), (B1), (B2), (C1) or (C2), (Rf-PFPE) β’ -X 3 -(SiR a k1 R b 11 R c m1 ) β …(B1) (R c m1 R b l1 R a k1 Si) β -X 3 -PFPE-X 3 -(SiR a k1 R b l1 R c m1 ) β …(B2) (Rf-PFPE) γ’ -X 5 -(CR d k2 R e l2 R f m2 ) γ …(C1) (R f m2 R e l2 R d k2 C) γ -X 5 -PFPE-X 5 -(CR d k2 R e l2 R f m2 ) γ …(C2) In the formula, PFPE is independently represented at each occurrence by the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3X F 6) d -(OC2F4) e -(OCF2) f - represents a group having at least one branched structure, wherein a, b, c, d, e and f are each independently an integer from 0 to 200, the sum of a, b, c, d, e and f is at least 1, and the order of existence of the repeating units marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary, and X F is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom; Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; X 1 Each occurrence independently represents a single bond or a 2- to 10-valent organic group; α is independently an integer from 1 to 9 at each occurrence; α′ is independently an integer from 1 to 9; R 11 represents independently at each occurrence a hydrogen atom or a halogen atom; R 12 represents independently at each occurrence a hydrogen atom or a lower alkyl group; X 2 Each occurrence independently represents a single bond or a divalent organic group; R 13 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing; R 14 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; n in each (-SiR 13 n R 14 3－n ) units independently represent an integer of 0 to 3 or more; t is independently an integer from 2 to 10 at each occurrence; Wherein, in formula (A1) and (A2), there are at least 2 SiR 13 ; X 3 Each occurrence independently represents a single bond or a 2- to 10-valent organic group; β is independently an integer from 1 to 9 at each occurrence; β' is independently an integer from 1 to 9; R a Each occurrence represents -Z independently 3 -SiR 71 p1 R 72 q1 R 73 r1 ; Z 3 Each occurrence independently represents an oxygen atom or a divalent organic group; R 71 Each occurrence represents R independently a′ ; R a′ The meaning of R a same; R a Via Z 3 The maximum number of Si groups connected in a straight chain is 5; R 72 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing; R 73 represents independently at each occurrence a hydrogen atom or a lower alkyl group; p1 is independently an integer from 0 to 3 at each occurrence; q1 is independently an integer from 0 to 3 each time it appears; r1 is independently an integer from 0 to 3 at each occurrence; Among them, in each (-Z 3 -SiR 71 p1 R 72 q1 R 73 r1 ), the sum of p1, q1 and r1 is 3; R b Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing; R c represents independently at each occurrence a hydrogen atom or a lower alkyl group; k1 is independently an integer from 0 to 3 at each occurrence; l1 is independently an integer from 0 to 3 each time it appears; m1 is independently an integer from 0 to 3 at each occurrence; Among them, in each (SiR a k1 R b l1 R c m1 ), the sum of k1, l1 and m1 is 3, and in formulas (B1) and (B2), there are at least 2 Si groups bonded to hydroxyl groups or hydrolyzable groups; X 5 Each independently represents a single bond or a 2- to 10-valent organic group; γ is independently an integer from 1 to 9; γ′ is independently an integer from 1 to 9; R d Each occurrence represents -Z independently 4 -CR 81 p2 R 82 q2 R 83 r2 ; Z 4 Each occurrence independently represents an oxygen atom or a divalent organic group; R 81 Each occurrence represents R independently d′ ; R d′ The meaning of R d same; R d Via Z 4 The maximum number of carbon atoms connected in a straight chain is 5. R 82 Each occurrence represents -Y-SiR independently 85 n2 R 86 3－n2 ; Y, at each occurrence, independently represents a divalent organic group; R 85 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing; R 86 represents independently at each occurrence a hydrogen atom or a lower alkyl group; n2 in each (-Y-SiR 85 n2 R 86 3－n2 ) units independently represent an integer from 0 to 3; R 83 represents independently at each occurrence a hydrogen atom, a hydroxyl group or a lower alkyl group; p2 is independently an integer from 0 to 3 at each occurrence; q2 is independently an integer from 0 to 3 at each occurrence; r2 is independently an integer from 0 to 3 at each occurrence; Among them, in each (-Z 4 -CR 81 p2 R 82 q2 R 83 r2 ), the sum of p2, q2 and r2 is 3; R e Each occurrence represents -Y-SiR independently 85 n2 R 86 3－n2 ; R f represents independently at each occurrence a hydrogen atom, a hydroxyl group or a lower alkyl group; k2 is independently an integer from 0 to 3 at each occurrence; l2 is independently an integer from 0 to 3 at each occurrence; m2 is independently an integer from 0 to 3 at each occurrence; Among them, in each (CR d k2 R e l2 R f m2 ), the sum of k2, l2 and m2 is 3, and in formulas (C1) and (C2), there are two or more -Y-SiR 85 The groups shown.

2. The fluorinated (poly)ether group-containing silane compound according to claim 1, characterized in that: X F A fluorine atom.

3. The fluorinated (poly)ether group-containing silane compound according to claim 1 or 2, characterized in that: PFPE is composed of the formula: -(OC3F6) d -express, The repeating unit OC3F6 of the above formula includes a branched structure, Furthermore, d is an integer of 2 to 200.

4. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 3, characterized in that: PFPE is composed of the formula: -(OC3F6) d -express, The repeating unit OC3F6 of the above formula is represented by OCF(CF3)CF2, Furthermore, d is an integer of 2 to 200.

5. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 4, characterized in that: α, α′, β, β′, γ and γ′ are 1.

6. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 5, characterized in that: X 1 , X 3 and X 5 Each time it occurs, it is independently -X 10 -CON(R 34 )-X 11 -, -X 10 -(OR 35 ) n4 -X 11 - or C 1－6 Any of the alkylene groups, In the formula, X 10 Each occurrence is independently a single bond or a divalent organic group; X 11 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group; R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 alkyl; R 35 Each time it occurs, it is independently C 1－6 of alkylene; n4 is independently an integer from 1 to 5 at each occurrence.

7. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 6, characterized in that: k1 is 2 or 3, and q1 is 2 or 3.

8. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 7, characterized in that: l2 is 2 or 3, and n2 is 2 or 3.

9. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 8, characterized in that: Represented by formula (B1), (B2), (C1) or (C2).

10. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 9, characterized in that: It is represented by formula (B1).

11. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 9, characterized in that: Represented by formula (C1) or (C2).

12. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 9 or 11, characterized in that: Represented by formula (C1).

13. The fluorinated (poly)ether group-containing silane compound according to any one of claims 1 to 12, characterized in that: R 83 and R f Each occurrence is independently a hydrogen atom or a lower alkyl group.

14. A surface treatment agent, characterized in that: A silane compound containing a fluorinated (poly)ether group according to any one of claims 1 to 13.

15. The surface treatment agent according to claim 14, characterized in that: Also contains solvent.

16. The surface treatment agent according to claim 14 or 15, characterized in that: The invention further contains one or more other components selected from the group consisting of fluorine-containing oil, silicone oil, alcohol, catalyst, transition metal, halide ion and a compound containing an atom having an unshared electron pair in its molecular structure.

17. The surface treatment agent according to any one of claims 14 to 16, characterized in that: Used as an antifouling coating or a water-repellent coating.

18. A pellet, characterized in that: Contains the surface treatment agent according to any one of claims 14 to 17.

19. An article comprising a substrate and a layer formed on the surface of the substrate using the surface treatment agent according to any one of claims 14 to 17.

20. An article, characterized in that: The water contact angle on the surface is more than 100 degrees. And, with respect to the water contact angle, the irradiation intensity is 0.63 W / m 2 The ratio of the water contact angle of the surface after irradiation with ultraviolet rays of 310 nm for 96 hours was 83% or more.

21. A method for producing a silane compound containing a fluorinated (poly) ether group, which is used to produce the silane compound containing a fluorinated (poly) ether group represented by formula (C1) or (C2) according to claim 1, wherein the method is characterized in that: The process comprises the following step (3): reacting a compound represented by formula (c1-3) or formula (c2-3) with HSiM ′ The compound shown in 3 and the formula as required: R 85 i L' represents a compound and / or a compound of the formula: R 86′ j The step of reacting the compound represented by L″, In formula (c1-3) and (c2-3), Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; PFPE is composed of (-OCF(CF3)CF2-) d express; d is an integer greater than 2 and less than 200; X 10 Each occurrence is independently a single bond or a divalent organic group; R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 alkyl; X 11 Each occurrence is independently a single bond or a divalent organic group; Y 11 is independently a single bond or a divalent organic group at each occurrence, Formula HSiM ′ 3, M ′ are independently a halogen atom or C 1－6 Alkoxy, Formula R 85 i In L′, R 85 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing; L′ indicates that it can be 85 Bonded groups; i is an integer from 1 to 3, Formula R 86′ j In L″, R 86′ In each occurrence, C is represented independently 1～22 alkyl; L″ indicates that it can be connected with R 86′ Bonded groups; j is an integer from 1 to 3.

22. The method of claim 21, wherein: The method for producing a fluorinated (poly)ether group-containing silane compound represented by formula (C1) or (C2) according to claim 1 further comprises the following steps (1) and (2): Step (1): a step of reacting a compound represented by formula (c1-1) or formula (c2-1) with SOM2 to obtain a compound represented by formula (c1-2) or formula (c2-2), Rf-PFPE-X 10 -C(O)OH…(c1-1) HOC(O)-X 10 -PFPE-X 10 -C(O)OH…(c2-1) In formula (c1-1) and (c2-1), Rf, PFPE and X 10 has the same meaning as in claim 21, In the formula SOM2, M is independently a chlorine atom or a fluorine atom at each occurrence, In formula (c1-2) and (c2-2), Rf, PFPE and X 10 The meaning is the same as that in claim 21; M has the same meaning as above. Step (2): reacting the compound represented by the formula (c1-2) or (c2-2) with a compound represented by the formula: HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3 to obtain a compound represented by formula (c1-3) or formula (c2-3), formula HN(R 34 )-X 11 -C(Y 11 -CH=CH2)3, R 34 , X 11 and Y 11 has the same meaning as in claim 21, In formula (c1-3) and (c2-3), Rf, PFPE, X 10 , R 34 and X 11 The meaning is the same as that of claim 21.

23. A compound represented by formula (c1-2) or (c2-2), characterized in that: In the formula, Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; PFPE is composed of (-OCF(CF3)CF2-) d express; d is an integer greater than 2 and less than 200; X 10 Each occurrence is independently a single bond or a divalent organic group; M is independently, at each occurrence, a chlorine atom or a fluorine atom.

24. A compound represented by formula (c1-3) or (c2-3), characterized in that: In the formula, Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; PFPE is composed of (-OCF(CF3)CF2-) d express; d is an integer greater than 2 and less than 200; X 10 Each occurrence is independently a single bond or a divalent organic group; R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 alkyl; X 11 Each occurrence is independently a single bond or a divalent organic group; Y 11 Each occurrence is independently a single bond or a divalent organic group.

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