Composition, substrate with surface layer, and method for producing substrate with surface layer

Abstract

Provided are: a composition capable of forming a surface layer having excellent wear resistance; a substrate with a surface layer; and a method for producing a substrate with a surface layer. A composition containing: a first component comprising at least one fluorine-containing ether compound selected from the group consisting of compounds represented by formula (A1), compounds represented by formula (A2), and compounds represented by formula (A3); and a second component comprising at least one fluorine-containing ether compound selected from the group consisting of compounds represented by formula (B1) and compounds represented by formula (B2).

Description

Technical Field

[0001] The present invention relates to a composition, a substrate with a surface layer, and a method for producing a substrate with a surface layer. Background Art

[0002] In order to impart water and oil repellency, fingerprint removability, lubricity (smoothness when touched with fingers), etc. to the surface of a substrate, it is known that a surface layer formed of a condensate of the fluorinated ether compound is formed on the surface of the substrate by surface treatment with a fluorinated ether compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group (Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2017 / 022437 Summary of the invention

[0006] Problem that the invention aims to solve

[0007] In recent years, the performance requirements for surface layers formed using fluorinated ether compounds have been continuously improved. For example, when the surface layer is applied to a component constituting a surface contacted by a finger, a surface layer whose performance (e.g., water repellency) is not easily reduced even after repeated abrasion, i.e., a surface layer with excellent abrasion resistance is required.

[0008] The present inventors evaluated a surface layer formed using a fluorine-containing ether compound as described in Patent Document 1 and found that there is room for improvement in the wear resistance of the surface layer.

[0009] Therefore, an object of the present invention is to provide a composition capable of forming a surface layer having excellent wear resistance, a substrate with a surface layer, and a method for producing a substrate with a surface layer.

[0010] Solutions for solving problems

[0011] The inventors have discovered that the above-mentioned problems can be solved by the following technical features.

[0012] [1]

[0013] A composition comprising a first component and a second component, wherein the first component is composed of at least one fluorine-containing ether compound selected from the group consisting of a compound represented by formula (A1), a compound represented by formula (A2) and a compound represented by formula (A3),

[0014] The second component is composed of at least one fluorine-containing ether compound selected from the group consisting of compounds represented by formula (B1) and compounds represented by formula (B2),

[0015] [R f1-(OR f11 ) y1 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 …(A1)

[0016] (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 …(A2)

[0017] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 …(A3)

[0018] R f14 -(OR f15 ) y4 -OR 5 -R b1 …(B1)

[0019] R f19 -(OR f18 ) y6 -OR 7 -L b1 -R 6 -O-(R f16 O) y5 -R f17 …(B2)

[0020] In formula (A1),

[0021] R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and there are multiple R f1 When there are multiple R f1 are optionally the same or different from each other,

[0022] R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f11 When there are multiple Rf11 are optionally the same or different from each other,

[0023] R 1 is an alkylene group or a fluoroalkylene group, and there are multiple R 1 When there are multiple R 1 are optionally the same or different from each other,

[0024] L 1 is a single bond, or is a j+x1-valent group optionally having N, O, S, Si and optionally having a branch point, bonded to R 1 and R 11 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O),

[0025] R 11 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein the group bonded to L 1 The atom of R is optionally an etheric oxygen atom. 11 When there are multiple R 11 are optionally the same or different from each other,

[0026] T 11 -SiR a11 z11 R a12 3-z11 , there are multiple T 11 When there are multiple T 11 are optionally the same or different from each other,

[0027] R a11 is a hydroxyl group or a hydrolyzable group, and there are multiple R a11 When there are multiple R a11 are optionally the same or different from each other,

[0028] R a12 It is a non-hydrolyzable group, and there are multiple R a12 When there are multiple R a12 are optionally the same or different from each other,

[0029] j is an integer greater than or equal to 1. When j is 1, y1 is an integer greater than or equal to 2, or R 1 is a fluoroalkylene group,

[0030] z11 is an integer from 1 to 3,

[0031] x1 is an integer greater than 1,

[0032] y1 is an integer greater than or equal to 1. When a plurality of y1 exist, the plurality of y1 exist may be the same as or different from each other.

[0033] In formula (A2),

[0034] R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f12 When there are multiple R f12 are optionally the same or different from each other,

[0035] R 2 and R 3 are each independently an alkylene group or a fluoroalkylene group,

[0036] L 2 is a single bond, or is a 1+x2 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 2 and R 21 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group,

[0037] L 3 is a single bond, or is a 1+x3 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 3 and R 31 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group,

[0038] R 21 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 2 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 21 When there are multiple R 21 are optionally the same or different from each other,

[0039] R 31 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 3 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 31 When there are multiple R 31 are optionally the same or different from each other,

[0040] T 21 and T 31 Each independently is -SiR a21 z21 R a22 3-z21 , there are multiple T 21 When there are multiple T 21 Optional to be the same or different from each other, there are multiple T 31 When there are multiple T 31 are optionally the same or different from each other,

[0041] Ra21 is a hydroxyl group or a hydrolyzable group, and there are multiple R a21 When there are multiple R a21 are optionally the same or different from each other,

[0042] R a22 It is a non-hydrolyzable group, and there are multiple R a22 When there are multiple R a22 are optionally the same as or different from each other,

[0043] z21 is an integer from 1 to 3,

[0044] x2 and x3 are each independently an integer greater than 1,

[0045] y2 is an integer greater than 1. When y2 is 1, R 2 is a fluoroalkylene group,

[0046] In formula (A3),

[0047] Q 1 is a r1-valent group having a branch point,

[0048] R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and the presence of multiple R f13 are optionally the same as or different from each other,

[0049] R 4 Each independently represents an alkylene group or a fluoroalkylene group, and the presence of multiple R 4 are optionally the same as or different from each other,

[0050] L 4 is a single bond, or is a 1+x4 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 4 and R 41 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group. 4 are optionally the same as or different from each other,

[0051] R 41 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 4 The adjacent atoms may be etheric oxygen atoms, and the presence of multiple R 41 are optionally the same as or different from each other,

[0052] T 41 -SiR a41 z41 R a42 3-z41 , there are multiple T 41 are optionally the same as or different from each other,

[0053] R a41 is a hydroxyl group or a hydrolyzable group, and the presence of multiple R a41 are optionally the same or different from each other,

[0054] R a42 It is a non-hydrolyzable group, and there are multiple R a42 When there are multiple R a42 are optionally the same or different from each other,

[0055] z41 is an integer from 1 to 3,

[0056] x4 is an integer greater than or equal to 1. When a plurality of x4 exist, the plurality of x4 exist may be the same as or different from each other.

[0057] y3 is an integer greater than or equal to 1. When a plurality of y3 exist, the plurality of y3 exist may be the same as or different from each other.

[0058] r1 is 3 or 4,

[0059] In formula (B1),

[0060] R f14 is a fluoroalkyl group having 1 to 20 carbon atoms,

[0061] R f15 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f15 When there are multiple R f15 are optionally the same or different from each other,

[0062] R 5 is an alkylene group which may have a substituent,

[0063] R b1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom,

[0064] y4 is an integer greater than 1,

[0065] In formula (B2),

[0066] R f17 and R f19 are each independently a fluoroalkyl group having 1 to 20 carbon atoms,

[0067] R f16 and R f18 Each independently represents a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f16 When there are multiple R f16 Optionally the same or different, there are multiple R f18 When there are multiple R f18 are optionally the same or different from each other,

[0068] R6 and R 7 are each independently an alkylene group which may have a substituent,

[0069] L b1 is a single bond or a divalent linking group, wherein the divalent linking group does not include (OR f18 ) y7 and (R f16 O) y8 , y7 and y8 are each independently an integer greater than 1,

[0070] y5 and y6 are each independently an integer of 1 or more.

[0071] [2]

[0072] The composition according to [1], wherein in the above formula (A1), R 11 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 11 Connected,

[0073] In the above formula (A2), at least one of the following is true: 21 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 21 connected; and R 31 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 31 Connected,

[0074] In the above formula (A3), R 41 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 41 are connected.

[0075] 〔3〕

[0076] The composition according to [1] or [2], wherein the mass ratio of the content of the second component to the content of the first component is 0.01 to 0.50.

[0077] [4]

[0078] The composition according to any one of [1] to [3], wherein in formula (B1), R 5 is a fluoroalkylene group,

[0079] In formula (B2), R 6 and R 7 are all fluoroalkylene groups, and L b1 For a single key.

[0080] 〔5〕

[0081] The composition according to [4], wherein in formula (B1), R 5 The carbon number of the fluoroalkylene group shown in

[0082] In formula (B2), R 6 The carbon number of the above fluoroalkylene group is 7 The total number of carbon atoms in the above-mentioned fluoroalkylene groups is 2 to 40.

[0083] [6]

[0084] A substrate with a surface layer, comprising: a substrate, and a surface layer formed on the substrate from the composition described in any one of [1] to [5].

[0085] 〔7〕

[0086] A method for producing a substrate with a surface layer, comprising forming the surface layer on the substrate by a dry coating method or a wet coating method using the composition described in any one of [1] to [5].

[0087] Effects of the Invention

[0088] According to the present invention, a composition capable of forming a surface layer having excellent wear resistance, a substrate with a surface layer, and a method for producing a substrate with a surface layer can be provided. DETAILED DESCRIPTION

[0089] In this specification, the compound represented by formula (B1) is referred to as compound (B1). The compounds represented by other formulae are also described in the same manner. The repeating unit represented by formula (f1) is referred to as unit (f1). The repeating units represented by other formulae are also described in the same manner. The group represented by formula (g1) is referred to as group (g1). The groups represented by other formulae are also described in the same manner.

[0090] Fluoroalkyl refers to a general term for perfluoroalkyl and partial fluoroalkyl groups. Perfluoroalkyl refers to a group in which all hydrogen atoms of an alkyl group are replaced by fluorine atoms. In addition, partial fluoroalkyl refers to an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom and has at least one hydrogen atom. That is, a fluoroalkyl group is an alkyl group having at least one fluorine atom.

[0091] The “reactive silyl group” is a general term for a hydrolyzable silyl group and a silanol group (Si—OH), and the “hydrolyzable silyl group” is a group that can undergo a hydrolysis reaction to form a silanol group.

[0092] The "organic group" refers to a hydrocarbon group which may have a substituent and may have a heteroatom or other bonds in the carbon chain.

[0093] "Hydrocarbon group" refers to a group composed of carbon atoms and hydrogen atoms, and is a group including aliphatic hydrocarbon groups (for example, straight-chain alkylene groups, branched alkylene groups, cycloalkylene groups, etc. as divalent aliphatic hydrocarbon groups), aromatic hydrocarbon groups (for example, phenylene groups as divalent aromatic hydrocarbon groups, etc.), and combinations thereof.

[0094] The “surface layer” refers to a layer formed on the surface of a substrate.

[0095] The partial structure of a fluoroether chain, a fluoropolyether chain, etc. and the "molecular weight" of a fluoroether compound are determined by 1 H-NMR and 19 F-NMR is a number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units based on the terminal groups.

[0096] The term “to” indicating a numerical range includes the numerical values ​​described before and after the “to” as the lower limit and the upper limit.

[0097] [Composition]

[0098] The composition of the present invention comprises a first component and a second component, wherein the first component is composed of at least one fluorine-containing ether compound selected from the group consisting of a compound represented by formula (A1) described below, a compound represented by formula (A2) described below, and a compound represented by formula (A3) described below,

[0099] The second component is composed of at least one fluorine-containing ether compound selected from the group consisting of a compound represented by formula (B1) described below and a compound represented by formula (B2) described below.

[0100] The present inventors have found that when a surface layer is formed on a substrate using the composition of the present invention, the water repellency and abrasion resistance of the surface layer are improved. The detailed reason is not clear, but it can be inferred that the inclusion of the specific first component and the specific second component greatly contributes to the appearance of the effect.

[0101] <First ingredient>

[0102] The first component contained in the composition of the present invention is at least one fluorine-containing ether compound selected from the group consisting of a compound represented by formula (A1), a compound represented by formula (A2) and a compound represented by formula (A3).

[0103] [R f1 -(OR f11 ) y1 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 …(A1)

[0104] (T31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 …(A2)

[0105] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 …(A3)

[0106] In formula (A1),

[0107] R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and there are multiple R f1 When there are multiple R f1 are optionally the same as or different from each other,

[0108] R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f11 When there are multiple R f11 are optionally the same as or different from each other,

[0109] R 1 is an alkylene group or a fluoroalkylene group, and there are multiple R 1 When there are multiple R 1 are optionally the same as or different from each other,

[0110] L 1 is a single bond, or is a j+x1-valent group optionally having N, O, S, Si and optionally having a branch point, bonded to R 1 and R 11 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O),

[0111] R 11 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein the group bonded to L 1 The atom of R is optionally an etheric oxygen atom. 11 When there are multiple R 11 are optionally the same as or different from each other,

[0112] T 11 -SiR a11 z11 R a12 3-z11 , there are multiple T 11 When there are multiple T 11 are optionally the same as or different from each other,

[0113] R a11 is a hydroxyl group or a hydrolyzable group, and there are multiple R a11 When there are multiple R a11 are optionally the same as or different from each other,

[0114] R a12 It is a non-hydrolyzable group, and there are multiple R a12 When there are multiple R a12 are optionally the same as or different from each other,

[0115] j is an integer greater than or equal to 1. When j is 1, y1 is an integer greater than or equal to 2, or R 1 is a fluoroalkylene group,

[0116] z11 is an integer from 1 to 3,

[0117] x1 is an integer greater than 2,

[0118] y1 is an integer greater than or equal to 1. When a plurality of y1 exist, the plurality of y1 exist may be the same as or different from each other.

[0119] In formula (A2),

[0120] R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f12 When there are multiple R f12 are optionally the same as or different from each other,

[0121] R 2 and R 3 are each independently an alkylene group or a fluoroalkylene group,

[0122] L 2 is a single bond, or is a 1+x2 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 2 and R 21 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group,

[0123] L 3 is a single bond, or is a 1+x3 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 3 and R 31The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group,

[0124] R 21 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 2 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 21 When there are multiple R 21 are optionally the same as or different from each other,

[0125] R 31 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 3 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 31 When there are multiple R 31 are optionally the same as or different from each other,

[0126] T 21 and T 31 Each independently is -SiR a21 z21 R a22 3-z21 , there are multiple T 21 When there are multiple T 21 Optional to be the same or different from each other, there are multiple T 31 When there are multiple T 31 are optionally the same as or different from each other,

[0127] R a21 is a hydroxyl group or a hydrolyzable group, and there are multiple R a21 When there are multiple R a21 are optionally the same as or different from each other,

[0128] R a22 It is a non-hydrolyzable group, and there are multiple R a22 When there are multiple R a22 are optionally the same as or different from each other,

[0129] z21 is an integer from 1 to 3,

[0130] x2 and x3 are each independently an integer greater than 2,

[0131] y2 is an integer greater than 1. When y2 is 1, R 2 It is a fluoroalkylene group.

[0132] In formula (A3),

[0133] Q 1 is a r1-valent group having a branch point,

[0134] Rf13 is a fluoroalkylene group having 1 to 6 carbon atoms, and the presence of multiple R f13 are optionally the same or different from each other,

[0135] R 4 Each independently represents an alkylene group or a fluoroalkylene group, and the presence of multiple R 4 are optionally the same or different from each other,

[0136] L 4 is a single bond, or is a 1+x4 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 4 and R 41 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group. 4 are optionally the same or different from each other,

[0137] R 41 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 4 The adjacent atoms may be etheric oxygen atoms, and the presence of multiple R 41 are optionally the same or different from each other,

[0138] T 41 -SiR a41 z41 R a42 3-z41 , there are multiple T 41 are optionally the same or different from each other,

[0139] R a41 is a hydroxyl group or a hydrolyzable group, and the presence of multiple R a41 are optionally the same or different from each other,

[0140] R a42 It is a non-hydrolyzable group, and there are multiple R a42 When there are multiple R a42 are optionally the same or different from each other,

[0141] z41 is an integer from 1 to 3,

[0142] x4 is an integer greater than or equal to 2, and a plurality of x4s present may be the same or different from each other.

[0143] y3 is an integer greater than 1, and a plurality of y3s present may be the same or different from each other.

[0144] r1 is 3 or 4.

[0145] Hereinafter, the constitution of each compound will be described, but symbols having the same structure will be represented as such and can be understood and referred to with appropriate substitution.

[0146] Since the reactive silyl group of the first component having a reactive silyl group at the terminal is strongly chemically bonded to the substrate, the surface layer formed using the first component is excellent in durability such as friction durability.

[0147] The fluoropolyether chain is a group having two or more oxyfluoroalkylene units.

[0148] The fluoropolyether chain optionally has hydrogen atoms. From the viewpoint of better friction resistance and fingerprint removability of the surface layer, the proportion of fluorine atoms represented by the following mathematical formula (I) of the fluoropolyether chain is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, that is, a perfluoropolyether chain. If the fluorine atoms are 60% or more, the fluorine content of the fluoropolyether chain increases, thereby further improving lubricity and fingerprint removability.

[0149] Mathematical formula (I): Ratio of fluorine atoms (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} × 100

[0150] From the viewpoint of both fingerprint removability and lubricity of the surface layer, the molecular weight of each fluoropolyether chain is preferably 2000 to 20000, more preferably 2500 to 15000, and even more preferably 3000 to 10000. If the molecular weight of the fluoropolyether chain is 2000 or more, the flexibility of the fluoropolyether chain is improved, and the amount of fluorine in the molecule is increased, and the lubricity and fingerprint removability are further improved. On the other hand, if the molecular weight of the fluoropolyether chain is 20000 or less, the friction resistance of the surface layer is more excellent.

[0151] (Compound (A1))

[0152] The compound (A1) has a structure represented by the following formula (A1).

[0153] [R f1 -(OR f11 ) y1 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 …(A1)

[0154] In addition, each symbol in formula (A1) is as described above.

[0155] R f1 The fluoroalkyl group is a fluoroalkyl group having 1 to 20 carbon atoms. The fluoroalkyl group may be linear, branched, and / or cyclic. From the viewpoint of abrasion resistance, a linear fluoroalkyl group is preferred. From the viewpoint of ease of synthesis, the fluoroalkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0156] R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f11 When there are multiple R f11 are optionally the same or different from each other. f11 ) y1 represents a fluoroether chain or a fluoropolyether chain (when y1 is 1, it represents a fluoroether chain, and when y1 is 2 or more, it represents a fluoropolyether chain as described above), y1 may be an integer of 1 or more, and is preferably 1-200.

[0157] (OR f11 ) y1 It preferably has a structure represented by the following formula (G11).

[0158] -[(OG f1 ) m1 (OG f2 ) m2 (OG f3 ) m3 (OG f4 ) m4 (OG f5 ) m5 (OG f6 ) m6 ]-…(G11)

[0159] in,

[0160] G f1 is a fluoroalkylene group having 1 carbon number,

[0161] G f2 is a fluoroalkylene group having 2 carbon atoms,

[0162] G f3 is a fluoroalkylene group having 3 carbon atoms,

[0163] G f4 is a fluoroalkylene group having 4 carbon atoms,

[0164] G f5 is a fluoroalkylene group having 5 carbon atoms,

[0165] G f6 is a fluoroalkylene group having 6 carbon atoms,

[0166] m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, and m1+m2+m3+m4+m5+m6 is preferably an integer of 1 to 200.

[0167] It should be noted that (OG f1 )~(OG f6) is an arbitrary bonding order. m1 to m6 in formula (G11) represent (OG f1 )~(OG f6 ) rather than the configuration method. For example, (OG f5 ) m5 Indicates (OG f5 ) is m5, but does not mean (OG f5 ) m5 Similarly, (OG f1 )~(OG f6 ) does not indicate the order of bonding of the individual units.

[0168] The fluoroalkylene group having 3 to 6 carbon atoms may be a linear fluoroalkylene group or a fluoroalkylene group having a branched or cyclic structure.

[0169] As G f1 Specific examples include -CF2- and -CHF-.

[0170] As G f2 Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, -CH2CHF- and the like.

[0171] As G f3Specific examples include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CHF -, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2 F)-CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, -CH(CH2F)-CH2-, etc.

[0172] As G f4 Specific examples include -CF2CF2CF2CF2-, -CHFCF2CF2CF2-, -CH2CF2CF2CF2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -C F2CHFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, -cycloC4F6-, etc.

[0173] As G f5Specific examples include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, and -cycloC5F8-.

[0174] As G f6 Specific examples include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, -cycloC6F 10 -wait.

[0175] Here, -cycloC4F6- refers to a perfluorocyclobutanediyl group, and a specific example thereof is perfluorocyclobutane-1,2-diyl. -cycloC5F8- refers to a perfluorocyclopentanediyl group, and a specific example thereof is perfluorocyclopentane-1,3-diyl. 10 - refers to a perfluorocyclohexanediyl group, and a specific example thereof includes a perfluorocyclohexane-1,4-diyl group.

[0176] For (OR f11 ) y1 From the viewpoint of achieving better water and oil repellency, friction durability, and fingerprint contamination removability, preferably, the structure is represented by the following formula (G2) to the following formula (G4).

[0177] (OG f1 ) m1 -(OG f2 ) m2 Formula (G2)

[0178] (OG f2 ) m2 -(OG f4 ) m4 Formula (G3)

[0179] (OG f3 ) m3 Formula (G4)

[0180] However, the symbols in formula (G2) to formula (G4) are the same as those in the above formula (G11).

[0181] In formula (G2) and formula (G3), (OG f1 ) and (OG f2 )、(OG f2 ) and (OG f4 ) are in any order. f1 ) and (OG f2 ) can be configured alternately, (OG f1 ) and (OG f2 ) may be arranged in blocks or randomly.

[0182] In formula (G2), m1 is preferably 1-30, and more preferably 1-20. In addition, m2 is preferably 1-30, and more preferably 1-20.

[0183] In formula (G3), m2 is preferably 1-30, and more preferably 1-20. In addition, m4 is preferably 1-30, and more preferably 1-20.

[0184] In formula (G4), m3 is preferably 1-30, more preferably 1-20.

[0185] From the viewpoint of excellent water-repellency and oil-repellency and fingerprint removability, the fluoroether chain or fluoropolyether chain (OR f11 ) y1 The ratio of fluorine atoms in the carbon atom [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more. The upper limit is, for example, 100%.

[0186] In addition, from the viewpoint of friction durability, the fluoroether chain or fluoropolyether chain (OR f11 ) y1 The molecular weight of the moiety is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, and even more preferably 3,000 to 10,000.

[0187] R 1 is an alkylene group or a fluoroalkylene group. 1 The alkylene and fluoroalkylene in R may be straight chain or may have a branched chain and / or a ring structure. From the viewpoint of ease of synthesis, it is preferably a straight chain or branched alkylene or fluoroalkylene, and more preferably a straight chain or alkylene or fluoroalkylene having a methylene or fluoromethylene group as a branch. 1 The carbon number of is preferably 1-30, more preferably 1-30, and further preferably 1-10.

[0188] j represents [Rf1 -(OR f11 ) y1 -OR 1 The number of ] may be an integer greater than 1, and is preferably 1-20, more preferably 1-10, and even more preferably 1-4.

[0189] R 11 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein the group bonded to L 1 The atom is optionally an ethereal oxygen atom.

[0190] R 11 The alkylene group in may be linear, branched, and / or cyclic. From the viewpoint of facilitating close arrangement of the compound (A1) when forming the surface layer, a linear or branched alkylene group is preferred, and a linear alkylene group is more preferred.

[0191] From the viewpoint of better water and oil repellency and fingerprint removal of the surface layer, and better durability such as friction durability, R 11 The alkylene group in the group preferably has a carbon chain in which two or more carbon atoms are linked.

[0192] R 11 The alkylene group in the above-mentioned carbon chain preferably has a carbon chain having 3 or more carbon atoms connected, more preferably has a carbon chain having 4 or more carbon atoms connected, particularly preferably has a carbon chain having 9 or more carbon atoms connected, and most particularly preferably has a carbon chain having 11 or more carbon atoms connected. The alkylene group having the carbon chain having the above-mentioned carbon number is adjacent to the hydrolyzable silyl group, so that the friction durability of the surface layer is further improved.

[0193] The upper limit of the carbon number is not particularly limited, but from the viewpoint of achieving better water and oil repellency and fingerprint removability, the carbon number is preferably 20 or less, and more preferably 19 or less.

[0194] Among them, as R 11 , preferably a straight-chain alkylene group having 3 to 20 carbon atoms, more preferably a straight-chain alkylene group having 4 to 20 carbon atoms, further preferably a straight-chain alkylene group having 9 to 20 carbon atoms, and particularly preferably a straight-chain alkylene group having 11 to 20 carbon atoms.

[0195] Here, a carbon chain having more than X carbon atoms connected is referred to as 11 In the case of an alkylene group having a branched chain and / or a ring structure, the carbon atoms of the branched chain and the ring structure are also included. Specifically, for example, -CH2CH2CH(-CH2CH3)-CH2CH2CH2CH2- has a carbon chain of 9 carbon atoms connected, including the carbon atoms of the branched chain.

[0196] Preferred R11 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 11 Connected, there are multiple R 11 When multiple R 11 All have carbon chains with more than 4 carbon atoms connected. 11 The preferred form of the number of carbon atoms connected to the above carbon chain is as described above.

[0197] Specifically, R 11 It can be expressed by formula (g2).

[0198] *-(O) a1 -(R g2 O) a2 -R g2 -**…(g2)

[0199] in,

[0200] R g2 is an alkylene group having 1 or more carbon atoms, and the presence of multiple R g2 are optionally the same as or different from each other,

[0201] a1 is 0 or 1,

[0202] a2 is an integer greater than 0,

[0203] * is bonded to L 1 The connection key,

[0204] ** is bonded to T 11 connection key.

[0205] When a1 is 0, the atom having the bond * is a carbon atom, and when a1 is 1, the atom having the bond * is an oxygen atom. In compound (A1), a1 may be either 0 or 1, and may be appropriately selected from the viewpoint of synthesis and the like.

[0206] a2 is R g2 The number of repetitions of O is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1 from the viewpoint of durability as a surface layer.

[0207] R g2 The alkylene group shown in the figure is the same as the above R 11 The alkylene groups in are the same and the preferred aspects are also the same.

[0208] From the viewpoint of having better water and oil repellency and fingerprint removal properties as a surface layer, and also having excellent durability such as abrasion resistance, R 11 More preferably, it is a group represented by formula (g3).

[0209] *-(O)a1 -R g3 -**…(g3)

[0210] in,

[0211] R g3 is an alkylene group,

[0212] a1, * and ** are the same as those in formula (g2).

[0213] R g3 The alkylene group shown in the figure is the same as the above R 11 The alkylene groups in are the same and the preferred aspects are also the same.

[0214] T 11 -SiR a11 z11 R a12 3-z11 The groups shown.

[0215] R a11 , R a12 , z11 are each independently the same as T constituting the above formula (A1) 11 R a11 , R a12 , z11 are the same, and the preferred method is also the same.

[0216] x1 represents R in 1 molecule 11 -T 11 The number may be an integer greater than 1, may be an integer greater than 2, is preferably an integer from 2 to 32, more preferably an integer from 2 to 18, and further preferably an integer from 2 to 12.

[0217] L 1 is a single bond, or is a j+x1-valent group optionally having N, O, S, Si and optionally having a branch point, bonded to R 1 and R 11 The atoms of R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O). 1 and R 11 The atoms can be the same atoms or different atoms.

[0218] L 1 When R in formula (A1) is a single bond, 1 With R 11 The compound (A1) is directly bonded and is represented by the following formula (A1').

[0219] R f1 -(OR f11 ) y1 -OR 1-R 11 -T 11 …(A1')

[0220] However, the symbols in formula (A1') are the same as those in formula (A1).

[0221] L 1 When L is a trivalent or higher group, 1 The present invention has at least one branch point (hereinafter also referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure and an organopolysiloxane residue with a valence of (j+x1). 1 ”).

[0222] N becomes the branch point P 1 When the branch point P 1 For example, it is represented by *-N(-**)2 or (*-)2N-**. 1 The connection key on the side, ** is R 11 side connection key.

[0223] C becomes the branch point P 1 When the branch point P 1 For example, *-C(-**)3, (*-)2C(-**)2, (*-)3C-**, *-CR 29 (-**)2 or (*-)2CR 29 -** indicates. Where * is R 1 The connection key on the side, ** is R 11 Side connection key, R 29 It is a monovalent group, for example, a hydrogen atom, a hydroxyl group, a hydrocarbon group, and an alkoxy group. As the hydrocarbon group, a straight-chain alkyl group, a branched alkyl group, an aliphatic hydrocarbon group such as a cycloalkyl group, an aromatic hydrocarbon group such as a phenyl group, or a group consisting of a combination thereof can be listed.

[0224] Si becomes the branch point P 1 When the branch point P 1 For example, *-Si(-**)3, (*-)2Si(-**)2, (*-)3Si-**, *-SiR 29 (-**)2、(*-)2SiR 29 -** indicates. Where * is R 1 The connection key on the side, ** is R 11 Side connection key, R 29 It is a monovalent group, for example, a hydrogen atom, a hydroxyl group, a hydrocarbon group, and an alkoxy group. As the hydrocarbon group, a straight-chain alkyl group, a branched alkyl group, an aliphatic hydrocarbon group such as a cycloalkyl group, an aromatic hydrocarbon group such as a phenyl group, or a group consisting of a combination thereof can be listed.

[0225] As the branch point P 1The ring structure is preferably selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocyclic ring, and a condensed ring formed by two or more of these rings, and more preferably a ring structure listed in the following formula, from the viewpoint of easy production of the compound (A1) and the viewpoint of better friction resistance, light resistance, and chemical resistance of the surface layer. The ring structure may have a substituent such as a halogen atom, an alkyl group (optionally containing an ethereal oxygen atom between carbon-carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, an oxo group (=O), or the like.

[0226]

[0227] As the branch point P 1 The organopolysiloxane residues include the following groups. 25 is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. 25 The carbon number of the alkyl group and the alkoxy group is preferably 1 to 10, more preferably 1. 25 They are optionally the same as or different from each other.

[0228]

[0229] L with two or more valences 1 It may have a selected from -C(O)N(R 26 )-、-N(R 26 )C(O)-, -C(O)O-, -OC(O)-, -C(O)-, -C(OH)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N(R 26 )-、-SO2N(R 26 )-、-N(R 26 )SO2-、-Si(R 26 )2-、-OSi(R 26 )2-, -Si(CH3)2-Ph-Si(CH3)2- and a divalent organopolysiloxane residue (hereinafter also referred to as "bond B 1 ”).

[0230] Among them, R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Ph is a phenylene group. From the viewpoint of facilitating the production of the compound (A1), R 26 The carbon number of the alkyl group is preferably 1-6, more preferably 1-3, and further preferably 1-2.

[0231] Examples of the divalent organopolysiloxane residue include groups of the following formula:27 is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. 27 The carbon number of the alkyl group and the alkoxy group is preferably 1 to 10, more preferably 1. 27 They are optionally the same as or different from each other.

[0232]

[0233] As key B 1 From the viewpoint of easy production of compound (A1), it is preferably selected from -C(O)NR 26 -、-N(R 26 )C(O)-, -C(O)- and -NR 26 At least one bond in the group consisting of -C(O)NR 26 -、-N(R 26 )C(O)- or -C(O)-.

[0234] As a divalent L 1 , bonded to R 1 and R 11 The atoms of R are each independently N, O, S, Si, or a carbon atom having a hydroxyl group or an oxo group (=O). 1 and R 11 The adjacent atoms are bond B 1 As a divalent L 1 Specific examples include one or more keys B 1 (For example, *-B 1 -**, *-B 1 -R 28 -B 1 -**). Among them, R 28 is a single bond or a divalent organic group, * is R 1 The connection key on the side, ** is R 11 side connection key.

[0235] L with a valence of three or more 1 In the bonded 1 and R 11 The atoms of R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O). 1 and R 11 The adjacent atoms are bond B 1 or branch point P 1 As a constituent element of trivalent or higher L 1 A specific example of this is that one or more branch points P 1 (For example{(*-)j P 1 (-**) x1}、{(*-) j P 1 -R 28 -P 1 (-**) x1}, etc.), one or more branch points P 1 With more than one key B 1 Combinations (e.g., {*-B 1 -R 28 -P 1 (-**) x1}, {*-B 1 -R 28 -P 1 (-R 28 -B 1 -**) x1}. Among them, R 28 is a single bond or a divalent organic group, * is R 1 The connection key on the side, ** is R 11 side connection key.

[0236] As the above R 28 The divalent organic group in the present invention includes divalent aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups, etc.), divalent aromatic hydrocarbon groups (phenylene groups, etc.), and the like, and the hydrocarbon groups may have a bond B between carbon atoms of the hydrocarbon groups. 1 The divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0237] From the viewpoint of facilitating the production of compound (A1), L 1 , preferably a group represented by any one of Formula (L1) to Formula (L7).

[0238]

[0239] (-A 1 -) d5 C(R e2 ) 4-d5―d6 (-Q 22 -) d6 …(L2)

[0240] (-A 2 -) d7 N(-Q 23 -) 3-d7 …(L3)

[0241] (-A 3 -) d8 Z 1 (-Q24 -) d9 …(L4)

[0242] (-A 2 -) d10 Si(R e3 ) 4-d10-d11 (-Q 25 -) d11 …(L5)

[0243] -A 1 -Q 26 -…(L6)

[0244] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -) d12 …(L7)

[0245] Among them, in formula (L1) to formula (L7), A 1 , A 2 or A 3 The side and R of formula (A1) 1 Connected, Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side and R 11 are connected.

[0246] Here, A 1 is a single bond, -B 3 -、-B 3 -R 30 -or-B 3 -R 30 -B 2 -, R 30 An alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms e6 -、-C(O)-、-NR e6 - or -O-, B 2 -C(O)NR e6 -、-C(O)-、-NR e6 -or-O-,B 3 -C(O)NR e6 -, -C(O)- or -NR e6 -,

[0247] A2 is a single bond or -B 3 -R 30 -,

[0248] A 3 Bonded Z 1 When the atom in is a carbon atom, 3 A 1 , A 3 Bonded Z 1 When the atom in is a nitrogen atom, 3 A 2 ,

[0249] Q 11 is a single bond, -O-, an alkylene group, or an alkylene group having a carbon number of 2 or more and having -C(O)NR between carbon atoms. e6 -、-C(O)-、-NR e6 - or -O-,

[0250] Q 22 is a single bond, -B 3 -、-R 30 -B 3 -or-B 2 -R 30 -B 3 -,

[0251] Q 23 is a single bond or -R 30 -B 3 -,

[0252] Q 24 Bonded Z 1 When the atom in is a carbon atom, Q 24 Q 22 , Q 24 Bonded Z 1 When the atom in is a nitrogen atom, Q 24 Q 23 ,

[0253] Q 25 is a single bond or -R 30 -B 3 -,

[0254] Q 26 is a single bond or -R 30 -B 3 -,

[0255] Z 1 is a (d8+d9)-valent group having a ring structure, wherein the (d8+d9)-valent group having a ring structure has A 3 The carbon atom or nitrogen atom directly bonded to the 24 The carbon or nitrogen atom to which it is directly bonded,

[0256] Re1 is a hydrogen atom or a hydrocarbon group (an aromatic hydrocarbon group such as an alkyl group or a phenyl group),

[0257] R e2 is a hydrogen atom, a hydroxyl group, a hydrocarbon group (an alkyl group, an aromatic hydrocarbon group such as a phenyl group, etc.), or an acyloxy group,

[0258] R e3 is a hydrocarbon group (an aromatic hydrocarbon group such as an alkyl group or a phenyl group),

[0259] R e6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group,

[0260] d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, d1+d2 is an integer from 1 to 3,

[0261] d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, d3+d4 is an integer from 1 to 3,

[0262] d1+d3 is an integer from 1 to 5,

[0263] d2+d4 is an integer from 2 to 5,

[0264] d5 is an integer of 1 to 3, d6 is an integer of 2 to 3, d5+d6 is an integer of 3 to 4,

[0265] d7 is 1,

[0266] d8 is an integer greater than 1,

[0267] d9 is an integer greater than 2,

[0268] d10 is an integer of 1 to 3, d11 is an integer of 2 to 3, d10+d11 is an integer of 3 to 4,

[0269] d12 is an integer from 1 to 3.

[0270] It should be noted that B 2 and B 3 There is no requirement for the direction of A. 1 When there are multiple A 1 are optionally the same as or different from each other. 2 , A 3 , Q 22 , Q 23 , Q 24 , Q 25 , R e1 , R e2 and R e3 Same here.

[0271] In addition, d1+d3, d5, d7, d8 and d10 are j, and d2+d4, d6, 3-d7, d9, d11 and 1+d12 are x1.

[0272] From the viewpoint of easy production of the compound (A1) and the viewpoint of better abrasion resistance, light resistance and chemical resistance of the surface layer, R 30 The carbon number of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. However, the lower limit of the carbon number of the alkylene group when having a specific bond between carbon atoms is 2.

[0273] As Z 1 The ring structure in can include the above-mentioned ring structures, and the preferred embodiments are also the same.

[0274] From the viewpoint of facilitating the production of compound (A1), R e1 , R e2 or R e3 The carbon number of the alkyl group is preferably 1-6, more preferably 1-3, and further preferably 1-2.

[0275] From the viewpoint of facilitating the production of compound (A1), R e2 The number of carbon atoms in the alkyl portion of the acyloxy group is preferably 1-6, more preferably 1-3, and even more preferably 1-2.

[0276] From the viewpoint of easy production of the compound (A1) and the viewpoint of better abrasion resistance and fingerprint removability of the surface layer, d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0277] As the above L 1 In another embodiment, a group represented by any one of formula (L11) to formula (L17) can be mentioned.

[0278]

[0279] (-A 1 -) d5 C(R e2 ) 4-d5―d6 (-Q 22 -G) d6 …(L12)

[0280] (-A 2 -) d7 N(-Q 23 -G) 3-d7 …(L13)

[0281] (-A 3 -) d8 Z 1 (-Q 24-G) d9 …(L14)

[0282] (-A 2 -) d10 Si(R e3 ) 4-d10-d11 (-Q 25 -G) d11 …(L15)

[0283] -A 1 -Q 26 -G…(L16)

[0284] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -G) d12 …(L17)

[0285] Among them, in formula (L11) to formula (L17),

[0286] A 1 , A 2 or A 3 The side and R of formula (A1) 1 Connected, Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side and R 11 G is the following group (G21), L 1 The two or more Gs present may be the same or different. Symbols other than G are the same as those in formula (L11) to formula (L17).

[0287] -Si(R 51 ) 3-k (-Q 3 -) k …(G21)

[0288] Among them, in the above group (G21),

[0289] Si side and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Connected, Q 3 Side and R 11 Connected. 51 Q is an alkyl group. 3 is a single bond or -R 31 -B 3 -, R31 An alkylene group or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms 32 -、-C(O)-、-NR 32 - or -O-, or -(OSi(R 22 )2) p11 -O-, 2 or more Q 3 are optionally the same or different. k is 2 or 3. 32 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 22 is alkyl, phenyl or alkoxy, 2 R 22 p11 is an integer of 0 to 5. When p11 is 2 or more, 2 or more (OSi(R 22 )2) can be the same or different.

[0290] Q 3 For-R 31 -B 3 -, from the viewpoint of easy production of the compound (A1) and the viewpoint of better abrasion resistance, light resistance and chemical resistance of the surface layer, R 31 The carbon number of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. However, the lower limit of the carbon number of the alkylene group when having a specific bond between carbon atoms is 2.

[0291] From the viewpoint of facilitating the production of compound (A1), R 51 The carbon number of the alkyl group is preferably 1-6, more preferably 1-3, and further preferably 1-2.

[0292] From the viewpoint of facilitating the production of compound (A1), R 22 The carbon number of the alkyl group is preferably 1-6, more preferably 1-3, and further preferably 1-2.

[0293] From the viewpoint of excellent storage stability of the compound (A1), R 22 The alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 to 2 carbon atoms.

[0294] p11 is preferably 0 or 1.

[0295] From the viewpoint of further improving the friction durability of the surface layer, L 1 -(R 11 -T 11 ) x1 The molecular weight of the group shown is preferably 300 or more, more preferably 450 or more, and further preferably 600 or more.

[0296] On the other hand, from the viewpoint of more excellent antifouling properties, the molecular weight is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less.

[0297] In addition, from the viewpoint of further improving the friction durability of the surface layer, [R f1 -(OR f11 ) y1 -OR 1 ] j The molecular weight of the fluoropolyether chain shown is relative to L 1 -(R 11 -T 11 ) x1 The ratio of the molecular weight of the group shown is preferably 10% or more, more preferably 12% or more, and further preferably 13% or more.

[0298] From the viewpoint of achieving more excellent antifouling properties, the upper limit of the ratio is preferably 40% or less, more preferably 25% or less.

[0299] As the compound (A1), for example, the following can be mentioned.

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306] Among them, R f2 Each independently and f1 -(OR f11 ) y1 -OR 1 ] or [R f1 -(OR f11 ) y1 -O-] is the same as T 11 Same, Me is methyl.

[0307] (Compound (A2))

[0308] The compound (A2) has a structure represented by the following formula (A2).

[0309] (T 31 -R 31 ) x3 -L3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 …(A2)

[0310] In addition, each symbol in formula (A2) is as described above.

[0311] R f12 OR f12 ) y2 With the above R f11 OR f11 ) y1 Same, the preferred method is also the same.

[0312] R 2 and R 3 Each independently of the above R 1 Same, the preferred method is also the same.

[0313] R 21 and R 31 With the above R 11 The same, the preferred mode is also the same. Among them, "bonded to L 1 In R 21 In the case of 2 "To understand, in R 31 In the case of 3 ". In addition, "bonded to T 11 In R 21 In the case of 21 "To understand, R 31 is replaced by "bonded to T 31 "To understand.

[0314] As R 21 and R 31 A specific example of a preferred embodiment is preferably at least one of the following: R 21 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 21 connected; and R 31 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 31 In addition, there are multiple R 21 When multiple R 21 All have carbon chains with more than 4 carbon atoms connected. 21 In addition, there are multiple R31 When multiple R 31 All have carbon chains with more than 4 carbon atoms connected. 31 The preferred form of the number of carbon atoms connected to the above carbon chain is as described above.

[0315] T 21 and T 31 Each independently is -SiR a21 z21 R a22 3-z21 , R a21 , R a22 and z21 independently form T 11 R a11 , R a12 Same as z11, the preferred method is also the same.

[0316] x2 and x3 are each independently the same as x1, and the preferred aspects are also the same.

[0317] L 2 and L 3 Each independently of the above L 1 The same is true when j is 1.

[0318] For example, L 2 and L 3 When it is a single bond, the compound (A2) is represented by the following formula (A2').

[0319] T 31 -R 31 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -R 21 -T 21 …(A2')

[0320] However, the symbols in formula (A2') are the same as those in formula (A2).

[0321] L 2 or L 3 When the trivalent or higher valent group is L 2 or L 3 The polysiloxane has at least one branch point (hereinafter also referred to as “branch point P”) selected from the group consisting of C, N, Si, a ring structure, and a (1+x2)-valent or (1+x3)-valent organopolysiloxane residue. 2 ”).

[0322] N becomes the branch point P 2 When the branch point P 2For example, it is represented by *-N(-**)2. Where * is R 2 or R 3 The connection key on the side, ** is R 21 or R 31 side connection key.

[0323] C becomes the branch point P 2 When the branch point P 2 For example, *-C(-**)3, or *-CR 29 (-**)2 represents. Where * is R 2 or R 3 The connection key on the side, ** is R 21 or R 31 Side connection key, R 29 is a monovalent group. 29 , a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group can be listed.

[0324] Si becomes the branch point P 2 When the branch point P 2 For example, *-Si(-**)3, or *-SiR 29 (-**)2 indicates.

[0325] Among them, * is R 2 or R 3 The connection key on the side, ** is R 21 or R 31 Side connection key, R 29 is a monovalent group. 29 , a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group can be listed.

[0326] Branch point P 2 The ring structure, the organopolysiloxane residue and the branch point P 1 Same, the preferred method is also the same.

[0327] In addition, L with a valence of 2 or more 2 or L 3 Each independently optionally has the above-mentioned bond B 1 . Key B 1 The method is as described above, and the preferred method is also the same.

[0328] For the divalent L 2 or L 3 , bonded to R 2 and R 21 or bonded to R 3 and R 31 The atoms of R are each independently N, O, S, Si, or a carbon atom having a hydroxyl group or an oxo group (=O). 2 and R21 Adjacent or with R 3 and R 31 The adjacent atoms are bond B 1 As a divalent L 2 or L 3 Specific examples include one or more keys B 1 (For example, *-B 1 -**, *-B 1 -R 28 -B 1 -**). Among them, R 28 is a single bond or a divalent organic group, * is R 2 or R 3 The connection key on the side, ** is R 21 or R 31 side connection key.

[0329] For L with a valence of three or more 2 or L 3 , bonded to R 2 and R 21 or bonded to R 3 and R 31 The atoms of R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O). 2 and R 21 Adjacent or with R 2 and R 31 The adjacent atoms are bond B 1 or branch point P 2 As a constituent element of trivalent or higher L 2 or L 3 A specific example of this is that one or more branch points P 2 (For example {*-P 2 (-**) x}、{*-P 2 -R 28 -P 2 -** x}, etc.), one or more branch points P 2 With more than one key B 1 Combinations (e.g., {*-B 1 -R 28 -P 2 (-**) x}、{*-B 2 -R 28 -P 2 (-R 28 -B 1 -**) x}, etc.) where L2 In the case of X=x2, L 3 In this case, X is x3. 28 is a single bond or a divalent organic group, * is R 2 or R 3 The connection key on the side, ** is R 21 or R 31 side connection key.

[0330] The above R 28 The method is as described above, and the preferred method is also the same.

[0331] From the viewpoint of facilitating the production of compound (A2), L 2 or L 3 , and are preferably each independently a group represented by any one of Formula (L21) to Formula (L27).

[0332]

[0333] -A 1 -C(R e2 ) 4-d6 (-Q 22 -) d6 …(L22)

[0334] -A 2 -N(-Q 23 -)2…(L23)

[0335] -A 3 -Z 1 (-Q 24 -) d9 …(L24)

[0336] -A 2 -Si(R e3 ) 4-d11 (-Q 25 -) d11 …(L25)

[0337] -A 1 -Q 26 -…(L26)

[0338] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -) d12 …(L27)

[0339] Among them, in formula (L21) to formula (L27), A 1 , A 2 or A3 Side and R 2 or R 3 Connected, Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side and R 21 or R 31 are connected.

[0340] Here, A 1 , A 2 , A 3 , Q 11 , Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , R e1 , R e2 , R e3 , R e6 With the above L 1 The same as described in, the preferred embodiment is also the same.

[0341] Z 1 is a (1+d9)-valent group having a ring structure, wherein the (1+d9)-valent group having a ring structure has A 3 The carbon atom or nitrogen atom directly bonded to the 24 The carbon or nitrogen atom to which it is directly bonded,

[0342] d2 is an integer from 0 to 3, d4 is an integer from 0 to 3, d2+d4 is an integer from 2 to 5,

[0343] d6 is an integer from 2 to 3,

[0344] d9 is an integer greater than 2,

[0345] d11 is an integer from 2 to 3,

[0346] d12 is an integer from 1 to 3.

[0347] It should be noted that d2+d4, d6, d9, d11, 1+d12 are x2 or x3.

[0348] From the viewpoint of easy production of the compound (A2) and the viewpoint of better friction durability and fingerprint removability of the surface layer, d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0349] As the above L 2 or L 3 In another embodiment, a group represented by any one of formula (L31) to formula (L37) can be mentioned.

[0350]

[0351] -A 1 -C(R e2 ) 4-d6 (-Q 22 -G) d6 …(L32)

[0352] -A 2 -N(-Q 23 -G)2…(L33)

[0353] -A 3 -Z 1 (-Q 24 -G) d9 …(L34)

[0354] -A 2 -Si(R e3 ) 4-d11 (-Q 25 -G) d11 …(L35)

[0355] -A 1 -Q 26 -…(L26)

[0356] -A 1 -CH(-Q 22 -G)-Si(R e3 ) 3-d12 (-Q 25 -G) d12 …(L37)

[0357] Among them, in formula (L31) to formula (L37), A 1 , A 2 or A 3 Side and R 2 or R 3 Connected, Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side and R 21 or R 31 G is the above-mentioned group (G21), and the preferred embodiment is the same. Symbols other than G are the same as those in formula (L21) to formula (L27), and the preferred embodiment is the same.

[0358] Among the compounds (A2), L 2 -(R 21 -T21 ) x2 The groups shown and (T 31 -R 31 ) x3 -L 3 The molecular weight of at least one of the molecular weights of the groups shown is preferably 300 or more, more preferably 450 or more, and even more preferably 600 or more.

[0359] On the other hand, from the viewpoint of more excellent antifouling properties, the molecular weight is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less.

[0360] In addition, L 2 -(R 21 -T 21 ) x2 The molecular weight and (T 31 -R 31 ) x3 -L 3 It is preferred that both molecular weights of the groups shown are within the above-mentioned ranges.

[0361] In addition, from the viewpoint of further improving the friction durability of the surface layer, R 3 -(OR f12 ) y2 -OR 2 The molecular weight of the groups shown is relative to L 2 -(R 21 -T 21 ) x2 The molecular weight of the group shown is related to (T 31 -R 31 ) x3 -L 3 The ratio of the total molecular weight of the groups shown is preferably 10% or more, more preferably 12% or more, and further preferably 13% or more.

[0362] From the viewpoint of achieving more excellent antifouling properties, the upper limit of the ratio is preferably 40% or less, more preferably 25% or less.

[0363] As the compound (A2), for example, the following can be mentioned.

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371] Among them, R f3 Each independently and 3 -(OR f12 ) y2 -OR 2 ] or [(OR f12 ) y2 -O] is the same as T 21 or T 31 same.

[0372] (Compound (A3))

[0373] The compound (A3) has a structure represented by the following formula (A3).

[0374] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 …(A3)

[0375] In addition, each symbol in formula (A3) is as described above.

[0376] R f13 OR f13 ) y3 With the above R f11 OR f11 ) y1 Same, the preferred method is also the same.

[0377] R 4 With the above R 1 Same, the preferred method is also the same.

[0378] R 41 With the above R 11 The same, the preferred mode is also the same. Among them, "bonded to L 1 " is replaced by "bonded to L 4 ". In addition, "bonded to T 11 " is replaced by "bonded to T 41 "To understand.

[0379] As R 41 Specific examples of preferred embodiments of the present invention are preferably R 41At least one of the carbon chains has 4 or more carbon atoms connected to each other. 41 Connected, there are multiple R 41 When multiple R 41 All have carbon chains with more than 4 carbon atoms connected. 41 The preferred form of the number of carbon atoms connected to the above carbon chain is as described above.

[0380] T 41 -SiR a41 z41 R a42 3-z41 , R a41 , R a42 and z41 independently form T 11 R a11 , R a12 Same as z11, the preferred method is also the same.

[0381] Q 1 It is a group with a valence of r1 having a branch point, and r1 is 3 or 4.

[0382] As a component of Q 1 The branch point (hereinafter referred to as "branch point P 3 ”), N, C, Si, ring structure can be listed. Branch point P 3 There may be one or two or more.

[0383] N becomes the branch point P 3 When the branch point P 3 For example, N(-*)3, NR 29 (-*)2 indicates.

[0384] C becomes the branch point P 3 When the branch point P 3 For example, C(-*)4, CR 29 (-*)2、C(R 29 )2(-*)2.

[0385] Si becomes the branch point P 3 When the branch point P 3 For example, Si(-*)4, SiR 29 (-*)3、Si(R 29 )2(-*)2.

[0386] Among them, * is OR f13 Side connection key, R 29 is a monovalent group. 29 For example, a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group,41 -T 41 of fluoropolyether chains.

[0387] As the branch point P 3 The ring structure of the branch point P can be listed. 1 The substituent of the ring structure may be a fluorine atom, a fluoroalkyl group, or a ring structure having no R. 41 -T 41 At least one group in the group consisting of a fluoropolyether chain.

[0388] From the viewpoint of facilitating the production of compound (A3), Q 1 , preferably a group represented by any one of Formula (Q1) to Formula (Q6).

[0389]

[0390] C(-A 11 -) d23 (R e12 ) 4-d23 …(Q2)

[0391] N(-A 12 -)3…(Q3)

[0392] Z 1 (-A 13 -) d24 …(Q4)

[0393] Si(-A 12 -) d25 (R e13 ) 4-d25 …(Q5)

[0394] CH(-A 11 -)3-Si(R e13 ) 3-d26 (-A 11 -) d26 …(Q6)

[0395] Among them, in formula (Q1) to formula (Q6), A 11 , A 12 or A 13 OR f13 ) are connected.

[0396] Here, A 11 is a single bond, -R 40 -、-B 13 -R 40 -, R 40An alkylene group, a fluoroalkylene group, or an alkylene group or a fluoroalkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. e16 -、-C(O)-、-CO(O)-、-NR e16 - or -O-, B 13 -C(O)NR e16 -、-C(O)-、-NR e16 -or-O-,

[0397] A 12 is a single bond or -R 40 -,

[0398] A 13 Bonded Z 1 When the atom in is a carbon atom, 13 A 11 , A 13 Bonded Z 1 When the atom in is a nitrogen atom, 13 A 12 ,

[0399] Z 1 is a group having a ring structure with a valence of r1, wherein the group having a ring structure with a valence of r1 has A 13 The carbon or nitrogen atom to which it is directly bonded,

[0400] Q 52 is a single bond, -O-, an alkylene group, a fluoroalkylene group, or a group having -C(O)NR between carbon atoms of an alkylene group or a fluoroalkylene group having 2 or more carbon atoms. e16 -、-C(O)-、-NR e16 - or -O-,

[0401] R e11 is a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, or a 41 -T 41 A fluoropolyether chain, or a -Q 52 -C(R e11 ) 3-d21 (-A 11 -) d21 The repeating structure of the group,

[0402] R e12 is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, or a group having no R 41 -T 41 The fluoropolyether chain

[0403] R e13 is an alkyl group or a fluoroalkyl group,

[0404] R e16 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group or a phenyl group which may be substituted with fluorine,

[0405] d21 is an integer from 0 to 3, d22 is an integer from 0 to 3, d21+d22 is an integer from 3 to 4,

[0406] d23 is 3 or 4,

[0407] d24 is 3 or 4,

[0408] d25 is 3 or 4,

[0409] d26 is 1 or 2.

[0410] It should be noted that B 13 There is no requirement for the direction of A. 11 When there are multiple A 11 are optionally the same as or different from each other. 12 , A 13 , R e11 , R e12 and R e13 Same here.

[0411] From the viewpoint of easy production of the compound (A3) and the viewpoint that the friction durability, light resistance and chemical resistance of the surface layer are more excellent, R 40 The carbon number of the alkylene group or fluoroalkylene group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. However, the lower limit of the carbon number of the alkylene group when having a specific bond between carbon atoms is 2.

[0412] As Z 1 The ring structure in the above structure can be listed as the branch point P 3 The preferred ring structure is the same.

[0413] From the viewpoint of easiness in producing compound (A3), R e11 , R e12 or R e13 The carbon number of the alkyl group or the fluoroalkylene group is preferably 1-6, more preferably 1-3, and further preferably 1-2.

[0414] Among the compounds (A3), L 4 -(R 41 -T 41 ) x4 The molecular weight of at least one of the groups shown is preferably 300 or more, more preferably 450 or more, and further preferably 600 or more.

[0415] On the other hand, from the viewpoint of more excellent antifouling properties, the molecular weight is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less.

[0416] In addition, L 4 -(R 41 -T 41 ) x4 The molecular weights of the groups shown are preferably all within the above-mentioned ranges.

[0417] In addition, from the viewpoint of further improving the friction durability of the surface layer, the (OR f13 ) y3 -OR 4 The sum of the molecular weights of the groups shown is related to Q 1 The sum of the molecular weights of the groups shown relative to r1 L 4 -(R 41 -T 41 ) x4 The ratio of the total molecular weight of the groups shown is preferably 10% or more, more preferably 12% or more, and further preferably 13% or more.

[0418] From the viewpoint of achieving more excellent antifouling properties, the upper limit of the ratio is preferably 40% or less, more preferably 25% or less.

[0419] As the compound (A3), for example, the following can be mentioned.

[0420]

[0421]

[0422]

[0423]

[0424] Among them, {-OR f4 -} independently with [-(OR f13 ) y3 -OR 4 -] r1 or [-(OR f13 ) y3 -O-] r1 Same, T and T 41 same.

[0425] The present composition may contain one type of the first component alone, or may contain two or more types.

[0426] The content of the first component is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, and even more preferably 10 to 90% by mass, relative to the total mass of the present composition.

[0427] The concentration of the first component is preferably 5 to 95 mol %, more preferably 10 to 90 mol %, based on the total molar amount of the first component and the second component contained in the present composition.

[0428] <Second ingredient>

[0429] The second component contained in the composition of the present invention is at least one fluorine-containing ether compound selected from the group consisting of compound (B1) and compound (B2). The second component may contain both compound (B1) and compound (B2), or only one of them.

[0430] R f14 -(OR f15 ) y4 -OR 5 -R b1 …(B1)

[0431] R f19 -(OR f18 ) y6 -OR 7 -L b1 -R 6 -O-(R f16 O) y5 -R f17 …(B2)

[0432] In formula (B1),

[0433] R f14 is a fluoroalkyl group having 1 to 20 carbon atoms,

[0434] R f15 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f15 When there are multiple R f15 are optionally the same as or different from each other,

[0435] R 5 is an alkylene group which may have a substituent,

[0436] R b1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom,

[0437] y4 is an integer greater than or equal to 1.

[0438] In formula (B2),

[0439] R f17 and R f19are each independently a fluoroalkyl group having 1 to 20 carbon atoms,

[0440] R f16 and R f18 Each independently represents a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f16 When there are multiple R f16 Optionally the same or different, there are multiple R f18 When there are multiple R f18 are optionally the same or different from each other,

[0441] R 6 and R 7 are each independently an alkylene group which may have a substituent,

[0442] L b1 is a single bond or a divalent linking group (wherein the divalent linking group does not include (OR f18 ) y7 and (R f16 O) y8 , y7 and y8 are each independently an integer greater than 1),

[0443] y5 and y6 are each independently an integer of 1 or more.

[0444] (Compound (B1))

[0445] The compound (B1) is a compound represented by the formula (B1).

[0446] R f14 -(OR f15 ) y4 -OR 5 -R b1 …(B1)

[0447] In addition, each symbol in formula (B1) is as described above.

[0448] R f14 It is a fluoroalkyl group having 1 to 20 carbon atoms.

[0449] The number of carbon atoms in the fluoroalkyl group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3, from the viewpoint of achieving more excellent water repellency of the surface layer.

[0450] The fluoroalkyl group may be linear, branched or cyclic.

[0451] The fluoroalkyl group is preferably a group in which all hydrogen atoms in the fluoroalkyl group are substituted with fluorine atoms (perfluoroalkyl group).

[0452] R f15 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0453] Rf15 The preferred embodiment is the same as R in the above formula (A1) f11 Same. In addition, (OR f15 ) is preferably the same as (OR f11 )same.

[0454] (OR f15 ) is an integer greater than 1. The preferred embodiment of y4 is the same as the above (OR f11 ) have the same number of repetitions y1.

[0455] R 5 It is an alkylene group which may have a substituent.

[0456] The carbon number of the optionally substituted alkylene group is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, and particularly preferably 1 to 6. When the substituent has a carbon atom, the carbon number of the substituent is not included in the carbon number of the optionally substituted alkylene group.

[0457] The alkylene group which may have a substituent may be linear, branched or cyclic.

[0458] The alkylene group may have a substituent, for example, a halogen atom, a hydroxyl group, and an amino group. As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom may be mentioned, preferably a fluorine atom. In the case where the alkylene group has a fluorine atom, that is, the fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are substituted by fluorine atoms (perfluoroalkylene group).

[0459] As R 5 , preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (ie, a fluoroalkylene group other than a perfluoroalkylene group), and further preferably -R fb1 -R b11 -. R fb1 is a perfluoroalkylene group having 1 to 6 carbon atoms, R b11 is an unsubstituted alkylene group having 1 to 6 carbon atoms, R b11 With R b1 Bonding. Among them, R fb1 The carbon number and R b11 The sum of the carbon numbers of the above R 5 The carbon number is the same.

[0460] R b1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.

[0461] As R b1 , preferably a hydrogen atom or an iodine atom, more preferably a hydrogen atom.

[0462] The compound (B1) may be used in combination of two or more types.

[0463] Specific examples of compound (B1) are shown below. It should be noted that PFPE in the following compound and R in formula (B1) f14 -(OR f15 ) y4 - is the same, and the preferred embodiment is also the same. fb1 is a perfluoroalkylene group having 1 to 6 carbon atoms, and R in the formula (B1) is 5 In addition, X in the following compound and R in formula (B1) b1 The same, preferred embodiments are also the same. R in the following compound is the same as R in formula (B1) 5 The substituents that the alkylene group which may have a substituent shown in the figure are the same, and the preferred aspects are also the same.

[0464]

[0465] The method for producing the compound (B1) is not particularly limited, and examples thereof include the method described in International Publication No. 2013 / 121984.

[0466] (Compound (B2))

[0467] The compound (B2) is a compound represented by formula (B2).

[0468] R f19 -(OR f18 ) y6 -OR 7 -L b1 -R 6 -O-(R f16 O) y5 -R f17 …(B2)

[0469] However, the symbols in formula (B2) are as described above.

[0470] R f17 and R f19 Each R is independently a fluoroalkyl group having 1 to 20 carbon atoms. f17 and R f19 The preferred embodiment is the same as R in the above formula (B1) f14 same.

[0471] R f16 and R f18 Each R is independently a fluoroalkylene group having 1 to 6 carbon atoms. f16 and R f18 The preferred embodiment is the same as R in the above formula (B1) f15 same.

[0472] (R f16 The number of repetitions y5 of (OR) is an integer greater than 1. The preferred embodiment of y5 is the same as the above (OR f15 ) are repeated with the same number y4.

[0473] (OR f18 ) is an integer greater than or equal to 1. The preferred embodiment of y6 is the same as the above (OR f15 ) are repeated with the same number y4.

[0474] From the viewpoint of further improving the effect of the present invention, R in formula (B2) f16 and R f18 It is preferably the same as R in the formula (A1) of the first component. f11 , R in formula (A2) f12 and R in formula (A3) f13 Same group.

[0475] R 6 and R 7 is an alkylene group which may have a substituent. 6 and R 7 The preferred embodiment is the same as R in the above formula (B1) 5 same.

[0476] R 6 The alkylene group optionally having a substituent and R 7 The total number of carbon atoms of the alkylene group optionally having a substituent is preferably 2 to 40, more preferably 2 to 20, and further preferably 2 to 16. When the substituent has a carbon atom, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkylene group optionally having a substituent.

[0477] R 6 and R 7 They may be the same group or different groups, but are preferably the same group.

[0478] As R 6 , preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (ie, a fluoroalkylene group other than a perfluoroalkylene group), and further preferably -R fb2 -R b12 -. R fb2 is a perfluoroalkylene group having 1 to 6 carbon atoms, R b12 is an unsubstituted alkylene group having 1 to 6 carbon atoms, R b12 With L b1 (L b1 When it is a single bond, it is R 6 ) bonding. Among them, R fb2 The carbon number and R b12 The sum of the carbon numbers of the above R6 The carbon number is the same.

[0479] As R 7 , preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (ie, a fluoroalkylene group other than a perfluoroalkylene group), and further preferably -R b13 -R fb3 -. R fb3 is a perfluoroalkylene group having 1 to 6 carbon atoms, R b13 is an unsubstituted alkylene group having 1 to 6 carbon atoms, R b13 With L b1 (L b1 When it is a single bond, it is R 7 ) bonding. Among them, R fb3 The carbon number and R b13 The sum of the carbon numbers of the above R 7 The carbon number is the same.

[0480] L b1 is a single bond or a divalent linking group (wherein the divalent linking group does not include (OR f18 ) y7 and (R f16 O) y8 , y7 and y8 are each independently an integer greater than 1).

[0481] Specific examples of divalent linking groups include alkylene groups, ethereal oxygen atoms, amide bonds, and groups formed by combinations thereof. From the perspective of ease of manufacturing compound (B2) and from the perspective of thermal stability and chemical stability, among the divalent linking groups, alkylene groups, groups formed by combinations of alkylene groups and ethereal oxygen atoms, and groups formed by combinations of alkylene groups and amide bonds are preferred.

[0482] L b1 The divalent linking group in does not include (OR f18 ) y7 and (R f16 O) y8 . (OR f18 ) and (R f16 O) is as defined above, and y7 and y8 are each independently an integer greater than 1.

[0483] From the viewpoint of further improving the effect of the present invention, L b1 Preferred is a single bond.

[0484] The compound (B2) may be used in combination of two or more types.

[0485] Specific examples of compound (B2) are shown below. It should be noted that PFPE in the following compound and R in formula (B2) f19 -(OR f18) y6 -or-(R f16 O) y5 -R f17 The same, the preferred mode is also the same. In addition, R fb2 is a perfluoroalkylene group having 1 to 6 carbon atoms, and R in the formula (B2) is 6 In addition, R fb3 is a perfluoroalkylene group having 1 to 6 carbon atoms, and R in the formula (B2) is 7 In addition, R in the following compound and R in formula (B2) 6 and R 7 The substituents that the alkylene group which may have a substituent shown in the figure are the same, and the preferred aspects are also the same.

[0486]

[0487] The method for producing the compound (B2) is not particularly limited, and examples thereof include a method of subjecting the compounds (B1) to a known coupling reaction.

[0488] <Liquid medium>

[0489] The composition of the present invention may be a composition used in a dry coating method or a composition used in a wet coating method.

[0490] When the composition of the present invention is a composition used in a wet coating method, the composition of the present invention preferably contains a liquid medium.

[0491] Specific examples of the liquid medium include water and organic solvents.

[0492] The liquid medium preferably contains an organic solvent, and more preferably contains an organic solvent having a boiling point of 35 to 250° C. from the viewpoint of excellent coating properties. Here, the boiling point refers to a normal boiling point.

[0493] Specific examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents, and fluorine-based organic solvents are preferred from the viewpoint of excellent solubility. The organic solvent may be used alone or in combination of two or more.

[0494] Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, fluorinated alkyl amines, fluorinated alcohols, and hydrofluoroolefins.

[0495] As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferred. Examples of commercially available products include C6F 13 H (AGC Corporation, ASAHIKLIN (registered trademark) AC-2000), C6F 13C2H5 (manufactured by AGC Corporation, ASAHIKLIN (registered trademark) AC-6000), C2F5CHFCHFCF3 (manufactured by Chemours Corporation, Vertrel (registered trademark) XF), and the like.

[0496] Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.

[0497] As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferred. Examples of commercially available products include CF3CH2OCF2CF2H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300).

[0498] Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.

[0499] Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0500] Specific examples of hydrofluoroolefins include 1-chloro-2,3,3-trifluoro-1-propylene (HCFO-1233yd), a reaction product of methanol and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene, and a reaction product of methanol and 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene. Commercially available products include AMOLEA (registered trademark) AS-300 manufactured by AGC and Opteon (registered trademark) (SF01, SF05, SF10, SF30, SF33, SF70, SF79, SF80) manufactured by Chemours.

[0501] As the non-fluorine-based organic solvent, preferred are compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms and oxygen atoms, and specifically, hydrocarbon-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, alcohol-based organic solvents, amide-based organic solvents and sulfoxide-based organic solvents.

[0502] The hydrocarbon organic solvent is a compound consisting only of hydrogen atoms and carbon atoms, and any of aromatic hydrocarbons, aliphatic hydrocarbons, and unsaturated hydrocarbons can be used.

[0503] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene.

[0504] Examples of the aliphatic hydrocarbon include n-hexane, n-heptane, n-octane, and n-decane.

[0505] As the unsaturated hydrocarbon, for example, cyclopentene, hexene, heptene and butene can be cited.

[0506] Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl aminoketone, 2-heptanone, diisobutyl ketone, and diacetone alcohol.

[0507] Specific examples of the ether-based organic solvent include diethyl ether, diisopropyl ether, methyl tert-butyl ether, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, cyclopentyl methyl ether, 4-methyltetrahydrofuran, 2-methyltetrahydrofuran, and glycol-based solvents.

[0508] As the glycol solvent, for example, mono- or di-alkylene glycol mono- or di-alkyl ethers and mono- or di-alkylene glycol mono- or di-alkyl ether acetates can be cited. The alkylene group is preferably an ethylene group or a propylene group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. As more specific glycol solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether can be cited.

[0509] Specific examples of the ester organic solvent include ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, methyl formate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate and ethyl 2-hydroxyisobutyrate, and ester compounds of the above-mentioned glycol solvents with carboxylic acids such as acetic acid.

[0510] Specific examples of the alcohol organic solvent include methanol, ethanol, propanol, isopropanol, and butanol. It should be noted that the diol solvent described below is not included in the alcohol solvent.

[0511] Examples of the amide-based organic solvent include N,N-dimethylformamide.

[0512] Examples of the sulfoxide-based organic solvent include dimethyl sulfoxide.

[0513] <Other ingredients>

[0514] The composition of the present invention may contain components other than those described above within a range not impairing the effects of the present invention.

[0515] Examples of other components include by-products generated in the production process of the first component and the second component, unreacted raw materials, and other unavoidable compounds in the production process.

[0516] <Content>

[0517] From the viewpoint of achieving more excellent effects of the present invention, the content of the first component is preferably 20 to 99% by mass, more preferably 30 to 90% by mass, further preferably 40 to 80% by mass, and particularly preferably 50 to 80% by mass, relative to the total solid mass of the composition of the present invention.

[0518] From the viewpoint of achieving a more excellent effect of the present invention, the content of the second component is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass relative to the total solid content of the composition of the present invention. It should be noted that the content of the second component refers to the total content of compound (B1) and compound (B2), and when only one of them is contained, it refers to the content of the compound.

[0519] The mass of the solid content of the composition refers to the mass of the solid content of the composition after removing the liquid medium when the composition contains the liquid medium.

[0520] The mass ratio of the content of the second component to the content of the first component (content of the second component / content of the first component) is preferably 0.01 to 4.00, more preferably 0.01 to 1.50, further preferably 0.01 to 1.00, and particularly preferably 0.01 to 0.50. When the mass ratio is within the above range, the wear resistance of the surface layer is further improved.

[0521] When the composition of the present invention contains the above-mentioned liquid medium, the content of the liquid medium is preferably 70 to 99.99% by mass, particularly preferably 80 to 99.9% by mass, based on the total mass of the composition of the present invention.

[0522] The content of other components in the composition of the present invention is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass, relative to the content of the specific fluorine-containing ether compound.

[0523] [Substrate with surface layer]

[0524] The substrate with a surface layer of the present invention comprises a substrate and a surface layer formed from the above composition. The substrate with a surface layer of the present invention comprises a surface layer formed from the above composition and therefore has excellent abrasion resistance and excellent water and oil repellency.

[0525] (Base material)

[0526] As a substrate, as long as it is a substrate that can be used by contacting with other articles (such as a stylus), people's fingers, a substrate that can be held by people's fingers during operation and / or a substrate placed on other articles (such as a mounting table), and it is a substrate that needs to be given water-repellent and oil-repellent properties, there is no particular limitation. As a specific example of the material of the substrate, metal, resin, glass, sapphire, ceramic, stone, and their composite materials can be listed. Glass can be chemically strengthened.

[0527] As the substrate, a touch panel substrate and a display substrate are preferred, and a touch panel substrate is more preferred. The touch panel substrate preferably has light transmittance. "Having light transmittance" means that the vertical incident visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. As the material of the touch panel substrate, glass and transparent resin are preferred.

[0528] In addition, as a substrate, glass or resin films used for building materials, decorative building materials, interior decoration, transportation equipment (such as automobiles), signs / announcements, drinking vessels / tableware, sinks, ornamental equipment (such as frames, boxes), experimental equipment, furniture, and artworks / sports / games; and glass sheets or resin films used in the outer shell parts (excluding the display part) of devices such as mobile phones (such as smartphones), personal digital assistants, game consoles, and remote controllers are also preferred.

[0529] The substrate may be a substrate subjected to surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc. on one surface or both surfaces.

[0530] The surface layer can be formed directly on the surface of the substrate, or it can be formed on the substrate via other films formed on the substrate surface. As specific examples of the above-mentioned other films, the substrate can be treated with the compounds described in paragraphs 0089 to 0095 of International Publication No. 2011 / 016458, SiO2, etc., to form a basement film on the surface of the substrate.

[0531] (Surface layer)

[0532] The surface layer is a layer formed from the above-mentioned composition.

[0533] As described above, the surface layer contains a condensate obtained by hydrolysis and dehydration condensation of part or all of the reactive silyl groups of the specific fluorine-containing ether compound as the first component. In addition, the surface layer contains the second component or a component derived therefrom.

[0534] The thickness of the surface layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. If the thickness of the surface layer is above the lower limit, the effect of the surface layer can be fully obtained. If the thickness of the surface layer is below the upper limit, the utilization efficiency is high.

[0535] The thickness of the surface layer can be calculated from the vibration period of an interference pattern of reflected X-rays obtained by X-ray reflectivity (XRR) using an X-ray diffractometer for thin film analysis.

[0536] [Method for producing substrate with surface layer]

[0537] The method for producing the substrate with a surface layer of the present invention is a method of forming a surface layer on a substrate by a dry coating method or a wet coating method using the above-mentioned composition.

[0538] The substrate with a surface layer of the present invention can be produced, for example, by the following method.

[0539] A method of obtaining a substrate with a surface layer having a surface layer formed on the surface of the substrate by treating the surface of the substrate by a dry coating method using the above composition (hereinafter also referred to as "dry coating composition") which does not contain a liquid medium.

[0540] A method of applying the above composition containing a liquid medium (hereinafter also referred to as "wet coating composition") on the surface of a substrate by a wet coating method and drying the composition to obtain a substrate with a surface layer having a surface layer formed on the surface of the substrate.

[0541] As a specific example of the dry coating method, vacuum evaporation method, CVD method, sputtering method can be listed. Among them, from the viewpoint of suppressing the decomposition of specific fluorine-containing ether compounds and the viewpoint of simplicity of the device, vacuum evaporation method is preferred. During vacuum evaporation, a granular material loaded with a dry coating composition in a metal porous body such as iron or steel or a granular material obtained by impregnating a wet coating composition and drying it can be used.

[0542] Specific examples of the wet coating method include spin coating, wipe coating, spray coating, blade coating, dip coating, die coating, inkjet, flow coating, roll coating, casting, Langmuir-Blodget method, and gravure coating.

[0543] The drying temperature after wet coating of the composition is preferably 20 to 200°C, particularly preferably 80 to 160°C.

[0544] Example

[0545] Hereinafter, the present invention will be described in detail with reference to examples. Examples 1-1 to 1-12 and 2-1 to 2-12 are embodiments, and Examples 1-13 and 2-13 are comparative examples. However, the present invention is not limited to these embodiments. It should be noted that the compounding amount of each component in the table described below represents a mass basis.

[0546] [Synthesis of Compound A1-1]

[0547] <Synthesis of Compound X1>

[0548] 2.0 g of dimethyl malonate, 10.6 g of 11-bromo-1-undecene (CH2=CH(CH2)9-Br), 8.4 g of potassium carbonate, and 50.0 g of dimethylformamide (DMF) were placed in a reaction container and stirred at 85° C. under a nitrogen atmosphere. After the reaction was completed, hydrochloric acid was added, and the organic phase was recovered and concentrated using an evaporator to obtain 6.1 g of compound X1.

[0549] Compound X1

[0550]

[0551] (In the formula, Me represents a methyl group.)

[0552] <Synthesis of Compound X2>

[0553] 6.1 g of compound X1, 24.4 g of dimethyl sulfoxide (DMSO), 2.4 g of lithium chloride, and 3.27 g of water were placed in a reaction container and stirred at 180° C. under a nitrogen atmosphere. After the reaction was completed, hydrochloric acid was added, and the organic phase was recovered, concentrated by an evaporator, and subjected to silica gel column chromatography to obtain 4.0 g of compound X2.

[0554] Compound X2

[0555]

[0556] <Synthesis of Compound X3>

[0557] 2.0 g of compound X2, 20.0 g of dehydrated tetrahydrofuran (THF), 6.6 mL of 2.0 M lithium diisopropylamide (THF solution), and 3.1 g of 11-bromo-1-undecene (CH2=CH(CH2)9-Br) were placed in a reaction container and stirred at about -70°C under a nitrogen atmosphere. After the reaction was completed, hydrochloric acid was added, and the organic phase was recovered, concentrated by an evaporator, and subjected to silica gel column chromatography to obtain 2.1 g of compound X3.

[0558] Compound X3

[0559]

[0560] <Synthesis of Compound X4>

[0561] 0.89 g of lithium aluminum hydride and 25 g of dehydrated THF were placed in a reaction container, and stirred at 0° C. under a nitrogen atmosphere. Next, 2.5 g of compound X3 was placed, and stirred at 0° C. under a nitrogen atmosphere. After the reaction was completed, water and 1 M sodium hydroxide were added, and the organic phase was recovered, concentrated with an evaporator, and subjected to silica gel column chromatography to obtain 2.0 g of compound X4.

[0562] Compound X4

[0563]

[0564] <Synthesis of Compound X5>

[0565] Using the above compound X4, the following compound X5 was obtained by referring to the methods of Examples 1 to 2 of International Publication No. 2021 / 054413.

[0566] Compound X5

[0567]

[0568] <Synthesis of Compound X7>

[0569] 1.03 g of the following compound B1-1 was suspended in 5 mL of dehydrated THF, 0.0025 g of copper chloride was added and stirred at room temperature (25°C). To the mixed solution, 1.15 g of the above-mentioned compound X5 adjusted to 17% by mass was slowly added dropwise, and then stirred at 55°C. After the mixed solution was cooled to room temperature (25°C), water was added, and after extraction with 5 mL of AE-3000 (manufactured by AGC, ASAHIKLIN (registered trademark) AE-3000), sodium sulfate was added. After filtration, the solvent was distilled off. Rapid column chromatography using silica gel was performed to obtain a mixture containing compound Y6. It was confirmed by NMR measurement that compound X7 was obtained with a selectivity of 79%. In the formula, the average value of the number of repeating units n is 13.

[0570] Compound X7

[0571]

[0572] <Synthesis of Compound A1-1>

[0573] 2.0 g of compound X7, 2.0 g of AC-6000, 0.12 g of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3%), 30.28 g of HSi(OCH3) and 0.02 g of aniline were placed in a nitrogen-purged reaction container and stirred at 40°C. After the reaction was completed, the solvent was removed by distillation under reduced pressure and filtered with a membrane filter with a pore size of 0.2 μm to obtain 2.1 g of compound A1-1. In the formula, the average value of the number of repeating units n is 13.

[0574] Compound A1-1

[0575]

[0576] (In the formula, Me represents a methyl group.)

[0577] [Synthesis of Compound B1-1]

[0578] According to the method described in Example 11 of International Publication No. 2013 / 121984, compound B1-1 was obtained.

[0579] CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2CH2I…(B1-1)

[0580] Wherein, the average value of the number of repeating units n is 13.

[0581] [Synthesis of Compound B1-2]

[0582] 3.0 g of the above compound B1-1, 22 mg of azobisisobutyronitrile, 6.0 g of 1,3-bis(trifluoromethyl)benzene and 574 mg of tributyltin hydride were placed in a flask and stirred at 70° C. for 2 hours. After cooling to room temperature (25° C.), the obtained reaction solution was purified by silica gel column chromatography to obtain 2.3 g of compound B1-2.

[0583] NMR spectrum of compound B1-2;

[0584] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 2.30~2.13 (m, 2H), 1.27 (t, J=7.1Hz, 3H).

[0585] 19F-NMR (376MHz, Chloroform-d) δ (ppm): -55.25, -82.83, -88.06, -90.16 (d, J=8.1Hz), -116.52, -125.26, -126.59.

[0586] CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2CH3…(B1-2)

[0587] Wherein, the average value of the number of repeating units n is 13.

[0588] [Synthesis of Compound B2-1]

[0589] In an argon atmosphere, 3.0 g of the above-mentioned compound B1-1, 104 mg of metallic copper, and 3.0 mL of DMSO were placed in a flask, and the mixture was stirred at 150° C. for 16 hours.

[0590] After cooling to room temperature (25° C.), the obtained reaction solution was purified by silica gel column chromatography to obtain 2.1 g of compound B2-1. wherein the average value of the number of repeating units n is 13.

[0591] NMR spectrum of compound B2-1;

[0592] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 2.31~2.14 (m, 4H), 1.91~1.78 (m, 4H).

[0593] 19 F-NMR (376MHz, Chloroform-d) δ (ppm): -55.25, -82.83, -88.06, -90.16 (d, J=8.1Hz), -114.33, -125.26, -126.59.

[0594] Compound B2-1

[0595]

[0596] [Synthesis of Compound C1-1]

[0597] <Synthesis of Compound Y1>

[0598] Add 60.0 g of diethyl diallylmalonate, 23.7 g (559 mmol) of lithium chloride, 6.45 g (360 mmol) of water, and 263 g of DMSO, and stir at 160°C. After cooling to room temperature (25°C), add water and extract with ethyl acetate. Add hexane to the organic layer, wash with saturated brine, and dry with sodium sulfate. After filtering, distill off the solvent to obtain 39.5 g of the following compound Y1. In the formula, Et represents ethyl.

[0599] Compound Y1

[0600]

[0601] NMR spectrum of compound Y1;

[0602] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): (ddt, J=17.1, 10.1, 7.0Hz, 2H), 5.06~4.94 (m, 4H), 4.09 (q, J=7.1Hz, 2H), 2. 47 (ddd, J=14.0, 8.0, 6.1Hz, 1H), 2.33 (dt, J=14.9, 7.5Hz, 2H), 2.22 (dt, J=14.1, 6.5Hz, 2H), 1.21 (t, J=7.1Hz, 3H).

[0603] <Synthesis of Compound Y2>

[0604] After adding THF 260mL and diisopropylamine 29.8mL, the solution was cooled to -78°C. Add 96.6mL of n-butyllithium hexane solution (2.76M) and heat to 0°C. After stirring, cool to -78°C and prepare a THF solution of lithium diisopropylamide (LDA). Add 39.5g of the above-mentioned compound Y1 to the THF solution, stir, and then add 24.1mL of allyl bromide. Heat to 0°C, add 100mL of 1M hydrochloric acid, and distill under reduced pressure to remove THF. After extraction with dichloromethane, sodium sulfate is added. After filtration, the solvent is distilled off, and rapid column chromatography using silica gel is performed to obtain 45.0g of compound Y2. In the formula, Et represents ethyl.

[0605] Compound Y2

[0606]

[0607] NMR spectrum of compound Y2;

[0608] 1H-NMR (400MHz, Chloroform-d) δ (ppm): 5.74~5.62 (m, 3H), 5.04 (dd, J=13.6, 1.9Hz, 6H), 4.10 (q, J=7.1Hz, 2H), 2.29 (d, J=7.4Hz, 6H), 1.22 (t, J=7.1Hz, 3H).

[0609] <Synthesis of Compound Y3>

[0610] The above 45.0 g of compound Y2 was dissolved in 620 mL of THF and cooled to 0°C. 104 mL of lithium aluminum hydride THF solution was added and stirred. Water and 15% sodium hydroxide aqueous solution were added, stirred at room temperature (25°C), and then diluted with dichloromethane. After filtering, the solvent was distilled off and flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound Y3.

[0611] Compound Y3

[0612]

[0613] NMR spectrum of compound Y3;

[0614] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.90~5.76 (m, 3H), 5.10~5.02 (m, 6H), 3.38 (s, 2H), 2.03 (dt, J=7.5, 1.2Hz, 6H), 1.45 (s, 1H).

[0615] <Synthesis of Compound Y4>

[0616] 380 mL of acetonitrile, 31.3 g of the above compound Y3, 64.3 g of triphenylphosphine, and 33.9 g of carbon tetrachloride were added, and the mixture was stirred at 90° C. After concentration, ethyl acetate / hexane was added, and the mixture was stirred. After filtration, the filtrate was concentrated and distilled to obtain 28.2 g of the following compound Y4.

[0617] Compound Y4

[0618]

[0619] NMR spectrum of compound Y4;

[0620] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.83~5.67 (m, 3H), 5.16~5.01 (m, 6H), 3.32 (s, 2H), 2.05 (dt, J=7.5, 1.1Hz, 6H).

[0621] <Synthesis of Compound Y5>

[0622] To 2.36 g of magnesium were added 35 mL of THF and 0.180 g of iodine, and the mixture was stirred at room temperature (25° C.) Then, 14.0 g of the above-mentioned compound Y4 and 35 mL of THF were added, and the mixture was heated under reflux to obtain a solution (0.80 M) of the following compound Y5.

[0623] Compound Y5

[0624]

[0625] NMR spectrum of compound Y5;

[0626] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.88 (m, 3H), 5.11 (m, 6h), 1.85 (m, 6h), 1.22 (s, 2h).

[0627] <Synthesis of Compound Y6>

[0628] 1.03 g of the above-mentioned compound B1-1 was suspended in 5 mL of dehydrated THF, 0.0025 g of copper chloride was added, and the mixture was stirred at room temperature (25°C). To the mixed solution, 0.31 g of the above-mentioned compound Y5 adjusted to 17% by mass was slowly added dropwise, and the mixture was stirred at 55°C. After the mixed solution was cooled to room temperature (25°C), water was added, extracted with 5 mL of AE-3000, and sodium sulfate was added. After filtering, the solvent was distilled off. Rapid column chromatography using silica gel was performed to obtain a mixture containing compound Y6. By NMR measurement, it was confirmed that compound Y6 was obtained with a selectivity of 84%. In the formula, the average value of the number of repeating units n is 13.

[0629] Compound Y6

[0630]

[0631] NMR spectrum of compound Y6;

[0632] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.80 (ddt, J=20.3, 9.3, 7.4Hz, 3H), 5.01 (dd, J=13.5 , 1.7Hz, 6H), 2.13~2.01(m, 2H), 1.97(d, J=7.5Hz, 6H), 1.67~1.55(m, 2H), 1.27~1.18(m, 2H).

[0633] 19F-NMR (376MHz, Chloroform-d) δ (ppm): -55.25, -82.83, -88.06, -90.16 (d, J=8.1Hz), -114.18, -125.26, -126.59.

[0634] <Synthesis of Compound C1-1>

[0635] 0.89 g of AC-2000, 0.139 g of compound Y6, 5.5 mg of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%), 0.8 mg of aniline, and 22.7 mg (0.185 mmol) of trimethoxysilane were added, stirred at 40° C., and the solvent was removed by reduced pressure distillation to obtain 0.140 g of compound C1-1. In the formula, the average value of the number of repeating units n is 13.

[0636] Compound C1-1

[0637]

[0638] (In the formula, Me represents a methyl group.)

[0639] NMR spectrum of compound C1-1;

[0640] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 3.60 (s, 27H), 2.23-1.95 (m, 2H), 1.63-1.28 (m, 14H), 0.67 (t, J=7.6Hz, 6H).

[0641] 19 F-NMR (376MHz, Chloroform-d) δ (ppm): -55.33, -82.95, -88.17, -90.13--90.40(m), -114.07--114.32(m), -125.38, -126.04.

[0642] [Example 1-1]

[0643] 99 parts by mass of the compound A1-1 as the first component and 1 part by mass of the compound B1-1 as the second component were mixed to obtain a composition (1-1).

[0644] The composition (1-1) (0.14 g) was filled into a molybdenum boat in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC KIKO, Inc.) as a deposition source, and the vacuum deposition apparatus was evacuated to 1×10 -3Pa or less. The boat equipped with the composition (1-1) is heated at a rate of less than 10°C / min. When the evaporation rate obtained by a quartz oscillation film thickness meter exceeds 1nm / sec, the shutter is opened to start film formation on the surface of the substrate (chemically strengthened glass). When the film thickness reaches about 50nm, the shutter is closed to end film formation on the surface of the substrate. The substrate deposited with the composition (1-1) is heat-treated at 200°C for 30 minutes and cleaned with dichloropentafluoropropane (manufactured by AGC, AK-225) to obtain a substrate with a surface layer having a surface layer on the surface of the substrate.

[0645] [Example 1-2 ~ Example 1-13]

[0646] Except having changed the kind and content of the 1st component and the 2nd component as described in Table 1 and Table 2, it carried out similarly to Example 1-1, and obtained the base material with the surface layer in each Example.

[0647] [Evaluation test]

[0648] The following evaluation tests were performed using the substrates with surface layers of Examples 1-1 to 1-13 and 2-1 to 2-13.

[0649] <Initial water contact angle>

[0650] The contact angle of about 2 μL of distilled water placed on the surface of the surface layer was measured at 20°C using a contact angle measuring device (DM-701 manufactured by Kyowa Interface Science Co., Ltd.). The measurement was performed at 3 different locations on the surface of the surface layer, and the average value was calculated as the initial water contact angle. The contact angle was calculated using the 2θ method. Based on the value of the initial water contact angle obtained, water repellency was evaluated according to the following evaluation criteria.

[0651] A: The contact angle is more than 115 degrees

[0652] B: The contact angle is 105 degrees or more and less than 115 degrees

[0653] C: Contact angle less than 105 degrees

[0654] <Abrasion resistance>

[0655] For the surface layer, a reciprocating traverse tester (manufactured by KNT) was used in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), and steel wool Bonstar (hand: #0000) was reciprocated at a pressure of 98.07 kPa and a speed of 320 cm / min. After 10,000 reciprocating steel wool abrasions, the contact angle of water on the surface layer was measured, and the wear resistance was evaluated according to the following evaluation criteria. The smaller the change in the contact angle of water before and after the abrasion test, the smaller the reduction in performance caused by abrasion, and the better the wear resistance. If the evaluation result is B or above, it can be said that the wear resistance is excellent.

[0656] A: The change in water contact angle is less than 2 degrees

[0657] B: The change in water contact angle is more than 2 degrees and less than 4 degrees

[0658] C: The change in water contact angle is 4 degrees or more and less than 6 degrees

[0659] D: The change in water contact angle is more than 6 degrees

[0660] <Evaluation Results>

[0661] The results of the above evaluation tests are shown in Tables 1 and 2.

[0662] The column "Second component / First component" shows the mass ratio of the content of the second component to the content of the first component.

[0663] [Table 1]

[0664]

[0665] [Table 2]

[0666]

[0667] As shown in Tables 1 and 2, it was confirmed that by using a composition comprising a first component and a second component, a surface layer having an excellent initial water contact angle and excellent wear resistance can be formed, wherein the first component is composed of at least one selected from the group consisting of compounds (A1), compounds (A2) and compounds (A3), and the second component is composed of at least one selected from the group consisting of compounds (B1) and compounds (B2).

[0668] It was confirmed that when the mass ratio of the content of the second component to the content of the first component was 0.01 to 0.50, the wear resistance was more excellent (Examples 1-1 to 1-12, and Examples 2-1 to 2-12).

[0669] It was confirmed that when R 11At least one of the carbon chains has 4 or more carbon atoms connected to each other. 11 Connected,

[0670] In formula (A2), at least one of the following is present: 21 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 21 connected; and R 31 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 31 Connected,

[0671] In formula (A3), R 41 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 41 When connected, the wear resistance is further improved (Example 1-4, Example 2-4).

[0672] It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2022-164546 filed on October 13, 2022 are incorporated herein by reference and introduced as the disclosed contents of the specification of the present invention.

Claims

1. A composition comprising a first component and a second component, wherein the first component is composed of at least one fluorine-containing ether compound selected from the group consisting of a compound represented by formula (A1), a compound represented by formula (A2) and a compound represented by formula (A3), The second component is composed of at least one fluorine-containing ether compound selected from the group consisting of compounds represented by formula (B1) and compounds represented by formula (B2), [R f1 -(OR f11 ) y1 -O-R 1 ] j -L 1 -(R 11 -T 11 ) x1 …(A1) (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -O-R 2 -L 2 -(R 21 -T 21 ) x2 …(A2) Q 1 [-(OR f13 ) y3 -O-R 4 -L 4 -(R 41 -T 41 ) x4 ] r1 …(A3) R f14 -(OR f15 ) y4 -O-R 5 -R b1 …(B1) R f19 -(OR f18 ) y6 -O-R 7 -L b1 -R 6 -O-(R f16 O) y5 -R f17 …(B2) In formula (A1), R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and there are multiple R f1 When there are multiple R f1 are optionally the same as or different from each other, R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f11 When there are multiple R f11 are optionally the same as or different from each other, R 1 is an alkylene group or a fluoroalkylene group, and there are multiple R 1 When there are multiple R 1 are optionally the same as or different from each other, L 1 is a single bond, or is a j+x1-valent group optionally having N, O, S, Si and optionally having a branch point, bonded to R 1 and R 11 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O), R 11 is an alkylene group which may have an ethereal oxygen atom between carbon atoms, wherein Bonded to L 1 The atom of R is optionally an etheric oxygen atom. 11 When there are multiple R 11 are optionally the same as or different from each other, T 11 -SiR a11 z11 R a12 3-z11 , there are multiple T 11 When there are multiple T 11 are optionally the same as or different from each other, R a11 is a hydroxyl group or a hydrolyzable group, and there are multiple R a11 When there are multiple R a11 are optionally the same as or different from each other, R a12 It is a non-hydrolyzable group, and there are multiple R a12 When there are multiple R a12 are optionally the same as or different from each other, j is an integer greater than or equal to 1. When j is 1, y1 is an integer greater than or equal to 2, or R 1 is a fluoroalkylene group, z11 is an integer from 1 to 3, x1 is an integer greater than 1, y1 is an integer greater than or equal to 1. When a plurality of y1 exist, the plurality of y1 exist may be the same as or different from each other. In formula (A2), R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f12 When there are multiple R f12 are optionally the same as or different from each other, R 2 and R 3 are each independently an alkylene group or a fluoroalkylene group, L 2 is a single bond, or is a 1+x2 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 2 and R 21 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group, L 3 is a single bond, or is a 1+x3 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 3 and R 31 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group, R 21 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 2 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 21 When there are multiple R 21 are optionally the same as or different from each other, R 31 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 3 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 31 When there are multiple R 31 are optionally the same as or different from each other, T 21 and T 31 Each independently is -SiR a21 z21 R a22 3-z21 , there are multiple T 21 When there are multiple T 21 Optional to be the same or different from each other, there are multiple T 31 When there are multiple T 31 are optionally the same as or different from each other, R a21 is a hydroxyl group or a hydrolyzable group, and there are multiple R a21 When there are multiple R a21 are optionally the same as or different from each other, R a22 It is a non-hydrolyzable group, and there are multiple R a22 When there are multiple R a22 are optionally the same as or different from each other, z21 is an integer from 1 to 3, x2 and x3 are each independently an integer greater than 1, y2 is an integer greater than 1. When y2 is 1, R 2 is a fluoroalkylene group, In formula (A3), Q 1 is a r1-valent group having a branch point, R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and the presence of multiple R f13 are optionally the same as or different from each other, R 4 Each independently represents an alkylene group or a fluoroalkylene group, and the presence of multiple R 4 are optionally the same or different from each other, L 4 is a single bond, or is a 1+x4 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 4 and R 41 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group. 4 are optionally the same as or different from each other, R 41 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 4 The adjacent atoms may be etheric oxygen atoms, and the presence of multiple R 41 are optionally the same as or different from each other, T 41 -SiR a41 z41 R a42 3-z41 , there are multiple T 41 are optionally the same as or different from each other, R a41 is a hydroxyl group or a hydrolyzable group, and the presence of multiple R a41 are optionally the same as or different from each other, R a42 It is a non-hydrolyzable group, and there are multiple R a42 When there are multiple R a42 are optionally the same as or different from each other, z41 is an integer from 1 to 3, x4 is an integer greater than or equal to 1. When a plurality of x4 exist, the plurality of x4 exist may be the same as or different from each other. y3 is an integer greater than or equal to 1. When a plurality of y3 exist, the plurality of y3 exist may be the same as or different from each other. r1 is 3 or 4, In formula (B1), R f14 is a fluoroalkyl group having 1 to 20 carbon atoms, R f15 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f15 When there are multiple R f15 are optionally the same as or different from each other, R 5 is an alkylene group which may have a substituent, R b1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom, y4 is an integer greater than 1, In formula (B2), R f17 and R f19 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, R f16 and R f18 Each independently represents a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f16 When there are multiple R f16 Optionally the same or different, there are multiple R f18 When there are multiple R f18 are optionally the same as or different from each other, R 6 and R 7 are each independently an alkylene group which may have a substituent, L b1 is a single bond or a divalent linking group, wherein the divalent linking group does not include (OR f18 ) y7 and (R f16 O) y8 , y7 and y8 are each independently an integer greater than 1, y5 and y6 are each independently an integer of 1 or more.

2. The composition according to claim 1, wherein In the formula (A1), R 11 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 11 Connected, In the formula (A2), at least one of the following is selected: 21 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 21 connected; and R 31 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 31 Connected, In the formula (A3), R 41 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 41 connect.

3. The composition according to claim 1, wherein The mass ratio of the content of the second component to the content of the first component is 0.01 to 0.

50.

4. The composition according to any one of claims 1 to 3, wherein In formula (B1), R 5 is a fluoroalkylene group, In formula (B2), R 6 and R 7 are all fluoroalkylene groups, and L b1 For a single key.

5. The composition according to claim 4, wherein In formula (B1), R 5 The carbon number of the fluoroalkylene group is 1 to 20, In formula (B2), R 6 The carbon number of the fluoroalkylene group shown is the same as R 7 The total number of carbon atoms in the fluoroalkylene group is 2-40. 6 . A substrate with a surface layer, comprising: a substrate; and a surface layer formed on the substrate from the composition according to claim 1 .

7. A method for producing a substrate with a surface layer, wherein: A surface layer is formed on a substrate by dry coating or wet coating using the composition according to any one of claims 1 to 3.

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