Extraction method of fluorine-containing ether compound

Abstract

Provided is a method for extracting a fluorine-containing ether compound with which it is possible to efficiently extract a desired fluorine-containing ether compound. This method for extracting a fluorine-containing ether compound uses an organic solvent that does not contain fluorine atoms to extract 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) from a composition containing the first component and a second component. 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 invention relates to a method for extracting fluorine-containing ether compounds. Background Art

[0002] Fluorine-containing ether compounds having a perfluoropolyether chain are used in various applications because they exhibit high lubricity, etc. When such fluorine-containing ether compounds are contained in a composition mixed with other components, methods for extracting the fluorine-containing ether compounds from the composition have been studied.

[0003] For example, Patent Document 1 discloses a method for extracting perfluoropolyether oil (fluorine-containing ether compound) contained in grease using liquid or supercritical carbon dioxide.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application No. 2017-503651 Summary of the invention

[0007] Problem that the invention aims to solve

[0008] As described in Patent Document 1, a technique for extracting a fluorine-containing ether compound using liquid or supercritical carbon dioxide is known, but there is still a need for a method for efficiently extracting a desired fluorine-containing ether compound using other methods than these.

[0009] An object of the present invention is to provide a method for extracting a fluorinated ether compound which can efficiently extract a desired fluorinated ether compound.

[0010] Solutions for solving problems

[0011] The present inventors have conducted intensive studies on the above-mentioned problems and have found that when a desired fluorinated ether compound is extracted from a plurality of fluorinated ether compounds, the desired fluorinated ether compound can be efficiently extracted by using an organic solvent containing no fluorine atoms, thereby completing the present invention.

[0012] That is, the inventors have discovered that the above-mentioned problems can be solved by the following technical features.

[0013] [1] A method for extracting a fluorine-containing ether compound, comprising extracting the first component from a composition comprising a first component and a second component using an organic solvent containing no fluorine atoms, 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,

[0021] In formula (A1),

[0022] R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and there are multiple Rf1 When there are multiple R f1 are optionally the same or different from each other,

[0023] 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,

[0024] 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,

[0025] 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 atoms, carbon atoms constituting branch points, carbon atoms having a hydroxyl group or an oxo group (=O),

[0026] 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,

[0027] T 11 -CH=CH2 or -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,

[0028] T 11 When -CH=CH2, R 11 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 11 Connected,

[0029] T 11 -SiR a11 z11 R a12 3-z11 When R 11 At least one of them has a carbon chain with more than 4 carbon atoms connected,

[0030] R a11 is a hydroxyl group or a hydrolyzable group, and there are multiple Ra11 When there are multiple R a11 are optionally the same or different from each other,

[0031] 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,

[0032] 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,

[0033] z11 is an integer from 1 to 3,

[0034] x1 is an integer greater than 1,

[0035] 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.

[0036] In formula (A2),

[0037] 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,

[0038] R 2 and R 3 are each independently an alkylene group or a fluoroalkylene group,

[0039] 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 atoms, carbon atoms constituting branch points, carbon atoms having a hydroxyl group or an oxo group (=O),

[0040] 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 atoms, carbon atoms constituting branch points, carbon atoms having a hydroxyl group or an oxo group (=O),

[0041] 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 21are optionally the same or different from each other,

[0042] 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,

[0043] T 21 and T 31 Each independently is -CH=CH2 or -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,

[0044] T 21 When -CH=CH2, R 21 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 21 Connected,

[0045] T 21 -SiR a21 z21 R a22 3-z21 When R 21 At least one of them has a carbon chain with more than 4 carbon atoms connected,

[0046] T 31 When -CH=CH2, R 31 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 31 Connected,

[0047] T 31 -SiR a21 z21 R a22 3-z21 When R 31 At least one of them has a carbon chain with more than 4 carbon atoms connected,

[0048] 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 or different from each other,

[0049] Ra22 It is a non-hydrolyzable group, and there are multiple R a22 When there are multiple R a22 are optionally the same or different from each other,

[0050] z21 is an integer from 1 to 3,

[0051] x2 and x3 are each independently an integer greater than 1,

[0052] y2 is an integer greater than 1. When y2 is 1, R 2 is a fluoroalkylene group,

[0053] In formula (A3),

[0054] Q 1 is a r1-valent group having a branch point,

[0055] R f13 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,

[0056] 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,

[0057] 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 atoms, carbon atoms constituting branch points, carbon atoms having hydroxyl groups or oxo groups (=O), and the presence of multiple L 4 are optionally the same or different from each other,

[0058] 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,

[0059] T 41 -CH=CH2 or -SiR a41 z41 R a42 3-z41 , there are multiple T 41 are optionally the same or different from each other,

[0060] T 41 When -CH=CH2, R 41 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T41 Connected,

[0061] T 41 -SiR a41 z41 R a42 3-z41 When R 41 At least one of them has a carbon chain with more than 4 carbon atoms connected,

[0062] 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,

[0063] 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,

[0064] z41 is an integer from 1 to 3,

[0065] 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.

[0066] 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.

[0067] In formula (B1),

[0068] R f14 is a fluoroalkyl group having 1 to 20 carbon atoms,

[0069] 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,

[0070] R 5 is an alkylene group which may have a substituent,

[0071] R b1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom,

[0072] y4 is an integer greater than 1,

[0073] In formula (B2),

[0074] R f17 and R f19 are each independently a fluoroalkyl group having 1 to 20 carbon atoms,

[0075] R f16 and R f18Each 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,

[0076] R 6 and R 7 are each independently an alkylene group which may have a substituent,

[0077] 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,

[0078] y5 and y6 are each independently an integer of 1 or more.

[0079] [2] The method for extracting a fluorinated ether compound according to [1], wherein the organic solvent is a non-halogen solvent.

[0080] [3] The method for extracting a fluorinated ether compound according to [2], wherein the relative dielectric constant of the non-halogen solvent is 30 or less.

[0081] [4] The method for extracting a fluorinated ether compound according to any one of [1] to [3], wherein the organic solvent is a hydrocarbon solvent.

[0082] [5] The method for extracting a fluorinated ether compound according to any one of [1] to [4], wherein in the formula (A1), T 11 When -CH=CH2, R 11 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 11 In the above formula (A1), T 11 -SiR a11 z11 R a12 3-z11 When R 11 At least one of them has a carbon chain with more than 6 carbon atoms connected,

[0083] In the above formula (A2), T 21 When -CH=CH2, R 21 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 21 In the above formula (A2), T 21-SiR a21 z21 R a22 3-z21 When R 21 At least one of them has a carbon chain with more than 6 carbon atoms connected,

[0084] In the above formula (A2), T 31 When -CH=CH2, R 31 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 31 In the above formula (A2), T 31 -SiR a21 z21 R a22 3-z21 When R 31 At least one of them has a carbon chain with more than 6 carbon atoms connected,

[0085] In the above formula (A3), T 41 When -CH=CH2, R 41 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 41 In the above formula (A3), T 41 -SiR a41 z41 R a42 3-z41 When R 41 At least one of the carbon atoms has a carbon chain having more than 6 carbon atoms connected.

[0086] [6] The method for extracting a fluorinated ether compound according to any one of [1] to [5], wherein (OR f11 ) y1 The molecular weight of the group shown is 2000 to 20000,

[0087] (OR f12 ) y2 The molecular weight of the group shown is 2000 to 20000,

[0088] (OR f13 ) y3 The molecular weight of the groups shown is 2,000 to 20,000.

[0089] [7] The method for extracting a fluorinated ether compound according to any one of [1] to [6], wherein [R f1 -(OR f11 ) y1 -OR 1 ] j The molecular weight of the groups shown is relative to L 1-(R 11 -T 11 ) x1 The ratio of the molecular weight of the group shown is 13% or more,

[0090] 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 sum of the molecular weights of the groups shown is 13% or more,

[0091] r1 (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 13% or more.

[0092] [8] The method for extracting a fluorinated ether compound according to any one of [1] to [7], wherein in the formula (B1), R 5 is a fluoroalkylene group,

[0093] In formula (B2), R 6 and R 7 are all fluoroalkylene groups, and L b1 For a single key.

[0094] [9] The method for extracting a fluorinated ether compound according to [8], wherein in formula (B1), R 5 The carbon number of the fluoroalkylene group shown in

[0095] In formula (B2), R 6 The above fluoroalkylene group and R 7 The total number of carbon atoms in the fluoroalkylene group is 2 to 40.

[0096] Effects of the Invention

[0097] According to the present invention, a method for extracting a fluorine-containing ether compound capable of efficiently extracting a desired fluorine-containing ether compound can be provided. DETAILED DESCRIPTION

[0098] In this specification, the compound represented by formula (A1) may be referred to as compound (A1). The same applies to compounds represented by other formulae.

[0099] Fluoroalkyl refers to a general term for perfluoroalkyl and partial fluoroalkyl. 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 having one or more hydrogen atoms replaced by fluorine atoms.

[0100] That is, the fluoroalkyl group is an alkyl group having one or more fluorine atoms.

[0101] 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.

[0102] 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.

[0103] "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, etc. as divalent aromatic hydrocarbon groups), and combinations thereof.

[0104] The “surface layer” refers to a layer formed on the surface of a substrate.

[0105] The "molecular weight" of a fluoropolyether chain is 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.

[0106] The molecular weight of the other parts of the fluorinated ether compound other than the fluoropolyether chain can be determined by 1 H-NMR and 19 The structural analysis of fluorinated ether compounds was performed by F-NMR.

[0107] The numerical range represented by "~" refers to a range that includes the numerical values ​​recorded before and after "~" as the lower limit and the upper limit. In the numerical range recorded in stages in this specification, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in this specification, the upper limit or lower limit recorded in a certain numerical range can be replaced by the value shown in the embodiment.

[0108] In this specification, each component may be used alone or in combination of two or more. Here, for each component, when two or more substances are used in combination, unless otherwise specified, the content of the component refers to the total content of the substances used in combination.

[0109] In the present specification, a combination of two or more preferred aspects is a more preferred aspect.

[0110] [Extraction method]

[0111] The method for extracting a fluorine-containing ether compound of the present invention (hereinafter also referred to as "the present extraction method") uses an organic solvent not containing fluorine atoms (hereinafter also referred to as "non-fluorine-based organic solvent") to extract the above-mentioned first component from a composition containing a first component and a second component (hereinafter also referred to as "the present composition"), 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 later, a compound represented by formula (A2) described later, and a compound represented by formula (A3) described later, and 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 later and a compound represented by formula (B2) described later.

[0112] According to the present extraction method, the first component can be efficiently extracted from the present composition. The detailed reason is not clear, but it is presumed that by making R 11 -T 11 The number of carbon atoms in the part, R 21 -T 21 Part and T 31 -R 31 The number of carbon atoms in the moiety, and R 41 -T 41 The number of carbon atoms in the moiety connected is set to a predetermined value, thereby improving the compatibility of the first component with the non-fluorine-based organic solvent.

[0113] [This composition]

[0114] The present composition comprises a first component and a second component, and may also comprise other components. Hereinafter, each component contained in the present composition will be described.

[0115] <First ingredient>

[0116] The first component is at least one fluorine-containing ether compound selected from the group consisting of compounds represented by the following formula (A1), compounds represented by the following formula (A2) and compounds represented by the following formula (A3), and is a compound to be extracted in the present extraction method.

[0117] [R f1 -(ORf11 ) y1 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 …(A1)

[0118] (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 …(A2)

[0119] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 …(A3)

[0120] In formula (A1),

[0121] 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,

[0122] 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,

[0123] 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,

[0124] 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),

[0125] 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,

[0126] T 11 -CH=CH2 or -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,

[0127] T 11 When -CH=CH2, R 11 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 11 Connected,

[0128] T 11 -SiR a11 z11 R a12 3-z11 When R 11 At least one of them has a carbon chain with more than 4 carbon atoms connected,

[0129] 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,

[0130] 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,

[0131] 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,

[0132] z11 is an integer from 1 to 3,

[0133] x1 is an integer greater than 1,

[0134] 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.

[0135] In formula (A2),

[0136] Rf12 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,

[0137] R 2 and R 3 are each independently an alkylene group or a fluoroalkylene group,

[0138] 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 (=O),

[0139] 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 (=O),

[0140] 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,

[0141] 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,

[0142] T 21 and T 31 Each independently is -CH=CH2 or -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,

[0143] T 21When -CH=CH2, R 21 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 21 Connected,

[0144] T 21 -SiR a21 z21 R a22 3-z21 When R 21 At least one of them has a carbon chain with more than 4 carbon atoms connected,

[0145] T 31 When -CH=CH2, R 31 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 31 Connected,

[0146] T 31 -SiR a21 z21 R a22 3-z21 When R 31 At least one of them has a carbon chain with more than 4 carbon atoms connected,

[0147] 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 or different from each other,

[0148] R a22 It is a non-hydrolyzable group, and there are multiple R a22 When there are multiple R a22 are optionally the same or different from each other,

[0149] z21 is an integer from 1 to 3,

[0150] x2 and x3 are each independently an integer greater than 1,

[0151] y2 is an integer greater than 1. When y2 is 1, R 2 It is a fluoroalkylene group.

[0152] In formula (A3),

[0153] Q 1 is a r1-valent group having a branch point,

[0154] R f13 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,

[0155] R 4Each 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,

[0156] 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 atoms, carbon atoms constituting branch points, carbon atoms having hydroxyl groups or oxo groups (=O), and the presence of multiple L 4 are optionally the same or different from each other,

[0157] 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 11 are optionally the same or different from each other,

[0158] T 41 -CH=CH2 or -SiR a41 z41 R a42 3-z41 , there are multiple T 41 are optionally the same or different from each other,

[0159] T 41 When -CH=CH2, R 41 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 41 Connected,

[0160] T 41 -SiR a41 z41 R a42 3-z41 When R 41 At least one of them has a carbon chain with more than 4 carbon atoms connected,

[0161] 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,

[0162] 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,

[0163] z41 is an integer from 1 to 3,

[0164] x4 is an integer greater than or equal to 1, and a plurality of x4s present may be the same or different from each other.

[0165] y3 is an integer greater than 1, and a plurality of y3s present may be the same or different from each other.

[0166] r1 is 3 or 4.

[0167] Since the first component has a fluoropolyether chain, the surface layer formed using the first component is excellent in water- and oil-repellency and fingerprint stain removability.

[0168] In addition, the first component having a -CH=CH2 group at the terminal is preferably used as a raw material of a compound having a reactive silyl group at the terminal, for example.

[0169] In addition, 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.

[0170] 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.

[0171] The first component has a fluoropolyether chain, and the fluoropolyether chain is a group having two or more oxyfluoroalkylene units.

[0172] These fluoropolyether chains optionally have hydrogen atoms. From the viewpoint of better friction durability of the surface layer and better fingerprint contaminant removal, 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 removal.

[0173] Mathematical formula (I): Ratio of fluorine atoms (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} × 100

[0174] From the viewpoint of taking into account both the fingerprint contaminant removal and lubricity of the surface layer, the molecular weight of each fluoropolyether chain (i.e., (OR f11 ) y1 The molecular weight of the group shown, (OR f12 ) y2 The molecular weight and (OR f13 ) y3The molecular weight of the group shown in ( ) is preferably 2000 to 20000, more preferably 2500 to 15000, and further 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 removal properties are further improved. On the other hand, if the molecular weight of the fluoropolyether chain is 20000 or less, the friction durability of the surface layer is more excellent.

[0175] (Compound (A1))

[0176] The compound (A1) has a structure represented by the following formula (A1).

[0177] [R f1 -(OR f11 ) y1 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 …(A1)

[0178] In addition, each symbol in formula (A1) is as described above.

[0179] R f1 The fluoroalkyl group has 1 to 20 carbon atoms. The fluoroalkyl group may be linear or branched and / or have a ring structure. From the viewpoint of friction durability, a linear fluoroalkyl group is preferred, and from the viewpoint of ease of synthesis, the fluoroalkyl group preferably has 1 to 6 carbon atoms.

[0180] 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. (OR f11 ) y1 represents a fluoropolyether chain, and y1 may be an integer greater than or equal to 1, and is preferably 1 to 200.

[0181] (OR f11 ) y1 It preferably has a structure represented by the following formula (G11).

[0182] -[(OG f1 ) m1 (OG f2 ) m2 (OG f3 ) m3 (OG f4 ) m4 (OG f5 ) m5 (OG f6 )m6 ]-…(G11)

[0183] in,

[0184] G f1 is a fluoroalkylene group having 1 carbon number,

[0185] G f2 is a fluoroalkylene group having 2 carbon atoms,

[0186] G f3 is a fluoroalkylene group having 3 carbon atoms,

[0187] G f4 is a fluoroalkylene group having 4 carbon atoms,

[0188] G f5 is a fluoroalkylene group having 5 carbon atoms,

[0189] G f6 is a fluoroalkylene group having 6 carbon atoms,

[0190] 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.

[0191] 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.

[0192] 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.

[0193] As G f1 Specific examples include -CF2- and -CHF-.

[0194] As G f2 Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, -CH2CHF- and the like.

[0195] As G f3 Specific 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.

[0196] 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.

[0197] As G f5Specific examples include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, and -cycloC5F8-.

[0198] As G f6 Specific examples include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, -cycloC6F 10 -wait.

[0199] 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.

[0200] 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).

[0201] (OG f1 ) m1 -(OG f2 ) m2 Formula (G2)

[0202] (OG f2 ) m2 -(OG f4 ) m4 Formula (G3)

[0203] (OG f3 ) m3 Formula (G4)

[0204] However, the symbols in formula (G2) to formula (G4) are the same as those in the above formula (G11).

[0205] In formula (G2) and formula (G3), (OG f1 ) and (OG f2 )、(OG f2 ) and (OG f4 ) are respectively arbitrary in bonding order. For example, in formula (G2), (OG f1 ) and (OG f2 ) can be configured alternately, (OG f1 ) and (OG f2 ) may be arranged in blocks or randomly.

[0206] 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.

[0207] 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.

[0208] In formula (G4), m3 is preferably 1-30, more preferably 1-20.

[0209] From the viewpoint of excellent water- and oil-repellency and fingerprint removability, the 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%.

[0210] In addition, from the viewpoint of friction durability, the 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.

[0211] 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 methyl or fluoromethyl group as a branch. 1 The carbon number of R is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, and particularly preferably 1 to 6. 1 When j is 1 and L 1In the case of a single bond, it is bonded to R 11 In this case, R 1 The bond in R 11 The carbon atom of the moiety is bonded to at least one fluorine atom or a fluoroalkyl group.

[0212] j represents [R f1 -(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.

[0213] 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.

[0214] 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.

[0215] Among them, T 11 When -CH=CH2, R 11 At least one of the carbon chains has two or more carbon atoms connected. From the perspective of more effective extraction of the first component, it is preferred that the carbon chain has four or more carbon atoms connected, more preferably seven or more carbon atoms connected, and even more preferably ten or more carbon atoms connected. In addition, from the perspective of ease of manufacture, the number of connected carbon atoms in the carbon chain is preferably 28 or less, more preferably 18 or less. It should be noted that T 11 When -CH=CH2, the above carbon chain and T 11 are connected.

[0216] On the other hand, T 11 -SiR a11 z11 R a12 3-z11 When R 11 At least one of the carbon chains has 4 or more carbon atoms connected, preferably has 6 or more carbon atoms connected, more preferably has 9 or more carbon atoms connected, and further preferably has 12 or more carbon atoms connected. In addition, from the aspect of ease of manufacture, the number of carbon atoms connected in the above carbon chain is preferably 30 or less, more preferably 20 or less.

[0217] Here, a carbon chain having more than X carbon atoms connected is represented by 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.

[0218] R 11 Specifically, it can be represented by the following formula (g2).

[0219] *-(O) a1 -(R g2 O) a2 -R g2 -**…(g2)

[0220] in,

[0221] R g2 is an alkylene group having 1 or more carbon atoms, and the presence of multiple R g2 are optionally the same or different from each other,

[0222] a1 is 0 or 1,

[0223] a2 is an integer greater than 0,

[0224] * is bonded to L 1 The connection key,

[0225] ** is bonded to T 11 connection key.

[0226] It should be noted that L 1 In the case of a single bond, R 11 With R 1 Direct bonding.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] From the perspective of having better water and oil repellency as a surface layer, better fingerprint removability, and better durability such as abrasion resistance, R 11 More preferably, it is a group represented by the following formula (g3).

[0231] *-(O) a1 -R g3 -**…(g3)

[0232] in,

[0233] R g3 is an alkylene group,

[0234] a1, * and ** are the same as those in formula (g2).

[0235] 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.

[0236] T 11 -CH=CH2 or -SiR a11 z11 R a12 3-z11 The groups shown.

[0237] in,

[0238] 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,

[0239] 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,

[0240] z11 is an integer from 1 to 3.

[0241] R a11 When it is a hydroxyl group, it forms a silanol (Si-OH) group together with the Si atom. In addition, the hydrolyzable group is a group that becomes a hydroxyl group (i.e., a silanol group) by a hydrolysis reaction. The silanol group further reacts between molecules to form a Si-O-Si bond. In addition, the silanol group undergoes a dehydration condensation reaction with the hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Compound (A1) has one or more T a11 , the friction durability after the surface layer is formed is excellent.

[0242] As R a11Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred. As the acyl group, an acyl group having 1 to 6 carbon atoms is preferred. As the acyloxy group, an acyloxy group having 1 to 6 carbon atoms is preferred.

[0243] From the viewpoint of facilitating the production of compound (A1), R a11 It is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. From the viewpoint of excellent storage stability of the compound (A1) and suppression of degassing during the reaction, R a11 The alkoxy group in is preferably an alkoxy group having 1 to 4 carbon atoms, and is particularly preferably an ethoxy group from the viewpoint of long-term storage stability, and is particularly preferably a methoxy group from the viewpoint of a short hydrolysis reaction time. In addition, the halogen atom is preferably a chlorine atom.

[0244] As R a12 Examples of the non-hydrolyzable group include a hydrogen atom and a monovalent hydrocarbon group.

[0245] Examples of the hydrocarbon group include alkyl, cycloalkyl, alkenyl, and allyl groups, and the hydrocarbon group may be substituted with fluorine. From the viewpoint of ease of manufacture, the hydrocarbon group is preferably an alkyl group. In addition, from the viewpoint of ease of manufacture, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and further preferably 1 to 2.

[0246] z11 may be an integer of 1 to 3, and is preferably 2 or 3, more preferably 3, from the viewpoint of adhesion to the substrate.

[0247] As T 11 -SiR a11 z11 R a12 3-z11 Specific examples include -Si(OCH3)3, -SiCH3(OCH3)2, -Si(OCH2CH3)3, -SiCl3, -Si(OCOCH3)3, -Si(NCO)3, -Si(OCH2CF3)3, etc. From the viewpoint of ease of operation during manufacture, -Si(OCH3)3 is preferred.

[0248] It should be noted that there are multiple T in one molecule. 11 When there are multiple T 11 Optional same or different.

[0249] x1 represents the (R 11 -T 11 ) may be an integer greater than 1, preferably 1 to 32, more preferably 1 to 18, and further preferably 2 to 12.

[0250] L1 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.

[0251] 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').

[0252] R f1 -(OR f11 ) y1 -OR 1 -R 11 -T 11 …(A1')

[0253] However, the symbols in formula (A1') are the same as those in formula (A1).

[0254] 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 a (j+x1)-valent organopolysiloxane residue. 1 ”).

[0255] 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.

[0256] 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 29It is a monovalent group, for example, a hydrogen atom, a hydroxyl group, a hydrocarbon group, an alkoxy group, etc. Examples of the hydrocarbon group include aliphatic hydrocarbon groups such as a linear alkyl group, a branched alkyl group, and a cycloalkyl group, an aromatic hydrocarbon group such as a phenyl group, or a group consisting of a combination thereof.

[0257] Si becomes the branch point P 1 When the branch point P 1 For example, *-Si(-**)3, (*-)2Si(-**)2, (*-)3Si-**, *-SiR 29 (-**)2, or (*-)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, an alkoxy group, etc. Examples of the hydrocarbon group include aliphatic hydrocarbon groups such as a linear alkyl group, a branched alkyl group, and a cycloalkyl group, an aromatic hydrocarbon group such as a phenyl group, or a group consisting of a combination thereof.

[0258] As the branch point P 1 The 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 compound (A1) and better friction durability, 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.

[0259]

[0260] As the branch point P 1 The organopolysiloxane residues include, for example, 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.

[0261]

[0262] 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 ”).

[0263] 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.

[0264] 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.

[0265]

[0266] 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)-.

[0267] Divalent L 1 In the bonded 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 B1 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.

[0268] 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.), more than one branch point 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}, etc.) 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.

[0269] As the above R 28The divalent organic group in the formula (a) includes, for example, a divalent aliphatic hydrocarbon group (alkylene group, cycloalkylene group, etc.), a divalent aromatic hydrocarbon group (phenylene group, etc.), and the like, and optionally has a bond B between carbon atoms of the hydrocarbon group. 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.

[0270] From the viewpoint of facilitating the production of compound (A1), L 1 , preferably a group represented by any one of the following formulae (L1) to (L7).

[0271]

[0272] (-A 1 -) d5 C(R e2 ) 4-d5―d6 (-Q 22 -) d6 …(L2)

[0273] (-A 2 -) d7 N(-Q 23 -) 3-d7 …(L3)

[0274] (-A 3 -) d8 Z 1 (-Q 24 -) d9 …(L4)

[0275] (-A 2 -) d10 Si(R e3 ) 4-d10-d11 (-Q 25 -) d11 …(L5)

[0276] -A 1 -Q 26 -…(L6)

[0277] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -) d12 …(L7)

[0278] Among them, in formula (L1) to formula (L7), A 1 , A 2 or A 3 The side and R of formula (A1) 1 Connected, Q22 , Q 23 , Q 24 , Q 25 or Q 26 Side and R 11 are connected.

[0279] 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)-、-CO(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 -,

[0280] A2 is a single bond or -B 3 -R 30 -,

[0281] 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 For A 2 ,

[0282] 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-,

[0283] Q 22 is a single bond, -B 3 -、-R 30 -B 3 -or-B 2 -R 30 -B 3 -,

[0284] Q23 is a single bond or -R 30 -B 3 -,

[0285] 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 ,

[0286] Q 25 is a single bond or -R 30 -B 3 -,

[0287] Q 26 is a single bond or -R 30 -B 3 -,

[0288] 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,

[0289] R e1 is a hydrogen atom or a hydrocarbon group (an aromatic hydrocarbon group such as an alkyl group or a phenyl group),

[0290] 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,

[0291] R e3 is a hydrocarbon group (an aromatic hydrocarbon group such as an alkyl group or a phenyl group),

[0292] R e6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group,

[0293] 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,

[0294] 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,

[0295] d1+d3 is an integer from 1 to 5,

[0296] d2+d4 is an integer from 1 to 5,

[0297] d5 is an integer of 1 to 3, d6 is an integer of 1 to 3, d5+d6 is an integer of 2 to 4,

[0298] d7 is 1 or 2,

[0299] d8 is an integer greater than 1,

[0300] d9 is an integer greater than 1,

[0301] d10 is an integer of 1 to 3, d11 is an integer of 1 to 3, d10+d11 is an integer of 2 to 4,

[0302] d12 is an integer from 1 to 3.

[0303] 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 , R e3 Same here.

[0304] In addition, d1+d3, d5, d7, d8, and d10 are j, and d2+d4, d6, 3-d7, d9, d11, and 1+d12 are x1.

[0305] From the viewpoint of easy production of the compound (A1) and the viewpoint of better friction durability, 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.

[0306] As Z 1 The ring structure in can include the above-mentioned ring structures, and the preferred embodiments are also the same.

[0307] 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.

[0308] From the viewpoint of easy preparation of compound 1, R e2The 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.

[0309] From the viewpoint of easy production of the compound (A1) and the viewpoint of better friction durability of the surface layer and better fingerprint contamination removability, d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0310] As the above L 1 In another embodiment, a group represented by any one of the following formulae (L11) to (L17) can be mentioned.

[0311]

[0312] (-A 1 -) d5 C(R e2 ) 4-d5―d6 (-Q 22 -G) d6 …(L12)

[0313] (-A 2 -) d7 N(-Q 23 -G) 3-d7 …(L13)

[0314] (-A 3 -) d8 Z 1 (-Q 24 -G) d9 …(L14)

[0315] (-A 2 -) d10 Si(R e3 ) 4-d10-d11 (-Q 25 -G) d11 …(L15)

[0316] -A 1 -Q 26 -G…(L16)

[0317] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -G) d12 …(L17)

[0318] Among them, in formula (L11) to formula (L17), A 1 , A 2 or A 3The 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).

[0319] -Si(R 51 ) 3-k (-Q 3 -) k …(G21)

[0320] In the formula (G21) of the above group,

[0321] 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 52 -B 3 -, R 52 An alkylene group, or an alkylene group having at least 2 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 Qs 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.

[0322] Q 3 For-R 52 -B 3 -, from the viewpoint of easy production of the compound (A1) and the viewpoint that the friction durability, light resistance and chemical resistance of the surface layer are more excellent, R 52The 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.

[0323] 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.

[0324] 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.

[0325] 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.

[0326] p11 is preferably 0 or 1.

[0327] 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.

[0328] 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.

[0329] 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.

[0330] 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.

[0331] Examples of the compound (A1) include the following.

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338] 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.

[0339] (Compound (A2))

[0340] The compound (A2) has a structure represented by the following formula (A2).

[0341] (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 …(A2)

[0342] In addition, each symbol in formula (A2) is as described above.

[0343] R f12 OR f12 ) y2 With the above R f11 OR f11 ) y1 The same, the preferred method is also the same.

[0344] R 2 and R 3 Each independently of the above R 1 The same, the preferred method is also the same.

[0345] R 21 and R 31With the above R 11 The same, the preferred method is also the same.

[0346] Among them, "bonded to L 1 In R 21 In the case of 2 "To understand, in R 31 In the case of 3 "To understand.

[0347] In addition, “T 11 Bonded to" in R 21 In the case of 21 "To understand, in R 31 is replaced by "bonded to T 31 "To understand.

[0348] In addition, “with T 11 Connected" in R 21 In this case, replace with "with T 21 Connected" to understand, in R 31 Replace with " and T 31 to understand.

[0349] In addition, the "for-SiR a11 z11 R a12 3-z11 When" is replaced by "for-SiR a21 z21 R a22 3-z21 time" to understand.

[0350] It should be noted that L 2 In the case of a single bond, R 21 With R 2 Direct bonding. In addition, L 3 In the case of a single bond, R 31 With R 3 Direct bonding.

[0351] T 21 and T 31 Each independently is -CH=CH2 or -SiR a21 z21 R a22 3-z21 , R a21 , R a22 , z21 are independently connected to form T 11 R a1 , R a2 , z1 are the same, and the preferred method is also the same.

[0352] x2 and x3 are each independently the same as x1, and the preferred aspects are also the same.

[0353] L 2 and L 3 Each independently of the above L 1 The same is true when j is 1.

[0354] For example, L 2 and L 3 When it is a single bond, the compound (A2) is represented by the following formula (A2').

[0355] T 31 -R 31 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -R 21 -T 21 …(A2')

[0356] However, the symbols in formula (A2') are the same as those in formula (A2).

[0357] 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 ”).

[0358] N becomes the branch point P 2 When the branch point P 2 For 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.

[0359] 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 , for example, a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group can be mentioned.

[0360] Si becomes the branch point P 2 When the branch point P 2 For example, *-Si(-**)3, or *-SiR 29 (-**)2 indicates.

[0361] 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 , for example, a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group can be mentioned.

[0362] Branch point P 2 The ring structure, the organopolysiloxane residue and the branch point P 1 The same, the preferred method is also the same.

[0363] 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.

[0364] 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 R 21 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 -**) etc. 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.

[0365] 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 3 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 -** x1}, etc.), more than one branch point P 2 With more than one key B 1 Combinations (e.g., {*-B 1 -R 28 -P 2 (-**) x}、{*-B 1 -R 28 -P 2 (-R 28 -B 1 -**) x}, etc.) where L 2 In the case of X being 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.

[0366] The above R 28 The method is as described above, and the preferred method is also the same.

[0367] From the viewpoint of facilitating the production of compound (A2), L 2 or L 3 , preferably each independently represents a group represented by any one of the following formulae (L21) to (L27).

[0368]

[0369] -A 1 -C(R e2 ) 4-d6 (-Q 22 -) d6 …(L22)

[0370] -A 2 -N(-Q 23 -)2…(L23)

[0371] -A 3 -Z 1 (-Q 24 -) d9 …(L24)

[0372] -A 2 -Si(R e3 ) 4-d11 (-Q 25 -) d11 …(L25)

[0373] -A 1 -Q 26 -…(L26)

[0374] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -) d12 …(L27)

[0375] Among them, in formula (L21) to formula (L27), 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 are connected.

[0376] Here, A 1 , A 2 , A 3 , Q 11 , Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Re1 , R e2 R e3 , R e6 With the above L 1 The same as described in, the preferred embodiment is also the same.

[0377] 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,

[0378] d2 is an integer from 0 to 3, d4 is an integer from 0 to 3, d2+d4 is an integer from 1 to 5,

[0379] d6 is an integer from 1 to 3,

[0380] d9 is an integer greater than 1,

[0381] d11 is an integer from 1 to 3,

[0382] d12 is an integer from 1 to 3.

[0383] It should be noted that d2+d4, d6, d9, d11, 1+d12 are x2 or x3.

[0384] From the viewpoint of easy production of the compound (A2) and from the viewpoint of better friction durability of the surface layer and better removability of fingerprint contaminants, d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0385] As the above L 2 or L 3 In another embodiment, a group represented by any one of the following formulae (L31) to (L37) can be mentioned.

[0386]

[0387] -A 1 -C(R e2 ) 4-d6 (-Q 22 -G) d6 …(L32)

[0388] -A 2 -N(-Q 23 -G)2…(L33)

[0389] -A 3 -Z 1 (-Q 24 -G) d9 …(L34)

[0390] -A 2 -Si(R e3 ) 4-d11 (-Q 25 -G) d11 …(L35)

[0391] -A 1 -Q 26 -…(L36)

[0392] -A 1 -CH(-Q 22 -G)-Si(R e3 ) 3-d12 (-Q 25 -G) d12 …(L37)

[0393] 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.

[0394] Among the compounds (A2), L 2 -(R 21 -T 21 ) 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.

[0395] 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.

[0396] In addition, L 2 -(R 21 -T 21 ) x2The molecular weight and (T 31 -R 31 ) x3 -L 3 It is preferred that the molecular weights of the groups shown are all within the above-mentioned ranges.

[0397] 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.

[0398] 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.

[0399] Examples of the compound (A2) include the following.

[0400]

[0401]

[0402]

[0403]

[0404]

[0405]

[0406]

[0407]

[0408] 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.

[0409] (Compound (A3))

[0410] The compound (A3) has a structure represented by the following formula (A3).

[0411] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 …(A3)

[0412] In addition, each symbol in formula (A3) is as described above.

[0413] R f13 OR f13 ) y3 With the above R f11 OR f11 ) y1 The same, the preferred method is also the same.

[0414] R 4 With the above R 1 The same, the preferred method is also the same.

[0415] R 41 With the above R 11 The same, the preferred method is also the same.

[0416] Among them, "bonded to L 1 " is replaced by "bonded to L 4 "To understand.

[0417] In addition, the "bonded to T 11 " is replaced by "bonded to T 41 "To understand.

[0418] In addition, the “with T 11 Connected" is replaced by "with T 41 to understand.

[0419] In addition, the "for-SiR a11 z11 R a12 3-z11 When" is replaced by "for-SiR a41 z41 R a42 3-z41 time" to understand.

[0420] It should be noted that L 4 In the case of a single bond, R41 With R 4 Direct bonding.

[0421] T 41 -CH=CH2 or -SiR a41 z41 R a42 3-z41 , R a41 , R a42 , z41 are independently connected to form T 11 R a1 , R a2 , z1 are the same, and the preferred method is also the same.

[0422] Q 1 It is a group with a valence of r1 having a branch point, and r1 is 3 or 4.

[0423] As a component of Q 1 The branch point (hereinafter referred to as "branch point P 3 ”), N, C, Si and ring structures can be listed. The branch point P 3 There may be one or two or more.

[0424] N becomes the branch point P 3 When the branch point P 3 For example, N(-*)3, NR 29 (-*)2 indicates.

[0425] C becomes the branch point P 3 When the branch point P 3 For example, C(-*)4, CR 29 (-*)3、C(R 29 )2(-*)2, etc.

[0426] 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, etc.

[0427] 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.

[0428] As the branch point P 3 The ring structure of the branch point P can be listed. 1The 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.

[0429] From the viewpoint of facilitating the production of compound (A3), Q 1 , preferably a group represented by any one of the following formulae (Q1) to (Q6).

[0430]

[0431] C(-A 11 -) d23 (R e12 ) 4-d23 …(Q2)

[0432] N(-A 12 -)3…(Q3)

[0433] Z 1 (-A 13 -) d24 …(Q4)

[0434] Si(-A 12 -) d25 (R e13 ) 4-d25 …(Q5)

[0435] CH(-A 11 -)2-Si(R e13 ) 3-d26 (-A 11 -) d26 …(Q6)

[0436] Among them, in formula (Q1) to formula (Q6), A 11 , A 12 or A 13 OR f13 ) are connected.

[0437] Here, A 11 is a single bond, -R 40 -、-B 13 -R 40 -, R 40 An 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-,

[0438] A 12 is a single bond or -R 40 -,

[0439] 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 ,

[0440] 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,

[0441] 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-,

[0442] 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,

[0443] 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

[0444] R e13 is an alkyl group or a fluoroalkyl group,

[0445] 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,

[0446] 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,

[0447] d23 is 3 or 4,

[0448] d24 is 3 or 4,

[0449] d25 is 3 or 4,

[0450] d26 is 1 or 2.

[0451] It should be noted that B 13 There is no requirement for the direction of A. 11 When there are multiple A 1 are optionally the same as or different from each other. 12 , A 13 , R e11 , R e12 , R e13 Same here.

[0452] 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.

[0453] As Z 1 The ring structure in the above-mentioned branch point P can be listed. 3 The preferred ring structure is the same.

[0454] 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.

[0455] 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.

[0456] 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.

[0457] In addition, L 4 -(R 41 -T 41 ) x4The molecular weights of the groups shown are preferably all within the above-mentioned ranges.

[0458] 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.

[0459] 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.

[0460] Examples of the compound (A3) include the following.

[0461]

[0462]

[0463]

[0464]

[0465] Among them, {-OR f4 -} independently with [-(OR f13 ) y3 -OR 4 -] r1 or [-(OR f13 ) y3 -O-] r1 Same, T and T 41 same.

[0466] The present composition may contain one type of the first component alone, or may contain two or more types.

[0467] 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.

[0468] 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.

[0469] <Second ingredient>

[0470] The second component is at least one fluorine-containing ether compound selected from the group consisting of a compound represented by the following formula (B1) and a compound represented by the following formula (B2), and is a compound to be removed in the present extraction method.

[0471] R f14 -(OR f15 ) y4 -OR 5 -R b1 (B1)

[0472] R f19 -(OR f18 ) y6 -OR 7 -L b1 -R 6 -O-(R f16 O) y5 -R f17 (B2)

[0473] In formula (B1),

[0474] R f14 is a fluoroalkyl group having 1 to 20 carbon atoms,

[0475] 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,

[0476] R 5 is an alkylene group which may have a substituent,

[0477] R b1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom,

[0478] y4 is an integer greater than or equal to 1.

[0479] R f17 and R f19 are each independently a fluoroalkyl group having 1 to 20 carbon atoms,

[0480] 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,

[0481] R 6 and R 7are each independently an alkylene group which may have a substituent,

[0482] 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,

[0483] y5 and y6 are each independently an integer of 1 or more.

[0484] (Compound (B1))

[0485] The compound (B1) has a structure represented by the following formula (B1).

[0486] R f14 -(OR f15 ) y4 -OR 5 -R b1 (B1)

[0487] In addition, each symbol in formula (B1) is as described above.

[0488] R f14 It is a fluoroalkyl group having 1 to 20 carbon atoms.

[0489] 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.

[0490] The fluoroalkyl group may be linear, branched or cyclic.

[0491] The fluoroalkyl group is preferably a group in which all hydrogen atoms in the fluoroalkyl group are substituted with fluorine atoms (perfluoroalkyl group).

[0492] R f15 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0493] R f15 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.

[0494] (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.

[0495] R 5It is an alkylene group which may have a substituent.

[0496] 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.

[0497] The alkylene group which may have a substituent may be linear, branched or cyclic.

[0498] As a substituent that the alkylene group may have, for example, a halogen atom, a hydroxyl group, and an amino group may be listed. As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom may be listed, 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).

[0499] As R 5 From the viewpoint of better extraction efficiency of the first component, it is preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (i.e., 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.

[0500] R b1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.

[0501] As R b1 , preferably a hydrogen atom or an iodine atom, more preferably a hydrogen atom.

[0502] The compound (B1) may be used in combination of two or more types.

[0503] 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.

[0504]

[0505] The method for producing the compound (B1) is not particularly limited, and examples thereof include the method described in International Publication No. 2013 / 121984.

[0506] (Compound (B2))

[0507] The compound (B2) has a structure represented by the following formula (B2).

[0508] R f19 -(OR f18 ) y6 -OR 7 -L b1 -R 6 -O-(R f16 O) y5 -R f17 (B2)

[0509] However, the symbols in formula (B2) are as described above.

[0510] 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.

[0511] 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.

[0512] (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.

[0513] (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.

[0514] R 6 and R7 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.

[0515] 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.

[0516] R 6 and R 7 They may be the same group or different groups, but are preferably the same group.

[0517] As R 6 From the viewpoint of better extraction efficiency of the first component, it is preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (i.e., 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 R 6 The carbon number is the same.

[0518] As R 7 From the viewpoint of better extraction efficiency of the first component, it is preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (i.e., 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.

[0519] 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).

[0520] Specific examples of the divalent linking group include an alkylene group, an etheric oxygen atom, an amide bond, and a group composed of a combination thereof. Among the divalent linking groups, an alkylene group, a group composed of a combination of an alkylene group and an etheric oxygen atom, and a group composed of a combination of an alkylene group and an amide bond are preferred.

[0521] L b1 The divalent linking group does not contain (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.

[0522] From the viewpoint of better extraction efficiency of the first component, L b1 Preferred is a single bond.

[0523] The compound (B2) may be used in combination of two or more types.

[0524] 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.

[0525]

[0526] 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.

[0527] The present composition may contain one type of the second component alone, or may contain two or more types.

[0528] The content of the second 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.

[0529] <Other ingredients>

[0530] The present composition may further contain components other than the first component and the second component (hereinafter also referred to as "other components").

[0531] Specific examples of other components include organic solvents containing fluorine atoms (hereinafter also referred to as "fluorine-based organic solvents").

[0532] Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, fluorinated alkyl amines, fluorinated alcohols, and hydrofluoroolefins.

[0533] As specific examples of fluorinated alkanes, compounds having 4 to 8 carbon atoms are preferred. Examples of commercially available products include C6F 13 H (AGC Corporation, ASAHIKLIN (registered trademark) AC-2000), C6F 13 C2H5 (manufactured by AGC Corporation, ASAHIKLIN (registered trademark) AC-6000), C2F5CHFCHFCF3 (manufactured by Chemours Corporation, Vertrel (registered trademark) XF), and the like.

[0534] Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.

[0535] 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).

[0536] Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.

[0537] Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0538] 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.

[0539] When the present composition contains a fluorinated organic solvent, the content of the fluorinated organic solvent is preferably 67% by mass or less, more preferably 50% by mass or less, and further preferably 33% by mass or less, based on the total mass of the present composition.

[0540] 〔Non-fluorinated organic solvent〕

[0541] The non-fluorine-based organic solvent is used to extract the first component in the extraction step described below. Since the first component has excellent compatibility with the non-fluorine-based organic solvent, the first component can be efficiently extracted by using the non-fluorine-based organic solvent.

[0542] The non-fluorine-based organic solvent may be any organic solvent that does not contain fluorine atoms, but a non-halogen-based solvent is preferred because the extraction efficiency of the first component is more excellent.

[0543] The non-halogen solvent refers to an organic solvent that does not contain a halogen atom, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, amide organic solvents, and sulfoxide organic solvents.

[0544] 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.

[0545] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene.

[0546] Examples of the aliphatic hydrocarbon include n-hexane, n-heptane, n-octane, and n-decane.

[0547] As the unsaturated hydrocarbon, for example, cyclopentene, hexene, heptene and butene can be cited.

[0548] 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.

[0549] 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.

[0550] 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.

[0551] 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.

[0552] 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.

[0553] Examples of the amide-based organic solvent include N,N-dimethylformamide.

[0554] Examples of the sulfoxide-based organic solvent include dimethyl sulfoxide.

[0555] The relative dielectric constant of the non-halogen solvent is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less, from the viewpoint of further improving the extraction efficiency of the first component.

[0556] In this specification, the relative dielectric constant of an organic solvent refers to the relative dielectric constant at 25° C., and can be measured using a known liquid dielectric constant meter.

[0557] In addition, the non-halogen solvent is preferably a hydrocarbon solvent because the extraction efficiency of the first component is more excellent.

[0558] The non-fluorine-based organic solvent may be used alone or in combination of two or more.

[0559] In the extraction step, the amount of the non-fluorinated organic solvent used is preferably 50 to 3,000 parts by mass, more preferably 100 to 2,000 parts by mass, and even more preferably 300 to 1,500 parts by mass, based on 100 parts by mass of the present composition.

[0560] When the amount of the non-fluorine-containing organic solvent used is 50 parts by mass or more, the amount of the first component eluted from the non-fluorine-containing organic solvent increases, and thus the first component can be extracted more efficiently.

[0561] When the amount of the non-fluorinated organic solvent used is 3000 parts by mass or less, the second component can be removed more effectively.

[0562] From the viewpoint of more excellent extraction efficiency of the first component, the mass ratio of the amount of the non-fluorinated organic solvent used to the amount of the first component used is preferably 50 to 15,000, more preferably 100 to 10,000, and even more preferably 300 to 7,500.

[0563] When the present composition contains a fluorinated organic solvent, the mass ratio of the non-fluorinated organic solvent used to the fluorinated organic solvent used is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more, from the perspective of better extraction efficiency of the first component.

[0564] 〔Extraction process〕

[0565] The present extraction method includes a step of extracting the first component from the present composition using a fluorine-free organic solvent (hereinafter also referred to as an "extraction step"), thereby obtaining an eluate in which the first component is more selectively eluted into the fluorine-free organic solvent than the second component.

[0566] As an example of a preferred method of the extraction process, the following method can be cited: after stirring the mixed solution obtained by mixing the present composition with a non-fluorine-based organic solvent, the mixed solution is allowed to stand to separate into two layers: an eluate in which the first component is more selectively eluted into the non-fluorine-based organic solvent than the second component, and a component that is not eluted into the non-fluorine-based organic solvent, and the layer formed by the eluate is recovered.

[0567] The temperature in the extraction step (for example, the temperature of the mixed solution) is preferably 0 to 50°C, more preferably 15 to 35°C.

[0568] The extraction step may include a removal treatment of removing the non-fluorinated organic solvent from the eluate.

[0569] Specific examples of the removal treatment method include distillation (for example, removal by reduced pressure distillation). The distillation can be carried out using a known distillation apparatus or the like.

[0570] The extraction step may further include a filtration process to remove solids that may be contained in the mixed solution or the eluate. The filtration process may be performed using a filter or the like.

[0571] The extraction step may be performed only once or twice or more. When the extraction step is performed twice or more, an extract containing the first component at a higher concentration can be obtained.

[0572] In the second and subsequent extraction steps, it is preferred to use a component obtained by removing the non-fluorinated organic solvent and solid matter from the extract obtained in the immediately preceding extraction step.

[0573] Example

[0574] Hereinafter, the present invention will be described in detail with reference to examples. Examples 1 to 3 are examples, and Examples 4 to 6 are comparative examples. However, the present invention is not limited to these examples. It should be noted that the blending amount of each component in the table described below is based on mass.

[0575] [Synthesis of Compound A1-1]

[0576] <Synthesis of Compound X1>

[0577] 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.

[0578] Compound X1

[0579]

[0580] (In the formula, Me represents a methyl group.)

[0581] <Synthesis of Compound X2>

[0582] 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.

[0583] Compound X2

[0584]

[0585] <Synthesis of Compound X3>

[0586] 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.

[0587] Compound X3

[0588]

[0589] <Synthesis of Compound X4>

[0590] 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.

[0591] Compound X4

[0592]

[0593] <Synthesis of Compound X5>

[0594] 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.

[0595] Compound X5

[0596]

[0597] <Synthesis of Compound A1-1>

[0598] 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 the mixture was 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 the mixture was 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 A1-1. By NMR measurement, it was confirmed that compound A1-1 was obtained with a selectivity of 79%. In the formula, the average value of the number of repeating units n is 13.

[0599] Compound A1-1

[0600]

[0601] [Synthesis of Compound B1-1]

[0602] According to the method described in Example 11 of International Publication No. 2013 / 121984, compound B1-1 was obtained.

[0603] CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2CH2I…Formula (B1-1)

[0604] The average value of the number of repeating units n is 13.

[0605] [Synthesis of Compound B1-2]

[0606] 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.

[0607] NMR spectrum of compound B1-2;

[0608] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 2.30~2.13 (m, 2H), 1.27 (t, J=7.1Hz, 3H)

[0609] 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.

[0610] CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2CH3…Formula (B1-2)

[0611] The average value of the number of repeating units n is 13.

[0612] [Synthesis of Compound B2-1]

[0613] In an argon atmosphere, 3.0 g of the 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.

[0614] 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.

[0615] NMR spectrum of compound B2-1;

[0616] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 2.31~2.14 (m, 4H), 1.91~1.78 (m, 4H)

[0617] 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.

[0618] Compound B2-1

[0619]

[0620] [Synthesis of Compound C1-1]

[0621] <Synthesis of Compound Y1>

[0622] Diethyl Diallylmalonate 60.0 g, lithium chloride 23.7 g (559 mmol), water 6.45 g (360 mmol), DMSO 263 g were added, and stirred at 160°C. After cooling to room temperature (25°C), water was added, and extraction was performed with ethyl acetate. Hexane was added to the organic layer, washed with saturated brine, and dried with sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following compound Y1.

[0623] Compound Y1

[0624]

[0625] (In the formula, Et represents ethyl.)

[0626] NMR spectrum of compound Y1;

[0627] 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).

[0628] <Synthesis of Compound Y2>

[0629] After adding THF 260mL and diisopropylamine 29.8mL, the solution was cooled to -78°C. 96.6mL of n-butyllithium hexane solution (2.76M) was added and the temperature was raised to 0°C. After stirring, the mixture was cooled to -78°C to prepare a THF solution of lithium diisopropylamide (LDA). 39.5g of the above-mentioned compound Y1 was added to the THF solution, and after stirring, 24.1mL of allyl bromide was added. The mixture was heated to 0°C, 100mL of 1M hydrochloric acid was added, and THF was removed by distillation under reduced pressure. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was distilled off, and rapid column chromatography using silica gel was performed to obtain 45.0g of compound Y2.

[0630] Compound Y2

[0631]

[0632] (In the formula, Et represents ethyl.)

[0633] NMR spectrum of compound Y2;

[0634] 1 H-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).

[0635] <Synthesis of Compound Y3>

[0636] 45.0 g of the above compound Y2 was dissolved in 620 mL of THF and cooled to 0°C. 104 mL of a THF solution of lithium aluminum hydride was added and stirred. Water and a 15% aqueous sodium hydroxide 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.

[0637] Compound Y3

[0638]

[0639] NMR spectrum of compound Y3;

[0640] 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).

[0641] <Synthesis of Compound Y4>

[0642] 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 stirred. After filtration, the filtrate was concentrated and distilled to obtain 28.2 g of the following compound Y4.

[0643] Compound Y4

[0644]

[0645] NMR spectrum of compound Y4;

[0646] 1H-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).

[0647] <Synthesis of Compound Y5>

[0648] 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.

[0649] Compound Y5

[0650]

[0651] NMR spectrum of compound Y5;

[0652] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.88 (m, 3H), 5.11 (m, 6h), 1.85 (m, 6h), 1.22 (s, 2h).

[0653] <Synthesis of Compound C1-1>

[0654] 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, and after extraction with 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 C1-1. By NMR measurement, it was confirmed that compound C1-1 was obtained with a selectivity of 84%. In the formula, the average value of the number of repeating units n is 13.

[0655] Compound C1-1

[0656]

[0657] NMR spectrum of compound C1-1;

[0658] 1H-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).

[0659] 19 F-NMR (376MHz, Chloroform-d) δ (ppm): -55.25, -82.83, -88.06, -90.16 (d, J=8.1Hz), -114.18, -125.26, -126.59.

[0660] [Example 1]

[0661] 1 g of a mixture containing compound A1-1 (16 mol%), compound B1-1 (10 mol%), compound B1-2 (17 mol%), and compound B2-1 (57 mol%) was prepared, and the obtained mixture was dissolved in 1 g of AC-6000 to obtain a reference composition X for extraction.

[0662] A mixed solution in which hexane (10 g) was added as an extraction solvent to the reference composition X was stirred at room temperature (23° C.) for 30 minutes. After stirring, the mixed solution was allowed to stand for 1 hour, and the upper layer of the mixed solution separated into two layers was recovered. The hexane and AC-6000 in the recovered upper layer were removed by vacuum distillation to obtain a sample 1 for purity measurement.

[0663] pass 1 H-NMR and 19 The concentration (mol %) of each compound contained in Sample 1 was measured by F-NMR. The results are shown in Table 1.

[0664] It should be noted that the above concentration refers to the concentration (mol %) of each compound relative to the total amount (100 mol %) of the fluorine-containing ether compounds contained in the sample. The same applies to the following examples.

[0665] [Example 2 and Example 3]

[0666] The concentration (mol %) of each compound contained in the samples of Examples 2 and 3 was measured in the same manner as in Example 1 except that the solvents listed in Table 1 were used instead of hexane as the extraction solvent.

[0667] [Example 4]

[0668] The same operation as in Example 1 was carried out except that AE-3000 was used instead of hexane as the extraction solvent. The mixed liquid after stirring was allowed to stand, but the mixed liquid did not separate into two layers.

[0669] In addition, the concentration (mol %) of each component contained in the mixed solution was measured in the same manner as in Example 1. The result was the same as the concentration of each compound contained in the reference composition X.

[0670] [Table 1]

[0671]

[0672] As shown in Table 1, when the first component (Compound A1-1) was extracted from the composition containing the first component and the second component, it was confirmed that the first component could be efficiently extracted by using an organic solvent containing no fluorine atom as the extraction solvent (Examples 1 to 3).

[0673] [Example 5]

[0674] 1 g of a mixture containing compound C1-1 (25 mol%), compound B1-1 (7 mol%), compound B1-2 (27 mol%), and compound B2-1 (41 mol%) was prepared, and the obtained mixture was dissolved in 1 g of AC-6000 to obtain a reference composition Y for extraction.

[0675] A mixed solution in which 10 g of hexane as an extraction solvent was added to the reference composition Y was stirred at room temperature (23° C.) for 30 minutes. After stirring, the mixed solution was allowed to stand for 1 hour, and the upper layer of the mixed solution separated into two layers was recovered. The hexane and AC-6000 in the recovered upper layer were removed by vacuum distillation to obtain a sample 5 for purity measurement.

[0676] The same operation as in Example 1 was carried out except that Sample 5 was used instead of Sample 1, and the concentration (mol %) of each compound contained in the sample of Example 5 was measured.

[0677] [Example 6]

[0678] The same operation as in Example 5 was carried out except that AE-3000 was used instead of hexane as the extraction solvent. The mixed liquid after stirring was allowed to stand, but the mixed liquid did not separate into two layers.

[0679] In addition, the concentration (mol %) of each component contained in the mixed solution was measured in the same manner as in Example 5. The result was the same as the concentration of each compound contained in the reference composition Y.

[0680] [Table 2]

[0681]

[0682] As shown in Table 2, when compound C1-1 (a compound other than the above-mentioned compound A1, compound A2, and compound A3) is used to replace the fluorinated ether compound set as the extraction target by compound A1-1, even if hexane, which can most effectively extract the fluorinated ether compound set as the extraction target in Examples 1 to 4, is used as the extraction solvent, the compound C1-1 set as the extraction target cannot be effectively extracted (Example 5).

[0683] It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2022-164649 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 method for extracting a fluorine-containing ether compound, comprising extracting the first component from a composition comprising a first component and a second component using an organic solvent containing no fluorine atoms, 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, 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 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 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 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 atoms, carbon atoms constituting branch points, carbon atoms having a hydroxyl group or an oxo group (=O), 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, T 11 -CH=CH2 or -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, T 11 When -CH=CH2, R 11 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 11 Connected, T 11 -SiR a11 z11 R a12 3-z11 When R 11 At least one of them has a carbon chain with more than 4 carbon atoms connected, 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, 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, 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 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 atoms, carbon atoms constituting branch points, carbon atoms having a hydroxyl group or an oxo group (=O), 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 atoms, carbon atoms constituting branch points, carbon atoms having a hydroxyl group or an oxo group (=O), 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, 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, T 21 and T 31 Each independently is -CH=CH2 or -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, T 21 When -CH=CH2, R 21 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 21 Connected, T 21 -SiR a21 z21 R a22 3-z21 When R 21 At least one of them has a carbon chain with more than 4 carbon atoms connected, T 31 When -CH=CH2, R 31 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 31 Connected, T 31 -SiR a21 z21 R a22 3-z21 When R 31 At least one of them has a carbon chain with more than 4 carbon atoms connected, 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 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 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 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 atoms, carbon atoms constituting branch points, carbon atoms having hydroxyl groups or oxo groups (=O), and the presence of multiple L 4 are optionally the same 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 or different from each other, T 41 -CH=CH2 or -SiR a41 z41 R a42 3-z41 , there are multiple T 41 are optionally the same or different from each other, T 41 When -CH=CH2, R 41 At least one of the carbon chains has two or more carbon atoms connected, and the carbon chain is connected to T 41 Connected, T 41 -SiR a41 z41 R a42 3-z41 When R 41 At least one of them has a carbon chain with more than 4 carbon atoms connected, 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, 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, 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 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 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 method for extracting fluorinated ether compounds according to claim 1, wherein: The organic solvent is a non-halogen solvent.

3. The method for extracting fluorinated ether compounds according to claim 2, wherein: The non-halogen solvent has a relative dielectric constant of 30 or less.

4. The method for extracting fluorinated ether compounds according to claim 1, wherein: The organic solvent is a hydrocarbon solvent.

5. The method for extracting fluorinated ether compounds according to claim 1, wherein In the formula (A1), T 11 When -CH=CH2, R 11 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 11 are connected, in the formula (A1), T 11 -SiR a11 z11 R a12 3-z11 When R 11 At least one of them has a carbon chain with more than 6 carbon atoms connected, In the formula (A2), T 21 When -CH=CH2, R 21 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 21 are connected, in the formula (A2), T 21 -SiR a21 z21 R a22 3-z21 When R 21 At least one of them has a carbon chain with more than 6 carbon atoms connected, In the formula (A2), T 31 When -CH=CH2, R 31 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 31 are connected, in the formula (A2), T 31 -SiR a21 z21 R a22 3-z21 When R 31 At least one of them has a carbon chain with more than 6 carbon atoms connected, In the formula (A3), T 41 When -CH=CH2, R 41 At least one of the carbon chains has 4 or more carbon atoms connected to each other. 41 are connected, in the formula (A3), T 41 -SiR a41 z41 R a42 3-z41 When R 41 At least one of the carbon atoms has a carbon chain having more than 6 carbon atoms connected.

6. The method for extracting fluorinated ether compounds according to claim 1, wherein (OR f11 ) y1 The molecular weight of the group shown is 2000 to 20000, (OR f12 ) y2 The molecular weight of the group shown is 2000 to 20000, (OR f13 ) y3 The molecular weight of the groups shown is 2,000 to 20,000.

7. The method for extracting fluorinated ether compounds according to claim 1, wherein [R f1 -(OR f11 ) y1 -OR 1 ] j The molecular weight of the groups shown is relative to L 1 -(R 11 -T 11 ) x1 The ratio of the molecular weight of the group shown is 13% or more, 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 sum of the molecular weights of the groups shown is 13% or more, r1 (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 13% or more.

8. The method for extracting fluorinated ether compounds according to claim 1, 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.

9. The method for extracting fluorinated ether compounds according to claim 8, wherein: In formula (B1), R 5 The carbon number of the fluoroalkylene group is 1 to 20, In formula (B2), R 6 The fluoroalkylene group shown in R 7 The total number of carbon atoms in the fluoroalkylene group is 2-40.

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