Surface treatment agent, article, and method for producing article

Abstract

Provided are: a surface treatment agent capable of forming a surface layer having excellent friction durability; an article having a surface layer having excellent friction durability; and a method for producing an article. This surface treatment agent contains: at least one fluorine-containing ether compound selected from the group consisting of compounds represented by formula (A1), compounds represented by formula (A2), and compounds represented by formula (A3); and an organic solvent that does not contain fluorine atoms.

Description

Technical Field

[0001] The present invention relates to a surface treatment agent, an article, and a method for producing the article. Background Art

[0002] It is known that fluorinated ether compounds having a fluoropolyether chain and a hydrolyzable silyl group can be used for surface treatment of substrates, and can form a surface layer on the surface of the substrate that exhibits high lubricity, water and oil repellency, etc. Therefore, the surface treatment agent containing the fluorinated ether compound is suitable for use in applications where the performance of the surface layer needs to be maintained for a long time, such as components constituting the surface of a touch panel that is touched by a finger, eyeglass lenses, and displays of wearable terminals.

[0003] For example, Patent Document 1 proposes a surface treatment agent containing a predetermined perfluoropolyether group-containing silane compound as a surface treatment agent for forming a surface treatment layer having water repellency, oil repellency, antifouling properties, and friction durability on the surface of a substrate.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2017 / 022437 Summary of the invention

[0007] Problem that the invention aims to solve

[0008] In recent years, the performance requirements for surface layers formed using fluorinated ether compounds have been continuously improved. For example, a surface layer having excellent performance (friction durability) is required even when formed on a member constituting a surface contacted by a finger, wherein the water and oil repellency is difficult to reduce even when repeatedly rubbed with a finger.

[0009] The present inventors evaluated a surface layer formed using a surface treatment agent containing a fluorine-containing ether compound as described in Patent Document 1, and found that the friction durability of the surface layer still has room for improvement.

[0010] An object of the present invention is to provide a surface treatment agent capable of forming a surface layer having excellent friction durability, an article having a surface layer having excellent friction durability, and a method for producing the article.

[0011] Solutions for solving problems

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

[0013] [1]

[0014] A surface treatment agent comprising: at least one fluorine-containing ether compound selected from the group consisting of a compound represented by formula (A1) described below, a compound represented by formula (A2) described below, and a compound represented by formula (A3) described below, and an organic solvent containing no fluorine atoms.

[0015] [2]

[0016] The surface treatment agent according to [1], wherein R 11 At least one of them has a carbon chain with more than 5 carbon atoms connected, R 21 and R 31 At least one of them has a carbon chain with more than 5 carbon atoms connected, R 41 At least one of the carbon atoms has a carbon chain having 5 or more carbon atoms connected.

[0017] 〔3〕

[0018] The surface treatment agent according to [1] or [2], wherein R 11 At least one of them has a carbon chain with 5 to 18 carbon atoms connected, R 21 and R 31 At least one of them has a carbon chain with 5 to 18 carbon atoms connected, R 41 At least one of the two has a carbon chain with 5 to 18 carbon atoms connected.

[0019] [4]

[0020] The surface treatment agent according to any one of [1] to [3], wherein the R 11 The alkylene in is a straight chain alkylene, and the above R 21 and R 31 The alkylene in is a straight chain alkylene, and the above R 41 The alkylene group is a straight chain alkylene group.

[0021] 〔5〕

[0022] The surface treatment agent according to any one of [1] to [4], wherein (OR f11 ) y1 The molecular weight of the group shown is 2000 to 10000, (OR f12 ) y2 The molecular weight of the group shown is 2000 to 10000, (OR f13 ) y3 The molecular weight of the groups shown is 2,000 to 10,000.

[0023] [6]

[0024] The surface treatment agent according to any one of [1] to [5], wherein [R f1 -(ORf11 ) y1 -OR 1 ] j The molecular weight of the groups shown is relative to L 1 -(R 11 -T 11 ) x1 The molecular weight ratio 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 total molecular weight of the groups shown is 13% or more, and 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.

[0025] 〔7〕

[0026] The surface treatment agent according to any one of [1] to [6], wherein the organic solvent not containing fluorine atoms comprises at least one selected from the group consisting of ketone solvents and ester solvents.

[0027] [8]

[0028] The surface treatment agent according to any one of [1] to [7], wherein the ratio of the content of the organic solvent not containing fluorine atoms to the content of the fluorine-containing ether compound is 60 to 99.999% by mass.

[0029] 〔9〕

[0030] An article having a surface layer formed of the surface treatment agent described in any one of [1] to [8] on the surface of a substrate.

[0031] 〔10〕

[0032] A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the surface treatment agent described in any one of [1] to [8].

[0033] Effects of the Invention

[0034] According to the present invention, it is possible to provide a surface treatment agent capable of forming a surface layer having excellent friction durability, an article having a surface layer having excellent friction durability, and a method for producing the article. DETAILED DESCRIPTION

[0035] In this specification, the group represented by formula (g1) may be referred to as group (g1). In addition, the compound represented by formula (A1) may be referred to as compound (A1). The same applies to compounds represented by other formulae.

[0036] Fluoroalkyl refers to a general term for perfluoroalkyl and partial fluoroalkyl groups. Perfluoroalkyl refers to a group in which all hydrogen atoms of an alkyl group are replaced by fluorine atoms. In addition, partial fluoroalkyl refers to an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom and has at least one hydrogen atom. That is, a fluoroalkyl group is an alkyl group having at least one fluorine atom.

[0037] 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.

[0038] 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.

[0039] "Hydrocarbon group" refers to a group composed of carbon atoms and hydrogen atoms, and is a group including aliphatic hydrocarbon groups (for example, straight-chain alkylene groups, branched alkylene groups, cycloalkylene groups, etc. as divalent aliphatic hydrocarbon groups), aromatic hydrocarbon groups (for example, phenylene groups as divalent aromatic hydrocarbon groups, etc.), and combinations thereof.

[0040] The “surface layer” refers to a layer formed on the surface of a substrate.

[0041] The "molecular weight" of a fluoropolyether chain and a fluoroether compound 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.

[0042] 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.

[0043] The term “to” indicating a numerical range includes the numerical values ​​described before and after the “to” as the lower limit and the upper limit.

[0044] [Surface treatment agent]

[0045] The surface treatment agent of the present invention (hereinafter also referred to as "the present treatment agent") comprises 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 an organic solvent that does not contain fluorine atoms (hereinafter also referred to as "non-fluorine organic solvent").

[0046] The present treatment agent can form a surface layer having excellent friction durability on the surface of the substrate. The detailed reason for this is not clear, but it is presumed to be due to the following reasons.

[0047] In the fluorinated ether compound represented by any one of the above formulas (A1) to (A3), if the molecular weight of the organic group containing a reactive silyl group other than the fluoropolyether chain is greater than a specified value, the organic group having a high affinity for the non-fluorinated organic solvent is more likely to be unevenly distributed on the non-fluorinated organic solvent side attached to the surface of the substrate than the fluoropolyether chain when forming the surface layer. As a result, it can be inferred that the orientation of the fluorinated ether compound is promoted and the friction durability of the formed surface layer is improved.

[0048] Hereinafter, each component contained in this treatment agent is demonstrated.

[0049] 〔Fluorinated ether compounds〕

[0050] The present treatment agent contains at least one fluorine-containing ether compound selected from the group consisting of a compound represented by the following formula (A1), a compound represented by the following formula (A2), and a compound represented by the following formula (A3).

[0051] Hereinafter, compound (A1), compound (A2) and compound (A3) are also collectively referred to as "the present compound".

[0052] [R f1 -(OR f11 ) y1 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 …(A1)

[0053] (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T21 ) x2 …(A2)

[0054] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 …(A3)

[0055] In formula (A1),

[0056] R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and there are multiple R f1 When there are multiple R f1 are optionally the same as or different from each other,

[0057] R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f11 When there are multiple R f11 are optionally the same as or different from each other,

[0058] R 1 is an alkylene group or a fluoroalkylene group, and there are multiple R 1 When there are multiple R 1 are optionally the same as or different from each other,

[0059] 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),

[0060] R 11 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein the group bonded to L 1 The atom of R is optionally an etheric oxygen atom. 11 When there are multiple R 11 are optionally the same as or different from each other,

[0061] T 11 -SiR a11 z11 R a12 3-z11 The group shown has multiple T 11 When there are multiple T 11 are optionally the same as or different from each other,

[0062] R a11 is a hydroxyl group or a hydrolyzable group, and there are multiple R a11 When there are multiple R a11 are optionally the same as or different from each other,

[0063] R a12 It is a non-hydrolyzable group, and there are multiple R a12 When there are multiple R a12 are optionally the same as or different from each other,

[0064] 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,

[0065] z11 is an integer from 1 to 3,

[0066] x1 is an integer greater than 1,

[0067] y1 is an integer greater than or equal to 1. When there are a plurality of y1, the plurality of y1 may be the same or different from each other. 1 -(R 11 -T 11 ) x1 The molecular weight of the groups shown is 600 or more.

[0068] In formula (A2),

[0069] R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f12 When there are multiple R f12 are optionally the same as or different from each other,

[0070] R 2 and R 3 are each independently an alkylene group or a fluoroalkylene group,

[0071] 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),

[0072] 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),

[0073] R21 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 2 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 21 When there are multiple R 21 are optionally the same as or different from each other,

[0074] R 31 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 3 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 31 When there are multiple R 31 are optionally the same as or different from each other,

[0075] T 21 and T 31 Each independently is -SiR a21 z21 R a22 3-z21 , there are multiple T 21 When there are multiple T 21 Optional to be the same or different from each other, there are multiple T 31 When there are multiple T 31 are optionally the same as or different from each other,

[0076] R a21 is a hydroxyl group or a hydrolyzable group, and there are multiple R a21 When there are multiple R a21 are optionally the same as or different from each other,

[0077] R a22 It is a non-hydrolyzable group, and there are multiple R a22 When there are multiple R a22 are optionally the same as or different from each other,

[0078] z21 is an integer from 1 to 3,

[0079] x2 and x3 are each independently an integer greater than 1,

[0080] y2 is an integer greater than 1. When y2 is 1, R 2 is a fluoroalkylene group,

[0081] L 2 -(R 21 -T 21 ) x2 The groups shown and (T 31 -R 31 ) x3 -L 3 At least one of the molecular weights of the groups shown is 600 or more.

[0082] In formula (A3),

[0083] Q 1 is a r1-valent group having a branch point,

[0084] R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f13 When there are multiple R f13 are optionally the same as or different from each other,

[0085] R 4 Each independently represents an alkylene group or a fluoroalkylene group, and the presence of multiple R 4 are optionally the same as or different from each other,

[0086] L 4 is a single bond, or is a 1+x4 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 4 and R 41 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, a carbon atom having a hydroxyl group or an oxo group (=O), and the presence of multiple L 4 are optionally the same as or different from each other,

[0087] 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 as or different from each other,

[0088] T 41 -SiR a41 z41 R a42 3-z41 , there are multiple T 41 are optionally the same as or different from each other,

[0089] R a41 is a hydroxyl group or a hydrolyzable group, and the presence of multiple R a41 are optionally the same as or different from each other,

[0090] R a42 It is a non-hydrolyzable group, and there are multiple R a42 When there are multiple R a42 are optionally the same as or different from each other,

[0091] z41 is an integer from 1 to 3,

[0092] 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.

[0093] 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.

[0094] L 4 -(R 41 -T 41 ) x4 At least one of the groups shown has a molecular weight of 600 or more.

[0095] Since this compound has a fluoropolyether chain, the water-repellent and oil-repellent properties and fingerprint contaminant removal properties of the surface layer formed using this compound are excellent. In addition, since this compound has a reactive silyl group, the reactive silyl group is firmly chemically bonded to the substrate, the durability such as the friction durability of the surface layer formed using this compound is excellent. Therefore, this compound is suitable for forming a surface treatment agent for the surface layer that gives the substrate surface with water-repellent and oil-repellent properties, friction durability, and fingerprint contaminant removal properties.

[0096] 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.

[0097] The present compound has a fluoropolyether chain, and the fluoropolyether chain is a group having two or more oxyfluoroalkylene units.

[0098] These fluoropolyether chains may 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) in the fluoropolyether chain is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, i.e., 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.

[0099] Mathematical formula (I): Ratio of fluorine atoms (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} × 100

[0100] From the viewpoint of achieving both fingerprint removability and lubricity of the surface layer, the (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 is preferably 1000 to 20000, more preferably 1500 to 15000, and further preferably 2000 to 10000. If the molecular weight of the above group is 1000 or more, the flexibility of the fluoropolyether chain is improved, and the amount of fluorine in the molecule is increased, thereby further improving the lubricity and fingerprint removal properties. On the other hand, if the molecular weight of the above group is 20000 or less, the friction durability of the surface layer is more excellent.

[0101] <Compound (A1)>

[0102] The compound (A1) has a structure represented by the following formula (A1).

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

[0104] In addition, each symbol in formula (A1) is as described above.

[0105] R f1 The fluoroalkyl group is a fluoroalkyl group having 1 to 20 carbon atoms. The fluoroalkyl group may be linear, branched, and / or cyclic. From the viewpoint of friction durability, a linear fluoroalkyl group is preferred. From the viewpoint of ease of synthesis, the fluoroalkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0106] R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f11 When there are multiple R f11 are optionally the same or different from each other. f11 ) y1 In the above, y1 may be an integer greater than or equal to 1, and is preferably 1 to 200, and more preferably 2 to 200.

[0107] (OR f11 ) y1 It preferably has a structure represented by the following formula (G11).

[0108] -[(OG f1 ) m1 (OG f2 ) m2 (OG f3 ) m3 (OG f4 ) m4 (OG f5 ) m5 (OGf6 ) m6 ]-…(G11)

[0109] in,

[0110] G f1 is a fluoroalkylene group having 1 carbon number,

[0111] G f2 is a fluoroalkylene group having 2 carbon atoms,

[0112] G f3 is a fluoroalkylene group having 3 carbon atoms,

[0113] G f4 is a fluoroalkylene group having 4 carbon atoms,

[0114] G f5 is a fluoroalkylene group having 5 carbon atoms,

[0115] G f6 is a fluoroalkylene group having 6 carbon atoms,

[0116] 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.

[0117] 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 indicating configuration. 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.

[0118] 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.

[0119] As G f1 Specific examples include -CF2- and -CHF-.

[0120] As G f2 Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, -CH2CHF- and the like.

[0121] 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.

[0122] 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.

[0123] As G f5Specific examples include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, and -cycloC5F8-.

[0124] As G f6 Specific examples include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, -cycloC6F 10 -wait.

[0125] 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.

[0126] 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).

[0127] (OG f1 ) m1 -(OG f2 ) m2 Formula (G2)

[0128] (OG f2 ) m2 -(OG f4 ) m4 Formula (G3)

[0129] (OG f3 ) m3 Formula (G4)

[0130] However, the symbols in formula (G2) to formula (G4) are the same as those in the above formula (G11).

[0131] In formula (G2) and formula (G3), (OG f1 ) and (OG f2 )、(OG f2 ) and (OG f4 ) are in any order. f1 ) and (OG f2 ) can be configured alternately, (OG f1 ) and (OG f2 ) may be arranged in blocks or randomly.

[0132] 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.

[0133] 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.

[0134] In formula (G4), m3 is preferably 1-30, more preferably 1-20.

[0135] From the viewpoint of excellent water- and oil-repellency and fingerprint removability, the above (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, 99.99%.

[0136] In addition, (OR f11 ) y1 The preferred ranges of molecular weight of the groups shown are as described above.

[0137] 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, a straight chain or branched alkylene or fluoroalkylene is preferred, and a straight chain or alkylene or fluoroalkylene having a methyl or fluoromethyl group as a branch is more preferred. 1 The carbon number of is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, and particularly preferably 1 to 6. 1 In the case of a single bond, R 1 Bonded to R 11 In this case, let R 1The bond in R 11 The carbon atom of the alkylene group is bonded to at least one fluorine atom or a fluoroalkyl group.

[0138] 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.

[0139] It should be noted that when j is 1, y1 is an integer greater than 2, or R 1 It is a fluoroalkylene group.

[0140] 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.

[0141] 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.

[0142] From the perspective of better water and oil repellency of the surface layer, better fingerprint removability, and better durability such as friction durability, R 11 The alkylene group in the group preferably has a carbon chain having 5 or more carbon atoms connected.

[0143] A carbon chain with more than 5 carbon atoms connected is a carbon chain with more than 5 carbon atoms connected. 11 The alkylene group includes an alkylene group having 5 or more carbon atoms. 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 having 9 carbon atoms connected, including the carbon atoms of the branched chain.

[0144] R 11 The alkylene group in the above-mentioned carbon chain preferably has 9 or more carbon atoms, and further preferably has 11 or more carbon atoms. The alkylene group having the carbon chain with the above-mentioned carbon number is adjacent to the hydrolyzable silyl group, thereby further improving the friction durability of the surface layer.

[0145] The upper limit of the carbon number is not particularly limited, but from the viewpoint of achieving better water and oil repellency and fingerprint stain removability, the carbon number is preferably 20 or less, and more preferably 18 or less.

[0146] Among them, as R 11, preferably a straight-chain alkylene group having 5 to 18 carbon atoms, and more preferably a straight-chain alkylene group having 11 to 18 carbon atoms.

[0147] R 11 Specifically, it can be represented by the following formula (g2).

[0148] *-(O) a1 -(R g2 O) a2 -R g2 -**…(g2)

[0149] in,

[0150] R g2 is an alkylene group having 1 or more carbon atoms, and the presence of multiple R g2 are optionally the same as or different from each other,

[0151] a1 is 0 or 1,

[0152] a2 is an integer greater than 0,

[0153] * is bonded to L 1 The connection key,

[0154] ** is bonded to T 11 connection key.

[0155] It should be noted that in L 1 In the case of a single bond, R 11 With R 1 Direct bonding.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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).

[0160] *-(O) a1 -R g3-**…(g3)

[0161] in,

[0162] R g3 is an alkylene group,

[0163] a1, * and ** are the same as those in formula (g2).

[0164] 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.

[0165] T 11 -SiR a11 z11 R a12 3-z11 The groups shown.

[0166] in,

[0167] R a11 is a hydroxyl group or a hydrolyzable group, and there are multiple R a11 When there are multiple R a11 are optionally the same as or different from each other,

[0168] R a12 It is a non-hydrolyzable group, and there are multiple R a12 When there are multiple R a12 are optionally the same as or different from each other,

[0169] z11 is an integer from 1 to 3.

[0170] 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.

[0171] As R a11 Examples 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.

[0172] As R a11The hydrolyzable group is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of facilitating the production of the compound (A1). 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.

[0173] As R a12 Examples of the non-hydrolyzable group include a hydrogen atom and a monovalent hydrocarbon group.

[0174] 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.

[0175] 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.

[0176] As T 11 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.

[0177] It should be noted that there are multiple T 11 When there are multiple T 11 Optional same or different.

[0178] x1 represents the (R 11 -T 11 ) may be an integer greater than 1, preferably 1 to 32, more preferably 1 to 18, and even more preferably 2 to 12.

[0179] L 1 is a single bond, or is a j+x1-valent group optionally having N, O, S, Si and optionally having a branch point, bonded to R 1 and R 11 The atoms of R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O). 1 and R 11 The atoms can be the same atoms or different atoms.

[0180] 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').

[0181] R f1 -(OR f11 ) y1 -OR 1 -R 11 -T 11 …(A1')

[0182] However, the symbols in formula (A1') are the same as those in formula (A1).

[0183] L 1 When L is a trivalent or higher group, 1 The present invention has at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure and an organopolysiloxane residue with a valence of (j+x1). 1 ”).

[0184] 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.

[0185] C becomes the branch point P 1 When the branch point P 1 For example, *-C(-**)3, (*-)2C(-**)2, (*-)3C-**, *-CR 29 (-**)2, or (*-)2CR 29 -** indicates. Where * is R 1 The connection key on the side, ** is R 11 Side connection key, R 29 It is a monovalent group, and examples thereof include 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, aromatic hydrocarbon groups such as a phenyl group, and groups composed of combinations thereof.

[0186] 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, and examples thereof include 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, aromatic hydrocarbon groups such as a phenyl group, and groups composed of combinations thereof.

[0187] 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 further excellent 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) and the like.

[0188]

[0189] 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.

[0190]

[0191] L with 2 or more valences 1 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 referred to as "bond B1 ”).

[0192] 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.

[0193] 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.

[0194]

[0195] 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 From the viewpoint of further improving the light resistance and chemical resistance of the surface layer, at least one bond in the group consisting of -C(O)NR 26 -、-N(R 26 )C(O)- or -C(O)-.

[0196] 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 B 1 As a divalent L 1 Specific examples include one or more keys B 1 (For example, *-B 1 -**, *-B 1 -R 28 -B 1 -**). Among them, R 28 is a single bond or a divalent organic group, * is R 1 The connection key on the side, ** is R 11 side connection key.

[0197] L with a valence of 3 or more 1 In the bonded1 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 As a specific example, there can be 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.

[0198] As the above R 28 The divalent organic group in the formula (a) may be a divalent aliphatic hydrocarbon group (such as an alkylene group, a cycloalkylene group, etc.), a divalent aromatic hydrocarbon group (such as a phenylene group), or a hydrocarbon group, and may have a bond B between carbon atoms of the hydrocarbon group. 1 The carbon number of the divalent organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0199] 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).

[0200]

[0201] (-A 1 -) d5 C(R e2 )4-d5―d6 (-Q 22 -) d6 …(L2)

[0202] (-A 2 -) d7 N(-Q 23 -) 3-d7 …(L3)

[0203] (-A 3 -) d8 Z 1 (-Q 24 -) d9 …(L4)

[0204] (-A 2 -) d10 Si(R e3 ) 4-d10-d11 (-Q 25 -) d11 …(L5)

[0205] -A 1 -Q 26 -…(L6)

[0206] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -) d12 …(L7)

[0207] Among them, in formula (L1) to formula (L7), A 1 , A 2 or A 3 The side and R of formula (A1) 1 Connected, Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side and R 11 are connected.

[0208] 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)-、-NRe6 - or -O- group, B 2 -C(O)NR e6 -、-C(O)-、-NR e6 -or-O-,B 3 -C(O)NR e6 -, -C(O)-, or -NR e6 -,

[0209] A2 is a single bond or -B 3 -R 30 -,

[0210] A 3 Bonded Z 1 When the atom in is a carbon atom, 3 A 1 , A 3 Bonded Z 1 When the atom in is a nitrogen atom, 3 A 2 ,

[0211] 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-,

[0212] Q 22 is a single bond, -B 3 -、-R 30 -B 3 -or-B 2 -R 30 -B 3 -,

[0213] Q 23 is a single bond or -R 30 -B 3 -,

[0214] In 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 ,

[0215] Q 25 is a single bond or -R 30 -B 3 -,

[0216] Q 26 is a single bond or -R 30 -B 3 -,

[0217] 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,

[0218] R e1 is a hydrogen atom or a hydrocarbon group (an aromatic hydrocarbon group such as an alkyl group or a phenyl group),

[0219] 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,

[0220] R e3 is a hydrocarbon group (an aromatic hydrocarbon group such as an alkyl group or a phenyl group),

[0221] R e6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group,

[0222] 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,

[0223] 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,

[0224] d1+d3 is an integer from 1 to 5,

[0225] d2+d4 is an integer from 1 to 5,

[0226] 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,

[0227] d7 is 1 or 2,

[0228] d8 is an integer greater than 1,

[0229] d9 is an integer greater than 1,

[0230] 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,

[0231] d12 is an integer from 1 to 3.

[0232] It should be noted that B 2 and B 3 There is no requirement for the direction of A. 1 When there are multiple A1 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.

[0233] In addition, d1+d3, d5, d7, d8, and d10 are j, and d2+d4, d6, 3-d7, d9, d11, and 1+d12 are x1.

[0234] From the viewpoint of easy production of the compound (A1) and the viewpoint of further improving the 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.

[0235] As Z 1 The ring structure in can include the above-mentioned ring structures, and the preferred embodiments are also the same.

[0236] 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.

[0237] From the viewpoint of easy preparation of compound 1, R e2 The number of carbon atoms in the alkyl portion of the acyloxy group is preferably 1-6, more preferably 1-3, and even more preferably 1-2.

[0238] From the viewpoint of easy production of the compound (A1) and the viewpoint of further improving the friction durability of the surface layer and the fingerprint contamination removability, d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0239] As the above L 1 As another embodiment of the present invention, for example, a group represented by any one of the following formulae (L11) to (L17) can be mentioned.

[0240]

[0241] (-A 1 -) d5 C(R e2 ) 4-d5―d6 (-Q 22 -G)d6 …(L12)(-A 2 -) d7 N(-Q 23 -G) 3-d7 …(L13)

[0242] (-A 3 -) d8 Z 1 (-Q 24 -G) d9 …(L14)

[0243] (-A 2 -) d10 Si(R e3 ) 4-d10-d11 (-Q 25 -G) d11 …(L15)

[0244] -A 1 -Q 26 -G…(L16)

[0245] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -G) d12 …(L17)

[0246] Among them, in formula (L11) to formula (L17), A 1 , A 2 or A 3 The side and R of formula (A1) 1 Connected, Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side and R 11 G is the following group (G21), L 1 The two or more Gs present may be the same or different. Symbols other than G are the same as those in formula (L11) to formula (L17).

[0247] -Si(R 51 ) 3-k (-Q 3 -) k …(G21)

[0248] In the above group (G21),

[0249] Si side and Q 22 , Q 23 , Q24 , 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.

[0250] Q 3 For-R 52 -B 3 -, from the viewpoint of easy production of the compound (A1) and further excellent friction durability, light resistance and chemical resistance of the surface layer, R 52 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.

[0251] 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.

[0252] 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.

[0253] 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.

[0254] p11 is preferably 0 or 1.

[0255] In compound (A1), L1 -(R 11 -T 11 ) x1 The molecular weight of the groups shown is 600 or more.

[0256] L 1 -(R 11 -T 11 ) x1 The molecular weight of the group represented by is preferably 610 or more, more preferably 615 or more, and further preferably 620 or more. 1 -(R 11 -T 11 ) x1 When the molecular weight of the group shown is within the above range, the friction durability of the surface layer is further improved.

[0257] 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.

[0258] 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.

[0259] From the viewpoint of further improving antifouling properties, the ratio is preferably 40% or less, and more preferably 25% or less.

[0260] As the compound (A1), for example, the following can be mentioned.

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267] Among them, R f2Each independently and f1 -(OR f11 ) y1 -OR 1 ] or [R f1 -(OR f11 ) y1 -O-] is the same as T 11 Likewise, Me represents a methyl group.

[0268] <Compound (A2)>

[0269] The compound (A2) has a structure represented by the following formula (A2).

[0270] (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 …(A2)

[0271] In addition, each symbol in formula (A2) is as described above.

[0272] R f12 OR f12 ) y2 With the above R f11 OR f11 ) y1 Same, the preferred method is also the same.

[0273] R 2 and R 3 Each independently of the above R 1 Same, the preferred method is also the same.

[0274] R 21 and R 31 With the above R 11 The same, the preferred mode is also the same. Among them, "bonded to L 1 In R 21 is replaced by "bonded to L 2 "To understand, R 31 is replaced by "bonded to L 3 ". In addition, "bonded to T 11 In R 21 is replaced by "bonded to T 21 "To understand, R 31 is replaced by "bonded to T31 "To understand. 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.

[0275] T 21 and T 31 Each independently is -SiR a21 z21 R a22 3-z21 , R a21 , R a22 , z21 are independently connected to form T 11 R a11 , R a12 , z11 are the same, and the preferred method is also the same.

[0276] x2 and x3 are each independently the same as x1, and the preferred aspects are also the same.

[0277] L 2 and L 3 Each independently of the above L 1 The same is true when j is 1.

[0278] For example, L 2 and L 3 When it is a single bond, the compound (A2) is represented by the following formula (A2').

[0279] T 31 -R 31 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -R 21 -T 21 …(A2')

[0280] However, the symbols in formula (A2') are the same as those in formula (A2).

[0281] 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 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 ”).

[0282] 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.

[0283] 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.

[0284] Si becomes the branch point P 2 When the branch point P 2 For example, *-Si(-**)3, or *-SiR 29 (-**)2 indicates.

[0285] 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.

[0286] Branch point P 2 The ring structure, the organopolysiloxane residue and the branch point P 1 Same, the preferred method is also the same.

[0287] 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.

[0288] For the 2-valent L 2 or L 3 , bonded to R 2 and R 21 , or R 3 and R 31The 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 or R 3 and R 31 The adjacent atoms are bond B 1 As a divalent L 2 or L 3 Specific examples include, for example, one or more keys B 1 (For example, *-B 1 -**, *-B 1 -R 28 -B 1 -**). Among them, R 28 is a single bond or a divalent organic group, * is R 2 or R 3 The connection key on the side, ** is R 21 or R 31 side connection key.

[0289] For L with a valence of 3 or more 2 or L 3 , bonded to R 2 and R 21 or 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 or 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 As a specific example, there can be one or more branch points P 2 (For example {*-P 2 (-**) x}、{*-P 2 -R 28 -P 2 -** x}, 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 (-R28 -B 1 -**) x}, etc.). Among them, in 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.

[0290] The above R 28 The method is as described above, and the preferred method is also the same.

[0291] 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).

[0292]

[0293] -A 1 -C(R e2 ) 4-d6 (-Q 22 -) d6 …(L22)

[0294] -A 2 -N(-Q 23 -)2…(L23)

[0295] -A 3 -Z 1 (-Q 24 -) d9 …(L24)

[0296] -A 2 -Si(R e3 ) 4-d11 (-Q 25 -) d11 …(L25)

[0297] -A 1 -Q 26 -…(L26)

[0298] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -) d12 …(L27)

[0299] 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.

[0300] Here, A 1 , A 2 , A 3 , Q 11 , Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , R e1 , R e2 R e3 , R e6 With the above L 1 The same as described in, the preferred embodiment is also the same.

[0301] 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,

[0302] 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,

[0303] d6 is an integer from 1 to 3,

[0304] d9 is an integer greater than 1,

[0305] d11 is an integer from 1 to 3,

[0306] d12 is an integer from 1 to 3.

[0307] It should be noted that d2+d4, d6, d9, d11, 1+d12 are x2 or x3.

[0308] From the viewpoint of easy production of the compound (A2) and the viewpoint of further improving the friction durability of the surface layer and the fingerprint contamination removability, d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0309] As the above L 2 or L 3 As another embodiment of the present invention, for example, a group represented by any one of the following formulae (L31) to (L37) can be mentioned.

[0310]

[0311] -A 1 -C(R e2 ) 4-d6 (-Q 22 -G) d6 …(L32)

[0312] -A 2 -N(-Q 23 -G)2…(L33)

[0313] -A 3 -Z 1 (-Q 24 -G) d9 …(L34)

[0314] -A 2 -Si(R e3 ) 4-d11 (-Q 25 -G) d11 …(L35)

[0315] -A 1 -Q 26 -…(L36)

[0316] -A 1 -CH(-Q 22 -G)-Si(R e3 ) 3-d12 (-Q 25 -G) d12 …(L37)

[0317] 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.

[0318] In compound (A2), L 2 -(R 21 -T 21 ) x2 The groups shown and (T 31 -R 31 ) x3 -L 3 At least one of the molecular weights of the groups shown has a molecular weight of 600 or more.

[0319] From the viewpoint of further improving the friction durability of the surface layer, the molecular weight is preferably 610 or more, more preferably 615 or more, and even more preferably 620 or more.

[0320] 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.

[0321] In addition, L 2 -(R 21 -T 21 ) x2 The 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.

[0322] 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.

[0323] From the viewpoint of further improving antifouling properties, the ratio is preferably 40% or less, and more preferably 25% or less.

[0324] As the compound (A2), for example, the following can be mentioned.

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333] 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.

[0334] <Compound (A3)>

[0335] The compound (A3) has a structure represented by the following formula (A3).

[0336] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 …(A3)

[0337] In addition, each symbol in formula (A3) is as described above.

[0338] R f13 OR f13 ) y3 With the above R f11 OR f11 ) y1 Same, the preferred method is also the same.

[0339] R 4 With the above R 1 Same, the preferred method is also the same.

[0340] R 41 With the above R 11 The same, the preferred mode is also the same. Among them, "bonded to L1 " is replaced by "bonded to L 4 ". In addition, "bonded to T 11 " is replaced by "bonded to T 41 "To understand. It should be noted that L 4 In the case of a single bond, R 41 With R 4 Direct bonding.

[0341] T 41 -SiR a41 z41 R a42 3-z41 , R a41 , R a42 , z41 are independently connected to form T 11 R a11 , R a12 , z11 are the same, and the preferred method is also the same.

[0342] Q 1 It is a group with a valence of r1 having a branch point, and r1 is 3 or 4.

[0343] As a component of Q 1 The branch point (hereinafter referred to as "branch point P 3 ”), for example, N, C, Si and ring structures can be listed. The branch point P 3 There may be one or two or more.

[0344] N becomes the branch point P 3 When the branch point P 3 For example, N(-*)3, NR 29 (-*)2 indicates.

[0345] 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.

[0346] 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.

[0347] Among them, * is OR f13 Side connection key, R 29 is a monovalent group. 29For example, a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, 41 -T 41 of fluoropolyether chains.

[0348] As the branch point P 3 The ring structure of the branch point P can be listed, for example. 1 The substituent of the ring structure may be a fluorine atom, a fluoroalkyl group, or a ring structure having no R. 41 -T 41 At least one group in the group consisting of a fluoropolyether chain.

[0349] 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).

[0350]

[0351] C(-A 11 -) d23 (R e12 ) 4-d23 …(Q2)

[0352] N(-A 12 -)3…(Q3)

[0353] Z 1 (-A 13 -) d24 …(Q4)

[0354] Si(-A 12 -) d25 (R e13 ) 4-d25 …(Q5)

[0355] CH(-A 11 -)2-Si(R e13 ) 3-d26 (-A 11 -) d26 …(Q6)

[0356] Among them, in formula (Q1) to formula (Q6), A 11 , A 12 or A 13 OR f13 ) are connected.

[0357] Here, A 11 is a single bond, -R 40 -、-B 13 -R 40 -, R40 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-,

[0358] A 12 is a single bond or -R 40 -,

[0359] 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 ,

[0360] 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,

[0361] 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-,

[0362] 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,

[0363] 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

[0364] R e13 is an alkyl group or a fluoroalkyl group,

[0365] 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,

[0366] 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,

[0367] d23 is 3 or 4,

[0368] d24 is 3 or 4,

[0369] d25 is 3 or 4,

[0370] d26 is 1 or 2.

[0371] 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.

[0372] From the viewpoint of easy production of the compound (A3) and the viewpoint of further improving the friction durability, light resistance and chemical resistance of the surface layer, 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.

[0373] As Z 1 The ring structure in the above branch point P can be listed as follows. 3 The preferred ring structure is the same.

[0374] 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.

[0375] In compound (A3), L 4 -(R 41 -T 41 ) x4 At least one molecular weight of the groups shown is 600 or greater.

[0376] From the viewpoint of further improving the friction durability of the surface layer, the molecular weight is preferably 610 or more, more preferably 615 or more, and even more preferably 620 or more.

[0377] 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.

[0378] In addition, L 4 -(R 41 -T 41 ) x4 The molecular weights of the groups shown are all within the above-mentioned ranges.

[0379] 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.

[0380] From the viewpoint of further improving antifouling properties, the ratio is preferably 40% or less, and more preferably 25% or less.

[0381] As the compound (A3), for example, the following can be mentioned.

[0382]

[0383]

[0384]

[0385]

[0386] Among them, {-OR f4 -} independently with [-(OR f13 ) y3 -OR 4 -] r1 or [-(OR f13 ) y3 -O-] r1 Same, T and T 41 same.

[0387] The present treatment agent may contain one kind of the present compound alone, or may contain two or more kinds of the present compounds.

[0388] The content of the present compound is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, further preferably 0.01 to 10% by mass, and particularly preferably 0.01 to 5% by mass, relative to the total mass of the present treatment agent.

[0389] <Method for producing the present compound>

[0390] The method for producing the present compound is not particularly limited, but a method of subjecting any of the following compound (B1), compound (B2) and compound (B3) to a hydrosilylation reaction with the following compound (C) is preferred from the viewpoint of ease of production.

[0391] Compound (B1), compound (B2) and compound (B3) are compounds represented by the following formula (B1), the following formula (B2) and the following formula (B3), respectively.

[0392] [R f1 -(OR f11 ) y1 -OR 1 ] j -L 1 -(R 11 -CH=CH2) x1 …(B1)

[0393] (CH2=CH-R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -CH=CH2) x2 …(B2)

[0394] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -CH=CH2) x4 ] r1 …(B3)

[0395] The symbols in the formula are as described above, and the preferred embodiments are also as described above.

[0396] The compound (C) is a compound represented by the following formula (C).

[0397] HkDJ a1 z1 R a2 3-z1…(C)

[0398] In the formula, R a1 , R a2 and Z1 independently form T 11 R a11 , R a12 Same as z11, the preferred method is also the same.

[0399] Compounds (B1) to (B3) can be synthesized according to a known synthesis method.

[0400] More specifically, there can be mentioned a method of introducing the following compound (E) into a precursor of the compounds (B1) to (B3) (for example, the following compounds (D1) to (D3)).

[0401] [R f1 -(OR f11 ) y1 -OR 1 ] j -L 1 -(E 1 ) x1 …(D1)

[0402] (E 1 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(E 1 ) x2 …(D2)

[0403] Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(E 1 ) x4 ] r1 …(D3)

[0404] E 2 -R g2 -CH=CH2…(E)

[0405] in,

[0406] E 1 is -OH, -OR, -C(O)-X, -I, -NH2, or -CH=CH2,

[0407] X is a halogen atom, an alkoxy group, a hydroxyl group or an amino group,

[0408] R is an alkyl group,

[0409] E 2 is -OH, -OR, -C(O)-X, -I, -NH2, or -CH=CH2, and according to E 1 Select a substituent that can undergo addition reaction,

[0410] R g2 For R 11 , R 21 , R 31 or R 41 , and is selected according to the synthesized compounds (B1) to (B3).

[0411] Other symbols are as described above.

[0412] The synthesis method of compounds (D1) to (D3) and the addition reaction of a compound corresponding to compound (E) include, for example, the method described in International Publication No. 2009 / 008380, the method described in International Publication No. 2013 / 121984, the method described in International Publication No. 2013 / 121986, the method described in International Publication No. 2015 / 087902, the method described in Patent Document 1, the method described in International Publication No. 2017 / 038832, the method described in International Publication No. 2018 / 143433, the method described in the specification of Japanese Patent Application No. 2017-104731, the method described in International Publication No. 2021 / 060537, the method described in International Publication No. 2021 / 054417, etc.

[0413] 〔Non-fluorinated organic solvent〕

[0414] The present treatment agent contains an organic solvent containing no fluorine atoms (non-fluorine-based organic solvent).

[0415] The non-fluorine-based organic solvent refers to an organic compound that does not contain fluorine atoms and is liquid at 25° C. and atmospheric pressure.

[0416] Examples of the non-fluorine-based organic solvent include hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, amide-based organic solvents, and sulfoxide-based organic solvents.

[0417] The hydrocarbon 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.

[0418] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, aniline, and nitrobenzene.

[0419] Examples of the aliphatic hydrocarbon include n-hexane, n-heptane, n-octane, and n-decane.

[0420] As the unsaturated hydrocarbon, for example, cyclopentene, hexene, heptene and butene can be cited.

[0421] Examples of the hydrocarbon solvent include petroleum ether and mineral spirits.

[0422] Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl aminoketone, 2-heptanone diisobutyl ketone, and diacetone alcohol.

[0423] Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, and butanol. Note that the following glycol solvents are not included in the alcohol solvents.

[0424] Examples of the ether 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 solvents.

[0425] 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, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether can be cited.

[0426] Examples of the ester 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.

[0427] Examples of the amide-based organic solvent include N,N-dimethylformamide.

[0428] Examples of the sulfoxide-based organic solvent include dimethyl sulfoxide.

[0429] As the non-fluorine-based organic solvent, from the viewpoint of better solubility and friction durability of the present compound, it is preferably at least one selected from the group consisting of alcohol-based organic solvents, ketone-based organic solvents, ether-based organic solvents and ester-based organic solvents, more preferably at least one selected from the group consisting of ketone-based organic solvents and ester-based organic solvents, and further preferably a ketone-based organic solvent.

[0430] The molecular weight of the non-fluorine-based organic solvent is preferably 30 to 500, more preferably 40 to 400, and even more preferably 50 to 300, from the viewpoint of further improving the solubility of the fluorine-containing ether compound.

[0431] Among them, the non-fluorine-based organic solvent is preferably acetone, ethyl acetate, methanol, toluene, methyl acetate, methyl ethyl ketone, propyl acetate or butyl acetate, and more preferably acetone, ethyl acetate, methyl ethyl ketone or propyl acetate.

[0432] The non-fluorine-based organic solvent may be used alone or in combination of two or more.

[0433] The content of the non-fluorine-containing organic solvent in the present treatment agent is preferably 60% by mass or more, more preferably 75 to 99.999% by mass, further preferably 85 to 99.99% by mass, particularly preferably 90 to 99.9% by mass.

[0434] In the present treatment agent, the ratio of the content of the non-fluorinated organic solvent to the content of the present compound is preferably 60 to 99.999% by mass, more preferably 90 to 99.99% by mass, and even more preferably 95 to 99.9% by mass, from the viewpoint of better uniformity during film formation.

[0435] 〔Other ingredients〕

[0436] The present treatment agent may contain other components in addition to the present compound and the non-fluorine-based organic solvent within a range not impairing the effects of the present invention.

[0437] Examples of other components include other fluorine-containing compounds other than the present compound, impurities described below, and known additives such as an acid catalyst and a preliminary basic catalyst for accelerating the hydrolysis and condensation reaction of the hydrolyzable silyl group.

[0438] The content of other components in the present treatment agent is preferably 10% by mass or less, more preferably 1% by mass or less. The lower limit may be 0% by mass.

[0439] Examples of other fluorine-containing compounds include fluorine-based organic solvents, fluorine-containing compounds by-produced in the production process of the present compound (hereinafter also referred to as by-product fluorine-containing compounds), and known fluorine-containing compounds used for applications similar to those of the present compound.

[0440] As other fluorine-containing compounds, compounds having a small risk of deteriorating the properties of the present compound are preferred.

[0441] The present treatment agent may contain a fluorine-based organic solvent.

[0442] Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and hydrofluoroolefins.

[0443] As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferred. Examples of commercially available products include C6F 13 H (AGC Corporation, ASAHIKLIN (registered trademark) AC-2000), C6F 13 C2H5 (ASAHIKLIN (registered trademark) AC-6000 manufactured by AGC Corporation), C2F5CHFCHFCF3 (Vertrel (registered trademark) XF manufactured by Chemours Corporation).

[0444] Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.

[0445] 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).

[0446] Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.

[0447] Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0448] 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.

[0449] Examples of the by-product fluorine-containing compound include unreacted fluorine-containing compounds in the synthesis process of the present compound. When the present treatment agent contains the by-product fluorine-containing compound, the purification process for removing the by-product fluorine-containing compound or reducing the amount of the by-product fluorine-containing compound can be simplified.

[0450] Examples of known fluorine-containing compounds include compounds described in the following documents.

[0451] Perfluoropolyether-modified aminosilane described in Japanese Patent Application Laid-Open No. 11-029585,

[0452] Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715,

[0453] The organosilicon compound described in Japanese Patent Application Laid-Open No. 2000-144097,

[0454] Perfluoropolyether-modified aminosilane described in Japanese Patent Application Laid-Open No. 2000-327772,

[0455] Fluorinated silicone described in Japanese Patent Publication No. 2002-506887,

[0456] The organosilicon compound described in JP-A-2008-534696,

[0457] Fluorinated modified hydrogen-containing polymers described in Japanese Patent No. 4138936,

[0458] Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, International Publication No. 2014 / 126064, and Japanese Patent Application Publication No. 2014-070163,

[0459] The organosilicon compounds described in International Publication No. 2011 / 060047 and International Publication No. 2011 / 059430,

[0460] The fluorinated organosilane compound described in International Publication No. 2012 / 064649,

[0461] The fluorine-containing oxyalkylene polymer described in Japanese Patent Application Laid-Open No. 2012-72272,

[0462] Fluorine-containing ether compounds described in International Publication No. 2013 / 042732, International Publication No. 2013 / 121984, International Publication No. 2013 / 121985, International Publication No. 2013 / 121986, International Publication No. 2014 / 163004, Japanese Patent Application Publication No. 2014-080473, International Publication No. 2015 / 087902, International Publication No. 2017 / 038830, International Publication No. 2017 / 038832, and International Publication No. 2017 / 187775,

[0463] Perfluoro(poly)ether-containing silane compounds described in Japanese Patent Application Publication No. 2014-218639, International Publication No. 2017 / 022437, International Publication No. 2018 / 079743, and International Publication No. 2018 / 143433,

[0464] Fluoropolyether-based polymer-modified silanes described in Japanese Patent Application Laid-Open Nos. 2015-199906, 2016-204656, 2016-210854, and 2016-222859,

[0465] Fluorine-containing ether compounds described in International Publication No. 2018 / 216630, International Publication No. 2019 / 039226, International Publication No. 2019 / 039341, International Publication No. 2019 / 039186, International Publication No. 2019 / 044479, Japanese Patent Application Publication No. 2019-44158, International Publication No. 2019 / 044479, and International Publication No. 2019 / 163282.

[0466] In addition, commercially available products of fluorine-containing compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., SURECO AF series such as SURECO (registered trademark) 2101S manufactured by AGC Corporation, OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, OPTOOL (registered trademark) UD509, etc. manufactured by Daikin Industries, Ltd.

[0467] When the present treatment agent contains other fluorine-containing compounds, the ratio of the other fluorine-containing compounds to the sum of the present compound and the other fluorine-containing compounds is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. The lower limit may be 0% by mass.

[0468] The ratio of the present compound in the present treatment agent to the total of the present compound and other fluorine-containing compounds is preferably 80% by mass or more, more preferably 85% by mass or more. The upper limit may be 100% by mass.

[0469] When the content of the present compound and other fluorine-containing compounds is within the above range, the surface layer is excellent in water and oil repellency, friction durability, fingerprint contaminant removability, lubricity, and appearance.

[0470] Examples of the impurities include compounds that are unavoidable in the production process of the present compound and other fluorine-containing compounds.

[0471] The present treatment agent is suitable for use as a coating liquid. When the present treatment agent is used as a coating liquid, it may be a liquid, and may be a solution or a dispersion.

[0472] The total concentration of components other than the non-fluorine-containing organic solvent and the fluorine-containing organic solvent in the present treatment agent (hereinafter also referred to as "solid content concentration") is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, further preferably 0.01 to 10% by mass, and particularly preferably 0.01 to 1% by mass.

[0473] The solid content concentration of the surface treatment agent is a value calculated from the mass of the surface treatment agent before heating and the mass of the surface treatment agent after heating in a convection dryer at 120° C. for 4 hours.

[0474] [thing]

[0475] The article of the present invention (hereinafter also referred to as "the present article") preferably comprises a substrate and a surface layer disposed on the substrate, and has a base layer between the substrate and the surface layer.

[0476] The surface layer is a layer formed of the above-mentioned surface treatment agent, and contains the condensate of the above-mentioned fluorine-containing ether compound.

[0477] The material and shape of the substrate can be appropriately selected according to the purpose of the article. As the material of the substrate, for example, glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof can be listed. The glass can be chemically strengthened. In particular, as a substrate that needs to be water-repellent and oil-repellent, a substrate for a touch panel, a substrate for a display, a substrate constituting a housing of an electronic device, etc. can be listed. The substrate for a touch panel and the substrate for a display are light-transmissive. "Light-transmissive" means that the vertical incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. As a material for a touch panel substrate, glass or a transparent resin is preferred.

[0478] The substrate may be a substrate to which a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment is applied on the surface provided with the base layer. The surface to which the surface treatment is applied has better adhesion to the substrate and the base layer, and as a result, the friction durability of the surface layer is further improved. As the surface treatment, corona discharge treatment or plasma treatment is preferably used from the viewpoint that the friction durability of the surface layer is better.

[0479] The base layer is preferably a layer containing a silicon-containing oxide (preferably silicon oxide), and may also contain other elements. When the base layer contains silicon oxide, the reactive silyl group of the fluorine-containing ether compound undergoes dehydration condensation to form Si-O-Si bonds with the base layer, thereby forming a surface layer with excellent friction durability.

[0480] The content of silicon oxide in the base layer is preferably 65% ​​by mass or more, more preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more. If the content of silicon oxide is above the lower limit, Si-O-Si bonds are fully formed in the base layer, and the mechanical properties of the base layer are fully ensured. The content of silicon oxide is the remainder obtained by removing the total content of other elements (in the case of oxides, the amount converted to oxides) from the mass of the base layer.

[0481] From the viewpoint of durability of the surface layer, the oxide in the base layer preferably further comprises one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum and tungsten. By including these elements, the bonding between the base layer and the above-mentioned fluorine-containing ether compound is enhanced, and the friction durability is improved.

[0482] The thickness of the base layer is preferably 1 to 200 nm, more preferably 2 to 20 nm. If the thickness of the base layer is above the lower limit, it is easy to fully obtain the effect of improving the adhesiveness brought by the base layer. If the thickness of the base layer is below the upper limit, the friction durability of the base layer itself becomes higher. As a method for measuring the thickness of the base layer, for example, a method for observing the cross section of the base layer using an electron microscope (SEM, TEM, etc.) and a method using an optical interference film thickness meter, a spectroscopic ellipsometer or a step difference meter can be listed.

[0483] Examples of the method for forming the base layer include a method of vapor-depositing a vapor deposition material having a desired composition of the base layer on the surface of the substrate.

[0484] An example of the vapor deposition method is the vacuum vapor deposition method, which is a method of causing a vapor deposition material to evaporate in a vacuum chamber and adhere to the surface of a substrate.

[0485] The temperature during vapor deposition (for example, the temperature of a boat on which the vapor deposition material is placed when a vacuum vapor deposition apparatus is used) is preferably 100 to 3000°C, more preferably 500 to 3000°C.

[0486] The pressure during vapor deposition (for example, when a vacuum vapor deposition apparatus is used, the absolute pressure in a tank containing the vapor deposition material) is preferably 1 Pa or less, and more preferably 0.1 Pa or less.

[0487] When the base layer is formed using a vapor deposition material, one type of vapor deposition material may be used, or two or more types of vapor deposition materials containing different elements may be used.

[0488] As the evaporation method of the evaporation material, there can be listed a resistance heating method in which the evaporation material is melted on a resistance heating boat made of a high melting point metal to evaporate it; an electron gun method in which an electron beam is irradiated to the evaporation material to directly heat the evaporation material to melt the surface and evaporate it. As the evaporation method of the evaporation material, the electron gun method is preferred from the viewpoint that local heating can be performed so that high melting point materials can also be evaporated, and the place where the electron beam is not irradiated is low temperature so there is no risk of reaction with the container and mixing with impurities. As the evaporation material used in the electron gun method, a molten granular body or a sintered body is preferred from the viewpoint that it is not easy to scatter even if an airflow is generated.

[0489] The surface layer contains the condensate of the above-mentioned fluorine-containing ether compound. The condensate of the fluorine-containing ether compound includes the following structures: a structure in which a silanol group (Si-OH) is formed by a hydrolysis reaction of a hydrolyzable silyl group in the fluorine-containing ether compound, and a silanol group undergoes a condensation reaction between molecules to form a structure with a Si-O-Si bond; and a structure in which a silanol group in the fluorine-containing ether compound undergoes a condensation reaction with a silanol group or a Si-OM group (wherein M is an alkali metal element) on the surface of a substrate or a base layer to form a structure with a Si-O-Si bond. In addition, the surface layer may also contain a condensate of a fluorine-containing compound other than the fluorine-containing ether compound. That is, the surface layer contains a fluorine-containing compound having a reactive silyl group in a state in which a part or all of the reactive silyl groups of the fluorine-containing compound undergo a condensation reaction.

[0490] The thickness of the surface layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. If the thickness of the surface layer is above the lower limit, the effect of the surface layer can be fully obtained. If the thickness of the surface layer is below the upper limit, the utilization efficiency is high.

[0491] The thickness of the surface layer is obtained by using an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis.

[0492] The present article is preferably a touch panel. In this case, the surface layer is preferably formed on the surface of a member constituting a finger contact surface of the touch panel.

[0493] [Production method]

[0494] The method for producing the article is a method of forming a surface layer on a substrate by dry coating or wet coating using the treatment agent.

[0495] The treatment agent can be suitably used in wet coating methods, such as spin coating, wipe coating, spray coating, blade coating, dip coating, die coating, inkjet, flow coating, roll coating, casting, Langmuir-Blodget, gravure coating, etc.

[0496] The treatment agent can be used in a dry coating method. Examples of dry coating methods include vacuum evaporation, CVD, and sputtering. From the perspective of suppressing the decomposition of the fluorine-containing ether compound and the simplicity of the apparatus, the vacuum evaporation method is preferably used.

[0497] In vacuum deposition, a granular material formed by supporting a fluorine-containing ether compound and a metal compound on a metal porous body formed of a metal material such as iron or steel can be used. The granular material supported with a fluorine-containing ether compound and a metal compound can be produced by impregnating the metal porous body with the treatment agent and removing the liquid medium by drying.

[0498] In order to improve the friction durability of surface layer, the operation for promoting the reaction of fluorinated ether compound and base material (or base layer) can be carried out as required.As the above-mentioned operation, heating, humidification, light irradiation etc. can be listed.For example, in the atmosphere with moisture, the base material heating that is formed with surface layer can promote the reaction of the hydrolysis reaction of hydrolyzable group, the surface hydroxyl etc. of base material with silanol group, the generation of siloxane bond based on the condensation reaction of silanol group.

[0499] After the surface treatment, the compounds in the surface layer that are not chemically bonded to other compounds or the substrate can be removed as needed. Specific examples include a method of flooding the surface layer with a solvent and a method of wiping with a cloth soaked with a solvent.

[0500] Example

[0501] Hereinafter, the present invention will be described in further detail using examples, but the present invention is not limited to these examples. Hereinafter, "%" means "mass %" unless otherwise specified. It should be noted that Examples 1 to 14 are examples, and Examples 15 to 18 are comparative examples.

[0502] [Synthesis of Compound 1]

[0503] <Synthesis example 1-1>

[0504] According to the method described in Synthesis Examples 3 and 4 of International Publication No. 2018 / 143433, the following compound 1 was obtained.

[0505] CF3O(CF2CF2O) 21 (CF2O) 29 CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3

[0506] [Synthesis of Compound 2]

[0507] <Synthesis example 2-1>

[0508] 2.1 g of methyl cyanoacetate, 11.9 g of 11-bromo-1-undecene (CH2=CH(CH2)9-Br), 11.2 g of potassium carbonate, and 52.5 g of N,N-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 8.1 g of the following compound (2-1).

[0509] Compound (2-1)

[0510]

[0511] <Synthesis example 2-2>

[0512] 8.1 g of the above compound (2-1), 24.3 g of dimethyl sulfoxide (DMSO), 3.0 g of lithium chloride and 4.7 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 and concentrated by an evaporator, and subjected to silica gel column chromatography to obtain 6.2 g of the following compound (2-2).

[0513] Compound (2-2)

[0514]

[0515] <Synthesis example 2-3>

[0516] 3.0 g of lithium aluminum hydride and 27.0 g of dehydrated tetrahydrofuran (THF) were placed in a reaction container, and stirred at 0° C. under a nitrogen atmosphere. Then, 5.4 g of the above compound (2-2) was placed, and stirred at 0° C. under a nitrogen atmosphere. After the reaction was completed, water and 1N sodium hydroxide were added, and the organic phase was recovered, concentrated with an evaporator, and subjected to silica gel column chromatography to obtain 4.3 g of the following compound (2-3).

[0517] Compound (2-3)

[0518]

[0519] <Synthesis example 2-4>

[0520] According to the method of (Example 6-1) to (Example 6-4) of International Publication No. 2013 / 121984, the following compound (2-4) was obtained.

[0521] Compound (2-4)

[0522]

[0523] The average value of the repeating unit n is 13.

[0524] <Synthesis example 2-5>

[0525] In a reaction container, 15 g of the above compound (2-4), 15 g of 1,3-bis(trifluoromethyl)benzene, and 2.8 g of the above compound (2-3) were placed and stirred at 60° C. under a nitrogen atmosphere. After the reaction was completed, the mixture was washed, concentrated with an evaporator, and subjected to silica gel column chromatography to obtain 11.4 g of the following compound (2-5).

[0526] Compound (2-5)

[0527]

[0528] The average value of the repeating unit n is 13.

[0529] <Synthesis example 2-6>

[0530] In a nitrogen-purged reaction vessel, 5.0 g of the above-mentioned compound (2-5), 5.0 g of 1,3-bis(trifluoromethyl)benzene, 0.21 g of a xylene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 30.48 g of HSi(OCH3) and 0.04 g of DMSO were placed and stirred at 40° C. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered with a membrane filter having a pore size of 0.2 μm to obtain 5.1 g of the following compound 2.

[0531] Compound 2

[0532]

[0533] The average value of the repeating unit n is 13.

[0534] [Synthesis of Compound 3]

[0535] <Synthesis example 3-1>

[0536] 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 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 the following compound (3-1).

[0537] Compound (3-1)

[0538]

[0539] <Synthesis example 3-2>

[0540] 6.1 g of the above compound (3-1), 24.4 g of 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 and concentrated by an evaporator and subjected to silica gel column chromatography to obtain 4.0 g of the following compound (3-2).

[0541] Compound (3-2)

[0542]

[0543] <Synthesis example 3-3>

[0544] 2.9 g of the above compound (3-2), 52.98 g of ethanol and 8.6 g of potassium hydroxide were placed in a reaction container and stirred at 120° 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 and subjected to silica gel column chromatography to obtain 2.5 g of the following compound (3-3).

[0545] Compound (3-3)

[0546]

[0547] <Synthesis Example 3-4>

[0548] 2.5 g of the compound (3-3), 25 g of dichloromethane, 2.6 g of oxalyl chloride and 0.04 g of DMF were placed in a reaction container and stirred at room temperature (25° C.) under a nitrogen atmosphere. After the reaction, the mixture was concentrated using an evaporator to obtain 2.6 g of the following compound (3-4).

[0549] Compound (3-4)

[0550]

[0551] <Synthesis example 3-5>

[0552] According to the method of (Example 1-1) to (Example 1-3) of International Publication No. 2021 / 131960, the following compound (3-5) was obtained.

[0553] Compound (3-5)

[0554]

[0555] The average value of the repeating unit n is 13.

[0556] <Synthesis Example 3-6>

[0557] In a reaction container, 10.0 g of the compound (3-5), 1.6 g of the compound (3-4) and 10 g of 1,3-bis(trifluoromethyl)benzene were placed and stirred at 40° C. under a nitrogen atmosphere. After the reaction, the mixture was concentrated with an evaporator and subjected to silica gel column chromatography to obtain 5.2 g of the following compound (3-6).

[0558] Compound (3-6)

[0559]

[0560] The average value of the repeating unit n is 13.

[0561] <Synthesis example 3-7>

[0562] In a nitrogen-purged reaction vessel, 2.0 g of the above-mentioned compound (3-6), 2.0 g of 1,3-bis(trifluoromethyl)benzene, 0.09 g of a xylene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 30.19 g of HSi(OCH3) and 0.02 g of DMSO were placed and stirred at 40° C. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered with a membrane filter having a pore size of 0.2 μm to obtain 2.0 g of the following compound 3.

[0563] Compound 3

[0564]

[0565] The average value of the repeating unit n is 13.

[0566] [Synthesis of Compound 4]

[0567] <Synthesis example 4-1>

[0568] 2.1 g of methyl cyanoacetate, 7.1 g of 7-bromo-1-heptene, 11.2 g of potassium carbonate, and 50 g of N,N-dimethylformamide were added to a reaction vessel and stirred at 85°C overnight (24 hours). Then, after cooling to room temperature (25°C), hydrochloric acid was added and extracted with dichloromethane. The solvent was distilled off to obtain 5.5 g of the following compound (4-1).

[0569] Compound (4-1)

[0570]

[0571] 1H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92 ~ 5.74 (m, 2H), 5.13 ~ 4.90 (m, 4H), 3.8 (s, 3H), 1.90 ~ 2.20 (m, 4H), 1.90 ~ 1.0 (m, 16H)

[0572] <Synthesis example 4-2>

[0573] 5.5 g of the above compound (4-1) and 30 g of DMSO were placed in a reaction container, stirred, and then 5 g of water and 3.2 g of lithium chloride were added. The mixture was heated to 180°C and stirred at 180°C overnight (24 hours). Then, after cooling to room temperature (25°C), extraction with dichloromethane was performed, the solvent was distilled off, and flash column chromatography using silica gel (developing solvent: ethyl acetate / hexane) was performed to obtain 4.4 g of the following compound (4-2).

[0574] Compound (4-2)

[0575]

[0576] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92 ~ 5.74 (m, 2H), 5.13 ~ 4.90 (m, 4H), 2.41 ~ 2.62 (m, 1H), 1.95 ~ 2.20 (m, 4H), 1.90 ~ 1.0 (m, 16H)

[0577] <Synthesis example 4-3>

[0578] After adding 2.3 g of the above compound (4-2) and 20 mL of dehydrated THF to a reaction container, 6.0 mL (12.5 mmol) of a THF solution of lithium diisopropylamide was added, and the mixture was stirred at -70°C for 15 minutes. Then, 2.0 g of 7-bromo-1-heptene was added to the reaction container, and the mixture was stirred at room temperature (25°C) overnight. Then, hydrochloric acid was added to the reaction container, and the mixture was extracted with dichloromethane, and the solvent was distilled off to obtain 2.9 g of the following compound (4-3).

[0579] Compound (4-3)

[0580]

[0581] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92 ~ 5.70 (m, 3H), 5.13 ~ 4.8 (m, 6H), 1.95 ~ 2.20 (m, 6H), 1.90 ~ 1.0 (m, 24H)

[0582] <Synthesis example 4-4>

[0583] 2.9 g of the above compound (4-3) was dissolved in 20 mL of dehydrated THF in a reaction container, and the solution was cooled to 0°C. 12 mL (12 mmol) of a THF solution of lithium aluminum hydride was added to the reaction container and stirred. Water and a 15% aqueous sodium hydroxide solution were added to the reaction container, stirred at room temperature (25°C), and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel (developing solvent: methanol) was performed to obtain 2.0 g of the following compound (4-4).

[0584] Compound (4-4)

[0585]

[0586] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92 ~ 5.70 (m, 3H), 5.13 ~ 4.8 (m, 6H), 2.40 ~ 2.60 (s, 2H), 1.95 ~ 2.20 (m, 6H), 1.90 ~ 1.0 (m, 24H)

[0587] <Synthesis Example 4-5>

[0588] After adding 10 g of the compound (2-4) and 10 g of AC-2000 to a reaction container, 1.1 g of the compound (4-4) was added. After stirring at 40°C overnight (24 hours), column chromatography using silica gel (developing solvent: C6F 13 H (manufactured by AGC Corporation, ASAHIKLIN (registered trademark) AC-2000) / CF3CH2OCF2CF2H (manufactured by AGC Corporation, ASAHIKLIN AE-3000)) to obtain 7.0 g of the following compound (4-5).

[0589] Compound (4-5)

[0590]

[0591] The average value of the repeating unit n is 13.

[0592] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 6.44~6.21(1H), 5.89~5.61(m, 3H), 5.11~4.55(6H), 3.49~3.23(m, 2H), 2.11~1.81(m, 6H), 1.52~1.02(24H)

[0593] 19F-NMR (376MHz, Chloroform-d) δ (ppm): -55.3, -82.8, -88.0, -90.2, -119.4, -125.2, -125.6

[0594] <Synthesis example 4-6>

[0595] 1.0 g of AC-6000, 0.5 g of the above compound (4-5), 8.3 mg of a toluene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%), 2.6 mg of aniline, and 0.25 g of trimethoxysilane were added to a reaction container and stirred at 40° C. Then, the solvent was distilled off under reduced pressure to obtain 0.52 g of the following compound 4.

[0596] Compound 4

[0597]

[0598] The average value of the repeating unit n is 13.

[0599] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 6.44~6.21(1H), 3.51~4.01(m, 27H), 3.25~3.50(2H), 1.58~1.02(36H), 0.92~0.57(6H)

[0600] 19 F-NMR (376MHz, Chloroform-d) δ (ppm): -55.3, -82.8, -88.0, -90.2, -119.4, -125.2, -125.6

[0601] [Synthesis of Compound 5]

[0602] <Synthesis example 5-1>

[0603] 3.0 g of 3,4-dimethylbenzonitrile, 8.14 g of N-bromosuccinimide, 0.74 g of benzoyl peroxide, and 44.6 g of 1,2-dichloroethane were placed in a reaction container and stirred at 85° C. under a nitrogen atmosphere. After the reaction was completed, the generated solid was filtered, and the recovered organic phase was concentrated with an evaporator and subjected to silica gel column chromatography to obtain 3.5 g of the following compound (5-1).

[0604] Compound (5-1)

[0605]

[0606] <Synthesis example 5-2>

[0607] 5.9 g of 11-bromo-1-undecene (CH2=CH(CH2)9-Br), 0.65 g of powdered magnesium and 19.5 g of THF were placed in a reaction container, and the mixture was stirred at 40°C for 24 hours.

[0608] Then, 0.35 g of cupric chloride, 3.5 g of the above compound (5-1) and 21.0 g of THF were added and stirred at 45° C. After the reaction, hydrochloric acid was added and the organic phase was recovered and concentrated by an evaporator and subjected to silica gel column chromatography to obtain 3.0 g of the following compound (5-2).

[0609] Compound (5-2)

[0610]

[0611] <Synthesis example 5-3>

[0612] 0.30 g of lithium aluminum hydride and 6.0 g of THF were placed in a reaction container, 1.2 g of the above compound (5-2) was dissolved in 6.0 g of THF, and the mixture was slowly added dropwise to the reaction container and stirred at 25° C. After the reaction was completed, an aqueous sodium hydroxide solution was added, the generated solid was filtered, and the recovered organic phase was concentrated with an evaporator and subjected to silica gel column chromatography to obtain 1.0 g of the following compound (5-3).

[0613] Compound (5-3)

[0614]

[0615] <Synthesis example 5-4>

[0616] According to the method of (Example 6-1) to (Example 6-4) of International Publication No. 2013 / 121984, the following compound (2-4) was obtained.

[0617] Compound (2-4)

[0618]

[0619] The average value of the repeating unit n is 13.

[0620] <Synthesis example 5-5>

[0621] 3.3 g of the above compound (2-4), 3.3 g of 1,3-bis(trifluoromethyl)benzene and 0.44 g of the above compound (5-3) were placed in a reaction container and stirred at 60° C. under a nitrogen atmosphere. After the reaction was completed, the mixture was washed, concentrated with an evaporator and subjected to silica gel column chromatography to obtain 2.5 g of the following compound (5-5).

[0622] Compound (5-5)

[0623]

[0624] The average value of the repeating unit n is 13.

[0625] <Synthesis Example 5-6>

[0626] In a nitrogen-purged reaction vessel, 2.5 g of the above-mentioned compound (5-5), 2.5 g of 1,3-bis(trifluoromethyl)benzene, 0.11 g of a xylene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 30.24 g of HSi(OCH3) and 0.02 g of DMSO were placed and stirred at 40° C. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered with a membrane filter having a pore size of 0.2 μm to obtain 2.5 g of the following compound 5.

[0627] Compound 5

[0628]

[0629] The average value of the repeating unit n is 13.

[0630] [Synthesis of Compound 6]

[0631] The following compound 6 was obtained by the method described in Synthesis Example 16-3 of International Publication No. 2023 / 074874.

[0632] Compound 6

[0633]

[0634] Among them, the average value of repeating unit q16 is 21, and the average value of repeating unit p16 is 29.

[0635] [Example 1]

[0636] The above-mentioned compound 2 was mixed with acetone as a liquid medium to prepare a surface treatment agent 1.

[0637] [Example 2]

[0638] Surface treatment agent 2 was prepared in the same manner as in Example 1 except that ethyl acetate ("ethyl acetate" manufactured by Kanto Chemical Co., Ltd.) was used as the liquid medium instead of acetone.

[0639] [Examples 3~4]

[0640] Surface treatment agent 3 and surface treatment agent 4 were prepared according to the methods described in Examples 1 and 2, respectively, except that compound 3 was used instead of compound 2 as the fluorine-containing ether compound.

[0641] [Examples 5~6]

[0642] Surface treatment agent 5 and surface treatment agent 6 were prepared according to the method described in Example 3, except that methanol ("methanol" manufactured by Kanto Chemical Co., Ltd.) and toluene ("toluene" manufactured by Kanto Chemical Co., Ltd.) were used as the liquid medium instead of acetone.

[0643] [Examples 7~8]

[0644] Surface treatment agent 7 and surface treatment agent 8 were prepared according to the methods described in Examples 1 and 2, respectively, except that compound 4 was used instead of compound 2 as the fluorine-containing ether compound.

[0645] [Examples 9~10]

[0646] Surface treatment agents 9 to 10 were prepared according to the methods described in Examples 1 and 2, except that the compound 5 was used instead of the compound 2 as the fluorine-containing ether compound.

[0647] [Examples 11~12]

[0648] Surface treatment agents 11 to 12 were prepared according to the methods described in Examples 1 and 2, respectively, except that Compound 1 was used instead of Compound 2 as the fluorine-containing ether compound.

[0649] [Examples 13~14]

[0650] Surface treatment agents 13 and 14 were prepared according to the methods described in Examples 1 and 2, respectively, except that Compound 6 was used instead of Compound 2 as the fluorine-containing ether compound.

[0651] [Example 16]

[0652] A surface treatment agent 16 was prepared in the same manner as in Example 1 except that hydrofluoroalkyl ether (C4F9OC2H5, "Novec (registered trademark) HFE-7200" manufactured by 3M Company) was used as the liquid medium instead of acetone.

[0653] [Example 15, Example 17, Example 18]

[0654] Surface treatment agent 15, surface treatment agent 17 and surface treatment agent 18 were prepared according to the method described in Example 16, except that compound 1, 3 and 4 were used instead of compound 2 as the fluorine-containing ether compound.

[0655] The content (solid content concentration) of the fluorine-containing ether compound in the surface treatment agents prepared in Examples 1 to 18 was 0.05% in all cases.

[0656] [Production and evaluation of items]

[0657] (Wet coating method)

[0658] The compounds of Examples 1 to 18 were used to treat the surface of the substrate to obtain articles having a surface layer. As the surface treatment method, the following dry coating method and wet coating method were used for each example. Chemically strengthened glass was used as the substrate. The obtained articles were evaluated by the following method. The results are shown in Table 1.

[0659] The substrate was immersed in the surface treatment agent (coating liquid) of Examples 1 to 18, left for 30 minutes, and then pulled out (dip coating method). The coating film was dried at 200° C. for 30 minutes and washed with AE-3000 to obtain an article having a surface layer on the surface of the substrate.

[0660] (Evaluation method)

[0661] <Initial water contact angle>

[0662] For each surface layer, the contact angle of about 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., DMo-701). The above measurement was performed at 5 different locations on the surface of the surface layer, and the arithmetic mean of the measured values ​​was calculated. The contact angle was calculated using the 2θ method.

[0663] From the calculated contact angle, the initial water contact angle was evaluated based on the following evaluation criteria.

[0664] The evaluation criteria of the initial water contact angle are as follows.

[0665] A (excellent): 110 degrees or more.

[0666] B (good): 108 degrees or more and less than 110 degrees.

[0667] C (not acceptable): less than 108 degrees.

[0668] <Friction durability>

[0669] For the surface layer, the water contact angle was measured by using a reciprocating traverse tester (manufactured by KNT) according to JIS L0849: 2013 (ISO 105-X12: 2001) and steel wool Bonstar (#0000) was reciprocated 30,000 times at a speed of 320 cm / min under a pressure of 98.07 kPa. The friction durability was evaluated based on the following evaluation criteria based on the difference in water contact angle before and after the friction test. The smaller the reduction in water repellency (water contact angle) caused by the friction test, the smaller the reduction in performance caused by friction, and the better the friction resistance.

[0670] The evaluation criteria for friction durability are as follows.

[0671] A (good): The change in the water contact angle before and after 30,000 reciprocations is within 5 degrees.

[0672] B (acceptable): The change in the water contact angle after 30,000 reciprocations is greater than 5 degrees and within 10 degrees.

[0673] C (unacceptable): The change in the water contact angle after 30,000 reciprocations is greater than 10 degrees.

[0674] <Solubility>

[0675] For each surface treatment agent, the solubility of the fluorine-containing ether compound was measured by the following method.

[0676] 500 g of each liquid medium was added to 0.5 g of the fluorinated ether compound, and the mixture was stirred at 25° C. for 1 hour in a 1 L eggplant flask. After stirring for 1 hour, stirring was stopped and the mixture was allowed to stand for 24 hours. After standing, the mixture was observed visually, and the solubility was evaluated based on the following evaluation criteria.

[0677] The evaluation criteria for solubility are as follows.

[0678] A (good): No precipitate was observed in the solution, and a uniform solution was obtained.

[0679] B (acceptable): Although no precipitate was observed, white turbidity was observed.

[0680] C (unacceptable): Precipitation was observed.

[0681] Table 1 shows the composition of each surface treatment agent and each evaluation result.

[0682] In the table, the column "Non-F-based partial structure molecular weight" indicates the molecular weight of the compound 1 to the compound 4 corresponding to L of the formula (A1). 1 -(R 11 -T 11 ) x1 The molecular weight of the partial structure of the group shown.

[0683] In the table, the column "PFPE molecular weight" indicates the molecular weight of the above compounds 1 to 4, which corresponds to (OR f11 ) y1 The molecular weight of the partial structure of the group shown.

[0684] In the table, the column "Non-F-based partial structure molecular weight ratio (mass %)" indicates the ratio of the molecular weight of the above-mentioned compounds 1 to 4 to the molecular weight of the above-mentioned compounds 1 to 4. f1 -(OR f11 ) y1 -OR 1 ] j The molecular weight of the partial structure of the group represented by 1 -(R 11 -T 11 )x1 The ratio of the molecular weights of the partial structures of the groups shown.

[0685] In the table, "HFE" means hydrofluoroalkyl ether.

[0686] [Table 1]

[0687]

[0688] As shown in Table 1, it was confirmed that a surface treatment agent comprising a fluorine-containing ether compound and an organic solvent containing no fluorine atoms can form a surface layer with excellent friction durability, wherein the fluorine-containing ether compound is represented by any one of the prescribed formulas (A1) to (A3), and the molecular weight of the organic group containing a reactive silyl group is greater than a prescribed value (Examples 1 to 14).

[0689] Industrial Applicability

[0690] As an example, articles having a surface layer formed by the surface treatment agent of the present invention can be used as: optical articles used as part of the components of the following products, touch panels, anti-reflection films, anti-reflection glass, SiO2-treated glass, tempered glass, sapphire glass, quartz substrates, mold metals, etc.

[0691] Products: Car navigation, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), copiers, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, templates and molds for nanoimprinting, etc.

[0692] It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2022-164739 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 surface treatment agent comprising: at least one fluorine-containing ether compound selected from the group consisting of a compound represented by the following formula (A1), a compound represented by the following formula (A2), and a compound represented by the following formula (A3); and Organic solvents containing no fluorine atoms, [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) 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 as or different from each other, R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f11 When there are multiple R f11 are optionally the same as or different from each other, R 1 is an alkylene group or a fluoroalkylene group, and there are multiple R 1 When there are multiple R 1 are optionally the same as or different from each other, L 1 is a single bond, or is a j+x1-valent group optionally having N, O, S, Si and optionally having a branch point, bonded to R 1 and R 11 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group, R 11 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein the group bonded to L 1 The atom of R is optionally an etheric oxygen atom. 11 When there are multiple R 11 are optionally the same as or different from each other, T 11 -SiR a11 z11 R a12 3-z11 The group shown has multiple T 11 When there are multiple T 11 are optionally the same as or different from each other, R a11 is a hydroxyl group or a hydrolyzable group, and there are multiple R a11 When there are multiple R a11 are optionally the same as or different from each other, R a12 It is a non-hydrolyzable group, and there are multiple R a12 When there are multiple R a12 are optionally the same as or different from each other, j is an integer greater than or equal to 1. When j is 1, y1 is an integer greater than or equal to 2, or R 1 is a fluoroalkylene group, z11 is an integer from 1 to 3, x1 is an integer greater than 1, y1 is an integer greater than or equal to 1. When a plurality of y1 exist, the plurality of y1 exist may be the same as or different from each other. L 1 -(R 11 -T 11 ) x1 The molecular weight of the group shown is 600 or more, In formula (A2), R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R f12 When there are multiple R f12 are optionally the same as or different from each other, R 2 and R 3 are each independently an alkylene group or a fluoroalkylene group, L 2 is a single bond, or is a 1+x2 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 2 and R 21 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group, L 3 is a single bond, or is a 1+x3 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 3 and R 31 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group, R 21 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 2 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 21 When there are multiple R 21 are optionally the same as or different from each other, R 31 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 3 The adjacent atoms are optionally etheric oxygen atoms, and there are multiple R 31 When there are multiple R 31 are optionally the same as or different from each other, T 21 and T 31 Each independently is -SiR a21 z21 R a22 3-z21 , there are multiple T 21 When there are multiple T 21 Optional to be the same or different from each other, there are multiple T 31 When there are multiple T 31 are optionally the same as or different from each other, R a21 is a hydroxyl group or a hydrolyzable group, and there are multiple R a21 When there are multiple R a21 are optionally the same as or different from each other, R a22 It is a non-hydrolyzable group, and there are multiple R a22 When there are multiple R a22 are optionally the same as or different from each other, z21 is an integer from 1 to 3, x2 and x3 are each independently an integer greater than 1, y2 is an integer greater than 1. When y2 is 1, R 2 is a fluoroalkylene group, L 2 -(R 21 -T 21 ) x2 The groups shown and (T 31 -R 31 ) x3 -L 3 At least one of the molecular weights of the groups shown is 600 or more, 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 there are multiple R f13 When there are multiple R f13 are optionally the same as or different from each other, R 4 Each independently represents an alkylene group or a fluoroalkylene group, and the presence of multiple R 4 are optionally the same or different from each other, L 4 is a single bond, or is a 1+x4 valent group optionally containing N, O, S, Si and optionally having a branch point, bonded to R 4 and R 41 The atoms are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group. 4 are optionally the same as or different from each other, R 41 is an alkylene group optionally having an ethereal oxygen atom between carbon atoms, wherein L 4 The adjacent atoms may be etheric oxygen atoms, and the presence of multiple R 11 are optionally the same as or different from each other, T 41 -SiR a41 z41 R a42 3-z41 , there are multiple T 41 are optionally the same as or different from each other, R a41 is a hydroxyl group or a hydrolyzable group, and the presence of multiple R a41 are optionally the same as or different from each other, R a42 It is a non-hydrolyzable group, and there are multiple R a42 When there are multiple R a42 are optionally the same as or different from each other, z41 is an integer from 1 to 3, x4 is an integer greater than or equal to 1. When a plurality of x4 exist, the plurality of x4 exist may be the same as or different from each other. y3 is an integer greater than or equal to 1. When a plurality of y3 exist, the plurality of y3 exist may be the same as or different from each other. r1 is 3 or 4, L 4 -(R 41 -T 41 ) x4 At least one of the groups shown has a molecular weight of 600 or more.

2. The surface treatment agent according to claim 1, wherein R 11 At least one of them has a carbon chain with 5 or more carbon atoms connected, R 21 and R 31 At least one of them has a carbon chain with 5 or more carbon atoms connected, R 41 At least one of the carbon atoms has a carbon chain having 5 or more carbon atoms connected.

3. The surface treatment agent according to claim 1, wherein R 11 At least one of them has a carbon chain with 5 to 18 carbon atoms connected, R 21 and R 31 At least one of them has a carbon chain with 5 to 18 carbon atoms connected, R 41 At least one of the two has a carbon chain with 5 to 18 carbon atoms connected.

4. The surface treatment agent according to claim 1, wherein The R 11 The alkylene group in is a straight chain alkylene group, The R 21 and R 31 The alkylene group in is a straight chain alkylene group, The R 41 The alkylene group is a straight chain alkylene group.

5. The surface treatment agent according to claim 1, wherein (OR f11 ) y1 The molecular weight of the group shown is 2000 to 10000, (OR f12 ) y2 The molecular weight of the group shown is 2000 to 10000, (OR f13 ) y3 The molecular weight of the groups shown is 2,000 to 10,000.

6. The surface treatment agent 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.

7. The surface treatment agent according to claim 1, wherein The organic solvent not containing fluorine atoms includes at least one selected from the group consisting of ketone solvents and ester solvents.

8. The surface treatment agent according to claim 1, wherein The ratio of the content of the organic solvent not containing fluorine atoms to the content of the fluorine-containing ether compound is 60 to 99.999% by mass. 9 . An article having a surface layer formed of the surface treatment agent according to claim 1 on the surface of a substrate. 10 . A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the surface treatment agent according to claim 1 .

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