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

Abstract

The subject is to provide a composition capable of forming a surface layer having excellent wear resistance, a substrate with a surface layer, and a method for producing a substrate with a surface layer. In addition, the subject is to provide a novel compound and a method for producing the same. The composition of the present invention comprises a first component and a second component, wherein the first component comprises a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group, and the second component is a compound (A) (R fa ‑(OX a ) m1 ‑L a ‑CZ a1 =CH 2 ) and compound (B)(CH 2 =CZ b2 ‑L b2 ‑(OX b ) m2 ‑L b1 ‑CZ b1 =CH 2 ). fa is a fluoroalkyl group, X a and X b is a fluoroalkylene group, L a is a single bond or a divalent linking group (excluding (OX a ) na ), L b1 and L b2 is a single bond or a divalent linking group (excluding (OX b ) nb ), Z a1 , Z b1 and Z b2 is a fluorine atom or a trifluoromethyl group, and m1 and m2 are integers greater than 2.

Description

Technical Field

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

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

[0003] Prior art literature

[0004] Patent Literature

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

[0006] Problem that the invention aims to solve

[0007] In recent years, the performance requirements for surface layers formed using fluorinated ether compounds have become higher. For example, when the surface layer is used to form a component that forms a surface that is touched by fingers, a surface layer whose performance (e.g., water repellency) is not easily reduced even when repeatedly worn, i.e., a surface layer with excellent wear resistance is required.

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

[0009] Therefore, the present invention aims to provide a composition capable of forming a surface layer having excellent wear resistance, a substrate with a surface layer, and a method for producing the substrate with a surface layer. In addition, the present invention aims to provide a novel compound and a method for producing the same.

[0010] Solutions for solving problems

[0011] The present inventors have found that the above-mentioned problems can be solved by the following configuration.

[0012] [1] A composition comprising a first component and a second component, wherein the first component comprises a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group, and the second component is at least one selected from the group consisting of a compound represented by the following formula (A) and a compound represented by the following formula (B).

[0013] R fa -(OX a )m1 -L a -CZ a1 =CH2…(A)

[0014] Wherein, in formula (A),

[0015] R fa is a fluoroalkyl group having 1 to 20 carbon atoms,

[0016] X a is a fluoroalkylene group having 1 to 6 carbon atoms,

[0017] L a is a single bond or a divalent linking group (excluding (OX a ) na na is an integer greater than 1), Z a1 is a fluorine atom or a trifluoromethyl group,

[0018] m1 is an integer greater than or equal to 2.

[0019] CH2=CZ b2 -L b2 -(OX b ) m2 -L b1 -CZ b1 =CH2…(B)

[0020] Wherein, in formula (B),

[0021] X b is a fluoroalkylene group having 1 to 6 carbon atoms,

[0022] L b1 and L b2 Each independently is a single bond or a divalent linking group (excluding (OX b ) nb . nb is an integer greater than 1),

[0023] Z b1 and Z b2 are each independently a fluorine atom or a trifluoromethyl group,

[0024] m2 is an integer greater than or equal to 2.

[0025] [2] The composition according to [1], wherein Z in the formula (A) is a1 A fluorine atom.

[0026] [3] The composition according to [1] or [2], wherein L in the formula (A) a It is an alkylene group, an ethereal oxygen atom, an amide bond, a group obtained by combining these, or a single bond.

[0027] [4] The composition according to [3], wherein L in the formula (A) a For a single key.

[0028] [5] The composition according to any one of [1] to [4], wherein Z in the formula (B) is b1 and Z b2 All are fluorine atoms.

[0029] [6] The composition according to any one of [1] to [5], wherein L in the formula (B) b1 and L b2 Each independently represents an alkylene group, an ethereal oxygen atom, an amide bond, a group obtained by combining these, or a single bond.

[0030] [7] The composition according to [6], wherein L in the above formula (B) b2 For a single key.

[0031] [8] The composition according to any one of [1] to [7], wherein the mass ratio of the content of the second component to the content of the first component is 0.01 to 4.0.

[0032] [9] A substrate with a surface layer, comprising a substrate and a surface layer, wherein the surface layer is formed on the substrate from the composition according to any one of [1] to [8].

[0033]

[10] A method for producing a substrate with a surface layer, comprising forming a surface layer on a substrate by a dry coating method or a wet coating method using the composition according to any one of [1] to [8].

[0034]

[11] A compound characterized by being represented by the following formula (A).

[0035] R fa -(OX a ) m1 -L a -CZ a1 =CH2…(A)

[0036] Among them, in formula (A),

[0037] R fa is a fluoroalkyl group having 1 to 20 carbon atoms,

[0038] X a is a fluoroalkylene group having 1 to 6 carbon atoms,

[0039] L a is a single bond or a divalent linking group (excluding (OX a ) nana is an integer greater than 1), Z a1 is a fluorine atom or a trifluoromethyl group,

[0040] m1 is an integer greater than or equal to 2.

[0041]

[12] A compound characterized by being represented by the following formula (B).

[0042] CH2=CZ b2 -L b2 -(OX b ) m2 -L b1 -CZ b1 =CH2…(B)

[0043] Wherein, in formula (B),

[0044] X b is a fluoroalkylene group having 1 to 6 carbon atoms,

[0045] L b1 and L b2 Each independently is a single bond or a divalent linking group (excluding (OX b ) nb . nb is an integer greater than 1),

[0046] Z b1 and Z b2 are each independently a fluorine atom or a trifluoromethyl group,

[0047] m2 is an integer greater than or equal to 2.

[0048]

[13] A method for producing a compound, characterized in that a metal or organometallic reagent is reacted with a compound represented by the following formula (a1) to obtain a compound represented by the following formula (A).

[0049] R fa -(OX a ) m1 -L a -CFZ a1 -CH2-Q a1 …(a1)

[0050] R fa -(OX a ) m1 -L a -CZ a1 =CH2…(A)

[0051] Among them, in formula (a1) and formula (A),

[0052] R fa is a fluoroalkyl group having 1 to 20 carbon atoms,

[0053] X a is a fluoroalkylene group having 1 to 6 carbon atoms,

[0054] L a is a single bond or a divalent linking group (excluding (OX a ) na . na is an integer greater than 1),

[0055] Z a1 is a fluorine atom or a trifluoromethyl group,

[0056] Q a1 is the leaving group,

[0057] m1 is an integer greater than or equal to 2.

[0058]

[14] A method for producing a compound, characterized in that a metal or organometallic reagent is reacted with a compound represented by the following formula (b1) to obtain a compound represented by the following formula (B).

[0059] Q b2 -CH2-CFZ b2 -L b2 -(OX b ) m2 -L b1 -CFZ b1 -CH2-Q b1 …(b1)

[0060] CH2=CZ b2 -L b2 -(OX b ) m2 -L b1 -CZ b1 =CH2…(B)

[0061] Among them, in formula (b1) and formula (B),

[0062] X b is a fluoroalkylene group having 1 to 6 carbon atoms,

[0063] L b1 and L b2 Each independently is a single bond or a divalent linking group (excluding (OX b ) nb . nb is an integer greater than 1),

[0064] Z b1 and Z b2 are each independently a fluorine atom or a trifluoromethyl group,

[0065] Q b1 and Q b2are each independently a leaving group,

[0066] m2 is an integer greater than or equal to 2.

[0067]

[15] The method for producing the compound according to

[13] or

[14] , which is carried out in the presence of a fluorinated organic solvent.

[0068] Effects of the Invention

[0069] According to the present invention, a composition capable of forming a surface layer having excellent wear resistance, a substrate with a surface layer, and a method for producing a substrate with a surface layer can be provided. In addition, according to the present invention, a novel compound and a method for producing the same can also be provided. DETAILED DESCRIPTION

[0070] In this specification, the compound represented by formula (A) is referred to as compound (A). The compounds represented by other formulae are described similarly. The repeating unit represented by formula (1) is referred to as unit (1). The repeating units represented by other formulae are described similarly. The group represented by formula (2) is referred to as group (2). The groups represented by other formulae are described similarly.

[0071] In the present specification, when "the alkylene group may have an A group", the alkylene group may have an A group between carbon atoms in the alkylene group, or may have an A group at a terminal like alkylene-A group-.

[0072] In the present specification, the "aryl group" in the "aryloxy group" includes not only an aryl group but also a heteroaryl group.

[0073] In this specification, "linking group" refers not only to a collection of atoms, but also atoms themselves are considered "linking groups" as long as they have the function of connecting predetermined groups to each other. For example, a nitrogen atom itself is considered a trivalent linking group.

[0074] The meanings of the terms in the present invention are as follows.

[0075] The "divalent organopolysiloxane residue" refers to a group represented by the following formula. x It is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. In addition, g1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

[0076]

[0077] The "number average molecular weight" of a compound is determined by using 1 H-NMR and 19 F-NMR was calculated by determining the number (average value) of oxyfluoroalkylene groups based on the terminal group.

[0078] [Composition]

[0079] The composition of the present invention comprises a first component and a second component, wherein the first component comprises a fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group (hereinafter also referred to as a "specific fluorinated ether compound"), and the second component is at least one selected from the group consisting of a compound (A) and a compound (B).

[0080] The present inventors have found that when a surface layer is formed on a substrate using the composition of the present invention, the water repellency and abrasion resistance of the surface layer are improved. The detailed reason for this is not clear, but it is presumed to be due to the following reasons.

[0081] Compound (A) has -CZ at one terminal portion a1 =CH2 represented by the group (Z a1 is a fluorine atom or a trifluoromethyl group). In addition, compound (B) has -CZ at both ends. b1 =CH2 and CH2=CZ b2 - the group (Z b1 and Z b2 are each independently a fluorine atom or a trifluoromethyl group).

[0082] As described above, a compound having at least one terminal being "=CH2" has a better affinity with water than a compound having both terminals being "-CF3". Therefore, it can be inferred that when the composition of the present invention is used to form a surface layer, the hydrolysis reaction of the specific fluorine-containing ether compound contained in the composition of the present invention can be promoted, and the water resistance and abrasion resistance of the obtained surface layer can be improved.

[0083] <First ingredient>

[0084] The first component contained in the composition of the present invention is composed of a specific fluorine-containing ether compound and is a compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group.

[0085] The poly(oxyfluoroalkylene) chain comprises a plurality of units (1).

[0086] (OX)…(1)

[0087] X is a fluoroalkylene group having one or more fluorine atoms.

[0088] The fluoroalkylene group preferably has 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, from the viewpoint of achieving better weather resistance and corrosion resistance of the surface layer.

[0089] The fluoroalkylene group may be linear, branched, or cyclic.

[0090] The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times, more preferably 1.7 to 2 times the number of carbon atoms, from the viewpoint of achieving better abrasion durability and water and oil repellency of the surface layer.

[0091] The fluoroalkylene group is particularly preferably a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group).

[0092] Specific examples of the unit (1) include -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2-, -OCF2CF2CF2CF2 CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, -OCF(CF3)CF2-, -OCF2CF2CF2CF2-, -OCF(CF3)CF2CF2-, -OCF2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CF2CF2-, -O-cycloC4F6-, -O-cycloC5F8-, -O-cycloC6F 10 -.

[0093] 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.

[0094] The number m of repetitions of the unit (1) contained in the poly(oxyfluoroalkylene) chain is an integer of 2 or more, more preferably an integer of 2-200, further preferably an integer of 5-150, particularly preferably an integer of 5-100, and most preferably an integer of 10-50.

[0095] The poly(oxyfluoroalkylene) chain may contain only one type of (OX) or two or more types of (OX).

[0096] The bonding order of two or more types of (OX) is not limited, and they may be arranged randomly, alternately, or in blocks.

[0097] Comprising two or more types of (OX) means that, in a specific fluorinated ether compound, there are two or more types of (OX) having different numbers of carbon atoms, there are two or more types of (OX) having different numbers of hydrogen atoms, there are two or more types of (OX) having different positions of hydrogen atoms, and there are two or more types of (OX) having the same number of carbon atoms but different presence or absence of side chains or types of side chains (the number of side chains, the number of carbon atoms in the side chains, etc.).

[0098] Regarding the configuration of two or more (OX), for example, {(OCF2) m21 (OCF2CF2) m22 The structure shown in} indicates that m21 (OCF2) and m22 (OCF2CF2) are randomly arranged. In addition, (OCF2CF2-OCF2CF2CF2CF2) m25 The structure shown indicates that m25 (OCF2CF2) and m25 (OCF2CF2CF2CF2) are arranged alternately.

[0099] As (OX) representing a poly(oxyfluoroalkylene) chain m , preferably [(OCH ma F (2-ma) ) m11 ·(OC2H mb F (4-mb) ) m12 ·(OC3H mc F (6-mc) ) m13 ·(OC4H md F (8-md) ) m14 ·(OC5H me F (10-me) ) m15 ·(OC6H mf F (12-mf) ) m16 ·(O-cycloC4H mg F (6-mg) ) m17 ·(O-cycloC5H mh F (8-mh) ) m18 ·(O-cycloC6H mi F (10-mi) ) m19 Here, -cycloC4H mg F (6-mg) -cycloC5H represents a fluorocyclobutanediyl group, preferably a fluorocyclobutane-1,2-diyl group. mh F (8-mh) -cycloC6H represents a fluorocyclopentanediyl group, preferably a fluorocyclopentane-1,3-diyl group. mi F(10-mi) It represents a fluorocyclohexanediyl group, and is preferably a fluorocyclohexane-1,4-diyl group.

[0100] ma is 0 or 1, mb is an integer of 0 to 3, mc is an integer of 0 to 5, md is an integer of 0 to 7, me is an integer of 0 to 9, mf is an integer of 0 to 11, mg is an integer of 0 to 5, mh is an integer of 0 to 7, and mi is an integer of 0 to 9.

[0101] m11, m12, m13, m14, m15, m16, m17, m18 and m19 are each independently an integer greater than or equal to 0, and preferably less than or equal to 100.

[0102] m11+m12+m13+m14+m15+m16+m17+m18+m19 is an integer greater than 2, more preferably an integer from 2 to 200, more preferably an integer from 5 to 150, further preferably an integer from 5 to 100, and particularly preferably an integer from 10 to 50.

[0103] Among them, m12 is preferably an integer greater than 2, and particularly preferably an integer from 2 to 200.

[0104] In addition, C3H mc F (6-mc) 、C4H md F (8-md) 、C5H me F (10-me) and C6H mf F (12-mf) The polyol may be linear or branched, but is preferably linear from the viewpoint of providing a more excellent abrasion resistance of the surface layer.

[0105] It should be noted that m11 (OCH ma F (2-ma) ), m12 (OC2H mb F (4-mb) ), m13 (OC3H mc F (6-mc) ), m14 (OC4H md F (8-md) ), m15 (OC5H me F (10-me) ), m16 (OC6H mf F (12-mf) )、m17 (O-cycloC4H mg F (6-mg) ), m18 (O-cycloC5H mh F (8-mh )), m19 (O-cycloC6H mi F (10-mi)) are not limited in the bonding order.

[0106] When m11 is 2 or more, multiple (OCH ma F (2-ma) ) can be the same or different.

[0107] When m12 is 2 or more, multiple (OC2H mb F (4-mb) ) can be the same or different.

[0108] When m13 is 2 or more, multiple (OC3H mc F (6-mc) ) can be the same or different.

[0109] When m14 is 2 or more, multiple (OC4H md F (8-md) ) can be the same or different.

[0110] When m15 is 2 or more, multiple (OC5H me F (10-me) ) can be the same or different.

[0111] When m16 is 2 or more, multiple (OC6H mf F (12-mf) ) can be the same or different.

[0112] When m17 is 2 or more, multiple (O-cycloC4H mg F (6-mg) ) can be the same or different.

[0113] When m18 is 2 or more, multiple (O-cycloC5H mh F (8-mh) ) can be the same or different.

[0114] When m19 is 2 or more, multiple (O-cycloC6H mi F (10-mi) ) can be the same or different.

[0115] (OX) m It preferably has the following structure.

[0116] {(OCF2) m21 (OCF2CF2) m22}、

[0117] (OCF2CF2) m23 ,

[0118] (OCF(CF3)CF2) m23 ,

[0119] (OCF2CF2CF2) m24 、

[0120] (OCF2CF2-OCF2CF2CF2CF2) m25 、

[0121] {(OCF2CF2CF2CF2CF2) m26 ·(OCF2) m27 }、

[0122] {(OCF2CF2CF2CF2CF2) m26 ·(OCF2CF2) m27 }、

[0123] {(OCF2CF2CF2CF2CF2CF2) m26 ·(OCF2) m27 }、

[0124] {(OCF2CF2CF2CF2CF2CF2) m26 ·(OCF2CF2) m27 }、

[0125] (OCF2CF2CF2CF2CF2-OCF2) m28 、

[0126] (OCF2CF2CF2CF2CF2-OCF2CF2) m28 、

[0127] (OCF2CF2CF2CF2CF2CF2-OCF2) m28 、

[0128] (OCF2CF2CF2CF2CF2CF2-OCF2CF2) m28 、

[0129] (OCF2-OCF2CF2CF2CF2CF2) m28 、

[0130] (OCF2-OCF2CF2CF2CF2CF2CF2) m28 、

[0131] (OCF2CF2-OCF2CF2CF2CF2CF2) m28 、

[0132] (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28 。

[0133] Among them, m21 is an integer greater than 1, m22 is an integer greater than 1, m21+m22 is an integer from 2 to 500, m23 and m24 are each independently an integer from 2 to 500, m25 is an integer from 1 to 250, m26 and m27 are each independently an integer greater than 1, m26+m27 is an integer from 2 to 500, and m28 is an integer from 1 to 250.

[0134] From the viewpoint of facilitating the production of a specific fluorine-containing ether compound, (OX) m The following structure is more preferable.

[0135] {(OCF2) m21 (OCF2CF2) m22}、

[0136] (OCF(CF3)CF2) m23 ,

[0137] (OCF2CF2CF2) m24 ,

[0138] (OCF2CF2)2{(OCF2) m21 (OCF2CF2) m22-2}、

[0139] (OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2,

[0140] (OCF2CF2CF2CF2CF2-OCF2) m28 ,

[0141] (OCF2CF2CF2CF2CF2CF2-OCF2) m28 ,

[0142] (OCF2CF2-OCF2CF2CF2CF2CF2) m28-1 OCF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28- 1OCF2CF2.

[0143] Among them, regarding m22-2, m25-1, and m28-1, the numbers of m22, m25, and m28 are selected so as to be integers greater than or equal to 1.

[0144] Among these, (OX) m Preferably {(OCF2) m21 (OCF2CF2) m22}.

[0145] In {(OCF2) m21 (OCF2CF2) m22}, from the viewpoint of better wear resistance and fingerprint dirt removability of the surface layer, m22 / m21 is preferably 0.1 to 10, more preferably 0.2 to 5.0, further preferably 0.2 to 2.0, particularly preferably 0.2 to 1.5, and most preferably 0.2 to 0.85.

[0146] The number average molecular weight of (OX)m is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, particularly preferably 3,000 to 10,000.

[0147] If the number-average molecular weight is more than the lower limit, the molecular chain of specific fluorinated ether compound is elongated, and therefore, the flexibility of the molecular chain of specific fluorinated ether compound improves.Thus, the reaction probability of the silanol group in source and the substrate or base layer with silanol group rises with the reactive silyl group of specific fluorinated ether compound, and therefore, the adhesion of the surface layer and substrate or base layer further improves.As a result, the wear resistance of the surface layer is more excellent.In addition, the fluorine content of the surface layer improves, and therefore, water and oil repellency is more excellent.

[0148] Moreover, when the number average molecular weight is at most the upper limit value, the workability during film formation will be more excellent.

[0149] The reactive silyl group is preferably the group (2).

[0150] -Si(R) n L 3-n …(2)

[0151] R is a monovalent hydrocarbon group.

[0152] The monovalent hydrocarbon group is preferably a monovalent aliphatic hydrocarbon group (which may be saturated or unsaturated) or a monovalent aromatic hydrocarbon group, more preferably a monovalent aliphatic hydrocarbon group, and particularly preferably an alkyl group.

[0153] The monovalent hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0154] L is a hydrolyzable group or a hydroxyl group.

[0155] The hydrolyzable group of L is a group that forms a hydroxyl group by a hydrolysis reaction. That is, a hydrolyzable silyl group represented by Si-L forms a silanol group represented by Si-OH by a hydrolysis reaction. The silanol groups further react with each other to form a Si-O-Si bond.

[0156] Specific examples of L as a hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanato group (-NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred. As the aryloxy group, an aryloxy group having 3 to 10 carbon atoms is preferred. As the halogen atom, a chlorine atom 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.

[0157] As L, from the viewpoint of easier production of the specific fluorine-containing ether compound, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferred. As L, from the viewpoint of less outgassing during coating and better storage stability of the specific fluorine-containing ether compound, an alkoxy group having 1 to 4 carbon atoms is preferred, when long-term storage stability of the specific fluorine-containing ether compound is required, an ethoxy group is particularly preferred, and when the reaction time after coating is set to a short time, a methoxy group is particularly preferred.

[0158] n is an integer from 0 to 2.

[0159] n is preferably 0 or 1, and particularly preferably 0. The presence of a plurality of Ls further strengthens the adhesion of the surface layer to the substrate.

[0160] When n is 0 or 1, a plurality of L present in one molecule may be the same or different. From the viewpoint of the ease of obtaining raw materials and the ease of manufacturing the specific fluorine-containing ether compound, they are preferably the same. When n is 2, a plurality of R present in one molecule may be the same or different. From the viewpoint of the ease of obtaining raw materials and the ease of manufacturing the specific fluorine-containing ether compound, they are preferably the same.

[0161] As the specific fluorine-containing ether compound, the compound (3) is preferred from the viewpoint of achieving better water and oil repellency and abrasion resistance of the film.

[0162] [A-(OX) m -O-] j Z[-Si(R) n L 3-n ] g …(3)

[0163] A is a perfluoroalkyl group or -Q[-Si(R) n L 3-n ] k .

[0164] The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 3, from the viewpoint of achieving better abrasion resistance of the film.

[0165] The perfluoroalkyl group may be linear or branched.

[0166] Where A is -Q[-Si(R) n L 3-n ] k In the case of , j is 1.

[0167] Examples of the perfluoroalkyl group include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-.

[0168] As the perfluoroalkyl group, CF3-, CF3CF2-, and CF3CF2CF2- are preferred from the viewpoint of achieving more excellent water and oil repellency of the film.

[0169] Q is a (k+1)-valent linking group. As described below, k is an integer of 1 to 10. Therefore, examples of Q include linking groups having 2 to 11 valencies.

[0170] Q preferably 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 (k+1)-valent organopolysiloxane residue.

[0171] As the ring structure, from the viewpoint of easy production of specific fluorinated ether compounds and the viewpoint of better abrasion resistance, light resistance and chemical resistance of the surface layer, it is preferably one 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 the ring structure listed in the following formula is particularly preferred.

[0172] The ring structure may have a substituent such as a halogen atom, an alkyl group (optionally containing an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, or an oxy group (═O).

[0173]

[0174] Specific examples of the (k+1)-valent organopolysiloxane residue include the following groups.

[0175] Among them, R in the following formula 5 is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. 5 The number of carbon atoms in the alkyl group and the alkoxy group is preferably 1 to 10, and 1 is particularly preferred.

[0176]

[0177] Q optionally has a group selected from an alkylene group, a fluoroalkylene group, a hydroxyalkylene group, an alkoxyalkylene group, a carbonyl group, an amide bond, an ether bond, a thioether bond, a urea bond, a urethane bond, a carbonate bond, an ester bond, 6 -、-Si(R 6 )2-、-OSi(R 6 )2-, -Si(CH3)2-Ph-Si(CH3)2- and a divalent organopolysiloxane residue.

[0178] Among them, R 6 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 a specific fluorine-containing ether compound, R 6 The number of carbon atoms in the alkyl group is preferably 1-3, particularly preferably 1-2.

[0179] In addition, each bond or group constituting Q may be arranged at any end in [A-(OX) m -O-] j For example, the amide bond can be configured with a carbon atom at [A-(OX) m -O-] j side, the nitrogen atom can be arranged on [A-(OX) m -O-] j The same applies to other bonds and groups.

[0180] Specific examples of divalent organopolysiloxane residues include groups of the following formula: 7 is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. 7 The number of carbon atoms in the alkyl group and the alkoxy group is preferably 1 to 10, particularly preferably 1.

[0181]

[0182] From the viewpoint of facilitating the production of the specific fluorine-containing ether compound, Q preferably has a member selected from the group consisting of -C(O)NR 6 -、-C(O)-、-C(O)OR 6 -、-NR 6 In view of the excellent light resistance and chemical resistance of the surface layer, at least one bond in the group consisting of - and -O- is particularly preferably -C(O)NR 6 -or -C(O)-.

[0183] Examples of Q include a combination of two or more divalent hydrocarbon groups and one or more branch points P, or a combination of two or more hydrocarbon groups, one or more branch points P, and one or more bonds B.

[0184] Specific examples of the divalent hydrocarbon group include divalent aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups, etc.) and divalent aromatic hydrocarbon groups (phenylene groups, etc.). The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0185] R, L, n, X and m are as defined above.

[0186] Z is a (j+g)-valent linking group.

[0187] The definition of Z is the same as that of Q above, except that the (k+1) valence is replaced by the (j+g) valence in Q above. In the specific fluorine-containing ether compound, Z and Q may be the same or different. From the viewpoint of the ease of manufacture of the specific fluorine-containing ether compound, Z and Q are preferably the same.

[0188] j is an integer of 1 or more, preferably an integer of 1 to 5 from the viewpoint of better water and oil repellency of the film, and particularly preferably 1 from the viewpoint of easy production of the compound (3).

[0189] g is an integer of 1 or more, and is preferably an integer of 2 to 4, more preferably 2 or 3, and particularly preferably 3, from the viewpoint of achieving better abrasion resistance of the film.

[0190] k is an integer of 1 to 10, and is preferably an integer of 1 to 8, and particularly preferably an integer of 2 to 6, from the viewpoint of further improving the wear resistance of the surface layer.

[0191] As compound (3), from the viewpoint of having a better initial water contact angle and abrasion resistance of the surface layer, preferably compound (3-11), compound (3-21) and compound (3-31). Among these, the initial water contact angle of the surface layer of compound (3-11) and compound (3-21) is particularly excellent, and the abrasion resistance of the surface layer of compound (3-31) is particularly excellent.

[0192] R f1 -(OX) m -OY 11 [-Si(R) n L 3-n ] g1 …(3-11)

[0193] [R f2 -(OX) m -O-] j2 Y 21 [-Si(R) n L 3-n ] g2 …(3-21)

[0194] [L 3-n (R)n Si-] k3 Y 32 -(OX) m -OY 31 [-Si(R) n L 3-n ] g3 …(3-31)

[0195] In formula (3-11), X, m, R, n and L have the same definitions as X, m, R, n and L in formula (3), respectively.

[0196] R f1 It is a perfluoroalkyl group, and suitable aspects and specific examples of the perfluoroalkyl group are as described above.

[0197] Y 11 It is a (g1+1)-valent linking group, and its specific examples are the same as those for Z in formula (3).

[0198] g1 is an integer of 1 or more, and is preferably an integer of 2 to 15, more preferably an integer of 2 to 4, further preferably 2 or 3, and particularly preferably 3, from the viewpoint of better abrasion resistance of the surface layer.

[0199] In formula (3-21), X, m, R, n and L have the same definitions as X, m, R, n and L in formula (3), respectively.

[0200] R f2 It is a perfluoroalkyl group, and suitable aspects and specific examples of the perfluoroalkyl group are as described above.

[0201] j2 is an integer greater than or equal to 2, preferably an integer from 2 to 6, and more preferably an integer from 2 to 4.

[0202] Y 21 It is a (j2+g2)-valent linking group, and its specific example is the same as Z in formula (3).

[0203] g2 is an integer of 1 or more, and is preferably an integer of 2 to 15, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 4, from the viewpoint of better abrasion resistance of the surface layer.

[0204] In formula (3-31), X, m, R, n and L have the same definitions as X, m, R, n and L in formula (3), respectively.

[0205] k3 is an integer greater than or equal to 1, preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 3.

[0206] Y 32 It is a (k3+1)-valent linking group, and its specific examples are the same as Q in formula (3).

[0207] Y31 It is a (g3+1)-valent linking group, and its specific examples are the same as those for Z in formula (3).

[0208] g3 is an integer greater than or equal to 1, preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 3.

[0209] Y in formula (3-11) 11 It can be a group (g2-1) (wherein d1+d3=1 (in other words, d1 or d3 is 0), g1=d2+d4, d2+d4≥1), a group (g2-2) (wherein e1=1, g1=e2, e2≥1), a group (g2-3) (wherein g1=2), a group (g2-4) (wherein h1=1, g1=h2, h2≥1), a group (g2-5) (wherein i1=1, g1=i2, i2≥1), a group (g2-6) (wherein g1=1), a group (g2-7) (wherein g1=i3+1), a group (g2-8) (wherein g1=i4, i4≥1) or a group (g2-9) (wherein g1=i5, i5≥1).

[0210] Y in formula (3-21) 21 It can be a group (g2-1) (where j2=d1+d3, d1+d3≥2, g2=d2+d4, d2+d4≥1), a group (g2-2) (where j2=e1, e1=2, g2=e2, e2≥1), a group (g2-4) (where j2=h1, h1≥2, g2=h2, h2≥1) or a group (g2-5) (where j2=i1, i1=2, g2=i2, i2≥1).

[0211] In addition, Y in formula (3-31) 31 and Y 32 Each of them independently can be a group (g2-1) (wherein g3=d2+d4, k3=d2+d4), a group (g2-2) (wherein g3=e2, k3=e2), a group (g2-3) (wherein g3=2, k3=2), a group (g2-4) (wherein g3=h2, k3=h2), a group (g2-5) (wherein g3=i2, k3=i2), a group (g2-6) (wherein g3=1, k3=1), a group (g2-7) (wherein g3=i3+1, k3=i3+1), a group (g2-8) (wherein g3=i4, k3=i4) or a group (g2-9) (wherein g3=i5, k3=i5).

[0212]

[0213] (-A 1 -) e1C(R e2 ) 4-e1-e2 (-Q 22 -) e2 …(g2-2)

[0214] -A 1 -N(-Q 23 -)2 formula (g2-3)

[0215] (-A 1 -) h1 Z 1 (-Q 24 -) h2 Formula (g2-4)

[0216] (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 …(g2-5)

[0217] -A 1 -Q 26 -Formula (g2-6)

[0218] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 …(g2-7)

[0219] -A 1 -[CH2C(R e4 )(-Q 27 -)] i4 -R e5 …(g2-8)

[0220] -A 1 -Z a (-Q 28 -) i5 …(g2-9)

[0221] Among them, in formula (g2-1) to formula (g2-9), A 1 Connect to (OX) m Side, Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 Connected to [-Si(R) n L 3-n]side.

[0222] A 1 is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-N(R 6 )SO2- groups, in each formula, there are 2 or more A 1 When more than 2 A 1 The hydrogen atoms of the alkylene group may be substituted by fluorine atoms.

[0223] Q 11 is a single bond, -O-, an alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 - or -O-.

[0224] Q 22 Alkylene; -C(O)NR between carbon atoms of alkylene with 2 or more carbon atoms 6 -、-C(O)-、-NR 6 - or -O-; having -C(O)NR at the end of the alkylene group not connected to Si 6 -、-C(O)-、-NR 6 - or -O-; or a group having -C(O)NR between carbon atoms of an alkylene group having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 - or -O- and having -C(O)NR at the end of the side not connected to Si 6 -、-C(O)-、-NR 6 - or -O-, in each formula, there are 2 or more Q 22 When more than 2 Q 22 Optional same or different.

[0225] Q 23 An alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms 6 -、-C(O)-、-NR 6 - or -O- group, 2 Q 23 Optional same or different.

[0226] In Q 24 Bonded Z 1When the atom in is a carbon atom, Q 24 Q 22 , in Q 24 Bonded Z 1 When the atom in is a nitrogen atom, Q 24 Q 23 , in each formula, there are more than 2 Q 24 When more than 2 Q 24 Optional same or different.

[0227] Q 25 An alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms 6 -、-C(O)-、-NR 6 - or -O-, in each formula, there are 2 or more Q 25 When more than 2 Q 25 Optional same or different.

[0228] Q 26 An alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms 6 -、-C(O)-、-NR 6 - or -O-.

[0229] R 6 It is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0230] Q 27 is a single bond or an alkylene group.

[0231] Q 28 It is an alkylene group, or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.

[0232] Z 1 is a group having a ring structure with a valence of h1+h2, the ring structure having 1 A carbon atom or nitrogen atom directly bonded to Q 24 Directly bonded carbon or nitrogen atoms.

[0233] R e1 is a hydrogen atom or an alkyl group. In each formula, there are two or more R e1 When more than 2 R e1 Optional same or different.

[0234] R e2 It is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.

[0235] R e3 It is an alkyl group.

[0236] R e4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom from the viewpoint of easy preparation of the compound. e4 When more than 2 R e4 Optional same or different.

[0237] R e5 It is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.

[0238] d1 is an integer of 0-3, preferably 1 or 2. d2 is an integer of 0-3, preferably 1 or 2. d1+d2 is an integer of 1-3.

[0239] d3 is an integer of 0-3, preferably 0 or 1. d4 is an integer of 0-3, preferably 2 or 3. d3+d4 is an integer of 1-3.

[0240] In Y 21 In the formula, d1+d3 is an integer of 1 to 5, preferably 1 or 2. 11 , Y 31 and Y 32 , d1+d3 is 1.

[0241] In Y 11 or Y 21 In the formula, d2+d4 is an integer of 1 to 5, preferably 4 or 5. 31 and Y 32 In the above formula, d2+d4 is an integer of 1 to 5, preferably an integer of 3 to 5, and particularly preferably 4 or 5.

[0242] e1+e2 is 3 or 4. 11 In the example, e1 is 1, and in Y 21 In the formula, e1 is an integer from 2 to 3. 31 and Y 32 In Y 11 or Y 21 In the formula, e2 is 1 to 3, preferably 2 or 3, and in Y 31 and Y 32 In the formula (a), e2 is 1 to 3, preferably 2 or 3.

[0243] In Y 11 In the example, h1 is 1, and in Y 21 In the formula, h1 is an integer greater than 2 (preferably 2), and Y 31 and Y 32 In Y 11 or Y 21 In the example, h2 is an integer greater than 1 (preferably 2 or 3), and in Y 31 and Y32 In the formula, h2 is an integer greater than or equal to 1 (preferably 2 or 3).

[0244] In Y 11 In the formula, i1+i2 is 2 to 4 (preferably 3 or 4), and in Y 12 In the formula, i1+i2 is 3 or 4 (preferably 4), and in Y 31 and Y 32 In Y, i1+i2 is an integer from 2 to 4 (preferably 3 or 4). 11 In the example, i1 is 1, and in Y 21 In the example, i1 is 2 or 3, and in Y 31 and Y 32 In Y 11 In the formula, i2 is an integer from 1 to 3 (preferably 2 or 3), 12 In the example, i2 is 1 or 2 (preferably 2), and in Y 31 and Y 32 In the formula, i2 is an integer from 1 to 3 (preferably 2 or 3).

[0245] i3 is an integer of 0 to 3, preferably 1 to 3, and particularly preferably 2 or 3.

[0246] In Y 11 In the formula (i), i4 is 1 or more (preferably an integer of 2 to 10, particularly preferably an integer of 2 to 6), 31 and Y 32 In the above description, i4 is 1 or more (preferably an integer of 1 to 10, particularly preferably an integer of 1 to 6).

[0247] In Y 11 In the example, i5 is 1 or more (preferably an integer of 2 to 7), and in Y 31 and Y 32 In the above, i5 is 1 or more (preferably an integer of 2 to 7).

[0248] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31) and the viewpoint of better abrasion resistance, light resistance and chemical resistance of the surface layer, Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 , Q 28 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, the lower limit of the number of carbon atoms in the alkylene group when having a specific bond between carbon atoms is 2.

[0249] As Z 1The ring structure in Z may be the above-mentioned ring structure, and the preferred form is also the same. 1 The ring structure in A 1 , Q 24 Direct bonding, therefore, the ring structure is not connected to, for example, an alkylene group and the alkylene group is not connected to A 1 , Q 24 connect.

[0250] Z a is an organopolysiloxane residue having a valence of (i5+1), preferably the following group. a It is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.

[0251]

[0252] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31), R e1 , R e2 , R e3 or R e4 The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0253] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31), R e2 The number of carbon atoms in the alkyl portion of the acyloxy group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, particularly preferably 1 to 2.

[0254] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31) and excellent abrasion resistance and fingerprint removability of the surface layer, h1 is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0255] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31) and excellent abrasion resistance and fingerprint removability of the surface layer, h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.

[0256] As Y 11Other forms of include group (g3-1) (wherein d1+d3=1 (in other words, d1 or d3 is 0), g1=d2×r1+d4×r1), group (g3-2) (wherein e1=1, g1=e2×r1), group (g3-3) (wherein g1=2×r1), group (g3-4) (wherein h1=1, g1=h2×r1), group (g3-5) (wherein i1=1, g1=i2×r1), group (g3-6) (wherein g1=r1), group (g3-7 (wherein g1=r1×(i3+1)), group (g3-8) (wherein g1=r1×i4), and group (g3-9) (wherein g1=r1×i5).

[0257] As Y 21 Other forms of include group (g3-1) (where j2 = d1+d3, d1+d3≥2, g2 = d2×r1+d4×r1), group (g3-2) (where j2 = e1, e1=2, g2 = e2×r1, e2=2), group (g3-4) (where j2 = h1, h1≥2, g2 = h2×r1), and group (g3-5) (where j2 = i1, i1 is 2 or 3, g2 = i2×r1, i1+i2 is 3 or 4).

[0258] As Y 31 and Y 32 Other forms of the group include the group (g3-1) (wherein g3 = d2 × r1 + d4 × r1, k3 = d2 × r1 + d4 × r1), the group (g3-2) (wherein g3 = e2 × r1, k3 = e2 × r1), the group (g3-3) (wherein g3 = 2 × r1, k3 = 2 × r1), the group (g3-4) (wherein g3 = h2 × r1, k3 = h2 × r1), the group (g3- 5) (wherein g3 = i2 × r1, k3 = i2 × r1), group (g3-6) (wherein g3 = r1, k3 = r1), group (g3-7) (wherein g3 = r1 × (i3+1), k3 = r1 × (i3+1)), group (g3-8) (wherein g3 = r1 × i4, k3 = r1 × i4), group (g3-9) (wherein g3 = r1 × i5, k3 = r1 × i5).

[0259]

[0260] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 …(g3-2)

[0261] -A 1 -N(-Q 23 -G 1 )2…(g3-3)

[0262] (-A 1 -) h1 Z 1 (-Q 24 -G 1 ) h2 …(g3-4)

[0263] (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -G 1 ) i2 …(g3-5)

[0264] -A 1 -Q 26 -G 1 …(g3-6)

[0265] -A 1 -CH(-Q 22 -G 1 )-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 …(g3-7)

[0266] -A 1 -[CH2C(R e4 )(-Q 27 -G 1 )] i4 -R e5 …(g3-8)

[0267] -A 1 -Z a (-Q 28 -G 1 ) i5 …(g3-9)

[0268] In formula (g3-1) to formula (g3-9), A 1 Connect to (OX) m Side, G 1 Connected to [-Si(R) n L 3-n ]side.

[0269] G 1is a group (g3), in each formula, there are two or more G 1 When more than 2 G 1 Optional same or different. Except G 1 The symbols other than these are the same as those in formula (g2-1) to formula (g2-9).

[0270] -Si(R 8 ) 3-r1 (-Q 3 -) r1 …(g3)

[0271] Wherein, in formula (g3), Si is connected to Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 Side, Q 3 Connected to [-Si(R) n L 3-n ] side. 8 Q is an alkyl group. 3 Alkylene; -C(O)NR between carbon atoms of alkylene with 2 or more carbon atoms 6 -、-C(O)-、-NR 6 - or -O-; or -(OSi(R 9 )2) p -O-, 2 or more Q 3 are the same or different. r1 is 2 or 3. 6 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 is alkyl, phenyl or alkoxy, 2 R 9 p is an integer from 0 to 5. When p is 2 or more, two or more (OSi(R 9 )2) can be the same or different.

[0272] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31) and the viewpoint of better abrasion resistance, light resistance and chemical resistance of the surface layer, Q 3 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, the lower limit of the number of carbon atoms in the alkylene group when having a specific bond between carbon atoms is 2.

[0273] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31), R 8The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0274] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31), R 9 The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0275] From the viewpoint of excellent storage stability of compound (3-11), compound (3-21) and compound (3-31), R 9 The number of carbon atoms in the alkoxy group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0276] p is preferably 0 or 1.

[0277] As compound (3-11), compound (3-21) and compound (3-31), for example, compounds of the following formula can be cited. From the viewpoint of easy industrial production, easy handling, excellent water and oil repellency, abrasion resistance, fingerprint dirt removal, lubricity, chemical resistance, light resistance and chemical resistance of the surface layer, and particularly excellent light resistance, the compound of the following formula is preferred.

[0278] In the compound of the following formula, R f For R f1 -(OX) m -O-(CF2) n - or R f2 -(OX) m -O-(CF2) n -. Here, R f1 , R f2 , X and m are as defined above, and n is an integer of 0-6.

[0279] In the compound of the following formula, Q f For -(OX) m -O-(CF2) n Here, X and m are as defined above, and n is an integer of 0 to 6.

[0280] As Y 11 Examples of the compound (3-11) that is the group (g2-1) include compounds of the following formula.

[0281]

[0282] As Y 11 Examples of the compound (3-11) that is the group (g2-2) include compounds of the following formula.

[0283]

[0284] As Y 21 Examples of the compound (3-21) that is the group (g2-2) include compounds of the following formula.

[0285]

[0286] As Y 11 Examples of the compound (3-11) that is the group (g2-3) include compounds of the following formula.

[0287]

[0288] As Y 11 Examples of the compound (3-11) that is a group (g2-4) include compounds of the following formula.

[0289]

[0290] As Y 11 Examples of the compound (3-11) that is the group (g2-5) include compounds of the following formula.

[0291]

[0292] As Y 11 Examples of the compound (3-11) that is the group (g2-6) include compounds of the following formula.

[0293]

[0294] As Y 11 Examples of the compound (3-11) that is the group (g2-7) include compounds of the following formula.

[0295]

[0296] As Y 11 Examples of the compound (3-11) that is the group (g3-1) include compounds of the following formula.

[0297]

[0298] As Y 11 Examples of the compound (3-11) that is the group (g3-2) include compounds of the following formula.

[0299]

[0300] As Y 11Examples of the compound (3-11) that is a group (g3-3) include compounds of the following formula.

[0301]

[0302] As Y 11 Examples of the compound (3-11) that is a group (g3-4) include compounds of the following formula.

[0303]

[0304] As Y 11 Examples of the compound (3-11) that is the group (g3-5) include compounds of the following formula.

[0305]

[0306] As Y 11 Examples of the compound (3-11) that is the group (g3-6) include compounds of the following formula.

[0307]

[0308] As Y 11 Examples of the compound (3-11) that is a group (g3-7) include compounds of the following formula.

[0309]

[0310] As Y 21 Examples of the compound (3-21) that is the group (g2-1) include compounds of the following formula.

[0311]

[0312] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-1) include compounds of the following formula.

[0313]

[0314] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-2) include compounds of the following formula.

[0315]

[0316] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-3) include compounds of the following formula.

[0317]

[0318] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-4) include compounds of the following formula.

[0319]

[0320] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-5) include compounds of the following formula.

[0321]

[0322] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-6) include compounds of the following formula.

[0323]

[0324] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-7) include compounds of the following formula.

[0325]

[0326] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g3-2) include compounds of the following formula.

[0327]

[0328] Specific examples of the specific fluorine-containing ether compound include those described in the following documents.

[0329] Perfluoropolyether-modified aminosilane described in Japanese Patent Application Laid-Open No. 11-029585 and Japanese Patent Application Laid-Open No. 2000-327772,

[0330] Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715,

[0331] The organosilicon compound described in Japanese Patent Application Laid-Open No. 2000-144097,

[0332] Fluorinated silicone described in Japanese Patent Publication No. 2002-506887,

[0333] The organosilicon compound described in JP-A-2008-534696,

[0334] Fluorinated modified hydrogen-containing polymers described in Japanese Patent No. 4138936,

[0335] Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, International Publication No. 2014 / 126064, and Japanese Patent Application Publication No. 2014-070163,

[0336] The organosilicon compounds described in International Publication Nos. 2011 / 060047 and 2011 / 059430,

[0337] The fluorinated organosilane compound described in International Publication No. 2012 / 064649,

[0338] The polymer containing fluorooxyalkylene described in Japanese Patent Application Laid-Open No. 2012-72272,

[0339] 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, International Publication No. Fluorine-containing ether compounds described in International Publication No. 2017 / 187775, International Publication No. 2018 / 216630, International Publication No. 2019 / 039186, International Publication No. 2019 / 039226, International Publication No. 2019 / 039341, International Publication No. 2019 / 044479, International Publication No. 2019 / 049753, International Publication No. 2019 / 163282, and Japanese Patent Application Publication No. 2019-044158,

[0340] Silane compounds containing perfluoro(poly)ether 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,

[0341] A silane compound containing a perfluoro(poly)ether group described in International Publication No. 2018 / 169002, a silane compound containing a fluoro(poly)ether group described in International Publication No. 2019 / 151442,

[0342] A (poly)ether group-containing silane compound described in International Publication No. 2019 / 151445,

[0343] A compound containing a perfluoropolyether group described in International Publication No. 2019 / 098230,

[0344] Fluoropolyether group-containing polymer-modified silanes described in Japanese Patent Application Laid-Open Nos. 2015-199906, 2016-204656, 2016-210854, and 2016-222859,

[0345] Fluorine-containing compounds described in International Publication No. 2019 / 039083 and International Publication No. 2019 / 049754.

[0346] Commercially available products of specific fluorinated ether compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd.; Afluid (registered trademark) S550 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.

[0347] The specific fluorine-containing ether compound may be used alone or in combination of two or more.

[0348] <Second ingredient>

[0349] The second component contained in the composition of the present invention is at least one selected from the group consisting of compound (A) and compound (B). The second component may contain both compound (A) and compound (B) or only one of them.

[0350] (Compound (A))

[0351] Compound (A) is a compound represented by formula (A).

[0352] R fa -(OX a ) m1 -L a -CZ a1 =CH2…(A)

[0353] R fa It is a fluoroalkyl group having 1 to 20 carbon atoms.

[0354] The fluoroalkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms, from the viewpoint of achieving better water repellency of the surface layer.

[0355] The fluoroalkyl group may be linear, branched or cyclic.

[0356] The fluoroalkyl group is preferably a group in which all hydrogen atoms in the fluoroalkyl group are substituted with fluorine atoms (perfluoroalkyl group).

[0357] X a X is a fluoroalkylene group having 1 to 6 carbon atoms. a The suitable form of is the same as that of X in the above formula (1). a ) is suitable in the same manner as (OX) in the above formula (1).

[0358] (OX a ) is an integer greater than or equal to 2. The preferred embodiment of m1 is the same as the repetition number m of (OX) described above.

[0359] When the specific fluorine-containing ether compound is a compound represented by formula (1), from the viewpoint of further improving the effect of the present invention, (OX) in formula (1) and (OX) in formula (A) are a ) are preferably the same group.

[0360] L a is a single bond or a divalent linking group (excluding (OX a ) na . na is an integer greater than 1).

[0361] Specific examples of the divalent linking group include an alkylene group, an etheric oxygen atom, an amide bond, and a group obtained by combining them. Among the divalent linking groups, an alkylene group, a group obtained by combining an alkylene group with an etheric oxygen atom, and a group obtained by combining an alkylene group with an amide bond are preferred from the viewpoint of easy production of the compound (A) and from the viewpoint of thermal stability and chemical stability.

[0362] L a The divalent linking group in (OX a ) na . (OX a ) is as defined above, and na is an integer greater than 1.

[0363] From the viewpoint of further improving the effect of the present invention, L a Preferred is a single bond.

[0364] Z a1 It is a fluorine atom or a trifluoromethyl group, and is preferably a fluorine atom from the viewpoint of further improving the effects of the present invention.

[0365] The compound (A) may be used in combination of two or more types.

[0366] Specific examples of compound (A) are shown below. It should be noted that PFPE in the following compound and R in formula (A) fa -(OX a ) m1 - is the same, and suitable aspects are also the same. n10 in the following compounds represents an integer of 1 to 10.

[0367] PFPE-CF=CH2

[0368] PFPE-CH2-O-(CH2) n10 -CF=CH2

[0369] PFPE-CH2-(CH2) n10 -CF=CH2

[0370] PFPE-C(O)-NH-(CH2) n10 -CF=CH2

[0371] The method for producing compound (A) is not particularly limited, and examples thereof include a method in which a metal or an organometallic reagent is reacted with compound (a1) to cause a leaving reaction of compound (a1) to obtain compound (A). Specifically, Q in compound (a1) a1 and CFZ a1 The fluorine atom in the reaction mixture leaves to give compound (A).

[0372] The compound (a1) is a compound represented by formula (a1).

[0373] R fa -(OX a ) m1 -L a -CFZ a1 -CH2-Q a1 …(a1)

[0374] In formula (a1), R fa , X a , L a , Z a1 , m1 is defined as above.

[0375] Q a1 is a leaving group, preferably a halogen atom or a sulfonate group (-O-SO2-R a1 ). a1 It is an organic group.

[0376] Specific examples of the halogen atom in the leaving group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom, a bromine atom or an iodine atom is preferred.

[0377] Specific examples of the sulfonate group in the leaving group include p-toluenesulfonate group (OTs), methanesulfonate group (OMs), trifluoromethanesulfonate group (OTf), and perfluorobutanesulfonate group (ONf), and trifluoromethanesulfonate group is preferred.

[0378] Specific examples of the metal include magnesium, copper, iron, zinc, tin, antimony and the like, and alloys of these metals with cadmium, palladium or mercury. The metal may be used alone or in combination of two or more.

[0379] Specific examples of the organometallic reagent include organolithium compounds, Grignard reagents, and organocopper compounds. The organometallic reagent may be used alone or in combination of two or more.

[0380] The amount of the metal used is preferably 1 to 30 mol based on 1 mol of the compound (a1).

[0381] From the viewpoint of obtaining an excellent yield of the compound (A), the above-mentioned leaving reaction is preferably carried out in the presence of an organic solvent, and particularly preferably carried out in the presence of a fluorinated organic solvent.

[0382] Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, fluorinated alkyl amines, and fluorinated alcohols.

[0383] The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, and examples thereof include C6F 13 H (AC-2000: product name, made by AGC), C6F 13 C2H5 (AC-6000: product name, manufactured by AGC Corporation), C2F5CHFCHFCF3 (Vertrel: product name, manufactured by DuPont Corporation).

[0384] Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene.

[0385] The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, and examples thereof include CF3CH2OCF2CF2H (AE-3000: product name, manufactured by AGC), C4F9OCH3 (NOVEC-7100: product name, manufactured by 3M), C4F9OC2H5 (NOVEC-7200: product name, manufactured by 3M), and C2F5CF(OCH3)C3F7 (NOVEC-7300: product name, manufactured by 3M).

[0386] Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.

[0387] Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0388] When a fluorinated organic solvent is used, the amount used is preferably 50 to 500 parts by mass based on 100 parts by mass of the compound (a1).

[0389] The reaction temperature is not particularly limited, but is usually 0 to 100°C.

[0390] The reaction may be carried out under atmospheric pressure or under increased pressure. When the reaction is carried out under increased pressure, the reaction pressure may be set to 0.2 MPa to 1 MPa.

[0391] The compound (A) can also be produced by a method other than using the above-mentioned compound (a1).

[0392] For example, when compound (A) is compound (A1) (L of formula (A) a In the case of a compound containing an etheric oxygen atom), the compound (A1) can be obtained by reacting the compound (a2-1) with the compound (a2-2).

[0393] R fa -(OX a ) m1 -L a11 -OH…(a2-1)

[0394] Q a11 -L a12 -CZ a1 =CH2…(a2-2)

[0395] R fa -(OX a ) m1 -L a11 -OL a12 -CZ a1 =CH2…(A1)

[0396] In formula (a2-1), R fa , X a , m1 is defined as above, L a11 A divalent linking group.

[0397] In formula (a2-2), Z a1 The definition of Q is as above. a11 is a halogen atom or a sulfonate group, L a12 A divalent linking group.

[0398] In formula (A1), R fa , X a , Z a1 , La11 , L a12 , m1 are as defined above. -L in compound (A1) a11 -OL a12 - corresponds to L in compound (A) a1 .

[0399] In addition, when compound (A) is compound (A2) (L in formula (A) a In the case of a compound in which a compound (a3-1) is an alkylene group), the compound (A2) can be obtained by coupling reaction of the compound (a3-1) with the compound (a3-2) which is a Grignard reagent.

[0400] R fa -(OX a ) m1 -L a13 -Q a13 …(a3-1)

[0401] Q a14 Mg-L a14 -CZ a1 =CH2…(a3-2)

[0402] R fa -(OX a ) m1 -L a13 -L a14 -CZ a1 =CH2…(A2)

[0403] In formula (a3-1), R fa , X a , m1 is defined as above, L a13 is an alkylene group, Q a13 is a halogen atom or a sulfonate group.

[0404] In formula (a3-2), Z a1 The definition of L is as mentioned above. a14 is an alkylene group, Q a14 A halogen atom.

[0405] In formula (A2), R fa , X a , Z a1 , L a13 , L a14 , m1 is defined as above.

[0406] -L in compound (A2) a13 -L a14 - corresponds to L in compound (A) a1 .

[0407] In addition, when compound (A) is compound (A3) (L in formula (A) a In the case of a compound containing an amide bond), the compound (A3) can be obtained by a substitution reaction between the compound (a4-1) and the compound (a4-2).

[0408] R fa -(OX a ) m1 -L a15 -C(O)OQ a15 …(a4-1)

[0409] NH2-L a16 -CZ a1 =CH2…(a4-2)

[0410] R fa -(OX a ) m1 -L a15 -C(O)-NH-L a16 -CZ a1 =CH2…(A3)

[0411] In formula (a4-1), R fa , X a , m1 is defined as above, L a15 is a divalent linking group, Q a15 It is an alkyl group.

[0412] In formula (a4-2), Z a1 The definition of L is as mentioned above. a16 A divalent linking group.

[0413] In formula (A3), R fa , X a , Z a1 , L a15 , L a16 , m1 is defined as above.

[0414] -L in compound (A3) a15 -C(O)-NH-L a16 - corresponds to L in compound (A) a1 .

[0415] (Compound (B))

[0416] The compound (B) is a compound represented by formula (B).

[0417] CH2=CZ b2 -L b2 -(OX b ) m2 -Lb1 -CZ b1 =CH2…(B)

[0418] In formula (B), X b X is a fluoroalkylene group having 1 to 6 carbon atoms. b The suitable form of is the same as that of X in the above formula (1). b ) is suitable in the same manner as (OX) in the above formula (1).

[0419] (OX b ) is an integer greater than 2. The suitable form of m2 is the same as the repetition number m of the above-mentioned (OX).

[0420] When the specific fluorine-containing ether compound is a compound represented by formula (1), from the viewpoint of further improving the effect of the present invention, (OX) in formula (1) and (OX) in formula (B) are b ) are preferably the same group.

[0421] L b1 and L b2 Each independently is a single bond or a divalent linking group (excluding (OX b ) nb . nb is an integer greater than 1).

[0422] Specific examples of the divalent linking group include an alkylene group, an etheric oxygen atom, an amide bond, and a group obtained by combining them. Among the divalent linking groups, an alkylene group, a group obtained by combining an alkylene group with an etheric oxygen atom, and a group obtained by combining an alkylene group with an amide bond are preferred from the viewpoint of easy production of the compound (B) and from the viewpoint of thermal stability and chemical stability.

[0423] L b1 and L b2 The divalent linking group in (OX b ) nb . (OX b ) is as defined above, and nb is an integer greater than 1.

[0424] L b1 and L b2 Optional same or different.

[0425] From the viewpoint of further improving the effect of the present invention, L b2 Preferred is a single bond.

[0426] Z b1 and Z b2 Each is independently a fluorine atom or a trifluoromethyl group.

[0427] Z b1 and Zb2 The two or more compounds may be the same or different, but are preferably the same from the viewpoint of easier production.

[0428] From the viewpoint of further improving the effect of the present invention, Z b1 and Z b2 Preferably, they are all fluorine atoms.

[0429] The compound (B) may be used in combination of two or more types.

[0430] Specific examples of compound (B) are shown below. It should be noted that PFPE in the following compound and -(OX b ) m2 - is the same, and suitable aspects are also the same. n11 and n12 in the following compounds each independently represent an integer of 1 to 10.

[0431] CH2=CF-PFPE-CF=CH2

[0432] CH2=CF-(CH2) n11 -O-CH2-PFPE-CH2-O-(CH2) n12 -CF=CH2

[0433] CH2=CF-(CH2) n11 -CH2-PFPE-CH2-(CH2) n12 -CF=CH2

[0434] CH2=CF-(CH2) n11 -NH-C(O)-PFPE-C(O)-NH-(CH2) n12 -CF=CH2

[0435] The method for producing compound (B) is not particularly limited, and examples thereof include a method in which a metal or an organic metal reagent is reacted with compound (b1) to cause a leaving reaction of compound (b1) to obtain compound (B). Specifically, Q in compound (b1) b1 CFZ b1 The fluorine atoms in Q b2 CFZ b2 The fluorine atom in is removed to obtain compound (B). The method for producing compound (B) is the same as the method for producing compound (A) using compound (a1) except that compound (b1) is used, so the description thereof is omitted.

[0436] The compound (b1) is a compound represented by the formula (b1).

[0437] Q b2 -CH2-CFZ b2 -Lb2 -(OX b ) m2 -L b1 -CFZ b1 -CH2-Q b1 …(b1)

[0438] In formula (b1), X b , L b1 , L b2 , Z b1 , Z b2 , m2 are defined as above.

[0439] Q b1 and Q b2 Each independently is a leaving group, preferably a halogen atom or a sulfonate group (-O-SO2-R b1 ). b1 Specific examples and suitable forms of the halogen atom and the sulfonate group are the same as those of Q in formula (a1). a1 same.

[0440] The compound (B) can also be produced by a method other than the method using the above-mentioned compound (b1).

[0441] For example, when compound (B) is compound (B1) (L of formula (B) b1 and L b2 In the case of a compound (b2-1) and a compound (b2-2), the compound (B1) can be obtained by reacting the compound (b2-1) with the compound (b2-2).

[0442] HO-L b12 -(OX b ) m2 -L b11 -OH…(b2-1)

[0443] Q b11 -L b13 -CZ b10 =CH2…(b2-2)

[0444] CH2=CZ b10 -L b13 -OL b12 -(OX b ) m2 -L b11 -OL b13 -CZ b10 =CH2…(B1)

[0445] In formula (b2-1), X b , m2 is defined as above, L b11 and Lb11 Each is independently a divalent linking group.

[0446] In formula (b2-2), Z b10 The definition of Z is the same as above b1 and Z b2 Same, Q b11 is a halogen atom or a sulfonate group, L b13 A divalent linking group.

[0447] In formula (B1), X b , Z b10 , L b11 , L b12 , L b13 , m2 are as defined above. -L in compound (B1) b11 -OL b13 - corresponds to L in compound (B) b1 , -L in compound (B1) b13 -OL b12 Equivalent to L in compound (B) b2 .

[0448] In addition, when compound (B) is compound (B2) (L in formula (B) b1 and L b2 In the case of a compound in which (a) is an alkylene group, the compound (B2) can be obtained by coupling reaction of the compound (b3-1) with the compound (b3-2) which is a Grignard reagent.

[0449] Q b13 -L b15 -(OX b ) m2 -L b14 -Q b12 …(b3-1)

[0450] Q b14 Mg-L b16 -CZ b11 =CH2…(b3-2)

[0451] CH2=CZ b11 -L b16 -L b15 -(OX b ) m2 -L b14 -L b16 -CZ b11 =CH2…(B2)

[0452] In formula (b3-1), X b , m2 is defined as above, L b14 and Lb15 Each is independently an alkylene group, Q b12 and Q b13 Each is independently a halogen atom or a sulfonate group.

[0453] In formula (b3-2), Z b11 The definition of Z is the same as above b1 and Z b2 Same, L b16 is an alkylene group, Q b14 A halogen atom.

[0454] In formula (B2), X b , Z b11 , L b14 , L b15 , L b16 , m2 are as defined above. -L in compound (B2) b14 -L b16 - corresponds to L in compound (B) b1 , -L in compound (B2) b16 -L b15 - corresponds to L in compound (B) b2 .

[0455] In addition, when compound (B) is compound (B3) (L in formula (B) b1 and L b2 In the case of a compound containing an amide bond), the compound (B3) can be obtained by reacting the compound (b4-1) with the compound (b4-2).

[0456] Q b16 -O(O)CL b18 -(OX b ) m2 -L b17 -C(O)OQ b15 …(b4-1)

[0457] NH2-L b19 -CZ b12 =CH2…(b4-2)

[0458] CH2=CZ b12 -L b19 -NH-C(O)-L b18 -(OX b ) m2 -L b17 -C(O)-NH-L b19 -CZ b12 =CH2

[0459] …(B3)

[0460] In formula (b4-1), X b , m2 is defined as above, L b17 and L b18 Each is independently a divalent linking group, Q a15 and Q b16 Each is independently an alkyl group.

[0461] In formula (b4-2), Z b12 The definition of Z is the same as above b1 and Z b2 Same, L b19 A divalent linking group.

[0462] In formula (B3), X b , Z b12 , L b17 , L b18 , L b19 , m2 are as defined above. -L in compound (B3) b17 -C(O)-NH-L b19 - corresponds to L in compound (B) b1 , -L in compound (B3) b19 -NH-C(O)-L b18 - corresponds to L in compound (B) b2 .

[0463] <Liquid medium>

[0464] The composition of the present invention may be a composition used in a dry coating method or a composition used in a wet coating method.

[0465] When the composition of the present invention is a composition used in a wet coating method, the composition of the present invention preferably contains a liquid medium.

[0466] Specific examples of the liquid medium include water and organic solvents.

[0467] The liquid medium preferably contains an organic solvent, and more preferably contains an organic solvent having a boiling point of 35 to 250° C. from the viewpoint of excellent coating properties. Here, the boiling point refers to a normal boiling point.

[0468] Specific examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents, and fluorine-based organic solvents are preferred from the viewpoint of excellent solubility. The organic solvent may be used alone or in combination of two or more.

[0469] Specific examples of the fluorinated organic solvent are the same as those exemplified in the production of the compound (A).

[0470] As non-fluorine-based organic solvents, preferred are compounds formed only of hydrogen atoms and carbon atoms; and compounds formed only of hydrogen atoms, carbon atoms and oxygen atoms, and specifically, hydrocarbon-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, and alcohol-based organic solvents.

[0471] Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.

[0472] Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0473] Specific examples of the ether-based organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.

[0474] Specific examples of the ester organic solvent include ethyl acetate and butyl acetate.

[0475] Specific examples of the alcohol-based organic solvent include isopropyl alcohol, ethanol, and n-butanol.

[0476] <Other ingredients>

[0477] The composition of the present invention may contain components other than those described above within a range not impairing the effects of the present invention.

[0478] Examples of other components include by-products generated in the production process of the first component and the second component, and unreacted raw materials and other unavoidable compounds in production.

[0479] <Content>

[0480] From the viewpoint of further improving the effects of the present invention, the content of the first component is preferably 20 to 99% by mass, more preferably 30 to 90% by mass, and particularly preferably 40 to 80% by mass based on the total solid mass of the composition of the present invention.

[0481] From the viewpoint of more excellent effect of the present invention, the content of the second component is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass relative to the total solid content mass of the composition of the present invention. It should be noted that the content of the second component refers to the total content of compound (A) and compound (B), and when only one of them is contained, it refers to the content thereof.

[0482] When the composition contains a liquid medium, the mass of the solid content of the composition refers to the mass obtained by removing the liquid medium from the composition.

[0483] The mass ratio of the content of the second component to the content of the first component (content of the second component / content of the first component) is preferably 0.01 to 4.0, more preferably 0.10 to 2.2, and particularly preferably 0.25 to 1.5. If the mass ratio is 0.01 or more, the wear resistance of the surface layer is more excellent. If the mass ratio is within the above range, the wear resistance of the surface layer is more excellent.

[0484] When the composition of the present invention contains the liquid medium, the content of the liquid medium is preferably 70 to 99.99% by mass, particularly preferably 80 to 99.9% by mass, based on the total mass of the composition of the present invention.

[0485] When the composition of the present invention contains the above-mentioned other components, the content of the other components is preferably 0 to 10 mass %, more preferably 0 to 5 mass %, particularly preferably 0 to 1 mass % based on the content of the specific fluorine-containing ether compound.

[0486] [Substrate with surface layer]

[0487] The substrate with a surface layer of the present invention comprises a substrate and a surface layer formed from the above composition. The substrate with a surface layer of the present invention comprises a surface layer formed from the above composition and therefore has excellent abrasion resistance and excellent water and oil repellency.

[0488] (Base material)

[0489] As long as the substrate is sometimes used in contact with other articles (such as a stylus), people's fingers, sometimes held with people's fingers during operation and / or sometimes placed on other articles (such as a mounting table), and requires to impart water- and oil-repellent substrates, there is no particular limitation. As a specific example of substrate material, metal, resin, glass, sapphire, ceramic, stone and their composite materials can be listed. Glass can be chemically strengthened.

[0490] As the substrate, a touch panel substrate and a display substrate are preferred, and a touch panel substrate is particularly preferred. The touch panel substrate preferably has light transmittance. "Having light transmittance" means that the vertical incidence visible light transmittance based on JIS R3106:1998 (ISO 9050:1990) is 25% or more. As the material of the touch panel substrate, glass and transparent resin are preferred.

[0491] In addition, as the substrate, glass or resin films used in building materials, decorative building materials, interior decoration, transportation machinery (such as automobiles), billboards / bulletin boards, drinking fountains / tableware, sinks, ornamental utensils (such as plaques, boxes), experimental equipment, furniture, art / sports / games, and glass sheets or resin films used in the outer packaging parts (excluding the display part) of devices such as mobile phones (such as smart phones), portable information terminals, game consoles, and remote controls are also preferred.

[0492] The substrate may be a substrate having one or both surfaces subjected to surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, or the like.

[0493] The surface layer can be formed directly on the surface of the substrate, or it can be formed on the substrate via other films formed on the surface of the substrate. As specific examples of the other films, there can be cited: a base film formed on the surface of the substrate by treating the substrate with a compound, SiO2, etc. as described in paragraphs 0089 to 0095 of International Publication No. 2011 / 016458.

[0494] (Surface layer)

[0495] The surface layer is a layer formed from the above-mentioned composition.

[0496] As described above, the surface layer comprises a condensate obtained by hydrolysis and dehydration condensation of part or all of the reactive silyl groups of the specific fluorine-containing ether compound as the first component. In addition, the surface layer comprises the second component or a component derived from the second component.

[0497] The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the surface layer is above the lower limit, the effect achieved by the surface layer can be fully obtained. If the thickness of the surface layer is below the upper limit, the utilization efficiency is high.

[0498] The thickness of the surface layer can be calculated from the vibration period of an interference pattern of reflected X-rays obtained by X-ray reflectivity (XRR) using an X-ray diffractometer for thin film analysis.

[0499] [Method for producing substrate with surface layer]

[0500] The method for producing the substrate with a surface layer of the present invention is a method of forming a surface layer on a substrate by a dry coating method or a wet coating method using the above-mentioned composition.

[0501] The substrate with a surface layer of the present invention can be produced, for example, by the following method.

[0502] A method of obtaining a substrate with a surface layer having a surface layer formed on the surface of a substrate by treating the surface of the substrate by a dry coating method using the above composition (hereinafter also referred to as "dry coating composition") which does not contain a liquid medium.

[0503] A method of obtaining a substrate with a surface layer having a surface layer formed on the surface of a substrate by applying the above composition containing a liquid medium (hereinafter also referred to as "wet coating composition") on the surface of a substrate by a wet coating method and drying the composition.

[0504] As specific examples of dry coating methods, vacuum evaporation, CVD, and sputtering methods can be cited. Among these, vacuum evaporation is suitable from the viewpoint of suppressing the decomposition of specific fluorinated ether compounds and the viewpoint of device simplicity. During vacuum evaporation, a granular material obtained by carrying a dry coating composition on a porous metal body such as iron or steel can be used; or a granular material obtained by impregnating a wet coating composition and drying it can be used.

[0505] Specific examples of the wet coating method include spin coating, wipe coating, spray coating, extrusion coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett method, and gravure coating.

[0506] The drying temperature after wet coating of the composition is preferably 20 to 200°C, particularly preferably 80 to 160°C.

[0507] [Compound]

[0508] The compound of the present invention is a compound represented by the above formula (A) (compound (A)) or a compound represented by the above formula (B) (compound (B)), and both are novel compounds.

[0509] The details of the compound (A) and the compound (B) are as described above in connection with the composition of the present invention, and therefore description thereof will be omitted.

[0510] As described above, the compound (A) and the compound (B) can be suitably used in the above composition.

[0511] In addition, the compound (A) and the compound (B) can also be suitably used for purposes other than being added to the above-mentioned composition.

[0512] For example, compound (A) and compound (B) can be used for improving the alkali resistance of the substrate. Specifically, the present inventors have found that when compound (A) or compound (B) is used in the surface treatment of a substrate having a nitride on the surface, the alkali resistance of the substrate is improved. The detailed reason is not clear, but it can be inferred that it is due to the following reasons.

[0513] As described above, compound (A) has -CZ at one terminal portion. a1 =CH2 represented by the group (Z a1 is a fluorine atom or a trifluoromethyl group). In addition, compound (B) has -CZ at both ends. b1 =CH2 and CH2=CZ b2 - the group (Z b1 and Z b2 are each independently a fluorine atom or a trifluoromethyl group).

[0514] Thus, Z of compound (A) a1 is a group having a fluorine atom, Z of the compound (B) b1 and Z b2 It is a group having a fluorine atom. Therefore, compared with a compound having a terminal part of -CH2=CH2, the water repellency near the terminal is improved. As a result, it is estimated that the alkali resistance of the substrate having the nitride is improved.

[0515] The compound (B) can also be suitably used in a curable composition for producing rubber.

[0516] Example

[0517] Hereinafter, the present invention will be described in detail by giving examples. Examples 1-1 to 1-5, 1-7 to 1-9, 2-1 to 2-3 are embodiments, and Examples 1-6, 1-10, and 2-4 are comparative examples. However, the present invention is not limited to these examples. It should be noted that the compounding amount of each component in the table described below represents a mass basis.

[0518] [Synthesis Example 1: Synthesis of fluorinated ether compound (3-1)]

[0519] <Synthesis of Compound (1-1)>

[0520] According to the method described in Example 7 of International Publication No. 2013 / 121984, the following compound (1-1) was obtained.

[0521] CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2OH…(1-1)

[0522] The average value of the number of repeating units n is 13.

[0523] <Synthesis of Compound (1-2)>

[0524] The above compound (1-1) (6.80 g, 1.48 mmol), 2,6-lutidine (0.759 g, 7.08 mmol), and AE-3000 (28.0 g) were added, and the mixture was stirred at 0°C. After adding trifluoromethanesulfonic anhydride (0.987 g, 3.50 mol), the mixture was stirred at room temperature. After washing with water, the solvent was distilled off, and flash column chromatography was performed using silica gel to obtain 6.81 g of the following compound (1-2).

[0525] CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2OTf…(1-2)

[0526] The average value of the number of repeating units n is 13, and OTf is trifluoromethanesulfonate: -OS(=O)2(-CF3).

[0527] NMR spectrum of compound (1-2);

[0528] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 4.78 (t, J = 12.3Hz, 2H).

[0529] 19 F-NMR (376MHz, Chloroform-d) δ (ppm): -55.28, -74.11, -82.86, -88.07, -90.20, -119.84, -125.28, -126.16.

[0530] <Synthesis of Compound (2-1)>

[0531] Diethyl diallylmalonate (60.0 g, 250 mmol), lithium chloride (23.7 g, 559 mmol), water (6.45 g, 360 mmol), and dimethyl sulfoxide (263 g) were added and stirred at 160°C. After cooling to room temperature, water was added and extracted with ethyl acetate. Hexane was added to the organic layer, washed with saturated brine, and dried over sodium sulfate. After filtering, the solvent was distilled off to obtain 39.5 g of the following compound (2-1).

[0532]

[0533] NMR spectrum of compound (2-1);

[0534] 1H-NMR (400MHz, Chloroform-d) δ (ppm): (ddt, J=17.1, 10.1, 7.0Hz, 2H), 5.06~4.94 (m, 4H), 4.09 (q, J=7.1Hz, 2H), 2. 47(ddd,J=14.0,8.0,6.1Hz,1H),2.33(dt,J=14.9,7.5Hz,2H),2.22(dt,J=14.1,6.5Hz,2H),1.21(t,J=7.1Hz,3H).

[0535] <Synthesis of Compound (2-2)>

[0536] After adding THF (260mL) and diisopropylamine (41.5mL, 294mmol), the solution was cooled to -78°C. Add n-butyllithium hexane solution (2.76M, 96.6mL, 294mmol) and heat to 0°C. After stirring, cool to -78°C and prepare a THF solution of lithium diisopropylamide (LDA). Add the above compound (2-1) (39.5g, 235mmol) to the THF solution, and after stirring, add allyl bromide (24.1mL, 278mmol). Warm up to 0°C, add 1M hydrochloric acid (100mL), and distill off THF under reduced pressure. After extraction with dichloromethane, sodium sulfate is added. After filtration, the solvent is distilled off and flash column chromatography is performed using silica gel to obtain 45.0g of compound (2-2).

[0537]

[0538] NMR spectrum of compound (2-2);

[0539] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.74 ~ 5.62 (m, 3H), 5.04 (dd, J = 13.6, 1.9Hz, 6H), 4.10 (q, J = 7.1Hz, 2H), 2.29 (d, J = 7.4Hz, 6H), 1.22 (t, J = 7.1Hz, 3H).

[0540] <Synthesis of Compound (2-3)>

[0541] The above compound (2-2) (45.0 g, 216 mmol) was dissolved in THF (620 mL) and cooled to 0°C. A THF solution of lithium aluminum hydride (104 mL, 260 mmol) was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, stirred at room temperature, and then diluted with dichloromethane. After filtering, the solvent was distilled off, and flash column chromatography was performed using silica gel to obtain 31.3 g of the following compound (2-3).

[0542]

[0543] NMR spectrum of compound (2-3);

[0544] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.90 ~ 5.76 (m, 3H), 5.10 ~ 5.02 (m, 6H), 3.38 (s, 2H), 2.03 (dt, J = 7.5, 1.2Hz, 6H), 1.45 (s, 1H).

[0545] <Synthesis of Compound (B1-1)>

[0546] Acetonitrile (380 mL), the above compound (2-3) (31.3 g, 188 mmol), triphenylphosphine (64.3 g, 245 mmol), and carbon tetrachloride (33.9 g, 221 mmol) were added, and the mixture was stirred at 90° C. After concentration, ethyl acetate / hexane was added and stirred. After filtration and concentration, 28.2 g of the following compound (B1-1) was obtained by distillation (70° C., 3 hPa).

[0547]

[0548] NMR spectrum of compound (B1-1);

[0549] 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.83 ~ 5.67 (m, 3H), 5.16 ~ 5.01 (m, 6H), 3.32 (s, 2H), 2.05 (dt, J = 7.5, 1.1Hz, 6H).

[0550] <Synthesis of Compound (B2-1)>

[0551] THF (35 mL) and iodine (0.180 g, 0.71 mmol) were added to magnesium (2.36 g, 97.2 mmol), and the mixture was stirred at room temperature. A solution of the above compound (B1-1) (14.0 g, 75.9 mmol) in THF (35 mL) was added, and the mixture was heated under reflux for 2 hours to prepare a solution (1.0 M) of the following compound (B2-1).

[0552]

[0553] <Synthesis of Compound (C1-1)>

[0554] After adding CuCl2 (16.0 mg, 0.119 mmol), 1-phenyl-1-propyne (0.052 g, 0.45 mmol), 1,3-bistrifluoromethylbenzene (24 mL), the above compound (1-2) (4.00 g), add the above compound (B2-1) (5.0 mL, 1.0 M, 5.0 mmol). After stirring at room temperature, wash with 1 M hydrochloric acid and dry with sodium sulfate. After filtering, distill off the solvent and add AC-6000. After washing with methanol, flash column chromatography is performed using silica gel to obtain 0.139 g of compound (C1-1).

[0555] CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2CF2-CH2CH2-C[CH2CH2=CH2]3…(C1-1)

[0556] The average value of the number of repeating units n is 10.

[0557] NMR spectrum of compound (C1-1);

[0558] 1 H-NMR (400MHz, Chloroform-d) δ5.77(ddt,J=14.9,10.7,7.4Hz,3H),5.07-4.99(m,6H),2.19-2.05(m,2H),1.97(d,J=7.4Hz,6H),1.59-1.50(m,2H).

[0559] 19 F-NMR(376MHz,Chloroform-d)δ-55.29,-82.90,-88.13,-90.24(d,J=8.0Hz),-114.62,-125.34,-126.49.

[0560] <Synthesis of Compound (3-1)>

[0561] AC-2000 (0.89 g), the above-mentioned compound (C1-1) (0.139 g), a xylene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content of 2%, 5.5 mg), aniline (0.8 mg), and trimethoxysilane (22.7 mg, 0.185 mmol) were added, and the mixture was stirred at 40° C., and the solvent was distilled off under reduced pressure to obtain 0.140 g of a fluorinated ether compound (3-1).

[0562] CF3-(OCF2CF2-OCF2CF2CF2CF2) n-OCF2CF2-OCF2CF2CF2-CH2CH2-C[CH2CH2CH2-Si(OCH3)3]3…(3-1)

[0563] The average value of the number of units m is 10.

[0564] NMR spectrum of compound (3-1);

[0565] 1 H-NMR (400MHz, Chloroform-d) δ3.60 (s, 27H), 2.23-1.95 (m, 2H), 1.63-1.28 (m, 14H), 0.67 (t, J = 7.6Hz, 6H).

[0566] 19 F-NMR(376MHz,Chloroform-d)δ-55.33,-82.95,-88.17,-90.13--90.40(m),-114.07--114.32(m),-125.38,-126.04.

[0567] [Synthesis Example 2: Synthesis of fluorinated ether compound (3-2)]

[0568] According to the method described in Example 6-2 of International Publication No. 2017 / 038830, a fluorinated ether compound (3-2) was obtained.

[0569] CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2OCH2-C[CH2CH2CH2-Si(OCH3)3]3…(3-2)

[0570] The average value of the number of repeating units n is 13.

[0571] [Synthesis Example 3: Synthesis of Compound (A-1)]

[0572] <Synthesis of Compound (a1-1)>

[0573] Compound (1-1) (6.20 g), triphenylphosphine (2.00 g), 1,3-bistrifluoromethylbenzene (10 mL), carbon tetrabromide (2.00 g) and DMF (4 mL) were added, followed by stirring at 100° C. After filtration, the solvent was distilled off and flash column chromatography was performed using silica gel to obtain 4.80 g of compound (a1-1).

[0574] CF3-(OCF2CF2-OCF2CF2CF2CF2) n-OCF2CF2-OCF2CF2-CF2-CH2-Br…(a1-1)

[0575] The average value of n is 13.

[0576] NMR spectrum of compound (a1-1);

[0577] 1 H-NMR (400MHz, Chloroform-d) δ3.63 (t, J = 15.6Hz, 2H).

[0578] 19 F-NMR(376MHz,Chloroform-d)δ-55.24,-82.81,-88.04,-90.16,-113.08,-125.24.

[0579] <Synthesis of Compound (A-1)>

[0580] After adding compound (a1-1) (500 mg), 1,3-bistrifluoromethylbenzene (2 mL), acetic acid (1 mL), and zinc (500 mg), the mixture was stirred at 110° C. After filtration, AC-6000 (30 mL) and 1M hydrochloric acid (3 mL) were added, and the mixture was washed with methanol (10 mL). The solvent was distilled off to obtain 412 mg of compound (A-1).

[0581] CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF=CH2…

[0582] (A-1)

[0583] The average value of the number of repeating units n is 13.

[0584] NMR spectrum of compound (A-1);

[0585] 1 H-NMR(400MHz,Chloroform-d)δ5.36-5.04(m,2H).

[0586] 19 F-NMR(376MHz,Chloroform-d)δ-55.01--55.21(m),-82.28--83.04(m),-85.95,-87.45--88.29 (m),-89.97(q,J=9.2Hz),-118.62(dtd,J=43.3,13.9,6.9Hz),-120.88(d,J=13.8Hz),-125.02.

[0587] [Synthesis Example 4: Synthesis of Compound (A-2)]

[0588] After adding compound (1-1) (200 mg), 1,3-bistrifluoromethylbenzene (0.2 mL), TBAI (1.6 mg), 30% sodium hydroxide aqueous solution (8.1 mg), and 3-bromo-2-fluoroprop-1-ene (22.1 mg), the mixture was stirred at 60°C. The mixture was washed with AC-6000 (60 mL) and methanol (20 mL). The solvent was distilled off, and flash column chromatography was performed using silica gel to obtain 158 mg of compound (A-2).

[0589] CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2CF2-CH2-O-CH2-CF=CH2…(A-2)

[0590] The average value of the number of repeating units n is 13.

[0591] NMR spectrum of compound (A-2);

[0592] 1 H-NMR (400MHz, Chloroform-d) δ4.75-4.42 (m, 2H), 4.08 (d, J = 13.2Hz, 2H), 3.98 (t, J = 13.4Hz, 2H).

[0593] 19 F-NMR(376MHz,Chloroform-d)δ-54.89,-82.39,-87.60,-89.75(q,J=9.3Hz),-105.23(dq,J=47.0,13.6Hz),-118.86--119.26(m),-124.80,-126.06.

[0594] [Synthesis Example 5: Synthesis of Compound (B-1)]

[0595] <Synthesis of Compound (a1-2)>

[0596] After adding FLUOROLINK D4000 (manufactured by Solvay Specialty Polymers) (5.01 g), triphenylphosphine (7.5 g), 1,3-bistrifluoromethylbenzene (50 mL), carbon tetrabromide (7.5 g), and DMF (5 mL), the mixture was stirred at 120° C. After filtration, the solvent was distilled off, and flash column chromatography was performed using silica gel to obtain 2.12 g of compound (a1-2).

[0597] Br-CH2-CF2-{(OCF2) n1 (OC2F4) n2}-O-CF2-CH2-Br…(a1-2)

[0598] The average value of the number of repeating units n1 is 22, and the average value of the number of repeating units n2 is 25.

[0599] NMR spectrum of compound (a1-2);

[0600] 1 H-NMR (400MHz, Chloroform-d) δ3.55 (q, J=9.8Hz, 4H).

[0601] <Synthesis of Compound (B-1)>

[0602] After adding compound (a1-2) (600 mg), 1,3-bistrifluoromethylbenzene (24 mL), and butylmagnesium chloride THF solution (6.0 mL, 6.0 mmol), the mixture was stirred at room temperature. AC-6000 (50 mL) and 1M hydrochloric acid (5 mL) were added, and the mixture was washed with methanol (20 mL). The solvent was distilled off, and flash column chromatography was performed using silica gel to obtain 45 mg of compound (B-1).

[0603] H2C=CF-{(OCF2) n1 (OC2F4) n2}-O-CF=CH2…(B-1)

[0604] The average value of the number of repeating units n1 is 22, and the average value of the number of repeating units n2 is 25.

[0605] NMR spectrum of compound (B-1);

[0606] 1 H-NMR(400MHz,Chloroform-d)δ4.32-4.14(m,4H).

[0607] [Synthesis Example 6: Synthesis of Compound (C-1)]

[0608] After adding compound (1-1) (200 mg), 1,3-bistrifluoromethylbenzene (0.2 mL), TBAI (1.6 mg), 30% sodium hydroxide aqueous solution (8.1 mg), and allyl bromide (22.1 mg), the mixture was stirred at 60°C. The mixture was washed with AC-6000 (60 mL) and methanol (20 mL). The solvent was distilled off, and flash column chromatography was performed using silica gel to obtain 161 mg of compound (C-1).

[0609] CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2CF2-CH2-O-CH2-CH=CH2…(C-1)

[0610] The average value of the number of repeating units n is 13.

[0611] NMR spectrum of compound (C-1);

[0612] 1 H-NMR (400MHz, Chloroform-d) δ5.80 (ddt, J=16.3, 10.8, 5.7Hz, 1H), 5.25 (dd, J=17.3, 1.6Hz, 1H), 5.15 (dd, J=10.5, 1.5Hz, 1H), 4.05 (d, J=5.6Hz, 2H), 3.89 (t, J=13.7Hz, 2H).

[0613] 19 F-NMR(376MHz,Chloroform-d)δ-55.11,-82.63,-87.86,-89.98(q,J=9.1Hz),-119.16(t,J=12.1Hz),-125.03,-126.28.

[0614] [Example 1-1]

[0615] 99 parts by mass of the fluorinated ether compound (3-1) as the first component and 1 part by mass of the compound (A-1) as the second component were mixed to obtain a composition (1-1).

[0616] A molybdenum boat in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC KIKO) was filled with 0.14 g of the composition (1-1) as a deposition source, and the vacuum deposition apparatus was evacuated to 1×10 -3 Pa or less. The boat equipped with the composition (1-1) is heated at a rate of less than 10°C / min, and the baffle is opened when the evaporation rate based on the crystal oscillation film thickness meter exceeds 1nm / sec, and the film formation on the surface of the substrate (chemically strengthened glass) begins. When the film thickness becomes about 50nm, the baffle is closed, and the film formation on the surface of the substrate is terminated. The substrate deposited with the composition (1-1) is heated at 200°C for 30 minutes, and cleaned with dichloropentafluoropropane (manufactured by AGC, AK-225) to obtain a substrate with a surface layer having a surface layer on the surface of the substrate.

[0617] [Example 1-2 ~ Example 1-10]

[0618] Except having changed the kind and content of the first component and the second component as described in Table 1, the same operation as in Example 1-1 was carried out to obtain a substrate with a surface layer in each example.

[0619] [Evaluation test]

[0620] The following evaluation tests were carried out using the substrates with surface layers of Examples 1-1 to 1-10.

[0621] <Water contact angle>

[0622] The contact angle of about 2 μL of distilled water placed on the surface of the surface layer was measured at 20°C using a contact angle measuring device (DM-701 manufactured by Kyowa Interface Science Co., Ltd.). The measurements were performed at three different locations on the surface of the surface layer, and the average value was calculated as the initial contact angle. The 2θ method was used to calculate the contact angle. Based on the value of the initial contact angle obtained, the water repellency was evaluated according to the following evaluation criteria.

[0623] A: The contact angle is more than 115 degrees

[0624] B: The contact angle is 105 degrees or more and less than 115 degrees

[0625] C: Contact angle less than 105 degrees

[0626] <Abrasion resistance>

[0627] For the surface layer, according to JIS L0849:2013 (ISO 105-X12:2001), a reciprocating traverse tester (manufactured by KNT) was used to reciprocate steel wool BONSTAR (number: #0000) under the conditions of pressure: 98.07 kPa and speed: 320 cm / min. After 10,000 reciprocating steel wool abrasions, the contact angle of water on the surface layer was measured, and the wear resistance was evaluated according to the following evaluation criteria. The smaller the change in the water contact angle before and after the abrasion test, the smaller the performance reduction caused by abrasion, and the better the wear resistance. If the evaluation result is B or above, it can be said that the wear resistance is excellent.

[0628] A: The change in water contact angle is less than 2 degrees

[0629] B: The change in water contact angle is more than 2 degrees and less than 4 degrees

[0630] C: The change in water contact angle is 4 degrees or more and less than 6 degrees

[0631] D: The change in water contact angle is more than 6 degrees

[0632] <Evaluation Results>

[0633] Table 1 shows the results of the above evaluation tests.

[0634] [Table 1]

[0635]

[0636] As shown in Table 1, it can be confirmed that when a composition comprising a specific fluorinated ether compound formed by a first component and at least one second component selected from the group consisting of compound (A) and compound (B) is used, a surface layer having an excellent initial water contact angle and excellent wear resistance can be formed (Examples 1-1 to 1-5, Examples 1-7 to 1-9).

[0637] [Example 2-1]

[0638] A substrate with a nitride film in which a silicon nitride film is formed on the surface of glass is obtained by a plasma CVD method using SiH4 and nitrogen gas.

[0639] A molybdenum boat in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC KIKO) was filled with 0.16 g of the compound (A-1) as a deposition source, and the vacuum deposition apparatus was evacuated to 1×10 -3 Pa or less. The boat equipped with the compound (A-1) is heated at a rate of 10°C / min or less, and the baffle is opened when the evaporation rate based on the crystal oscillation film thickness meter exceeds 1nm / sec, and the film formation on the surface of the substrate with the nitride film begins. The baffle is closed when the film thickness reaches about 50nm, and the film formation on the surface of the substrate with the nitride film is terminated. In this way, a substrate with a surface layer having a surface layer on the surface of the silicon nitride film is obtained.

[0640] [Example 2-2~Example 2-4]

[0641] Except having changed the kind of compound as described in Table 2, it carried out similarly to Example 2-1, and obtained the base material with the surface layer in each example.

[0642] [Evaluation test]

[0643] The following evaluation tests were carried out using the substrates with surface layers of Examples 2-1 to 2-4.

[0644] <Water contact angle>

[0645] The contact angle of about 2 μL of distilled water placed on the surface of the surface layer was measured at 20°C using a contact angle measuring device (DM-701 manufactured by Kyowa Interface Science Co., Ltd.). The measurements were performed at three different locations on the surface of the surface layer, and the average value was calculated as the initial contact angle. The 2θ method was used to calculate the contact angle. Based on the value of the initial contact angle obtained, the water repellency was evaluated according to the following evaluation criteria.

[0646] A: The contact angle is more than 115 degrees

[0647] B: The contact angle is 105 degrees or more and less than 115 degrees

[0648] C: Contact angle less than 105 degrees

[0649] <Alkali resistance>

[0650] Alkali aqueous solution (25 mass % KOH aqueous solution, pH 14) was added to the surface layer, and after standing for 60 minutes, the water contact angle of the surface layer was measured, and the alkali resistance was evaluated according to the following evaluation criteria. The smaller the change of the water contact angle before and after the alkali resistance test, the smaller the performance reduction caused by the alkali, and the more excellent the alkali resistance. If the evaluation result is more than B, it can be said that the alkali resistance is excellent.

[0651] A: The change in water contact angle is less than 1 degree

[0652] B: The change in water contact angle is more than 1 degree and less than 3 degrees

[0653] C: The change in water contact angle is more than 3 degrees

[0654] <Evaluation Results>

[0655] Table 2 shows the results of the above evaluation tests.

[0656] [Table 2]

[0657]

[0658] As shown in Table 2, it was confirmed that the use of the compound (A) or the compound (B) can improve the alkali resistance of the substrate having a nitride and can impart excellent water repellency to the substrate (Examples 2-1 to 2-3).

[0659] Industrial Applicability

[0660] The compound and composition of the present invention can be used for various purposes. It can be used for display input devices such as touch panels, transparent glass or transparent plastic components, lenses for glasses, etc., kitchen antifouling components, electronic equipment, heat exchangers, batteries, etc., water-repellent and moisture-proof components or antifouling components, cosmetic antifouling components, components that need to be both conductive and liquid-repellent, heat exchangers, water-repellent / waterproof / water-slip components, vibrating screens or barrels, etc., low-wear components on the surface. As a more specific example of use, the front surface protection plate of the display, anti-reflection plate, polarizing plate, anti-glare plate or the product obtained by applying anti-reflection film treatment to their surfaces, portable phones (such as smart phones), portable information terminals, game consoles, remote controllers, etc., touch panel sheets or touch panel displays, etc., have various devices (such as glass or film used in the display unit, etc., and glass or film used in the outer packaging part other than the display unit) of the display input device operated on the screen by people's fingers or palms. In addition to the above, the following can also be cited: decorative building materials for water-related places such as toilets, baths, washrooms, and kitchens; waterproof components for wiring boards; water-repellent / waterproof / water-slide components for heat exchangers; water-repellent components for solar cells; waterproof / water-repellent components for printed circuit boards; waterproof / water-repellent components for electronic device housings or electronic components; components for improving the insulation of power transmission lines; waterproof / water-repellent components for various filters; waterproof components for radio wave absorbing materials or sound absorbing materials; anti-fouling components for baths, kitchen equipment, and cosmetics; low-wear components for surfaces such as vibrating screens or the inside of barrels; mechanical parts, vacuum equipment parts, bearing parts, parts for transportation equipment such as automobiles, and surface protection components for tools.

[0661] It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2020-155260 filed on September 16, 2020 are cited herein and introduced as the disclosed contents of the specification of the present invention.

Claims

1. A surface treatment agent, which is composed of a composition, wherein the composition is characterized in that it contains a first component and a second component, The first component comprises a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group, The second component is a compound represented by the following formula (A), R fa -(OX a ) m1 -L a -CZ a1 =CH2…(A) in, In formula (A), R fa is a fluoroalkyl group having 1 to 20 carbon atoms, X a is a fluoroalkylene group having 1 to 6 carbon atoms, L a is a single bond or a divalent linking group, excluding (OX a ) na , na is an integer greater than 1, Z a1 is a fluorine atom or a trifluoromethyl group, m1 is an integer greater than 2; The reactive silyl group is group (2), -Si(R) n IT 3-n …(2) R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, n is an integer from 0 to 2, The content of the first component is 30 to 90% by mass based on the total solid content mass of the composition of the present invention.

2. The surface treatment agent according to claim 1, wherein In the formula (A), Z a1 A fluorine atom.

3. The surface treatment agent according to claim 1 or 2, wherein In the formula (A), L a It is an alkylene group, an ethereal oxygen atom, an amide bond, a group obtained by combining these, or a single bond.

4. The surface treatment agent according to claim 3, wherein In the formula (A), L a For a single key.

5. The surface treatment agent according to claim 1 or 2, wherein The mass ratio of the content of the second component to the content of the first component is 0.01 to 4.

0.

6. A substrate with a surface layer, characterized in that: The surface treatment agent comprises a substrate and a surface layer, wherein the surface layer is formed on the substrate using the surface treatment agent according to any one of claims 1 to 5.

7. A method for producing a substrate with a surface layer, wherein: Using the surface treatment agent according to any one of claims 1 to 5, a surface layer is formed on a substrate by a dry coating method or a wet coating method.

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