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

Abstract

The present invention addresses the problem of providing: a composition which makes it possible to form a surface layer having excellent wear resistance; a substrate with a surface layer; and a method for producing a substrate with a surface layer. The present invention also addresses the problem of providing: a novel compound; and a method for producing the compound.　The composition according to the present invention comprises: a first component comprising a fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group; and a second component comprising at least one compound selected from a compound (A) (Rfa-(OXa)m1-La-CZa1=CH2) and a compound (B) (CH2=CZb2-Lb2-(OXb)m2-Lb1-CZb1=CH2). Rfa represents a fluoroalkyl group, Xa and Xb independently represent a fluoroalkylene group, and La represents a single bond or a bivalent linking group (excluding OXa)na); Lb1 and Lb2 independently represent a single bond or a bivalent linking group (excluding OXb)nb); and Za1, Zb1 and Zb2 independently represent a fluorine atom or a trifluoromethyl group, and m1 and m2 independently represent an integer of 2 or more.

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 technology]

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

[0003] [Patent Document 1] International Publication No. 2017 / 022437 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, the performance requirements for surface layers formed using fluorinated ether compounds have been increasing. For example, when a surface layer is applied to a member that constitutes a surface that is touched by fingers, the surface layer is required to have performance (for example, water repellency) that does not deteriorate even when repeatedly worn, i.e., to have excellent abrasion resistance. The present inventors evaluated a surface layer formed using a fluorine-containing ether compound as described in Patent Document 1 and found that there was room for improvement in the abrasion resistance of the surface layer.

[0005] Therefore, an object of the present invention is to provide a composition capable of forming a surface layer having excellent abrasion resistance, a substrate with a surface layer, and a method for producing a substrate with a surface layer. Another object of the present invention is to provide a novel compound and a method for producing the same. [Means for solving the problem]

[0006] The inventors have found that the above problems can be solved by the following configuration. [1] A first component consisting of a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group; A composition comprising: a compound represented by the following formula (A) and at least one second component selected from the group consisting of a compound represented by the following formula (B): R fa -(OX a ) m1 -L a -CZ a1 =CH2 (A) However, 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 (wherein (OX a ) na na is an integer equal to or greater than 1. Z a1 is a fluorine atom or a trifluoromethyl group, m1 is an integer of 2 or greater. CH2=CZ b2 -L b2 -(OX b ) m2 -L b1 -CZ b1 =CH2 (B) However, in formula (B), X b is a fluoroalkylene group having 1 to 6 carbon atoms, L b1 and L b2 are each independently a single bond or a divalent linking group (provided that (OX b ) nb nb is an integer equal to or greater than 1; Z b1 and Z b2each independently represents a fluorine atom or a trifluoromethyl group, m2 is an integer of 2 or greater.

[0007] [2] Z in the formula (A) a1 is a fluorine atom. [3] L in the formula (A) a is an alkylene group, an ether oxygen atom, an amide bond, a group combining these, or a single bond. [4] L in the formula (A) a is a single bond. [5] Z in the formula (B) b1 and Z b2 The composition according to any one of [1] to [4], wherein each of [6] L in the formula (B) b1 and L b2 The composition according to any one of [1] to [5], wherein each of the groups independently represents an alkylene group, an etheric oxygen atom, an amide bond, a group combining these, or a single bond. [7] L in the formula (B) b2 is a single bond. [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.

[0008] [9] A substrate with a surface layer, comprising: a substrate; and a surface layer formed on the substrate from the composition according to any one of [1] to [8].

[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].

[0009]

[11] A compound represented by the following formula (A): R fa -(OX a ) m1-L a -CZ a1 =CH2 (A) However, 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 (wherein (OX a ) na na is an integer equal to or greater than 1. Z a1 is a fluorine atom or a trifluoromethyl group, m1 is an integer of 2 or greater.

[12] A compound represented by the following formula (B): CH2=CZ b2 -L b2 -(OX b ) m2 -L b1 -CZ b1 =CH2 (B) However, in formula (B), X b is a fluoroalkylene group having 1 to 6 carbon atoms, L b1 and L b2 are each independently a single bond or a divalent linking group (provided that (OX b ) nb nb is an integer equal to or greater than 1; Z b1 and Z b2 each independently represents a fluorine atom or a trifluoromethyl group, m2 is an integer of 2 or greater.

[13] A method for producing a compound, comprising reacting a metal or organometallic reagent with a compound represented by the following formula (a1) to obtain a compound represented by the following formula (A): R fa -(OX a ) m1 -L a -CFZ a1 -CH2-Q a1(a1) R fa -(OX a ) m1 -L a -CZ a1 =CH2 (A) However, in formula (a1) and 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 (wherein (OX a ) na na is an integer equal to or greater than 1. Z a1 is a fluorine atom or a trifluoromethyl group, Q a1 is a leaving group, m1 is an integer of 2 or greater.

[14] A method for producing a compound, comprising reacting a metal or organometallic reagent with a compound represented by the following formula (b1) to obtain a compound represented by the following formula (B): Q b2 -CH2-CFZ b2 -L b2 -(OX b ) m2 -L b1 -CFZ b1 -CH2-Q b1 (b1) CH2=CZ b2 -L b2 -(OX b ) m2 -L b1 -CZ b1 =CH2 (B) However, in formula (b1) and formula (B), X b is a fluoroalkylene group having 1 to 6 carbon atoms, L b1 and L b2 are each independently a single bond or a divalent linking group (provided that (OX b ) nbnb is an integer equal to or greater than 1; Z b1 and Z b2 each independently represents a fluorine atom or a trifluoromethyl group, Q b1 and Q b2 are each independently a leaving group, m2 is an integer of 2 or greater.

[15] A method for producing the compound according to

[13] or

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

[0010] According to the present invention, there are provided a composition capable of forming a surface layer having excellent abrasion resistance, a substrate with a surface layer, and a method for producing a substrate with a surface layer. Furthermore, according to the present invention, there are also provided a novel compound and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0011] In this specification, a compound represented by formula (A) will be referred to as compound (A). Compounds represented by other formulas will be similarly described. A repeating unit represented by formula (1) will be referred to as unit (1). Repeating units represented by other formulas will be similarly described. A group represented by formula (2) will be referred to as group (2). Groups represented by other formulas will be similarly described. As used herein, when it is stated that "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 the terminal, such as alkylene group-A group-. In this specification, the "aryl group" in the "aryloxy group" includes not only aryl groups but also heteroaryl groups. In this specification, the term "linking group" refers not only to an aggregate of atoms, but also to an atom itself as long as it has the function of linking specific groups together. For example, a nitrogen atom itself is considered to be a trivalent linking group.

[0012] The terms used in the present invention have the following meanings. The "divalent organopolysiloxane residue" is a group represented by the following formula: x is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. Furthermore, g1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4. [ka]

[0013] The "number average molecular weight" of a compound is 1 H-NMR and 19 It is calculated by determining the number (average value) of oxyfluoroalkylene groups based on the number of terminal groups using F-NMR.

[0014] [Composition] The composition of the present invention comprises a first component consisting of a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group (hereinafter also referred to as a "specific fluorine-containing ether compound"), and at least one second component selected from the group consisting of compound (A) and compound (B). 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. Although the details of the reason for this are not clear, it is presumed to be due to the following reasons. Compound (A) has -CZ at one end. a1 A group represented by =CH2 (Z a1 is a fluorine atom or a trifluoromethyl group.) Also, compound (B) has -CZ at both terminal portions. b1 Groups represented by =CH2 and CH2=CZ b2 - (Z b1 and Z b2 are each independently a fluorine atom or a trifluoromethyl group. Thus, a compound in which at least one of the terminals is "=CH2" has a better affinity with water than a compound in which both terminals are "-CF3." Therefore, when a surface layer is formed using the composition of the present invention, it is presumed that the progress of the hydrolysis reaction of the specific fluorinated ether compound contained in the composition of the present invention is accelerated, thereby improving the water resistance and abrasion resistance of the obtained surface layer.

[0015] <First component> The first component contained in the composition of the present invention is a specific fluorine-containing ether compound, which is a compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group.

[0016] The poly(oxyfluoroalkylene) chain contains a plurality of units (1). (OX) (1) X is a fluoroalkylene group having one or more fluorine atoms. The number of carbon atoms in the fluoroalkylene group is preferably 2 to 6, particularly preferably 2 to 4, in that the surface layer has better weather resistance and corrosion resistance. The fluoroalkylene group may be linear, branched or cyclic. The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times, and more preferably 1.7 to 2 times, the number of carbon atoms, in order to provide a surface layer with better abrasion resistance and water and oil repellency. The fluoroalkylene group is particularly preferably a group in which all hydrogen atoms in the fluoroalkylene group have been substituted with fluorine atoms (perfluoroalkylene group).

[0017] Specific examples of the unit (1) include -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2-, and -OCF2CF2C F2CF2CF2CH2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, -OCF(CF3)CF2-, -OCF2CF2CF2CF2-, - OCF(CF3)CF2CF2-, -OCF2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CF2CF2-, -O-cycloC4F6-, -O-cycloC5F8-, -O-cycloC6F 10 - are some examples. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, a specific example of which is perfluorocyclobutane-1,2-diyl, -cycloC5F8- means a perfluorocyclopentanediyl group, a specific example of which is perfluorocyclopentane-1,3-diyl, -cycloC6F 10 - means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0018] The repeat number m of the unit (1) contained in the poly(oxyfluoroalkylene) chain is an integer of 2 or more, more preferably an integer of 2 to 200, even more preferably an integer of 5 to 150, particularly preferably an integer of 5 to 100, and most preferably an integer of 10 to 50.

[0019] The poly(oxyfluoroalkylene) chain may contain only one type of (OX), or may contain two or more types of (OX). The bonding order of two or more types of (OX) is not limited, and they may be arranged randomly, alternately, or in blocks. Containing two or more types of (OX) means that, in the specific fluorinated ether compound, there are two or more types of (OX) with different numbers of carbon atoms, there are two or more types of (OX) with different numbers of hydrogen atoms, there are two or more types of (OX) with different positions of hydrogen atoms, and there are two or more types of (OX) with the same number of carbon atoms but different in the presence or absence of side chains or the type of side chain (the number of side chains, the number of carbon atoms in the side chain, etc.). For the arrangement of two or more (OX), for example, {(OCF2) m21 (OCF2CF2) m22 The structure represented by} indicates that m21 (OCF2) and m22 (OCF2CF2) are randomly arranged. m25 The structure represented by the formula indicates that m25 (OCF2CF2) and m25 (OCF2CF2CF2CF2) are alternately arranged.

[0020] (OX) represents a poly(oxyfluoroalkylene) chain m As for [(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-cycloCH mg F (6-mg) ) m17 (O-cycloCH mh F (8-mh) ) m18 (O-cycloCH mi F (10-mi) ) m19 In this case, -cycloCH mg F (6-mg)represents a fluorocyclobutanediyl group, and preferably a fluorocyclobutane-1,2-diyl group. mh F (8-mh) represents a fluorocyclopentanediyl group, and preferably a fluorocyclopentane-1,3-diyl group. mi F (10-mi) represents a fluorocyclohexanediyl group, and is preferably a fluorocyclohexane-1,4-diyl group. ma is 0 or 1, mb is an integer from 0 to 3, mc is an integer from 0 to 5, md is an integer from 0 to 7, me is an integer from 0 to 9, mf is an integer from 0 to 11, mg is an integer from 0 to 5, mh is an integer from 0 to 7, and mi is an integer from 0 to 9. m11, m12, m13, m14, m15, m16, m17, m18 and m19 each independently represent an integer of 0 or more, and preferably 100 or less. m11+m12+m13+m14+m15+m16+m17+m18+m19 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, still more preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50. Among these, m12 is preferably an integer of 2 or more, and an integer of 2 to 200 is particularly preferred. Also, C3H mc F (6-mc) , C4H md F (8-md) , C5H me F (10-me) and C6H mf F (12-mf) The may be linear or branched, and is preferably linear in that the surface layer has better abrasion resistance.

[0021] In addition, m11 (OCH ma F (2-ma) ), m12 pieces (OC2H mb F (4-mb) ), m13 pieces (OC3H mc F (6-mc) ), m14 pieces (OC4H md F (8-md) ), m15 pieces (OC5Hme F (10-me) ), m16 pieces (OC6H mf F (12-mf) ), m17 (O-cycloCH mg F (6-mg) ), m18 (O-cycloCH mh F (8-mh) ), m19 (O-cycloCH mi F (10-mi) ) may be joined in any order. If m11 is 2 or more, multiple (OCH ma F (2-ma) ) may be the same or different. If m12 is 2 or more, multiple (OC2H mb F (4-mb) ) may be the same or different. If m13 is 2 or more, multiple (OC3H mc F (6-mc) ) may be the same or different. If m14 is 2 or more, multiple (OC4H md F (8-md) ) may be the same or different. If m15 is 2 or more, multiple (OC5H me F (10-me) ) may be the same or different. If m16 is 2 or more, multiple (OC6H mf F (12-mf) ) may be the same or different. When m17 is 2 or more, multiple (O-cycloCH mg F (6-mg) ) may be the same or different. When m18 is 2 or more, multiple (O-cycloCH mh F (8-mh) ) may be the same or different. When m19 is 2 or more, multiple (O-cycloCH mi F (10-mi) ) may be the same or different.

[0022] (OX) mPreferably, has the following structure: {(OCF2) m21 (OCF2CF2) m22}, (OCF2CF2) m23 , (OCF(CF3)CF2) m23 , (OCF2CF2CF2) m24 , (OCF2CF2-OCF2CF2CF2CF2) m25 , {(OCF2CF2CF2CF2CF2) m26 (OCF2) m27}, {(OCF2CF2CF2CF2CF2) m26 (OCF2CF2) m27}, {(OCF2CF2CF2CF2CF2CF2) m26 (OCF2) m27}, {(OCF2CF2CF2CF2CF2CF2) m26 (OCF2CF2) m27}, (OCF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2-OCF2CF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2CF2) m28 , (OCF2-OCF2CF2CF2CF2CF2) m28 , (OCF2-OCF2CF2CF2CF2CF2CF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28 . Here, m21 is an integer of 1 or more, m22 is an integer of 1 or more, m21+m22 is an integer of 2 to 500, m23 and m24 are each independently an integer of 2 to 500, m25 is an integer of 1 to 250, m26 and m27 are each independently an integer of 1 or more, m26+m27 is an integer of 2 to 500, and m28 is an integer of 1 to 250.

[0023] (OX) m More preferably, the specific fluorine-containing ether compound has the following structure, from the viewpoint of ease of production. {(OCF2) m21 (OCF2CF2) m22}, (OCF(CF3)CF2) m23 , (OCF2CF2CF2) m24 , (OCF2CF2)2{(OCF2) m21 (OCF2CF2) m22-2}, (OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2, (OCF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28-1 OCF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2. However, the numbers m22, m25 and m28 are selected so that m22-2, m25-1 and m28-1 are integers of 1 or greater. Among these, (OX) is the most preferred because of its superior wear resistance on the surface layer. m is {(OCF2) m21 (OCF2CF2) m22} is preferred. {(OCF2) m21 (OCF2CF2) m22In the formula}, m22 / m21 is preferably 0.1 to 10, more preferably 0.2 to 5.0, even more preferably 0.2 to 2.0, particularly preferably 0.2 to 1.5, and most preferably 0.2 to 0.85, in order to provide a surface layer with better abrasion resistance and fingerprint removability.

[0024] (OX) m The number average molecular weight is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, and particularly preferably from 3,000 to 10,000. If the number average molecular weight is equal to or greater than the lower limit, the molecular chain of the specific fluorine-containing ether compound becomes longer, thereby improving the flexibility of the molecular chain of the specific fluorine-containing ether compound.This increases the probability of reaction between the silanol group derived from the reactive silyl group of the specific fluorine-containing ether compound and the substrate or underlayer having a silanol group, thereby further improving the adhesion between the surface layer and the substrate or underlayer.As a result, the abrasion resistance of the surface layer becomes better.In addition, the fluorine content of the surface layer increases, thereby improving the water and oil repellency. Furthermore, if the number average molecular weight is equal to or less than the upper limit, the handling properties during film formation are better.

[0025] The reactive silyl group is preferably group (2). -Si(R) n L 3-n ···(2) R is a monovalent hydrocarbon group. 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. The monovalent hydrocarbon group may be linear, branched, or cyclic, and is preferably linear or branched. The monovalent hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0026] L is a hydrolyzable group or a hydroxyl group. The hydrolyzable group L is a group that becomes a hydroxyl group upon hydrolysis. That is, a hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH upon hydrolysis. The silanol groups further react with each other to form Si-O-Si bonds.

[0027] Specific examples of the hydrolyzable group L include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The aryloxy group is preferably an aryloxy group having 3 to 10 carbon atoms. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms. L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, since production of the specific fluorinated ether compound is easier. L is preferably an alkoxy group having 1 to 4 carbon atoms, since outgassing during coating is less and the storage stability of the specific fluorinated ether compound is better, and an ethoxy group is particularly preferred when long-term storage stability of the specific fluorinated ether compound is required, and a methoxy group is particularly preferred when the reaction time after coating is short.

[0028] n is an integer of 0 to 2. n is preferably 0 or 1, and particularly preferably 0. When a plurality of Ls are present, the adhesion of the surface layer to the substrate becomes stronger. When n is 0 or 1, multiple Ls present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of the specific fluorinated ether compound, it is preferable that they are the same. When n is 2, multiple Rs present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of the specific fluorinated ether compound, it is preferable that they are the same.

[0029] As the specific fluorine-containing ether compound, the compound (3) is preferred in that it provides a film with superior water and oil repellency and abrasion resistance. [A-(OX) m -O-] j Z[-Si(R) n L 3-n ] g ···(3)

[0030] A is a perfluoroalkyl group or -Q[-Si(R) n L 3-n ] k is. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3, in terms of better abrasion resistance of the film. The perfluoroalkyl group may be linear or branched. However, A is -Q[-Si(R) n L 3-n ] k If j is 1, then

[0031] Examples of perfluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, CF3CF(CF3)-, and the like. As the perfluoroalkyl group, CF3-, CF3CF2-, and CF3CF2CF2- are preferred in terms of providing a film with better water and oil repellency.

[0032] Q is a (k+1)-valent linking group, where k is an integer of 1 to 10, as described below. Therefore, examples of Q include divalent to eleven-valent linking groups. 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.

[0033] As the ring structure, 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 heterocycle, and a fused ring consisting of two or more of these rings is preferred, from the viewpoints of ease of production of the specific fluorine-containing ether compound and further improved abrasion resistance, light resistance, and chemical resistance of the surface layer, and the ring structure shown in the following formula is particularly preferred. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, or an oxo group (═O).

[0034] [ka]

[0035] Specific examples of the (k+1)-valent organopolysiloxane residue include the following groups. However, R in the following formula 5 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 5 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0036] [ka]

[0037] Q is 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, or -SO2NR 6 -, -Si(R 6 )2-, -OSi(R 6 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and a group containing one or more selected from the group consisting of a divalent organopolysiloxane residue. However, R 6is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 6 The number of carbon atoms in the alkyl group is preferably 1 to 3, particularly preferably 1 or 2, from the viewpoint of ease of production of the specific fluorine-containing ether compound. In addition, each bond or group constituting Q has a terminal that is [A-(OX) m -O-] j For example, an amide bond can be formed by placing the carbon atom at the side of [A-(OX) m -O-] j The nitrogen atom may be located at the side of [A-(OX) m -O-] j The same applies to other bonds and groups.

[0038] Specific examples of the divalent organopolysiloxane residue include groups of the following formula: 7 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 7 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0039] [ka]

[0040] Q is -C(O)NR because it is easy to produce the specific fluorine-containing ether compound. 6 -, -C(O)-, -C(O)OR 6 -, -NR 6 It is preferable that the surface layer has at least one bond selected from the group consisting of - and -O-. In terms of excellent light resistance and chemical resistance of the surface layer, it is preferable that the surface layer has a bond of -C(O)NR 6 It is particularly preferred to have - or -C(O)-.

[0041] Q may be a combination of two or more divalent hydrocarbon groups and one or more branching points P, or a combination of two or more hydrocarbon groups, one or more branching points P, and one or more bonds B. Specific examples of the divalent hydrocarbon group include divalent aliphatic hydrocarbon groups (such as alkylene groups and cycloalkylene groups) and divalent aromatic hydrocarbon groups (such as phenylene groups). 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.

[0042] The definitions of R, L, n, X and m are as described above.

[0043] Z is a (j+g)-valent linking group. The definition of Z is the same as that of Q described above, except that the (k+1) valence in Q described above is replaced with (j+g) valence. In the specific fluorine-containing ether compound, Z and Q may be the same or different. From the viewpoint of ease of production of the specific fluorine-containing ether compound, it is preferable that Z and Q are the same.

[0044] j is an integer of 1 or more, and is preferably an integer of 1 to 5 in order to provide a film with better water and oil repellency, and is particularly preferably 1 in order to facilitate the production of compound (3). 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, in that the abrasion resistance of the film is superior. k is an integer of 1 to 10, preferably an integer of 1 to 8, and particularly preferably an integer of 2 to 6, in that the surface layer has better abrasion resistance.

[0045] As the compound (3), the compounds (3-11), (3-21), and (3-31) are preferred because they provide a surface layer with excellent initial water contact angle and abrasion resistance. Among these, the compounds (3-11) and (3-21) provide a surface layer with particularly excellent initial water contact angle, and the compound (3-31) provides a surface layer with particularly excellent abrasion resistance.

[0046] R f1 -(OX) m -OY 11 [-Si(R) n L 3-n ] g1 (3-11) [R f2-(OX) m -O-] j2 Y 21 [-Si(R) n L 3-n ] g2 (3-21) [L 3-n (R) n Si-] k3 Y 32 -(OX) m -OY 31 [-Si(R) n L 3-n ] g3 (3-31)

[0047] In formula (3-11), X, m, R, n, and L are defined as X, m, R, n, and L in formula (3), respectively. R f1 is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above. Y 11 is a (g1+1)-valent linking group, and specific examples thereof are the same as Z in formula (3). 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, in that the surface layer has better abrasion resistance.

[0048] In formula (3-21), X, m, R, n, and L are defined as X, m, R, n, and L in formula (3), respectively. R f2 is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above. j2 is an integer of 2 or more, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4. Y 21 is a (j2+g2)-valent linking group, and specific examples thereof are the same as Z in formula (3). g2 is an integer of 1 or more, and is preferably an integer of 2 to 15, more preferably 2 to 6, even more preferably 2 to 4, and particularly preferably 4, in that the surface layer has better abrasion resistance.

[0049] In formula (3-31), X, m, R, n, and L are defined as X, m, R, n, and L in formula (3), respectively. k3 is an integer of 1 or more, preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 3. Y 32 is a (k3+1)-valent linking group, and specific examples thereof are the same as Q in formula (3). Y 31 is a (g3+1)-valent linking group, and specific examples thereof are the same as Z in formula (3). g3 is an integer of 1 or more, preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 3.

[0050] Y in equation (3-11) 11 are the group (g2-1) (where d1+d3=1 (i.e., d1 or d3 is 0), g1=d2+d4, d2+d4≧1), the group (g2-2) (where e1=1, g1=e2, e2≧1), the group (g2-3) (where g1=2), and the group (g2-4) (where h1=1, g1=h2, h2≧1). ), a group (g2-5) (where i1=1, g1=i2, and i2≧1), a group (g2-6) (where g1=1), a group (g2-7) (where g1=i3+1), a group (g2-8) (where g1=i4, and i4≧1), or a group (g2-9) (where g1=i5, and i5≧1). Y in equation (3-21) 21 may 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). Also, Y in formula (3-31) 31 and Y 32may each independently be a group (g2-1) (wherein g3 = d2 + d4 and k3 = d2 + d4), a group (g2-2) (wherein g3 = e2 and k3 = e2), a group (g2-3) (wherein g3 = 2 and k3 = 2), a group (g2-4) (wherein g3 = h2 and k3 = h2), a group (g2-5) (wherein g3 = i2 and k3 = i2), a group (g2-6) (wherein g3 = 1 and k3 = 1), a group (g2-7) (wherein g3 = i3 + 1 and k3 = i3 + 1), a group (g2-8) (wherein g3 = i4 and k3 = i4), or a group (g2-9) (wherein g3 = i5 and k3 = i5).

[0051] [ka]

[0052] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -) e2 ···(g2-2) -A 1 -N(-Q 23 -)2 formula (g2-3) (-A 1 -) h1 Z 1 (-Q 24 -) h2 Formula (g2-4) (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 ···(g2-5) -A 1 -Q 26 - Formula (g2-6) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 ···(g2-7) -A 1 -[CH2C(Re4 )(-Q 27 -)] i4 -R e5 ···(g2-8) -A 1 -Z a (-Q 28 -) i5 ···(g2-9)

[0053] However, in formulas (g2-1) to (g2-9), A 1 (OX) m Connect to the Q side 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 is [-Si(R) n L 3-n ] side.

[0054] A 1 represents a single bond, an alkylene group, or an alkylene group with two or more carbon atoms with -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-, and in each formula, A 1 If there are two or more, there are two or more A 1 may be the same or different. A hydrogen atom of the alkylene group may be substituted with a fluorine atom. Q 11 represents a single bond, -O-, an alkylene group, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-. Q 22 is an alkylene group, an alkylene group with two or more carbon atoms that has -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 a group having - or -O-, and -C(O)NR at the end of the alkylene group not connected to Si;6 -, -C(O)-, -NR 6 - or -O-, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms 6 -, -C(O)-, -NR 6 - or -O- and -C(O)NR at the end not connected to Si 6 -, -C(O)-, -NR 6 - or -O-, and in each formula, Q 22 If there are two or more, there are two or more Q 22 may be the same or different. Q 23 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and two Q 23 may be the same or different. Q 24 Q 24 Z bonded to 1 If the atom in is a carbon atom, then Q 22 and Q 24 Z bonded to 1 If the atom in is a nitrogen atom, Q 23 In each formula, Q 24 If there are two or more, there are two or more Q 24 may be the same or different. Q 25 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and in each formula, Q 25 If there are two or more, there are two or more Q 25 may be the same or different. Q 26 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-. R 6is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Q 27 is a single bond or an alkylene group. Q 28 is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms in an alkylene group having two or more carbon atoms.

[0055] Z 1 is A 1 has a carbon atom or nitrogen atom to which Q is directly bonded, 24 is a group having an h1+h2 valent ring structure having a carbon atom or nitrogen atom to which is directly bonded.

[0056] R e1 is a hydrogen atom or an alkyl group, and in each formula, R e1 If there are two or more, there are two or more R e1 may be the same or different. R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. R e3 is an alkyl group. R e4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom in view of ease of producing the compound. e4 If there are two or more, there are two or more R e4 may be the same or different. R e5 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom in view of ease of producing the compound.

[0057] d1 is an integer of 0 to 3, and preferably 1 or 2. d2 is an integer of 0 to 3, and preferably 1 or 2. d1+d2 is an integer of 1 to 3. d3 is an integer of 0 to 3, and preferably 0 or 1. d4 is an integer of 0 to 3, and preferably 2 or 3. d3+d4 is an integer of 1 to 3. d1+d3 is Y 21is an integer of 1 to 5, preferably 1 or 2, and Y 11 , Y 31 and Y 32 In this case, it is 1. d2+d4 is Y 11 or Y 21 is an integer of 1 to 5, preferably 4 or 5, and Y 31 and Y 32 is an integer of 1 to 5, preferably an integer of 3 to 5, and particularly preferably 4 or 5. e1+e2 is 3 or 4. e1 is Y 11 is 1 in Y 21 is an integer between 2 and 3, and Y 31 and Y 32 e2 is 1 in Y 11 or Y 21 is 1 to 3, preferably 2 or 3, and Y 31 and Y 32 In the formula, the number is 1 to 3, and 2 or 3 is preferred. h1 is Y 11 is 1 in Y 21 is an integer of 2 or more (preferably 2), and Y 31 and Y 32 h2 is 1 in Y 11 or Y 21 is an integer of 1 or more (preferably 2 or 3), and Y 31 and Y 32 is an integer of 1 or more (preferably 2 or 3). i1+i2 is Y 11 is 2 to 4 (preferably 3 or 4), and Y 12 is 3 or 4 (4 is preferred), and Y 31 and Y 32 is an integer of 2 to 4 (preferably 3 or 4). 11 is 1 in Y 21 is 2 or 3 in Y 31 and Y 32 In Y 11is an integer of 1 to 3 (preferably 2 or 3), and Y 12 is 1 or 2 (2 is preferred), and Y 31 and Y 32 is an integer of 1 to 3 (preferably 2 or 3). i3 is an integer of 0 to 3, preferably 1 to 3, and particularly preferably 2 or 3. i4 is Y 11 is 1 or more (preferably an integer of 2 to 10, particularly preferably an integer of 2 to 6), and Y 31 and Y 32 is 1 or more (preferably an integer of 1 to 10, particularly preferably an integer of 1 to 6). i5 is Y 11 is 1 or more (preferably an integer of 2 to 7), and Y 31 and Y 32 is 1 or more (preferably an integer of 2 to 7).

[0058] 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, from the viewpoint of ease of production of compounds (3-11), (3-21), and (3-31) and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.

[0059] Z 1 The ring structure in Z includes the ring structures described above, and the preferred embodiments are also the same. 1 The ring structure in 1 YaQ 24 is directly bonded, so that, for example, an alkylene group is connected to the ring structure, and A 1 YaQ 24 are never connected. Z ais an organopolysiloxane residue having a valence of (i5+1), and the following group is preferred: a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.

[0060] [ka]

[0061] R e1 , R e2 , R e3 or R e4 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compounds (3-11), (3-21), and (3-31). R e2 The number of carbon atoms in the alkyl group of the acyloxy group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compound (3-11), compound (3-21), and compound (3-31). h1 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1, from the viewpoint of ease of production of compound (3-11), compound (3-21), and compound (3-31) and of further improving the 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, from the viewpoint of ease of production of compound (3-11), compound (3-21), and compound (3-31) and of further improving the abrasion resistance and fingerprint removability of the surface layer.

[0062] Y 11Other forms of include the group (g3-1) (where d1 + d3 = 1 (i.e., d1 or d3 is 0), g1 = d2 × r1 + d4 × r1), the group (g3-2) (where e1 = 1, g1 = e2 × r1), the group (g3-3) (where g1 = 2 × r1), the group (g3-4) (where h1 = 1, g1 = h2 × r1), the group (g3-5) (where i1 = 1, g1 = i2 × r1), the group (g3-6) (where g1 = r1), the group (g3-7 (where g1 = r1 × (i3 + 1)), the group (g3-8) (where g1 = r1 × i4), and the group (g3-9) (where g1 = r1 × i5). Y 21 Other forms of include a group (g3-1) (where j2=d1+d3, d1+d3≧2, g2=d2×r1+d4×r1), a group (g3-2) (where j2=e1, e1=2, g2=e2×r1, e2=2), a group (g3-4) (where j2=h1, h1≧2, g2=h2×r1), and a group (g3-5) (where j2=i1, i1 is 2 or 3, g2=i2×r1, i1+i2 is 3 or 4). Y 31 and Y 32 Other forms of (g3-1) include the group (g3-1) (wherein g3 = d2 × r1 + d4 × r1 and k3 = d2 × r1 + d4 × r1), the group (g3-2) (wherein g3 = e2 × r1 and k3 = e2 × r1), the group (g3-3) (wherein g3 = 2 × r1 and k3 = 2 × r1), the group (g3-4) (wherein g3 = h2 × r1 and k3 = h2 × r1), and the group (g3-5) (wherein , g3=i2×r1, k3=i2×r1), group (g3-6) (where g3=r1, k3=r1), group (g3-7) (where g3=r1×(i3+1), k3=r1×(i3+1)), group (g3-8) (where g3=r1×i4, k3=r1×i4), group (g3-9) (where g3=r1×i5, k3=r1×i5).

[0063] [ka]

[0064] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 ···(g3-2) -A 1 -N(-Q 23 -G 1 )2···(g3-3) (-A 1 -) h1 Z 1 (-Q 24 -G 1 ) h2 ···(g3-4) (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Connect to the G side 1 is [-Si(R) n L 3-n ] side.

[0066] G 1 is a group (g3), and in each formula, G 1 If there are two or more, there are two or more G 1 may be the same or different. 1 The symbols other than are the same as those in formulas (g2-1) to (g2-9). -Si(R 8 ) 3-r1 (-Q 3 -) r1 (g3) However, in equation (g3), Si is Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 Connect to the Q side 3 is [-Si(R) n L 3-n Connect to the ] side. 8 is an alkyl group. 3 is an alkylene group, an alkylene group with two or more carbon atoms that has -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-, or -(OSi(R 9 )2) p -O- and 2 or more Q 3 may be the same or different. r1 is 2 or 3. R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 is an alkyl group, a phenyl group, or an alkoxy group, and two R 9 may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSi(R 9 )2) may be the same or different.

[0067] Q 3The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoint of ease of production of compounds (3-11), (3-21), and (3-31) and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 8 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compounds (3-11), (3-21), and (3-31). R 9 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compounds (3-11), (3-21), and (3-31). R 9 The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, in view of excellent storage stability of compound (3-11), compound (3-21), and compound (3-31). p is preferably 0 or 1.

[0068] Examples of compound (3-11), compound (3-21), and compound (3-31) include compounds of the following formula: The compound of the following formula is preferred because it is easy to produce industrially, easy to handle, and provides a surface layer with excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance, light fastness, and chemical resistance, with light fastness being particularly excellent. R in the compound of the formula f is R f1 -(OX) m -O-(CF2) n - or R f2 -(OX) m -O-(CF2) n -, where R f1 , R f2 The definitions of , X and m are as described above, and n is an integer of 0 to 6. Q in the compound of the formula f is -(OX) m -O-(CF2) n Here, X and m are defined as above, and n is an integer of 0 to 6.

[0069] Y 11 As the compound (3-11) in which is the group (g2-1), for example, the compound of the following formula can be mentioned. [ka]

[0070] Y 11 As the compound (3-11) in which is a group (g2-2), for example, the compound of the following formula can be mentioned. [ka]

[0071] Y 21 As the compound (3-21) in which is a group (g2-2), for example, the compound of the following formula can be mentioned. [ka]

[0072] Y 11 As the compound (3-11) in which is the group (g2-3), for example, the compound of the following formula can be mentioned. [ka]

[0073] Y 11 Examples of the compound (3-11) in which is a group (g2-4) include compounds of the following formula: [ka]

[0074] Y 11Examples of the compound (3-11) in which is a group (g2-5) include compounds of the following formula: [ka]

[0075] Y 11 Examples of the compound (3-11) in which is a group (g2-6) include compounds of the following formula: [ka]

[0076] Y 11 Examples of the compound (3-11) in which is a group (g2-7) include compounds of the following formula: [ka]

[0077] Y 11 As the compound (3-11) in which is the group (g3-1), for example, the compound of the following formula can be mentioned. [ka]

[0078] Y 11 As the compound (3-11) in which is the group (g3-2), for example, the compound of the following formula can be mentioned. [ka]

[0079] Y 11 Examples of the compound (3-11) in which is the group (g3-3) include compounds of the following formula: [ka]

[0080] Y 11As the compound (3-11) in which is the group (g3-4), for example, the compound of the following formula can be mentioned. [ka]

[0081] Y 11 Examples of the compound (3-11) in which is the group (g3-5) include compounds of the following formula: [ka]

[0082] Y 11 Examples of the compound (3-11) in which is the group (g3-6) include compounds of the following formula: [ka]

[0083] Y 11 Examples of the compound (3-11) in which is the group (g3-7) include compounds of the following formula: [ka]

[0084] Y 21 Examples of the compound (3-21) in which is a group (g2-1) include compounds of the following formula: [ka]

[0085] Y 31 and Y 32 Examples of the compound (3-31) in which is a group (g2-1) include compounds of the following formula: [ka]

[0086] Y 31and Y 32 As the compound (3-31) in which is a group (g2-2), for example, the compound of the following formula can be mentioned. [ka]

[0087] Y 31 and Y 32 As the compound (3-31) in which is a group (g2-3), for example, the compound of the following formula can be mentioned. [ka]

[0088] Y 31 and Y 32 Examples of the compound (3-31) in which is a group (g2-4) include compounds of the following formula: [ka]

[0089] Y 31 and Y 32 Examples of the compound (3-31) in which is a group (g2-5) include compounds of the following formula: [ka]

[0090] Y 31 and Y 32 Examples of the compound (3-31) in which is a group (g2-6) include compounds of the following formula: [ka]

[0091] Y 31 and Y 32 Examples of the compound (3-31) in which is a group (g2-7) include compounds of the following formula: [ka]

[0092] Y 31 and Y 32 As the compound (3-31) in which is a group (g3-2), for example, the compound of the following formula can be mentioned. [ka]

[0093] Specific examples of the specific fluorine-containing ether compound include those described in the following documents: perfluoropolyether-modified aminosilanes described in JP-A-11-029585 and JP-A-2000-327772; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in JP-A-2000-144097, Fluorinated siloxanes described in JP-A-2002-506887, Organosilicon compounds described in JP-A-2008-534696; Fluorinated modified hydrogen-containing polymers described in Japanese Patent No. 4138936; Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064 and JP 2014-070163 A; Organosilicon compounds as described in WO 2011 / 060047 and WO 2011 / 059430; fluorine-containing organosilane compounds described in WO 2012 / 064649; Fluorooxyalkylene group-containing polymers described in JP 2012-72272 A; 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, JP 2014-080473 A, International Publication No. 2015 / 087902, International Publication No. 2017 / 038830, International Publication No. 2017 / 038832, International Publication No. 2017 fluorine-containing ether compounds described in WO 2019 / 039186, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 044479, WO 2019 / 049753, WO 2019 / 163282 and JP 2019-044158 A; perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437 A, WO 2018 / 079743 A, and WO 2018 / 143433 A; a perfluoro(poly)ether group-containing silane compound described in WO 2018 / 169002; Fluoro(poly)ether group-containing silane compounds described in WO 2019 / 151442; (Poly)ether group-containing silane compounds described in WO 2019 / 151445; a perfluoropolyether group-containing compound described in WO 2019 / 098230; Fluoropolyether group-containing polymer-modified silanes described in JP-A-2015-199906, JP-A-2016-204656, JP-A-2016-210854, and JP-A-2016-222859; Fluorine-containing compounds described in WO 2019 / 039083 and WO 2019 / 049754.

[0094] Commercially available specific fluorine-containing 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, and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0095] The specific fluorine-containing ether compounds may be used alone or in combination of two or more.

[0096] <Second component> 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 may contain only one of them.

[0097] (Compound (A)) Compound (A) is a compound represented by formula (A). R fa -(OX a ) m1 -L a -CZ a1 =CH2 (A) R fa is a fluoroalkyl group having 1 to 20 carbon atoms. The number of carbon atoms in the fluoroalkyl group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3, in that the surface layer has better water repellency. The fluoroalkyl group may be linear, branched or cyclic. The fluoroalkyl group is preferably a group in which all hydrogen atoms in the fluoroalkyl group have been substituted with fluorine atoms (perfluoroalkyl group).

[0098] X a is a fluoroalkylene group having 1 to 6 carbon atoms. a The preferred embodiments of X are the same as those of X in the above formula (1). aThe preferred embodiments of (OX) are the same as those of (OX) in the above formula (1). (OX a The number of repetitions m1 of (OX) is an integer of 2 or more. Preferred embodiments of m1 are the same as the number of repetitions m of (OX) described above.

[0099] When the specific fluorine-containing ether compound is a compound represented by formula (1), in order to improve the effects of the present invention, it is preferable to use a compound having a structure in which (OX) in formula (1) and (OX) in formula (A) are the same or different. a ) are preferably the same group.

[0100] L a is a single bond or a divalent linking group (wherein (OX a ) na Except for . na is an integer greater than or equal to 1. Specific examples of the divalent linking group include an alkylene group, an etheric oxygen atom, an amide bond, and a group formed by combining these. Among the divalent linking groups, an alkylene group, a group formed by combining an alkylene group with an etheric oxygen atom, and a group formed by combining an alkylene group with an amide bond are preferred in terms of ease of production of compound (A) and thermal and chemical stability. L a The divalent linking group in (OX a ) na (OX a ) is defined as above, and na is an integer of 1 or greater. L a is preferably a single bond in that the effects of the present invention are more excellent.

[0101] Z a1 is a fluorine atom or a trifluoromethyl group, and is preferably a fluorine atom in view of the superior effect of the present invention.

[0102] Two or more types of compound (A) may be used in combination.

[0103] Specific examples of the compound (A) are shown below. In the following compounds, PFPE is represented by R fa -(OXa ) m1 In the following compounds, n10 represents an integer of 1 to 10.

[0104] PFPE-CF=CH2 PFPE-CH2-O-(CH2) n10 -CF=CH2 PFPE-CH2-(CH2) n10 -CF=CH2 PFPE-C(O)-NH-(CH2) n10 -CF=CH2

[0105] The method for producing the compound (A) is not particularly limited, but for example, a method can be mentioned in which a metal or organometallic reagent is reacted with the compound (a1) to cause an elimination reaction of the compound (a1) to obtain the compound (A). a1 and CFZ a1 The fluorine atom in the formula (I) is eliminated to give compound (A).

[0106] The compound (a1) is a compound represented by the formula (a1). R fa -(OX a ) m1 -L a -CFZ a1 -CH2-Q a1 (a1)

[0107] In formula (a1), R fa , X a , L a , Z a1 , m1 are defined as above. Q a1 is a leaving group and is a halogen atom or a sulfonate group (-O-SO2-R a1 ) is preferred. a1 is an organic group. Specific examples of the halogen atom in the leaving group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom, a bromine atom or an iodine atom being preferred. Specific examples of the sulfonate group in the leaving group include a tosylate group (OTs), a mesylate group (OMs), a triflate group (OTf) and a nonaflate group (ONf), with a triflate group being preferred.

[0108] Specific examples of metals include magnesium, copper, iron, zinc, tin, antimony, and alloys of these metals with cadmium, palladium, or mercury. The metals may be used alone or in combination of two or more. Specific examples of the organometallic reagent include organolithium compounds, Grignard reagents, and organocopper compounds. The organometallic reagents may be used alone or in combination of two or more. The amount of the metal used is preferably 1 to 30 moles per mole of the compound (a1).

[0109] The above-mentioned elimination reaction is preferably carried out in the presence of an organic solvent, particularly preferably in the presence of a fluorine-containing organic solvent, in view of the excellent yield of compound (A). Specific examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, for example, CF 13 H (AC-2000: product name, manufactured by AGC), C6F 13 Examples include C2H5 (AC-6000: product name, manufactured by AGC), and C2F5CHFCHFCF3 (Bertrel: product name, manufactured by DuPont). Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, such as 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). Specific examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0110] When a fluorine-based organic solvent is used, the amount used is preferably 50 to 500 parts by mass per 100 parts by mass of the compound (a1).

[0111] The reaction temperature is not particularly limited, but is usually 0 to 100°C. 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 can be set to 0.2 MPa to 1 MPa.

[0112] Compound (A) can also be produced by a method other than using the above-mentioned compound (a1). For example, compound (A) is compound (A1) (L of formula (A) a is a compound containing an etheric oxygen atom), compound (A1) is obtained by reacting compound (a2-1) with compound (a2-2). R fa -(OX a ) m1 -L a11 -OH (a2-1) Q a11 -L a12 -CZ a1 =CH2 (a2-2) R fa -(OX a ) m1 -L a11-OL a12 -CZ a1 =CH2 (A1) In formula (a2-1), R fa , X a , m1 are defined as above, and L a11 is a divalent linking group. In formula (a2-2), Z a1 The definition of is as above, and Q a11 is a halogen atom or a sulfonate group, and L a12 is a divalent linking group. In formula (A1), R fa , X a , Z a1 , L a11 , L a12 The definition of m1 is as described above. a11 -OL a12 - is L in compound (A). a1 is equivalent to

[0113] In addition, compound (A) is compound (A2) (L in formula (A) a is an alkylene group), compound (A2) can be obtained by a coupling reaction between compound (a3-1) and compound (a3-2), which is a Grignard reagent. R fa -(OX a ) m1 -L a13 -Q a13 ···(a3-1) Q a14 Mg-L a14 -CZ a1 =CH2 (a3-2) R fa -(OX a ) m1 -L a13 -L a14 -CZ a1 =CH2 (A2) In formula (a3-1), R fa , X a , m1 are defined as above, and L a13 is an alkylene group, and Q a13is a halogen atom or a sulfonate group. In formula (a3-2), Z a1 The definition of is as above, and L a14 is an alkylene group, and Q a14 is a halogen atom. In formula (A2), R fa , X a , Z a1 , L a13 , L a14 , m1 are defined as above. -L in compound (A2) a13 -L a14 - is L in compound (A). a1 is equivalent to

[0114] In addition, compound (A) is compound (A3) (L in formula (A) a is a compound containing an amide bond), compound (A3) is obtained by a substitution reaction between compound (a4-1) and compound (a4-2). R fa -(OX a ) m1 -L a15 -C(O)OQ a15 ···(a4-1) NH2-L a16 -CZ a1 =CH2 (a4-2) R fa -(OX a ) m1 -L a15 -C(O)-NH-L a16 -CZ a1 =CH2 (A3) In formula (a4-1), R fa , X a , m1 are defined as above, and L a15 is a divalent linking group, and Q a15 is an alkyl group. In formula (a4-2), Z a1 The definition of is as above, and L a16 is a divalent linking group. In formula (A3), R fa , X a , Z a1, L a15 , L a16 , m1 are defined as above. -L in compound (A3) a15 -C(O)-NH-L a16 - is L in compound (A). a1 is equivalent to

[0115] (Compound (B)) The compound (B) is a compound represented by the formula (B). CH2=CZ b2 -L b2 -(OX b ) m2 -L b1 -CZ b1 =CH2 (B)

[0116] In formula (B), X b is a fluoroalkylene group having 1 to 6 carbon atoms. b The preferred embodiments of X are the same as those of X in the above formula (1). b The preferred embodiments of (OX) are the same as those of (OX) in the above formula (1). (OX b The number of repetitions m2 of (OX) is an integer of 2 or more. Preferred embodiments of m2 are the same as the number of repetitions m of (OX) described above.

[0117] When the specific fluorine-containing ether compound is a compound represented by formula (1), in order to improve the effects of the present invention, it is preferable that (OX) in formula (1) and (OX) in formula (B) b ) are preferably the same group.

[0118] L b1 and L b2 are each independently a single bond or a divalent linking group (provided that (OX b ) nb Except for nb, where nb is an integer greater than or equal to 1. Specific examples of the divalent linking group include an alkylene group, an etheric oxygen atom, an amide bond, and a group formed by combining these. Among the divalent linking groups, an alkylene group, a group formed by combining an alkylene group with an etheric oxygen atom, and a group formed by combining an alkylene group with an amide bond are preferred in terms of ease of production of compound (B) and thermal and chemical stability. L b1 and L b2 The divalent linking group in (OX b ) nb (OX b ) is defined as above, and nb is an integer of 1 or more. L b1 and L b2 may be the same or different. L b2 is preferably a single bond in that the effects of the present invention are more excellent.

[0119] Z b1 and Z b2 are each independently a fluorine atom or a trifluoromethyl group. Z b1 and Z b2 may be the same or different, but are preferably the same in terms of easier production. Z b1 and Z b2 are preferably fluorine atoms, since the effects of the present invention are more excellent.

[0120] Two or more types of compound (B) may be used in combination.

[0121] Specific examples of the compound (B) are shown below. In the following compounds, PFPE is -(OX) in the formula (B). b ) m2 In the following compounds, n11 and n12 each independently represent an integer of 1 to 10.

[0122] CH2=CF-PFPE-CF=CH2 CH2=CF-(CH2) n11 -O-CH2-PFPE-CH2-O-(CH2) n12 -CF=CH2 CH2=CF-(CH2) n11 -CH2-PFPE-CH2-(CH2) n12 -CF=CH2 CH2=CF-(CH2) n11 -NH-C(O)-PFPE-C(O)-NH-(CH2) n12 -CF=CH2

[0123] The method for producing compound (B) is not particularly limited, but for example, a method can be mentioned in which compound (b1) is reacted with a metal or organometallic reagent to cause an elimination reaction of compound (b1) to obtain compound (B). Specifically, Q in compound (b1) b1 , CFZ b1 fluorine atoms in Q b2 , CFZ b2 The fluorine atom in is eliminated to give 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, and therefore a description thereof will be omitted.

[0124] The compound (b1) is a compound represented by the formula (b1). Q b2 -CH2-CFZ b2 -L b2 -(OX b ) m2 -L b1 -CFZ b1 -CH2-Q b1 (b1) In formula (b1), X b , L b1 , L b2 , Z b1 , Z b2 , m2 are defined as above. Q b1 and Q b2 are each independently a leaving group, and are a halogen atom or a sulfonate group (-O-SO-R b1 ) is preferred. b1is an organic group. Specific examples and preferred embodiments of the halogen atom and sulfonate group are a1 is the same as:

[0125] Compound (B) can also be produced by a method other than the method using the above-mentioned compound (b1). For example, when compound (B) is compound (B1) (L of formula (B) b1 and L b2 is a compound containing an etheric oxygen atom), compound (B1) is obtained by reacting compound (b2-1) with compound (b2-2). HO-L b12 -(OX b ) m2 -L b11 -OH (b2-1) Q b11 -L b13 -CZ b10 =CH2 (b2-2) CH2=CZ b10 -L b13 -OL b12 -(OX b ) m2 -L b11 -OL b13 -CZ b10 =CH2 (B1) In formula (b2-1), X b , m2 is defined as above, and L b11 and L b11 are each independently a divalent linking group. In formula (b2-2), Z b10 The definition of Z b1 and Z b2 and Q b11 is a halogen atom or a sulfonate group, and L b13 is a divalent linking group. In formula (B1), X b , Z b10 , L b11 , L b12 , L b13 The definition of m2 is as described above. b11 -OL b13 - is L in compound (B)b1 and -L in compound (B1) b13 -OL b12 is L in compound (B) b2 is equivalent to

[0126] In addition, compound (B) is compound (B2) (L in formula (B) b1 and L b2 is an alkylene group), compound (B2) can be obtained by a coupling reaction between compound (b3-1) and compound (b3-2), which is a Grignard reagent. Q b13 -L b15 -(OX b ) m2 -L b14 -Q b12 ···(b3-1) Q b14 Mg-L b16 -CZ b11 =CH2 (b3-2) CH2=CZ b11 -L b16 -L b15 -(OX b ) m2 -L b14 -L b16 -CZ b11 =CH2 (B2) In formula (b3-1), X b , m2 is defined as above, and L b14 and L b15 are each independently an alkylene group, and Q b12 and Q b13 are each independently a halogen atom or a sulfonate group. In formula (b3-2), Z b11 The definition of Z b1 and Z b2 is the same as L b16 is an alkylene group, and Q b14 is a halogen atom. In formula (B2), X b , Z b11 , L b14 , L b15 , L b16The definition of m2 is as described above. b14 -L b16 - is L in compound (B) b1 and -L in compound (B2) b16 -L b15 - is L in compound (B) b2 is equivalent to

[0127] In addition, compound (B) is compound (B3) (L in formula (B) b1 and L b2 is a compound containing an amide bond), compound (B3) is obtained by reacting compound (b4-1) with compound (b4-2). Q b16 -O(O)CL b18 -(OX b ) m2 -L b17 -C(O)OQ b15 ···(b4-1) NH2-L b19 -CZ b12 =CH2 (b4-2) CH2=CZ b12 -L b19 -NH-C(O)-L b18 -(OX b ) m2 -L b17 -C(O)-NH-L b19 -CZ b12 =CH2 (B3) In formula (b4-1), X b , m2 is defined as above, and L b17 and L b18 are each independently a divalent linking group, and Q a15 and Q b16 are each independently an alkyl group. In formula (b4-2), Z b12 The definition of Z b1 and Z b2 is the same as L b19 is a divalent linking group. In formula (B3), X b , Z b12 , L b17 , Lb18 , L b19 The definition of m2 is as described above. b17 -C(O)-NH-L b19 - is L in compound (B) b1 and -L in compound (B3) b19 -NH-C(O)-L b18 - is L in compound (B) b2 is equivalent to

[0128] <Liquid medium> 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. When the composition of the present invention is a composition to be used in a wet coating method, the composition of the present invention preferably contains a liquid medium. Specific examples of the liquid medium include water and organic solvents. The liquid medium preferably contains an organic solvent, and from the viewpoint of excellent coating properties, more preferably contains an organic solvent having a boiling point of 35 to 250° C. Here, the boiling point means the normal boiling point. Specific examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents, and fluorine-based organic solvents are preferred because of their excellent solubility. The organic solvents may be used alone or in combination of two or more.

[0129] Specific examples of the fluorine-containing organic solvent are the same as those fluorine-containing organic solvents mentioned in the production of compound (A).

[0130] The non-fluorine-based organic solvent is preferably a compound consisting of only hydrogen atoms and carbon atoms, or a compound consisting of only hydrogen atoms, carbon atoms, and oxygen atoms, and specific examples thereof include hydrocarbon-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, and alcohol-based organic solvents. Specific examples of hydrocarbon organic solvents include hexane, heptane, and cyclohexane. Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of the ether-based organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether. Specific examples of the ester-based organic solvent include ethyl acetate and butyl acetate. Specific examples of the alcohol-based organic solvent include isopropyl alcohol, ethanol, and n-butanol.

[0131] <Other ingredients> The composition of the present invention may contain components other than those described above, provided that the effects of the present invention are not impaired. Examples of other components include compounds that are unavoidable in the production process, such as by-products produced in the production process of the first component or the second component, and unreacted raw materials.

[0132] <Content> The content of the first component is preferably 20 to 99 mass %, more preferably 30 to 90 mass %, and particularly preferably 40 to 80 mass %, based on the total solid mass of the composition of the present invention, in order to obtain better effects of the present invention. The content of the second component is preferably 1 to 80 mass%, more preferably 10 to 70 mass%, and particularly preferably 20 to 60 mass%, based on the total solid mass of the composition of the present invention, in order to obtain better effects of the present invention. The content of the second component means the total content of compound (A) and compound (B), and when only one of them is contained, it means the content of that compound. The mass of the solid content of the composition refers to the mass of the composition excluding the liquid medium when the composition contains a liquid medium. 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 surface layer will have better abrasion resistance. If the mass ratio is within the above range, the surface layer will have better abrasion resistance.

[0133] When the composition of the present invention contains the above-mentioned liquid medium, the content of the liquid medium is preferably 70 to 99.99 mass %, particularly preferably 80 to 99.9 mass %, based on the total mass of the composition of the present invention.

[0134] When the composition of the present invention contains the other components described above, the content of the other components is preferably 0 to 10 mass%, more preferably 0 to 5 mass%, and particularly preferably 0 to 1 mass%, relative to the content of the specific fluorinated ether compound.

[0135] [Substrate with surface layer] The substrate with a surface layer of the present invention has a substrate and a surface layer formed from the above-mentioned composition. Since the substrate with a surface layer of the present invention has a surface layer formed from the above-mentioned composition, it has excellent abrasion resistance and also excellent water and oil repellency.

[0136] (base material) The substrate is not particularly limited as long as it is a substrate that may be used by coming into contact with other articles (e.g., a stylus) or a person's fingers, a substrate that may be held by a person's fingers during operation, and / or a substrate that may be placed on other articles (e.g., a mounting table), and is required to be water- and oil-repellent. Specific examples of substrate materials include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. As the substrate, a substrate for a touch panel and a substrate for a display are preferred, and a substrate for a touch panel is particularly preferred. The substrate for a touch panel is preferably light-transmitting. "Light-transmitting" means that the normal incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. As the material for the substrate for a touch panel, glass and transparent resin are preferred. Further preferred substrates include glass or resin films used for building materials, decorative building materials, interiors, transportation equipment (e.g., automobiles), signs and notices, drinking vessels and tableware, aquariums, ornamental equipment (e.g., frames, boxes), laboratory equipment, furniture, art, sports, and games, and glass sheets or resin films used for the exterior parts (excluding the display part) of devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles, and remote controls.

[0137] The substrate may be a substrate whose one or both surfaces have been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment.

[0138] The surface layer may be formed directly on the surface of the substrate, or may be formed on the substrate via another film formed on the surface of the substrate. Specific examples of such another film include an undercoat film formed on the surface of the substrate by subjecting the substrate to a surface treatment using compounds described in paragraphs 0089 to 0095 of WO 2011 / 016458, SiO2, or the like.

[0139] (Surface layer) The surface layer is a layer formed from the above-mentioned composition. As described above, the surface layer contains a condensate obtained by hydrolysis and dehydration condensation of some or all of the reactive silyl groups of the specific fluorine-containing ether compound as the first component, and also contains the above-mentioned second component or a component derived therefrom.

[0140] The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer is equal to or greater than the lower limit, the effect of the surface layer can be sufficiently obtained. When the thickness of the surface layer is equal to or less than the upper limit, the utilization efficiency is high. The thickness of the surface layer can be calculated from the oscillation period of an interference pattern of reflected X-rays obtained by X-ray reflectometry (XRR) using an X-ray diffractometer for thin film analysis.

[0141] [Method of manufacturing substrate with surface layer] The method for producing the substrate with a surface layer of the present invention is a method for forming a surface layer on a substrate by dry coating or wet coating using the above-mentioned composition.

[0142] The substrate with a surface layer of the present invention can be produced, for example, by the following method. A method for obtaining a substrate with a surface layer by treating the surface of a substrate by a dry coating method using the above-mentioned composition that does not contain a liquid medium (hereinafter also referred to as a "dry coating composition"), thereby forming a surface layer on the surface of the substrate. A method of applying the above-mentioned composition containing a liquid medium (hereinafter also referred to as "wet coating composition") to the surface of a substrate by a wet coating method, and drying the composition to obtain a substrate with a surface layer formed on the surface of the substrate.

[0143] Specific examples of dry coating methods include vacuum deposition, CVD, and sputtering. Among these, vacuum deposition is preferred from the viewpoint of suppressing decomposition of the specific fluorine-containing ether compound and from the viewpoint of the simplicity of the equipment. For vacuum deposition, a pellet-like material in which a metal porous body such as iron or steel is supported with a dry coating composition, or a pellet-like material obtained by impregnating a wet coating composition and drying it, may be used.

[0144] Specific examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0145] The drying temperature after wet-coating the composition is preferably 20 to 200°C, particularly preferably 80 to 160°C.

[0146] [Compound] 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)), both of which are novel compounds. The details of the compound (A) and the compound (B) are as explained above in the composition of the present invention, and therefore will not be explained again.

[0147] As mentioned above, the compound (A) and the compound (B) can be suitably used in the above-mentioned composition.

[0148] Furthermore, the compounds (A) and (B) can also be suitably used for purposes other than adding them to the above-mentioned compositions. For example, Compound (A) and Compound (B) can be used to improve the alkali resistance of a substrate. Specifically, the present inventors have found that when Compound (A) or Compound (B) is used for surface treatment of a substrate having a nitride on its surface, the alkali resistance of the substrate is improved. Although the details of the reason for this are not clear, it is presumed to be due to the following reasons. As described above, compound (A) has -CZ at one end. a1 A group represented by =CH2 (Z a1 is a fluorine atom or a trifluoromethyl group.) Also, compound (B) has -CZ at both terminal portions. b1 Groups represented by =CH2 and CH2=CZ b2 - (Z b1 and Z b2 are each independently a fluorine atom or a trifluoromethyl group. Thus, Z of compound (A) a1 is a group having a fluorine atom, and Z of compound (B) b1 and Z b2 is a group containing a fluorine atom. Therefore, compared to compounds with a terminal group of -CH2=CH2, the water repellency near the terminal is improved. As a result, it is presumed that the alkali resistance of the substrate containing the nitride is improved.

[0149] The compound (B) can also be suitably used in curable compositions for producing rubber. [Example]

[0150] The present invention will be described in detail below with reference to examples. Examples 1-1 to 1-5, 1-7 to 1-9, and 2-1 to 2-3 are working examples, and Examples 1-6, 1-10, and 2-4 are comparative examples. However, the present invention is not limited to these examples. The blending amounts of each component in the tables below are based on mass.

[0151] [Synthesis Example 1: Synthesis of Fluorine-Containing Ether Compound (3-1)] <Synthesis of Compound (1-1)> According to the method described in Example 7 of WO 2013 / 121984, the following compound (1-1) was obtained. CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2OH ···(1-1) The average number of repeating units, n, is 13.

[0152] <Synthesis of Compound (1-2)> 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 stirred at 0°C. Trifluoromethanesulfonic anhydride (0.987 g, 3.50 mol) was added, and the mixture was stirred at room temperature. After washing with water, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 6.81 g of the following compound (1-2). CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2OTf ···(1-2) The average number of repeating units, n, is 13, and OTf is triflate: -OS(=O)2(-CF3).

[0153] NMR spectrum of compound (1-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):4.78(t,J=12.3Hz,2H). 19F-NMR(376MHz,Chloroform-d) δ(ppm):-55.28,-74.11,-82.86,-88.07,-90.20,-119.84,-125.28,-126.16.

[0154] <Synthesis of Compound (2-1)> Diethyldiallylmalonate (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, which was washed with saturated saline and dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following compound (2-1).

[0155] [ka]

[0156] NMR spectrum of compound (2-1); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):(ddt,J=17.1,10.1,7.0Hz,2H),5.06~4.94(m,4H),4.09(q,J=7.1Hz,2H),2.47(ddd,J=14.0 ,8.0,6.1Hz,1H),2.33(dt,J=14.9,7.5Hz,2H),2.22(dt,J=14.1,6.5Hz,2H),1.21(t,J=7.1Hz,3H).

[0157] <Synthesis of compound (2-2)> After adding THF (260 mL) and diisopropylamine (41.5 mL, 294 mmol), the solution was cooled to -78 °C. A n-butyllithium hexane solution (2.76 M, 96.6 mL, 294 mmol) was added, and the mixture was heated to 0 °C. After stirring, the mixture was cooled to -78 °C to prepare a THF solution of lithium diisopropylamide (LDA). The above compound (2-1) (39.5 g, 235 mmol) was added to the THF solution, and after stirring, allyl bromide (24.1 mL, 278 mmol) was added. The mixture was heated to 0 °C, 1 M hydrochloric acid (100 mL) was added, and the THF was evaporated under reduced pressure. Extraction with dichloromethane was followed by the addition of sodium sulfate. After filtration, the solvent was evaporated, and the mixture was subjected to flash column chromatography using silica gel to obtain 45.0 g of compound (2-2).

[0158] [ka]

[0159] NMR spectrum of compound (2-2); 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).

[0160] <Synthesis of compound (2-3)> 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, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound (2-3).

[0161] [ka]

[0162] NMR spectrum of compound (2-3); 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).

[0163] <Synthesis of Compound (B1-1)> 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 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).

[0164] [ka]

[0165] NMR spectrum of compound (B1-1); 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).

[0166] <Synthesis of Compound (B2-1)> To magnesium (2.36 g, 97.2 mmol), THF (35 mL) and iodine (0.180 g, 0.71 mmol) were added and 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).

[0167] [ka]

[0168] <Synthesis of Compound (C1-1)> CuCl2 (16.0 mg, 0.119 mmol), 1-phenyl-1-propyne (0.052 g, 0.45 mmol), 1,3-bistrifluoromethylbenzene (24 mL), and the above compound (1-2) (4.00 g) were added, followed by the above compound (B2-1) (5.0 mL, 1.0 M, 5.0 mmol). After stirring at room temperature, the mixture was washed with 1 M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off, and AC-6000 was added. After washing with methanol, flash column chromatography using silica gel was performed to obtain 0.139 g of compound (C1-1). CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2CF2-CH2CH2-C[CH2CH2=CH2]3...(C1-1) The average number of repeating units, n, is 10.

[0169] NMR spectrum of compound (C1-1); 1 H-NMR(400MHz,Chloroform-d) δ 5.77(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). 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.

[0170] <Synthesis of compound (3-1)> AC-2000 (0.89 g), the above compound (C1-1) (0.139 g), a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%, 5.5 mg), aniline (0.8 mg), and trimethoxysilane (22.7 mg, 0.185 mmol) were added and stirred at 40°C. The solvent was then distilled off under reduced pressure, yielding 0.140 g of fluorine-containing ether compound (3-1). CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2CF2-CH2CH2-C[CH2CH2CH2-Si(OCH3)3]3...(3-1) The average value of the number of units m is 10.

[0171] NMR spectrum of compound (3-1); 1 H-NMR(400MHz,Chloroform-d) δ 3.60(s,27H),2.23-1.95(m,2H),1.63-1.28(m,14H),0.67(t,J=7.6Hz,6H). 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.

[0172] [Synthesis Example 2: Synthesis of fluorine-containing ether compound (3-2)] A fluorine-containing ether compound (3-2) was obtained according to the method described in Example 6-2 of WO 2017 / 038830. CF3-(OCF2CF2-OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-CH2OCH2-C[CH2CH2CH2-Si(OCH3)3]3...(3-2) The average number of repeating units, n, is 13.

[0173] [Synthesis Example 3: Synthesis of Compound (A-1)] <Synthesis of compound (a1-1)> 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, and the mixture was stirred at 100° C. After filtration, the solvent was distilled off, and the mixture was subjected to flash column chromatography using silica gel to obtain 4.80 g of compound (a1-1). CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-CH2-Br ···(a1-1) The average value of n is 13.

[0174] NMR spectrum of compound (a1-1); 1 H-NMR(400MHz,Chloroform-d) δ 3.63(t,J=15.6Hz,2H). 19 F-NMR(376MHz,Chloroform-d) δ -55.24,-82.81,-88.04,-90.16,-113.08,-125.24.

[0175] <Synthesis of Compound (A-1)> Compound (a1-1) (500 mg), 1,3-bistrifluoromethylbenzene (2 mL), acetic acid (1 mL), and zinc (500 mg) were added, followed by stirring at 110°C. After filtration, AC-6000 (30 mL) and 1 M 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). CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF=CH2...(A-1) The average number of repeating units, n, is 13.

[0176] NMR spectrum of compound (A-1); 1 H-NMR(400MHz,Chloroform-d) δ 5.36-5.04(m,2H). 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.

[0177] [Synthesis Example 4: Synthesis of Compound (A-2)] Compound (1-1) (200 mg), 1,3-bistrifluoromethylbenzene (0.2 mL), TBAI (1.6 mg), 30% aqueous sodium hydroxide solution (8.1 mg), and 3-Bromo-2-fluoroprop-1-ene (22.1 mg) were added and stirred at 60 °C. The mixture was washed with AC-6000 (60 mL) and methanol (20 mL). The solvent was removed by distillation, and the mixture was purified by flash column chromatography using silica gel to obtain 158 mg of compound (A-2). CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2CF2-CH2-O-CH2-CF=CH2...(A-2) The average number of repeating units, n, is 13.

[0178] NMR spectrum of compound (A-2); 1 H-NMR(400MHz,Chloroform-d) δ 4.75-4.42(m,2H),4.08(d,J=13.2Hz,2H),3.98(t,J=13.4Hz,2H). 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.

[0179] [Synthesis Example 5: Synthesis of Compound (B-1)] <Synthesis of compound (a1-2)> FLUOROLINK D4000 (Solvay Specialty Polymers) (5.01 g), triphenylphosphine (7.5 g), 1,3-bistrifluoromethylbenzene (50 mL), carbon tetrabromide (7.5 g), and DMF (5 mL) were added, followed by stirring at 120° C. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 2.12 g of compound (a1-2). Br-CH2-CF2-{(OCF2) n1 (OC2F4) n2}-O-CF2-CH2-Br (a1-2) The average number of repeating units n1 is 22, and the average number of repeating units n2 is 25.

[0180] NMR spectrum of compound (a1-2); 1 H-NMR(400MHz,Chloroform-d) δ 3.55(q,J=9.8Hz,4H).

[0181] <Synthesis of Compound (B-1)> Compound (a1-2) (600 mg), 1,3-bistrifluoromethylbenzene (24 mL), and butylmagnesium chloride THF solution (6.0 mL, 6.0 mmol) were added and stirred at room temperature. AC-6000 (50 mL) and 1 M hydrochloric acid (5 mL) were added, followed by washing with methanol (20 mL). The solvent was evaporated, and the mixture was purified by flash column chromatography using silica gel to obtain 45 mg of compound (B-1). H2C=CF-{(OCF2) n1 (OC2F4) n2}-O-CF=CH2···(B-1) The average number of repeating units n1 is 22, and the average number of repeating units n2 is 25.

[0182] NMR spectrum of compound (B-1); 1 H-NMR(400MHz,Chloroform-d) δ 4.32-4.14(m,4H).

[0183] [Synthesis Example 6: Synthesis of Compound (C-1)] Compound (1-1) (200 mg), 1,3-bistrifluoromethylbenzene (0.2 mL), TBAI (1.6 mg), 30% aqueous sodium hydroxide solution (8.1 mg), and allyl bromide (22.1 mg) were added and stirred at 60 °C. The mixture was washed with AC-6000 (60 mL) and methanol (20 mL). The solvent was removed by distillation, and the mixture was purified by flash column chromatography using silica gel to obtain 161 mg of compound (C-1). CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2CF2-CH2-O-CH2-CH=CH2...(C-1) The average number of repeating units, n, is 13.

[0184] NMR spectrum of compound (C-1); 1 H-NMR(400MHz,Chloroform-d) δ 5.80(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). 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.

[0185] [Example 1-1] A composition (1-1) was obtained by mixing 99 parts by mass of the fluorine-containing ether compound (3-1) as the first component and 1 part by mass of the compound (A-1) as the second component. A molybdenum boat in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.) was filled with 0.14 g of composition (1-1) as a deposition source, and the inside of the vacuum deposition apparatus was heated to 1×10 -3The boat containing the composition (1-1) was heated at a rate of 10°C / min or less, and when the deposition rate measured by a quartz crystal oscillator film thickness meter exceeded 1 nm / sec, the shutter was opened to start film formation on the surface of the substrate (chemically strengthened glass). When the film thickness reached approximately 50 nm, the shutter was closed to terminate film formation on the surface of the substrate. The substrate on which the composition (1-1) had been deposited was heat-treated at 200°C for 30 minutes and washed with dichloropentafluoropropane (AK-225, manufactured by AGC Corporation) to obtain a substrate with a surface layer having a surface layer on the surface of the substrate.

[0186] [Example 1-2 to Example 1-10] Except for changing the types and contents of the first and second components as shown in Table 1, a substrate with a surface layer in each example was obtained in the same manner as in Example 1-1.

[0187] [Evaluation test] The following evaluation tests were carried out using the substrates with surface layers of Examples 1-1 to 1-10.

[0188] <Water contact angle> The contact angle of approximately 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.). Measurements were taken at three different locations on the surface of the surface layer, and the average value was calculated to determine the initial contact angle. The 2θ method was used to calculate the contact angle. Based on the obtained initial contact angle value, the water repellency was evaluated according to the following evaluation criteria. A: Contact angle is 115 degrees or more B: Contact angle is 105 degrees or more and less than 115 degrees C: Contact angle less than 105 degrees

[0189] <Wear resistance> The surface layer was subjected to a reciprocating traverse test using a reciprocating traverse tester (manufactured by KNT Corporation) in accordance with JIS L0849:2013 (ISO 105-X12:2001) with steel wool Bonstar (count: #0000) at a pressure of 98.07 kPa and a speed of 320 cm / min. After 10,000 reciprocating strokes of steel wool, the water contact angle of the surface layer was measured, and the abrasion resistance was evaluated according to the following evaluation criteria. The smaller the change in water contact angle before and after the abrasion test, the smaller the deterioration in performance due to abrasion, and the more excellent the abrasion resistance. A rating of B or higher can be considered to be excellent abrasion resistance. A: The change in water contact angle is less than 2 degrees B: Change in water contact angle is 2 degrees or more but less than 4 degrees C: Change in water contact angle is 4 degrees or more but less than 6 degrees D: Change in water contact angle is 6 degrees or more

[0190] <Evaluation results> The results of the above evaluation tests are shown in Table 1.

[0191] [Table 1]

[0192] As shown in Table 1, it was confirmed that by using a composition containing a specific fluorine-containing ether compound consisting of a first component and at least one second component selected from the group consisting of compound (A) and compound (B), it is possible to form a surface layer that is excellent in initial water contact angle and abrasion resistance (Examples 1-1 to 1-5, Examples 1-7 to 1-9).

[0193] [Example 2-1] A substrate with a nitride film was obtained by forming a silicon nitride film on the surface of glass by plasma CVD using SiH4 and nitrogen gas. A molybdenum boat in a vacuum deposition apparatus (ULVAC VTR-350M) was filled with 0.16 g of compound (A-1) as a deposition source, and the inside of the vacuum deposition apparatus was heated to 1×10 -3The pressure was evacuated to a pressure of 10 Pa or less. The boat containing the compound (A-1) was heated at a temperature increase rate of 10°C / min or less, and when the deposition rate measured by a quartz crystal oscillator film thickness meter exceeded 1 nm / sec, the shutter was opened to start film formation on the surface of the nitride film-coated substrate. When the film thickness reached approximately 50 nm, the shutter was closed to terminate film formation on the surface of the nitride film-coated substrate. In this way, a substrate with a surface layer was obtained, which had a surface layer on the surface of the silicon nitride film.

[0194] [Example 2-2 to Example 2-4] Except for changing the type of compound as shown in Table 2, the same procedure as in Example 2-1 was carried out to obtain a substrate with a surface layer in each example.

[0195] [Evaluation test] The following evaluation tests were carried out using the surface layer-attached substrates of Examples 2-1 to 2-4.

[0196] <Water contact angle> The contact angle of approximately 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.). Measurements were taken at three different locations on the surface of the surface layer, and the average value was calculated to determine the initial contact angle. The 2θ method was used to calculate the contact angle. Based on the obtained initial contact angle value, the water repellency was evaluated according to the following evaluation criteria. A: Contact angle is 115 degrees or more B: Contact angle is 105 degrees or more and less than 115 degrees C: Contact angle less than 105 degrees

[0197] <Alkali resistance> An alkaline aqueous solution (25% by mass KOH aqueous solution, pH 14) was dropped onto the surface layer and allowed to stand for 60 minutes, after which 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 in water contact angle before and after the alkali resistance test, the smaller the deterioration in performance due to alkali and the more excellent the alkali resistance. An evaluation result of B or higher can be said to be excellent in alkali resistance. A: The change in water contact angle is less than 1 degree B: Change in water contact angle is 1 degree or more but less than 3 degrees C: Change in water contact angle is 3 degrees or more

[0198] <Evaluation results> The results of the above evaluation tests are shown in Table 2.

[0199] [Table 2]

[0200] As shown in Table 2, it was confirmed that the use of the above-mentioned compound (A) or compound (B) can improve the alkali resistance of a substrate having a nitride, and can also impart excellent water repellency to the substrate (Examples 2-1 to 2-3). [Industrial Applicability]

[0201] The compounds and compositions of the present invention can be used in a variety of applications. For example, they can be used in display input devices such as touch panels, transparent glass or transparent plastic components, lenses for eyeglasses, antifouling materials for kitchens, water-repellent and moisture-proof or antifouling materials for electronic devices, heat exchangers, batteries, etc., antifouling materials for toiletries, materials that require electrical conductivity and liquid repellency, water-repellent, waterproof, and water-slippery materials for heat exchangers, and low-wear surface materials for vibrating screens and cylinder interiors. More specific examples of use include front protective plates for displays, antireflection plates, polarizing plates, antiglare plates, or those with antireflection film-treated surfaces, and various devices with display input devices that allow operations on the screen with a user's finger or palm, such as touch panel sheets and touch panel displays for devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles, and remote controls (e.g., glass or film used in the display, etc., and glass or film used in exterior parts other than the display). In addition to the above, examples include decorative building materials for wet areas such as toilets, baths, washrooms and kitchens, waterproofing materials for wiring boards, water-repellent, waterproof and water-slip materials for heat exchangers, water-repellent materials for solar cells, waterproofing and water-repellent materials for printed wiring boards, waterproofing and water-repellent materials for electronic device housings and electronic components, materials for improving the insulation of power transmission lines, waterproofing and water-repellent materials for various filters, waterproofing materials for radio wave absorbers and sound absorbers, stain-resistant materials for baths, kitchen equipment and toiletries, low-wear surface materials for vibrating screens and the inside of cylinders, etc., machine parts, vacuum equipment parts, bearing parts, transportation equipment parts for automobiles etc., surface protection materials for tools etc. The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2020-155260, filed on September 16, 2020, are hereby incorporated by reference as part of the disclosure of the specification of the present invention.

Claims

1. a first component consisting of a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group; and at least one second component selected from the group consisting of a compound represented by the following formula (A) and a compound represented by the following formula (B), A composition characterized in that the fluorine-containing ether compound is a compound represented by the following formula (3): R ｆａ -(OX ａ ) ｍ１ -L ａ -CZ ａ１ =CH ２ ・・・(A) However, 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 represents a single bond or a divalent linking group (wherein (OX ａ ) ｎａ Except. na is an integer of 1 or more; Z ａ１ is a fluorine atom or a trifluoromethyl group, m1 is an integer of 2 or more. CH ２ =CZ ｂ２ -L ｂ２ -(OX ｂ ) ｍ２ -L ｂ１ -CZ ｂ１ =CH ２ ・・・(B) However, in formula (B), X ｂ is a fluoroalkylene group having 1 to 6 carbon atoms, L ｂ１ and L ｂ２ each independently represents a single bond or a divalent linking group (provided that (OX ｂ ) ｎｂ Except. nb is an integer of 1 or more; Z ｂ１ and Z ｂ２ each independently represents a fluorine atom or a trifluoromethyl group, m2 is an integer of 2 or more. [A-(OX) ｍ -O-] ｊ Z[-Si(R) ｎ L ３－ｎ ] ｇ ・・・(3) However, in formula (3), A is a perfluoroalkyl group or -Q[-Si(R) ｎ L ３－ｎ ] ｋ and X is a fluoroalkylene group having one or more fluorine atoms, m is an integer of 2 or greater; j is an integer equal to or greater than 1, Z is a (j+g)-valent linking group, R is a monovalent hydrocarbon group; L is a hydrolyzable group or a hydroxyl group; n is an integer from 0 to 2, g is an integer of 1 or greater; Q is a (k+1)-valent linking group, k is an integer from 1 to 10.

2. Z in the formula (A) ａ１ The composition of claim 1 , wherein is a fluorine atom.

3. L in the formula (A) ａ The composition according to claim 1 or 2, wherein is an alkylene group, an ether oxygen atom, an amide bond, or a group consisting of a combination thereof, or a single bond.

4. L in the formula (A) ａ The composition of claim 3 , wherein is a single bond.

5. Z in the formula (B) ｂ１ and Z ｂ２ The composition according to any one of claims 1 to 4, wherein each of

6. L in the formula (B) ｂ１ and L ｂ２ The composition according to any one of claims 1 to 5, wherein each independently represents an alkylene group, an etheric oxygen atom, an amide bond, a group consisting of a combination thereof, or a single bond.

7. L in the formula (B) ｂ２ The composition of claim 6 , wherein is a single bond.

8. The composition according to any one of claims 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.

9. A substrate with a surface layer, comprising: a substrate; and a surface layer formed on the substrate from the composition according to any one of claims 1 to 8.

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 claims 1 to 8.

11. A compound represented by the following formula (B): CH ２ =CZ ｂ２ -L ｂ２ -(OX ｂ ) ｍ２ -L ｂ１ -CZ ｂ１ =CH ２ ・・・(B) However, in formula (B), X ｂ is a fluoroalkylene group having 1 to 6 carbon atoms, L ｂ１ and L ｂ２ each independently represents a single bond or a divalent linking group (provided that (OX ｂ ) ｎｂ Except. nb is an integer of 1 or more; Z ｂ１ and Z ｂ２ each independently represents a fluorine atom or a trifluoromethyl group, m2 is an integer of 2 or more, (OX ｂ ) ｍ２ is {(OCF ２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ }, m21 is an integer of 1 or more, and m22 is an integer of 1 or more.

12. A method for producing a compound, comprising reacting a metal or organometallic reagent with a compound represented by the following formula (b1) to obtain a compound represented by the following formula (B): Q ｂ２ -CH ２ -CFZ ｂ２ -L ｂ２ -(OX ｂ ) ｍ２ -L ｂ１ -CFZ ｂ１ -CH ２ -Q ｂ１ ・・・(b1) CH ２ =CZ ｂ２ -L ｂ２ -(OX ｂ ) ｍ２ -L ｂ１ -CZ ｂ１ =CH ２ ・・・(B) However, in formula (b1) and formula (B), X ｂ is a fluoroalkylene group having 1 to 6 carbon atoms, L ｂ１ and L ｂ２ each independently represents a single bond or a divalent linking group (provided that (OX ｂ ) ｎｂ Except. nb is an integer of 1 or more; Z ｂ１ and Z ｂ２ each independently represents a fluorine atom or a trifluoromethyl group, Q ｂ１ and Q ｂ２ are each independently a leaving group, m2 is an integer of 2 or more, (OX ｂ ) ｍ２ is {(OCF ２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ }, m21 is an integer of 1 or more, and m22 is an integer of 1 or more.

13. The method for producing the compound according to claim 12, which is carried out in the presence of a fluorine-containing organic solvent.

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