Composition, method for producing composition, coating liquid, article, and method for producing article

Abstract

Provided are: a composition capable of forming a surface layer having excellent lubricity; a method for producing the composition; a coating liquid; an article; and a method for producing the article.　This composition contains two or more types of fluorine-containing ether compounds having a fluoropolyether chain and a reactive silyl group. At least two of said fluorine-containing ether compounds have a fluoropolyether chain including a structure represented by formula (G11). If the fluorine-containing ether compound having the highest M in m31 / m32=M is denoted as compound A and the fluorine-containing ether compound having the lowest M is denoted as compound B, the ratio (MA / MB) of M (=MA) for compound A to M (=MB) for compound B is 1.35 or more.　Formula (G11): (OCF2)m31·(OCF2CF2)m32 . In formula (G11), m31 denotes the number of (OCF2) groups and is an integer of 2 or more, and m32 denotes the number of (OCF2CF2) groups and is an integer of 2 or more.

Description

Composition, method for producing composition, coating liquid, article, and method for producing article

[0001] The present invention relates to a composition, a method for producing a composition, a coating liquid, an article, and a method for producing an article.

[0002] It is known that in order to impart water- and oil-repellency, stain resistance, 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 fluoropolyether chain and a reactive silyl group (Patent Document 1).

[0003] Patent No. 5761305

[0004] In recent years, the performance requirements for surface layers formed using fluorine-containing ether compounds have been increasing. For example, when the surface layer is applied to a member that constitutes a surface that is touched with fingers, the surface layer is required to have excellent lubricity (smoothness when touched with fingers). The present inventors evaluated surface layers formed using fluorine-containing ether compounds as described in Patent Document 1 and found that there is room for improvement in the lubricity of the surface layer.

[0005] Therefore, an object of the present invention is to provide a composition capable of forming a surface layer with excellent lubricity, a method for producing the composition, a coating liquid, an article, and a method for producing the article.

[0006] As a result of extensive research into the above-mentioned problems, the present inventors have found that at least two of the fluorine-containing ether compounds contained in the composition are ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ The present inventors have found that a surface layer having excellent lubricity can be formed by compound A having a fluoropolyether chain containing a structure represented by the formula (I) and compound B having the smallest M, and the ratio of M between compound A and compound B having the largest M / m is 1.35 or more, and have arrived at the present invention. ２ ) ｍ１１ ・(OCF ２ CF ２ ) ｍ１２ a first compound having a fluoropolyether chain having a structure represented by (OCF２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ The compound can be prepared by mixing a first compound having a fluoropolyether chain with a second compound having a structure represented by the following formula:

[0007] That is, the inventors have found that the above-mentioned problems can be solved by the following constitution: [1] A composition containing two or more kinds of fluorine-containing ether compounds each having a fluoropolyether chain and a reactive silyl group, wherein at least two kinds of the fluorine-containing ether compounds have a fluoropolyether chain containing a structure represented by the following formula (G11), and when the fluorine-containing ether compound having the largest m31 / m32 = M is compound A and the fluorine-containing ether compound having the smallest M is compound B, M (=M) of compound A is Ａ ) and M (=M) of the compound B Ｂ ) and the ratio (M Ａ / M Ｂ ) is 1.35 or more. ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ ...(G11) In formula (G11), m31 is (OCF ２ ) and is an integer of 2 or more, and m32 is (OCF ２ CF ２ ) and is an integer of 2 or more. [2] The M Ａ [3] The composition according to [1], wherein M Ｂ [4] The composition according to [1] or [2], wherein the M Ａ / M Ｂ The composition according to any one of [1] to [3], wherein the M Ａ / M Ｂ The composition according to any one of [1] to [4], wherein the M Ａ / M Ｂ[7] The composition according to any one of [1] to [6], wherein the content of each of the compound A and the compound B is 0.1 mass% or more relative to the total mass of the composition. [8] The composition according to any one of [1] to [7], wherein the mass ratio of the content of the compound A to the content of the compound B is 0.01 to 100. [9] A method for producing a composition containing two or more kinds of fluorine-containing ether compounds having a fluoropolyether chain and a reactive silyl group, wherein a first compound among the fluorine-containing ether compounds has a fluoropolyether chain having a structure represented by the following formula (G1), and a second compound among the fluorine-containing ether compounds has a fluoropolyether chain having a structure represented by the following formula (G2), wherein m11 in the following formula (G1) is different from m21 in the following formula (G2), and / or m12 in the following formula (G1) is different from m22 in the following formula (G2), and the first compound and the second compound are mixed. (OCF ２ ) ｍ１１ ・(OCF ２ CF ２ ) ｍ１２ ...(G1) (OCF ２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ In formula (G1), m11 is (OCF ２ m12 means the average number of (OCF ２ CF ２ In formula (G2), m21 represents the average number of (OCF ２ m22 means the average number of (OCF ２ CF ２

[10] When the compound constituting the first compound having the largest m11 / m12 = M is compared with the compound constituting the second compound having the largest m21 / m22 = M, and the compound having the largest m21 / m22 = M is designated as compound A, the M (= M) of compound A is Ａ

[11] The method for producing a composition according to [9], wherein the compound constituting the first compound and the compound constituting the second compound, which have the smallest m11 / m12 = M, are compared, and the compound constituting the second compound and which has the smallest m21 / m22 = M is designated as compound B, and the M (= M) of compound B is Ｂ

[12] The method for producing a composition according to [9] or

[10] , wherein the M is less than 1.00.

[13] The method for producing a composition according to

[11] , wherein the first compound contains the compound A, and the second compound contains the compound B.

[14] The method for producing a composition according to

[12] , wherein the M is less than 1.00. Ａ / M Ｂ

[14] The method for producing a composition according to

[12] , wherein the M Ａ / M Ｂ

[15] The method for producing a composition according to

[12] or

[13] , wherein M is 1.50 or more. Ａ / M Ｂ

[16] The method for producing a composition according to any one of

[12] to

[14] , wherein the M Ａ / M Ｂis 4.00 or more.

[17] A method for producing a composition according to any one of

[12] to

[16] , wherein the contents of the first compound and the second compound are each 0.1 mass% or more relative to the total mass of the composition.

[18] A method for producing a composition according to any one of

[12] to

[17] , wherein the mass ratio of the content of the first compound to the content of the second compound is 0.01 to 100.

[19] A coating liquid comprising the composition according to any one of [1] to [8] and a liquid medium.

[20] An article having, on a substrate, a surface layer formed from the composition according to any one of [1] to [8] or the coating liquid according to

[19] .

[21] The article according to

[20] , wherein the article is a touch panel, and the surface layer is formed on a surface of a member constituting the surface of the touch panel that is touched with a finger.

[22] A method for producing an article, 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] or the coating liquid according to

[19] .

[0008] According to the present invention, it is possible to provide a composition capable of forming a surface layer having excellent lubricity, a method for producing the composition, a coating liquid, an article, and a method for producing the article.

[0009] The terms used in the present invention have the following meanings.

[0010] In this specification, a group represented by formula (g1) may be referred to as group (g1). A structure represented by formula (G1) may be referred to as structure (G1). A compound represented by formula (1-1) may be referred to as compound (1-1). Compounds represented by other formulas may also be referred to as such. A fluoroalkyl group is a collective term that includes perfluoroalkyl groups and partial fluoroalkyl groups. A perfluoroalkyl group refers to a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms. A partial fluoroalkyl group refers to an alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms and which also has one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group having one or more fluorine atoms. A "reactive silyl group" is a collective term for a hydrolyzable silyl group and a silanol group (Si—OH), and a "hydrolyzable silyl group" refers to a group that can form a silanol group by hydrolysis. An "organic group" refers to a hydrocarbon group that may have a substituent and may have a heteroatom or other bond in the carbon chain. The term "hydrocarbon group" refers to a group consisting of carbon atoms and hydrogen atoms, and includes aliphatic hydrocarbon groups (for example, divalent aliphatic hydrocarbon groups such as linear alkylene groups, branched alkylene groups, and cycloalkylene groups), aromatic hydrocarbon groups (for example, divalent aromatic hydrocarbon groups such as phenylene groups), and groups consisting of combinations thereof. The term "surface layer" refers to a layer formed on a substrate. The "molecular weight" of the fluoropolyether chain is １ H-NMR and １９ The number average molecular weight is calculated by F-NMR to determine the number (average value) of oxyfluoroalkylene units based on the terminal groups. The range of values ​​indicated by "to" means that the values ​​before and after it are included as the lower and upper limits.

[0011] In this specification, OCF ２ CH ２ In an alkylene structure containing a fluorine atom sandwiched between two oxygen atoms, such as —O, a repeating unit consisting of a partial structure sandwiched between two oxygen atoms and an oxygen atom (in the above case, “OCF ２ CH ２ ") is interpreted as being

[0012] [Composition] The composition of the present invention (hereinafter also referred to as "the present composition") is a composition containing two or more fluorinated ether compounds having a fluoropolyether chain and a reactive silyl group, wherein at least two of the fluorinated ether compounds have a fluoropolyether chain containing a structure represented by the following formula (G11), and when the fluorinated ether compound having the largest m31 / m32 = M is compound A and the fluorinated ether compound having the smallest M is compound B, M (=M) of compound A is Ａ ) and M (=M) of the compound B Ｂ ) and the ratio (M Ａ / M Ｂ ) is 1.35 or more. ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ ...(G11) In formula (G11), m31 is (OCF ２ ) and is an integer of 2 or more, and m32 is (OCF ２ CF ２ ) and is an integer of 2 or more.

[0013] This composition can form a surface layer with excellent lubricity. The reason for this is not clear, but is presumed to be due to the following reasons. (OCF ２ ) or the average number of structures represented by (OCF ２ CF ２ When a surface layer is formed using the present composition containing two or more fluorinated ether compounds having different average numbers of structures represented by (OCF), the packing of molecular chains between the fluorinated ether compounds having different average numbers of the structures tends to be poor (i.e., the molecular chains are less likely to be densely arranged on the substrate). ２ CF ２ ) for the number of (OCF ２ ) the compound A having the largest ratio M of the number of the compound A and the compound B having the smallest ratio M, Ａ / M ＢThis tendency becomes more pronounced when the σ is 1.35 or more. As a result, it is presumed that the degree of freedom of each molecular chain is improved, the surface free energy of the surface layer is increased, and the lubricity of the surface layer is improved.

[0014] The composition is suitable as a surface treatment agent for forming a surface layer on a substrate that imparts water and oil repellency, abrasion resistance, and fingerprint stain removability.

[0015] <Fluorine-containing ether compound> The fluorine-containing ether compound has a fluoropolyether chain and a reactive silyl group, and two or more types are contained in the composition. The composition may contain, among the two or more fluorine-containing ether compounds, at least two of them have a fluoropolyether chain containing a structure represented by the above formula (G11), and may further contain a fluorine-containing ether compound having another fluoropolyether chain. Since the fluorine-containing ether compound has a fluoropolyether chain, the surface layer obtained using the composition has excellent water and oil repellency and fingerprint stain removability. The fluorine-containing ether compound has a reactive silyl group. Since the reactive silyl group forms a strong chemical bond with the substrate or the underlayer, the surface layer obtained using the composition has excellent durability such as abrasion resistance.

[0016] The fluoropolyether chain is a group having two or more oxyfluoroalkylene units. The fluoropolyether chain may have a hydrogen atom. From the viewpoint of achieving better abrasion resistance and fingerprint stain removability of the surface layer, the proportion of fluorine atoms in the fluoropolyether chain represented by the following mathematical formula (I) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, i.e., a perfluoropolyether chain. If the fluorine atoms are 60% or more, the amount of fluorine in the fluoropolyether chain increases, further improving lubricity and fingerprint removability. Formula (I): Proportion of fluorine atoms (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} × 100

[0017] The molecular weight per fluoropolyether chain is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, and even more preferably 3,000 to 10,000, from the viewpoint of achieving both fingerprint removability and lubricity of the surface layer. If the molecular weight of the fluoropolyether chain is 2,000 or more, the flexibility of the fluoropolyether chain is improved and the amount of fluorine in the molecule is increased, thereby further improving lubricity and fingerprint removability. On the other hand, if the molecular weight of the fluoropolyether chain is 20,000 or less, the surface layer will have better abrasion resistance.

[0018] The fluoropolyether chain preferably has the structure (f1). (OR ｆ１１ ) ｙ１ ...(f1)

[0019] R ｆ１１ is a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R ｆ１１ may be the same or different. y1 may be an integer of 2 or more, preferably 2 to 200.

[0020] (OR ｆ１１ ) ｙ１ It is preferable that the compound has a structure represented by the following formula (f2): -[(OG ｆ１ ) ｍ１ (OG ｆ２ ) ｍ２ (OG ｆ３ ) ｍ３ (OG ｆ４ ) ｍ４ (OG ｆ５ ) ｍ５ (OG ｆ６ ) ｍ６ ]-・・・(f2) However, G ｆ１ is a fluoroalkylene group having 1 carbon atom, ｆ２ is a fluoroalkylene group having 2 carbon atoms, ｆ３ is a fluoroalkylene group having 3 carbon atoms, ｆ４ is a fluoroalkylene group having 4 carbon atoms, ｆ５ is a fluoroalkylene group having 5 carbon atoms, ｆ６is a fluoroalkylene group having 6 carbon atoms, m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, and m1+m2+m3+m4+m5+m6 is preferably an integer of 2 to 200. ｆ１ ) ~ (OG ｆ６ The bonding order of m1 to m6 in formula (f2) is arbitrary. ｆ１ ) ~ (OG ｆ６ ) and does not represent the arrangement. For example, (OG ｆ５ ) ｍ５ (OG ｆ５ ) is m5, and (OG ｆ５ ) ｍ５ Similarly, it does not represent the block arrangement structure of (OG ｆ１ ) ~ (OG ｆ６ The order of the units does not represent the bonding order of the units. The fluoroalkylene group having 3 to 6 carbon atoms may be a linear fluoroalkylene group or a fluoroalkylene group having a branched or cyclic structure.

[0021] G ｆ１ Specific examples of the group include -CF ２ -, -CHF-. ｆ２ Specific examples of the group include -CF ２ CF ２ -, -CHFCF ２ -, -CHFCHF-, -CH ２ CF ２ -, -CH ２ CHF-, etc. ｆ３ Specific examples of the group include -CF ２ CF ２ CF ２ -, -CF ２ CHFCF ２ -, -CF ２ CH ２ CF ２ -, -CHFCF ２ CF ２ -, -CHFCHFCF ２ -, -CHFCHFCHF-, -CHFCH ２ CF ２ -, -CH２ CF ２ CF ２ -、-CH ２ CHFCF ２ -、-CH ２ CH ２ CF ２ -、-CH ２ CF ２ CHF-、-CH ２ CHFCHF-、-CH ２ CH ２ CHF-、-CF(CF ３ )-CF ２ -、-CF(CHF ２ )-CF ２ -、-CF(CH ２ F)-CF ２ -、-CF(CH ３ )-CF ２ -、-CF(CF ３ )-CHF-、-CF(CHF ２ )-CHF-、-CF(CH ２ F)-CHF-、-CF(CH ３ )-CHF-、-CF(CF ３ )-CH ２ -、-CF(CHF ２ )-CH ２ -、-CF(CH ２ F)-CH ２ -、-CF(CH ３ )-CH ２ -、-CH(CF ３ )-CF ２ -、-CH(CHF ２ )-CF ２ -、-CH(CH ２ F)-CF ２ -、-CH(CH ３ )-CF ２ -、-CH(CF ３ )-CHF-、-CH(CHF ２ )-CHF-、-CH(CH ２ F)-CHF-、-CH(CH ３ )-CHF-、-CH(CF ３ )-CH ２ -、-CH(CHF ２ )-CH ２ -、-CH(CH ２ F)-CH２ - etc. can be mentioned. G ｆ４ As a specific example of G, -CF ２ CF ２ CF ２ CF ２ -, -CHFCF ２ CF ２ CF ２ -, -CH ２ CF ２ CF ２ CF ２ -, -CF ２ CHFCF ２ CF ２ -, -CHFCHFCF ２ CF ２ -, -CH ２ CHFCF ２ CF ２ -, -CF ２ CH ２ CF ２ CF ２ -, -CHFCH ２ CF ２ CF ２ -, -CH ２ CH ２ CF ２ CF ２ -, -CHFCF ２ CHFCF ２ -, -CH ２ CF ２ CHFCF ２ -, -CF ２ CHFCHFCF ２ -, -CHFCHFCHFCF ２ -, -CH ２ CHFCHFCF ２ -, -CF ２ CH ２ CHFCF ２ -, -CHFCH ２ CHFCF ２ -, -CH ２ CH ２ CHFCF ２ -, -CF ２ CH ２ CH ２ CF ２ -, -CHFCH ２ CH ２ CF ２ -, -CH２ CH ２ CH ２ CF ２ —, —CHFCH ２ CH ２ CHF—, —CH ２ CH ２ CH ２ CHF—, —cycloC ４ F ６ — etc. can be mentioned. G ｆ５ As a specific example of, —CF ２ CF ２ CF ２ CF ２ CF ２ —, —CHFCF ２ CF ２ CF ２ CF ２ —, —CH ２ CHFCF ２ CF ２ CF ２ —, —CF ２ CHFCF ２ CF ２ CF ２ —, —CHFCHFCF ２ CF ２ CF ２ —, —CF ２ CH ２ CF ２ CF ２ CF ２ —, —CHFCH ２ CF ２ CF ２ CF ２ —, —CH ２ CH ２ CF END]] ２ CF ２ CF ２ —, —CF ２ CF ２ CHFCF ２ CF ２ —, —CHFCF ２ CHFCF ２ CF ２ —, —CH ２ CF ２ CHFCF ２ CF ２ —, —CH ２ CF ２ CF ２CF ２ CH ２ -, -cycloC ５ F ８ - and others. ｆ６ Specific examples of the group include -CF ２ CF ２ CF ２ CF ２ CF ２ CF ２ -, -CF ２ CF ２ CHFCHFCF ２ CF ２ -, -CHFCF ２ CF ２ CF ２ CF ２ CF ２ -, -CHFCHFCHFCHFCHFCHF-, -CHFCF ２ CF ２ CF ２ CF ２ CH ２ -, -CH ２ CF ２ CF ２ CF ２ CF ２ CH ２ -, -cycloC ６ F １０ -, etc. Here, -cycloC ４ F ６ - means a perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group. ５ F ８ - means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,3-diyl group. ６ F １０ "-" means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0022] (OR ｆ１１ ) ｙ１In particular, it is preferable that the compound has any of the structures represented by the following formulas (f3) to (f5), because it has excellent water and oil repellency, abrasion resistance, and fingerprint stain removability. ｆ１ ) ｍ１ ・(OG ｆ２ ) ｍ２ ...(f3) (OG ｆ２ ) ｍ２ ・(OG ｆ４ ) ｍ４ ...(f4) (OG ｆ３ ) ｍ３ ...(f5) However, the symbols in formulas (f3) to (f5) are the same as those in formula (f2) above.

[0023] In formula (f3) and formula (f4), (OG ｆ１ ) and (OG ｆ２ ), (OG ｆ２ ) and (OG ｆ４ ) can be bonded in any order. For example, in formula (f3), ｆ１ ) and (OG ｆ２ ) may be alternately arranged, and (OG ｆ１ ) and (OG ｆ２ ) may be arranged in blocks or randomly. The same applies to formula (f4). In formula (f3), m1 is preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. Furthermore, m2 is preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. In formula (f4), m2 is preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. Furthermore, m4 is preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. In formula (f5), m3 is preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20.

[0024] The fluoropolyether chain (OR ｆ１１ ) ｙ１ The proportion of fluorine atoms in the fluoropolyether chain (OR) [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, from the viewpoint of excellent water and oil repellency and fingerprint removability. ｆ１１ )ｙ１ From the viewpoint of abrasion resistance, the molecular weight of the portion is preferably from 2,000 to 20,000, more preferably from 2,500 to 15,000, and even more preferably from 3,000 to 10,000.

[0025] The reactive silyl group is preferably the group (g1): —SiR ａ１ ｚ１ R ａ２ ３－ｚ１ ... (g1) where R ａ１ is a hydroxyl group or a hydrolyzable group, and R ａ１ If there are multiple R ａ１ may be the same or different, R ａ２ is a non-hydrolyzable group, and R ａ２ If there are multiple R ａ２ may be the same or different, and z1 is an integer of 1 to 3.

[0026] R ａ１ is a hydroxyl group, it forms a silanol (Si—OH) group together with the Si atom. Furthermore, a hydrolyzable group is a group that becomes a hydroxyl group (i.e., a silanol group) through a hydrolysis reaction. The silanol group further reacts with other molecules to form a Si—O—Si bond. Furthermore, the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (substrate (or underlayer)-OH) on the surface of the substrate (or underlayer) to form a chemical bond (substrate (or underlayer)-O—Si). By having one or more groups (g1), the fluorine-containing ether compound has excellent abrasion resistance after the formation of a surface layer.

[0027] R ａ１ Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. 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.

[0028] R ａ１ In view of ease of production of the fluorine-containing ether compound, R is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. ａ１In particular, the alkoxy group in is preferably an alkoxy group having 1 to 4 carbon atoms, from the viewpoint of providing excellent storage stability to the fluorinated ether compound and suppressing outgassing during the reaction, more preferably an ethoxy group from the viewpoint of long-term storage stability, and more preferably a methoxy group from the viewpoint of shortening the hydrolysis reaction time. Of the halogen atoms, a chlorine atom is preferred.

[0029] R ａ２ Examples of the non-hydrolyzable group include a hydrogen atom or a monovalent hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group, with an alkyl group being preferred from the standpoint of ease of production. Furthermore, from the standpoint of ease of production, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0030] z1 may be an integer of 1 to 3, and is preferably 2 or 3, more preferably 3, from the viewpoint of adhesion to the substrate (or underlayer). Specific examples of the group (g1) include -Si(OCH ３ ) ３ , -SiCH ３ (OCH ３ ) ２ , -Si(OCH ２ CH ３ ) ３ , -SiCl ３ , -Si(OCOCH ３ ) ３ , —Si(NCO) ３ From the viewpoint of ease of handling in production, -Si(OCH ３ ) ３ When there are a plurality of groups (g1) in one molecule, the plurality of groups (g1) may be the same or different.

[0031] In the fluorine-containing ether compound, the fluoropolyether chain and the group (g1) are bonded directly or via a linking group. Examples of the linking group include organic groups with a valence of two or more, and specifically, the L １ , L in formula (1-2) ２ and L ３ , L in formula (1-3) ４The number of fluoropolyether chains in one molecule of the fluorine-containing ether compound may be one or two or more. From the viewpoint of ease of synthesis, etc., the number of fluoropolyether chains in one molecule is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. Furthermore, the number of groups (g1) in one molecule of the fluorine-containing ether compound may be one or two or more. From the viewpoint of achieving both abrasion resistance and water and oil repellency, etc., the number of groups (g1) is preferably 1 to 32, more preferably 1 to 18, and even more preferably 2 to 12. When there are multiple fluoropolyether chains, the multiple fluoropolyether chains may be the same or different. When there are multiple groups (g1), the multiple groups (g1) may be the same or different.

[0032] Examples of the fluorine-containing ether compound include compounds represented by the following formula (1), (2) or (3): [R ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ ] ｊ -L １ - (R １１ -T) ｘ１ ...(1) (T-R ３１ ) ｘ３ -L ３ -R ３ - (OR ｆ１１ ) ｙ１ -O-R ２ -L ２ - (R ２１ -T) ｘ２ ... (2) Q １ [-(OR ｆ１１ ) ｙ１ -O-R ４ -L ４ - (R ４１ -T ４１ ) ｘ４ ] ｒ１ ... (3) However, (OR ｆ１１ ) ｙ１ is as described above, and T is the —SiR ａ１ ｚ１ R ａ２ ３－ｚ１The other symbols are the same as those in the formulas (1-1), (1-2), and (1-3) described below.

[0033] The content of the fluorinated ether compound is preferably 0.01 to 100% by mass, more preferably 0.10 to 99.99% by mass, and even more preferably 1.00 to 99.00% by mass, relative to the total mass of the composition. When the content of the fluorinated ether compound is within the above range, the surface layer is more excellent in water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

[0034] (Fluorine-containing ether compounds (compound A and compound B) having a fluoropolyether chain containing a structure represented by formula (G11)) The present composition contains two or more compounds selected from the above-mentioned fluorine-containing ether compounds. Furthermore, in the present composition, at least two of the multiple fluorine-containing ether compounds have a fluoropolyether chain containing a structure represented by the following formula (G11). (OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ ...(G11) In formula (G11), m31 is (OCF ２ ) and is an integer of 2 or more, and m32 is (OCF ２ CF ２ ) and is an integer of 2 or more. Hereinafter, a fluorine-containing ether compound having a fluoropolyether chain containing a structure represented by formula (G11) may be referred to as "compound (G11)".

[0035] The above formula (G11) represents a fluoropolyether chain containing a perfluoroalkylene group having 1 to 2 carbon atoms. The fluoropolyether chain of formula (G11) has excellent flexibility, abrasion resistance, and lubricity due to the inclusion of a fluoroalkylene group having 1 to 2 carbon atoms. Furthermore, the fluoropolyether chain of (G11) has excellent water and oil repellency and fingerprint stain removability due to the inclusion of a perfluoroalkylene group. Furthermore, the present composition has a structure represented by (G11), and (OCF ２ CF ２ ) and (OCF ２) and two or more kinds of fluorine-containing ether compounds with different ratios. ２ CF ２ ) and (OCF ２ Fluorine-containing ether compounds with different ratios of m31 / m32 are less likely to cause stacking due to the shift in the position of the ether bond. This maintains the flexibility of the fluoropolyether chain even in the surface layer, further improving lubricity. Among these, compounds with a ratio of m31 / m32 = M that is the largest (i.e., (OCF ２ Compound A having the largest ratio of M (i.e., (OCF ２ In combination with compound B, the ratio of M (=M) of compound A is the smallest. Ａ ) and M (=M) of the compound B Ｂ ) and the ratio (M Ａ / M Ｂ ) is 1.35 or more, the lubricity is further improved.

[0036] In formula (G11), (OCF ２ ) and (OCF ２ CF ２ ) can be bonded in any order. For example, in formula (G11), ２ ) and (OCF ２ CF ２ ) may be alternately arranged, and (OCF ２ ) and (OCF ２ CF ２ ) may be arranged in blocks or randomly. m31 is an integer of 2 or more, preferably an integer of 2 to 100, more preferably an integer of 3 to 80, and still more preferably an integer of 4 to 60. m32 is an integer of 2 or more, preferably an integer of 2 to 100, more preferably an integer of 3 to 80, and still more preferably an integer of 4 to 60. The value M of m31 / m32 is preferably 0.3 to 10.0, more preferably 0.4 to 8.0, and still more preferably 0.5 to 6.0. When two or more fluoropolyether chains are present in one molecule of compound (G11), in the calculation of the above M, m31 is calculated based on the ratio of (OCF ２ ) in the molecule, and m32 represents the total number of (OCF ２ CF ２ ) represents the total number of

[0037] (OCF in compound (G11) ２ ) and (OCF ２ CF ２ ) is １９ It is measured by F-NMR.

[0038] The fluoropolyether chain in the compound (G11) is (OCF ２ ) and (OCF ２ CF ２ ) in the above formula (f2) (hereinafter, also referred to as "other oxyfluoroalkylene units"). Specific examples of other oxyfluoroalkylene units include (OG ｆ１ ) ｍ１ (However, G ｆ１ Ga-CF ２ - Except when ｆ２ ) ｍ２ (However, G ｆ２ Ga-CF ２ CF ２ - Except when ｆ３ ) ｍ３ , (OG ｆ４ ) ｍ４ , (OG ｆ５ ) ｍ５ , (OG ｆ６ ) ｍ６ Examples include: ｆ１ ~G ｆ６ The definitions of m1 to m6 are as described above.

[0039] The compound (G11) may be any compound as long as it satisfies the above-mentioned constitution. In terms of ease of synthesis and ease of handling of the compound, among others, a compound represented by the following formula (1-1), (1-2) or (1-3) is preferred. [R ｆ１ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R １ ] ｊ -L １ - (R １１ -T １１ ) ｘ１ ...(1-1) (T３１ -R ３１ ) ｘ３ -L ３ -R ３ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R ２ -L ２ - (R ２１ -T ２１ ) ｘ２ ... (1-2) Q １ [-(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R ４ -L ４ - (R ４１ -T ４１ ) ｘ４ ] ｒ１ ... (1-3) However, R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms, and R ｆ１ If there are multiple R ｆ１ may be the same or different, and (OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ is as described above, and R １ is an alkylene group or a fluoroalkylene group, and R １ If there are multiple R １ may be the same or different (provided that R １ is a fluoroalkylene group, R １ Ha-CF ２ - and -CF ２ CF ２ ), L is a fluoroalkylene group other than -. １ represents a single bond or a j+x monovalent organic group which may contain N, O, S, or Si and which may have a branch point, and R １ and R １１Atoms bonded to R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １１ Is, L １ The atom bonded to T may be an ethereal oxygen atom, or an alkylene group which may have an ethereal oxygen atom between carbon atoms, １１ is -SiR ａ１１ ｚ１１ R ａ１２ ３－ｚ１１ and R ａ１１ is a hydroxyl group or a hydrolyzable group, and R ａ１１ If there are multiple R ａ１１ may be the same or different, R ａ１２ is a non-hydrolyzable group, and R ａ１２ If there are multiple R ａ１２ may be the same or different, j is an integer of 1 or more, z11 is an integer of 1 to 3, x1 is an integer of 1 or more, R ２ and R ３ are each independently an alkylene group or a fluoroalkylene group (provided that R ２ or R ３ is a fluoroalkylene group, ２ or R ３ Ha-CF ２ - and -CF ２ CF ２ ), L is a fluoroalkylene group other than -. ２ represents a single bond or a 1+x divalent organic group which may contain N, O, S, or Si and which may have a branch point, and R ２ and R ２１ Atoms bonded to R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), ２１ Is, L ２ an atom adjacent to L may be an ethereal oxygen atom, or an alkylene group which may have an ethereal oxygen atom between carbon atoms, ３ represents a single bond or a 1+x trivalent organic group which may contain N, O, S, or Si and which may have a branch point, and R ３and R ３１ Atoms bonded to R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), ３１ Is, L ３ The atom adjacent to T may be an ethereal oxygen atom, or an alkylene group may have an ethereal oxygen atom between carbon atoms, ２１ and T ３１ are each independently —SiR ａ２１ ｚ２１ R ａ２２ ３－ｚ２１ and R ａ２１ is a hydroxyl group or a hydrolyzable group, and R ａ２１ If there are multiple R ａ２１ may be the same or different, R ａ２２ is a non-hydrolyzable group, and R ａ２２ If there are multiple R ａ２２ may be the same or different, z21 is an integer of 1 to 3, x2 and x3 are each independently an integer of 1 or more, Q １ is a 1-valent group having a branch point, R ４ are each independently an alkylene group or a fluoroalkylene group (provided that R ４ is a fluoroalkylene group, R ４ Ha-CF ２ - and -CF ２ CF ２ ), L is a fluoroalkylene group other than -. ４ represents a single bond or a 1+x tetravalent organic group which may contain N, O, S, or Si and which may have a branch point, and R ４ and R ４１ Atoms bonded to R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), ４１ Is, L ４ The atom adjacent to T may be an ethereal oxygen atom, or an alkylene group may have an ethereal oxygen atom between carbon atoms, ４１ is -SiR ａ４１ ｚ４１ R ａ４２３－ｚ４１ and R ａ４１ is a hydroxyl group or a hydrolyzable group, and R ａ４１ If there are multiple R ａ４１ may be the same or different, R ａ４２ is a non-hydrolyzable group, and R ａ４２ If there are multiple R ａ４２ may be the same or different, z41 is an integer of 1 to 3, x4 is an integer of 1 or more, and r1 is 3 or 4. The structure of each compound will be explained below, but symbols having similar structures will be indicated as such and can be read interchangeably as appropriate.

[0040] Compound (1-1) Compound (1-1) has a structure represented by the following formula (1-1): [R ｆ１ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R １ ] ｊ -L １ - (R １１ -T １１ ) ｘ１ ...(1-1) where the symbols in formula (1-1) are as described above.

[0041] R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms. The fluoroalkyl group may be linear or may have a branched and / or cyclic structure. From the viewpoint of abrasion resistance, a linear fluoroalkyl group is preferred, and from the viewpoint of ease of synthesis, the fluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

[0042] (OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ is as described above.

[0043] R １ is an alkylene group or a fluoroalkylene group. １ is a fluoroalkylene group, R１ Ha-CF ２ - and -CF ２ CF ２ is a fluoroalkylene group other than -. １ The alkylene group and fluoroalkylene group in R may be linear or may have a branched and / or cyclic structure. From the viewpoint of ease of synthesis, a linear or branched alkylene group or fluoroalkylene group is preferred, and a linear or branched alkylene group or fluoroalkylene group having a methyl group or a fluoromethyl group is more preferred. １ The number of carbon atoms in R is preferably 1 to 6, and more preferably 1 to 3. １ Is, L １ When is a single bond, R １１ In this case, R １ R in １１ is bonded to at least one fluorine atom or fluoroalkyl group.

[0044] j is the [R ｆ１ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R １ ], and may be an integer of 1 or more, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.

[0045] R １１ Is, L １ The atom bonded to R may be an ethereal oxygen atom, or an alkylene group may have an ethereal oxygen atom between carbon atoms. １１ The alkylene group in R may be linear or may have a branched and / or cyclic structure. In view of the ease with which the present composition is densely arranged when forming a surface layer, an alkylene group having a methyl group as a linear or branched group is preferred, and a linear alkylene group is more preferred. １１ Specifically, it can be expressed by the following formula (g2): *-(O) ａ１ - (R ｇ２ O) ａ２ -R ｇ２-** ... (g2) where R ｇ２ is an alkylene group having one or more carbon atoms, and ｇ２ may be the same or different, a1 is 0 or 1, a2 is an integer of 0 or more, * is L １ is a bond bonded to T １１ is the bond that bonds to

[0046] When a1 is 0, the atom having the bond * is a carbon atom, and when a1 is 1, the atom having the bond * is an oxygen atom. In compound (1-1), a1 may be either 0 or 1, and may be appropriately selected from the viewpoint of synthesis, etc. a2 is R ｇ２ This is the number of repetitions of O, and is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1, from the viewpoint of durability as a surface layer.

[0047] R １１ is more preferably a group represented by the following formula (g3) in that the surface layer has better water and oil repellency and fingerprint stain removability, and is also excellent in durability such as abrasion resistance. ａ１ -R ｇ３ -** ... (g3) where R ｇ３ represents an alkylene group, and a1, *, and ** are the same as in formula (g2).

[0048] R ｇ３ The alkylene group in R may be linear or may have a branched and / or cyclic structure. A linear alkylene group is preferred in that the compound (1-1) is likely to be densely arranged when forming a surface layer. ｇ３ The number of carbon atoms of may be 1 or more, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 6.

[0049] T １１ Ha-SiR ａ１１ ｚ１１ R ａ１２ ３－ｚ１１ and R ａ１１ , R ａ１２ , z11 are R constituting the group (g1) ａ１ , R ａ２ , z1, and the preferred embodiments are also the same.

[0050] x1 is -R in one molecule １１ -T １１ It is sufficient if it is an integer of 1 or more, and it is preferably 1 to 32, more preferably 1 to 18, and even more preferably 2 to 12.

[0051] L １ is a single bond or a j+x monovalent group which may contain N, O, S, or Si and may have a branch point, and R １ and R １１ The atoms bonded to R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O). １ and R １１ The atoms bonded to may be the same atom or different atoms.

[0052] L １ When is a single bond, R in formula (1-1) １ and R １１ is directly bonded, and the compound (1-1) is represented by the following formula (1-1'): ｆ１ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R １ -R １１ -T １１ ...(1-1') However, the symbols in formula (1-1') are the same as those in formula (1-1).

[0053] L １ When L is a trivalent or higher valent group, １ is 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 (j+x1)-valent organopolysiloxane residue. １ ").

[0054] N is the branch point P １ If so, the branch point P １ For example, *-N(-**) ２ or (*-) ２ It is expressed as N-**, where * is R １ is a bond on the side, and ** is R １１C is the branch point P １ If so, the branch point P １ For example, *-C(-**) ３ , (*-) ２ C (-**) ２ , (*-) ３ C-**, *-CR ２９ (-**) ２ , or (*-) ２ CR ２９ -**, where * is R １ is a bond on the side, and ** is R １１ side bond, R ２９ is a monovalent group, and examples thereof include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group. １ If so, the branch point P １ For example, *-Si(-**) ３ , (*-) ２ Si(-**) ２ , (*-) ３ Si-**, *-SiR ２９ (-**) ２ , or (*-) ２ SiR ２９ -**, where * is R １ is a bond on the side, and ** is R １１ side bond, R ２９ is a monovalent group, examples of which include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.

[0055] Branch point P １ As the ring structure constituting the formula (1-1), from the viewpoints of ease of production of compound (1-1) and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer, 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, and a ring structure represented by the following formula is more preferred. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between the carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group (═O).

[0056]

[0057] Branch point P １ Examples of the organopolysiloxane residue constituting the formula include the following groups: ２５ is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. ２５ The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 carbon atom.

[0058]

[0059] Divalent or higher L １ is -C(O)N(R ２６ ) -, -N(R ２６ )C(O)-, -C(O)O-, -OC(O)-, -C(O)-, -O-, -N(R ２６ )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N(R ２６ ) -, -SO ２ N (R ２６ ) -, -N(R ２６ ) SO ２ -, -Si(R ２６ ) ２ -, -OSi(R ２６ ) ２ -, -Si(CH ３ ) ２ -Ph-Si(CH ３ ) ２ - and at least one bond selected from the group consisting of divalent organopolysiloxane residues (hereinafter referred to as "bond B １ ) may be present. However, R ２６ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. ２６ The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1).

[0060] Examples of the divalent organopolysiloxane residue include groups of the following formula: ２７ is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. ２７The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 carbon atom.

[0061]

[0062] Join B １ As the group, —C(O)NR is preferred in terms of ease of production of compound (1-1). ２６ -, -N(R ２６ )C(O)—, —C(O)—, and —NR ２６ In view of the superior light resistance and chemical resistance of the surface layer, at least one bond selected from the group consisting of —C(O)NR ２６ -, -N(R ２６ )C(O)- or -C(O)- is more preferred.

[0063] Divalent L １ As for R １ and R １１ are each independently N, O, S, Si, or a carbon atom having an oxo group (=O). １ and R １１ The atoms adjacent to each bond B １ It is a constituent element of the divalent L １ Specific examples of B include a single bond, one or more bonds B １ (For example, *-B １ -**, *-B １ -R ２８ -B １ -**), etc. However, R ２８ is a single bond or a divalent organic group, * is R １ is a bond on the side, and ** is R １１ It is the connecting hand on the side.

[0064] Trivalent or higher L １ is R １ and R １１ are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O). １ and R １１ The atoms adjacent to each bond B １ Or branch point P １ It is a constituent element of trivalent or higher L １As a specific example of １ (for example{(*-) ｊ P １ (-**) ｘ１}, {(*-) ｊ P １ -R ２８ -P １ (-**) ｘ１}, etc.), one or more branch points P １ and one or more bonds B １ and combinations (for example, *-B １ -R ２８ -P １ (-**) ｘ１}, {*-B １ -R ２８ -P １ (-R ２８ -B １ -**) ｘ１}, etc.) where R ２８ is a single bond or a divalent organic group, * is R １ is a bond on the side, and ** is R １１ It is the connecting hand on the side.

[0065] The above R ２８ Examples of the divalent organic group in the formula (I) include hydrocarbon groups such as divalent aliphatic hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups), and divalent aromatic hydrocarbon groups (e.g., phenylene groups), and the hydrocarbon groups may have a bond B between carbon atoms. １ The divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0066] The above L １ As the group, a group represented by any one of the following formulae (L1) to (L7) is preferred in terms of ease of production of the compound (1-1).

[0067]

[0068] (-A １ -) ｄ５ C (R ｅ２ ) ４－ｄ５―ｄ６ (-Q ２２ -) ｄ６ ...(L2) (-A ２ -) ｄ７ N(-Q２３ -) ３－ｄ７ ...(L3) (-A ３ -) ｄ８ Z １ (-Q ２４ -) ｄ９ ...(L4) (-A ２ -) ｄ１０ Si(R ｅ３ ) ４－ｄ１０－ｄ１１ (-Q ２５ -) ｄ１１ ... (L5) -A １ -Q ２６ -...(L6) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -) ｄ１２ ... (L7)

[0069] However, in the formulas (L1) to (L7), A １ , A ２ or A ３ side is R of formula (1-1) １ Connect with Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ Side is R １１ where A １ is a single bond, -B ３ -, -B ３ -R ３０ -, -B ３ -R ３０ -B ２ -, -R ３３ - or -R ３３ -B ２ - and R ３０ represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. ｅ６ -, -C(O)-, -NR ｅ６ - or -O-, and B ２ is -C(O)NR ｅ６ -, -C(O)-, -NR ｅ６ - or -O-, and B ３ -C(O)NR ｅ６ -, -C(O)-, or -NRｅ６ - and R ３３ is R １ An oxyalkylene group having an O atom at the side terminal, and a —C(O)NR ｅ６ -, -C(O)-, -NR ｅ６ - or -O-, A ２ represents a single bond, -C(O)-, -B ３ -R ３０ - or -R ３３ - and A ３ A ３ Z to which １ If the atom in is a carbon atom, A １ and A ３ Z to which １ If the atom in is a nitrogen atom, A ２ and 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. ｅ６ -, -C(O)-, -NR ｅ６ - or -O-, ２２ is a single bond, -B ３ -, -R ３０ -B ３ -or-B ２ -R ３０ -B ３ - and Q ２３ is a single bond or -R ３０ -B ３ - and Q ２４ Is, Q ２４ Z to which １ If the atom in is a carbon atom, Q ２２ and Q ２４ Z to which １ When the atom in is a nitrogen atom, Q ２３ and Q ２５ is a single bond or -R ３０ -B ３ - and Q ２６ is a single bond or -R ３０ -B ３ - and Z １ A ３ has a carbon atom or nitrogen atom to which Q is directly bonded,２４ is a group having a (d8+d9)-valent ring structure having a carbon atom or a nitrogen atom to which R is directly bonded, ｅ１ is a hydrogen atom or an alkyl group, R ｅ２ is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, and R ｅ３ is a hydroxyl group or an alkyl group, R ｅ６ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1+d2 is an integer of 1 to 3, d3 is an integer of 0 to 3, d4 is an integer of 0 to 3, and d3+d4 is an integer of 1 to 3, d1+d3 is an integer of 1 to 5, d2+d4 is an integer of 1 to 5, d5 is an integer of 1 to 3, d6 is an integer of 1 to 3, and d5+d6 is an integer of 2 to 4, d7 is 1 or 2, d8 is an integer of 1 or more, d9 is an integer of 1 or more, d10 is an integer of 1 to 3, d11 is an integer of 1 to 3, and d10+d11 is an integer of 2 to 4, and d12 is an integer of 1 to 3. １ If there are multiple A １ may be the same or different. ２ , A ３ , Q ２２ , Q ２３ , Q ２４ , Q ２５ , R ｅ１ , R ｅ２ , R ｅ３ Also, d1+d3, d5, d7, d8, and d10 are j, and d2+d4, d6, 3-d7, d9, d11, and 1+d12 are x1.

[0070] R ３０ The number of carbon atoms in the alkylene group and R ３３ The number of carbon atoms in the oxyalkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of the compound (1-1) and further superior 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. １Examples of the ring structure in the formula (I) include the ring structures described above, and the preferred forms are also the same.

[0071] R ｅ１ , R ｅ２ or R ｅ３ The number of carbon atoms in the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1). ｅ２ From the viewpoint of ease of production of compound (1-1), the number of carbon atoms in the alkyl group portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. d9 is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 or 3, from the viewpoint of ease of production of compound (1-1) and further improved abrasion resistance and fingerprint removability of the surface layer.

[0072] The above L １ Other examples of the group include groups represented by any of the following formulae (L11) to (L17).

[0073]

[0074] (-A １ -) ｄ５ C (R ｅ２ ) ４－ｄ５―ｄ６ (-Q ２２ -G) ｄ６ ...(L12) (-A ２ -) ｄ７ N(-Q ２３ -G) ３－ｄ７ ...(L13) (-A ３ -) ｄ８ Z １ (-Q ２４ -G) ｄ９ ...(L14) (-A ２ -) ｄ１０ Si(R ｅ３ ) ４－ｄ１０－ｄ１１ (-Q ２５ -G) ｄ１１ ...(L15) -A １ -Q ２６ -G...(L16) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -G)ｄ１２ ... (L17)

[0075] However, in the formulas (L11) to (L17), A １ , A ２ or A ３ side is R of formula (1-1) １ Connect with Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ Side is R １１ G is the following group (G21), and L １ The two or more Gs in the formula (L1) may be the same or different. The symbols other than G are the same as those in the formula (L1) to the formula (L7). ２１ ) ３－ｋ (-Q ３ -) ｋ ... (G21) However, in formula (G21), the Si side is Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ Connect to Q ３ Side is R １１ Connect to R ２１ is an alkyl group. ３ is a single bond or -R ３１ -B ３ - and R ３１ represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. ３２ -, -C(O)-, -NR ３２ - or -O- containing group, or -(OSi(R ２２ ) ２ ) ｐ１１ -O-, and two or more Q ３ may be the same or different. k is 2 or 3. R ３２ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. ２２ is an alkyl group, a phenyl group, or an alkoxy group, and two R ２２ may be the same or different. p11 is an integer of 0 to 5, and when p11 is 2 or more, there are 2 or more (OSi(R ２２ )２ ) may be the same or different.

[0076] Q ３ The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of the compound (1-1) and further superior abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when there is a specific bond between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. ２１ The number of carbon atoms in the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1). ２２ The number of carbon atoms in the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1). ２２ In view of excellent storage stability of the compound (1-1), the number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. p11 is preferably 0 or 1.

[0077] Examples of the compound (1-1) include the following: ｆ is [R ｆ１ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R １ ].

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] Compound (1-2) Compound (1-2) has a structure represented by the following formula (1-2): (T ３１ -R ３１ ) ｘ３ -L ３ -R ３ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R ２ -L ２ - (R ２１ -T ２１ ) ｘ２ ...(1-2) where the symbols in formula (1-2) are as described above.

[0092] (OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ is as described above.

[0093] R ２ and R ３ are each independently the above R １ The same applies to the preferred embodiments.

[0094] R ２１ and R ３１ is the above R １１ The same applies to the preferred embodiments, except that "L １ "Binds to" is R ２１ In the case of "L ２ "Combines with" and R ３１ In the case of "L ３ "Binds to" shall be read as "T １１ "Binds to" is R ２１ In the case of "T ２１"Combines with" and R ３１ In the case of "T ３１ This should be read as "bonded to." ２ When is a single bond, R ２１ is R ２ It is directly bonded to L ３ When is a single bond, R ３１ is R ３ directly binds to

[0095] T ２１ and T ３１ are each independently -SiR ａ２１ ｚ２１ R ａ２２ ３－ｚ２１ and R ａ２１ , R ａ２２ , z21 are R constituting the group (g1) ａ１ , R ａ２ , z1, and the preferred embodiments are also the same.

[0096] x2 and x3 each independently represent the same as x1, and the preferred embodiments are also the same.

[0097] L ２ and L ３ are each independently the above L １ The same as when j is 1. For example, L ２ and L ３ When T is a single bond, the compound (1-2) is represented by the following formula (1-2'): ３１ -R ３１ -R ３ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R ２ -L ２ -R ２１ -T ２１ ...(1-2') However, the symbols in formula (1-2') are the same as those in formula (1-2).

[0098] L ２ or L ３ When L is a trivalent or higher valent group, ２ or L ３is at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and a (1+x2)- or (1+x3)-valent organopolysiloxane residue. ２ ").

[0099] N is the branch point P ２ If so, the branch point P ２ For example, *-N(-**) ２ where * is R ２ or R ３ is a bond on the side, and ** is R ２１ or R ３１ C is the branch point P ２ If so, the branch point P ２ For example, *-C(-**) ３ , or *-CR ２９ (-**) ２ where * is R ２ or R ３ is a bond on the side, and ** is R ２１ or R ３１ side bond, R ２９ is a monovalent group, and examples thereof include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group. ２ If so, the branch point P ２ For example, *-Si(-**) ３ , or *-SiR ２９ (-**) ２ where * is R ２ or R ３ is a bond on the side, and ** is R ２１ or R ３１ side bond, R ２９ is a monovalent group, examples of which include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.

[0100] Branch point P ２ The ring structure and organopolysiloxane residue constituting the above-mentioned branch point P １ The preferred embodiments are also the same as those of the above. ２ or L ３ Each independently represents the bond B １ Bond B １The embodiments are as described above, and the preferred embodiments are also the same.

[0101] Divalent L ２ or L ３ is R ２ and R ２１ , or R ３ and R ３１ are each independently N, O, S, Si, or a carbon atom having an oxo group (=O). ２ and R ２１ , or R ３ and R ３１ The atoms adjacent to each bond B １ It is a constituent element of the divalent L ２ or L ３ Specific examples of B include a single bond, one or more bonds B １ (For example, *-B １ -**, *-B １ -R ２８ -B １ -**), etc. However, R ２８ is a single bond or a divalent organic group, * is R ２ or R ３ is a bond on the side, and ** is R ２１ or R ３１ It is the connecting hand on the side.

[0102] Trivalent or higher L ２ or L ３ is R ２ and R ２１ , or R ３ and R ３１ are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O). ２ and R ２１ , or R ３ and R ３１ The atoms adjacent to each bond B １ Or branch point P ２ It is a constituent element of trivalent or higher L ２ or L ３ As a specific example of ２ (For example, {*-P ２ (-**) ｘ}, {*-P１ -R ２８ -P １ -** ｘ１}, etc.), one or more branch points P ２ and one or more bonds B １ and combinations (for example, *-B １ -R ２８ -P １ (-**) ｘ}, {*-B １ -R ２８ -P １ (-R ２８ -B １ -**) ｘ}, etc.) where x is L ２ In the case of x2, L ３ In the case of R, it is x3. ２８ is a single bond or a divalent organic group, * is R ２ or R ３ is a bond on the side, and ** is R ２１ or R ３１ The R ２８ The embodiments are as described above, and the preferred embodiments are also the same.

[0103] The above L ２ or L ３ As the groups, it is preferable that each of them is independently a group represented by any one of the following formulae (L21) to (L27), in view of ease of production of the compound (1-2).

[0104]

[0105] -A １ -C(R ｅ２ ) ４－ｄ６ (-Q ２２ -) ｄ６ ...(L22) -A ２ -N(-Q ２３ -) ２ ...(L23) -A ３ -Z １ (-Q ２４ -) ｄ９ ...(L24) -A ２ -Si(R ｅ３ ) ４－ｄ１１ (-Q ２５ -) ｄ１１ ...(L25) -A１ -Q ２６ -...(L26) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -) ｄ１２ ... (L27)

[0106] However, in formulas (L21) to (L27), A １ , A ２ or A ３ The side is formula R ２ or R ３ Connect with Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ Side is R ２１ or R ３１ where A １ , A ２ , A ３ , Q １１ , Q ２２ , Q ２３ , Q ２４ , Q ２５ , Q ２６ , R ｅ１ , R ｅ２ , R ｅ３ , R ｅ６ is the above L １ The same applies to the preferred embodiments as those described in the above. １ A ３ has a carbon atom or nitrogen atom to which Q is directly bonded, ２４ is a group having a (1+d9)-valent ring structure having a carbon atom or a nitrogen atom to which is directly bonded, d2 is an integer of 0 to 3, d4 is an integer of 0 to 3, and d2+d4 is an integer of 1 to 5, d6 is an integer of 1 to 3, d9 is an integer of 1 or more, d11 is an integer of 1 to 3, and d12 is an integer of 1 to 3. Note that d2+d4, d6, d9, d11, and 1+d12 are x2 or x3. d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoints of ease of production of compound (1-2) and further excellent abrasion resistance and fingerprint removability of the surface layer.

[0107] The above L ２ or L ３ Other examples of the group include groups represented by any of the following formulae (L31) to (L37).

[0108]

[0109] -A １ -C(R ｅ２ ) ４－ｄ６ (-Q ２２ -G) ｄ６ ...(L32) -A ２ -N(-Q ２３ -G) ２ ...(L33) -A ３ -Z １ (-Q ２４ -G) ｄ９ ...(L34) -A ２ -Si(R ｅ３ ) ４－ｄ１１ (-Q ２５ -G) ｄ１１ ...(L35) -A １ -Q ２６ -G...(L36) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -G) ｄ１２ ... (L37)

[0110] However, in formulas (L31) to (L37), A １ , A ２ or A ３ The side is the R of the formula ２ or R ３ Connect with Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ Side is R ２１ or R ３１ G is the above group (G21), and preferred embodiments are also the same. The symbols other than G are the same as the symbols in formulae (L21) to (L27), and preferred embodiments are also the same.

[0111] Examples of the compound (1-2) include the following: ｆHa-R ３ -(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R ２ - is.

[0112]

[0113]

[0114]

[0115] Compound (1-3) Compound (1-3) has a structure represented by the following formula (1-3): １ [-(OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R ４ -L ４ - (R ４１ -T ４１ ) ｘ４ ] ｒ１ ...(1-3) where the symbols in formula (1-3) are as described above.

[0116] (OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ is as described above.

[0117] R ４ is the above R １ The same applies to the preferred embodiments.

[0118] R ４１ is the above R １１ The same applies to the preferred embodiments, except that "L １ "Binds to" means "L ４ "Binds to" shall be read as "T １１ "Binds to" means "T ４１ This should be read as "bonded to." ４ When is a single bond, R ４１ is R ４ directly binds to

[0119] T ４１ is -SiR ａ４１ ｚ４１ R ａ４２ ３－ｚ４１ and R ａ４１ , R ａ４２ , z41 are R constituting the group (g1) ａ１ , R ａ２ , z1, and the preferred embodiments are also the same.

[0120] x4 is the same as x1, and the preferred embodiments are also the same. ４ Is, L ２ or L ３ The same applies to the preferred embodiments.

[0121] Q １ is an r1-valent group having a branch point, and r1 is 3 or 4.

[0122] Q １ The branch point P that constitutes ３ Examples of the branch point P include N, C, Si, and a ring structure. ３ may be one or may have two or more.

[0123] N is the branch point P ３ If so, the branch point P １ For example, N(-*) ３ , N.R. ２９ (-*) ２ C is the branch point P ３ If so, the branch point P ３ For example, C(-*) ４ , C.R. ２９ (-*) ３ , C(R ２９ ) ２ (-*) ２ Si is the branch point P ３ If so, the branch point P ３ For example, Si(-*) ４ , SiR ２９ (-*) ３ , Si(R ２９ ) ２ (-*) ２ However, * indicates (OCF ２ ) ｍ３１・(OCF ２ CF ２ ) ｍ３２ side bond, R ２９ is a monovalent group. ２９ Examples of the alkyl group include a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, and R ４１ -T ４１ and the like, for example, a fluoropolyether chain having no such group.

[0124] Branch point P ３ The ring structure constituting the １ The substituents of the ring structure may be the same as those described above, and may further include a fluorine atom, a fluoroalkyl group, R ４１ -T ４１ It may have a fluoropolyether chain that does not have the formula:

[0125] The above Q １ As the group, a group represented by any one of the following formulae (Q1) to (Q8) is preferred in terms of ease of production of compound (1-3).

[0126]

[0127] C (-A １１ -) ｄ２３ (R ｅ１２ ) ４－ｄ２３ ...(Q2) N(-A １２ -) ３ ... (Q3) Z １ (-A １３ -) ｄ２４ ...(Q4) Si(-A １２ -) ｄ２５ (R ｅ１３ ) ４－ｄ２５ ...(Q5) CH(-A １１ -) ２ -Si(R ｅ１３ ) ３－ｄ２６ (-A １１ -) ｄ２６ ...(Q6)

[0128]

[0129]

[0130] However, in formulas (Q1) to (Q8), A １１ , A １２ or A １３ (OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ where A １１ is a single bond, -R ４０ -, -B １３ -R ４０ - and R ４０ represents an alkylene group, a fluoroalkylene group, or an alkylene group or fluoroalkylene group having two or more carbon atoms, with —C(O)NR between carbon atoms. ｅ１７ -, -C(O)-, -NR ｅ１７ - or -O-, and B １３ is -C(O)NR ｅ６ -, -C(O)-, -NR ｅ６ - or -O-, A １２ is a single bond or -R ４０ - and A １３ A １３ Z to which １ If the atom in is a carbon atom, A １１ and A １３ Z to which １ If the atom in is a nitrogen atom, A １２ and Z １ A １３ is a group having a 1-valent ring structure having a carbon atom or a nitrogen atom to which Q is directly bonded, ５２ represents a single bond, —O—, an alkylene group, a fluoroalkylene group, or an alkylene group or fluoroalkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. ｅ１７ -, -C(O)-, -NR ｅ１７ - or -O-, R ｅ１１ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, R ４１ -T ４１ or a fluoropolyether chain having no -Q in the range of r1 being 3 to 4. ５２ -C(R ｅ１１ ) ３－ｄ２１ (-A１１ -) ｄ２１ is a group having a repeating structure of R ｅ１２ is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, or R ４１ -T ４１ is a fluoropolyether chain having no R ｅ１３ is an alkyl group or a fluoroalkyl group, R ｅ１４ , R ｅ１５ , and R ｅ１６ are each independently a hydrogen atom, a fluorine atom, an alkyl group, or a fluoroalkyl group; R ｅ１７ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, or a phenyl group which may be substituted with fluorine, d21 is an integer of 0 to 3, d22 is an integer of 0 to 3, and d21 + d22 is an integer of 3 to 4, d23 is 3 or 4, d24 is 3 or 4, d25 is 3 or 4, d26 is 1 or 2, d27 is an integer of 1 to 3, d28 is 1 or 2, d29 is an integer of 1 to 3, d30 is an integer of 1 to 3, d31 is 1 or 2, d32 is 1 or 2, and d33 is an integer of 1 to 3. １１ If there are multiple A １１ may be the same or different. １２ , A １３ , R ｅ１１ , R ｅ１２ , R ｅ１３ The same is true for .

[0131] R ４０ The number of carbon atoms in the alkylene group or fluoroalkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of the compound (1-3) and further superior 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. １ Examples of the ring structure in the formula (I) include the ring structures described above, and the preferred forms are also the same.

[0132] R ｅ１１ , Rｅ１２ , R ｅ１３ , R ｅ１４ , R ｅ１５ and R ｅ１６ In view of ease of production of the compound (1-3), the number of carbon atoms in the alkyl group or fluoroalkylene group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0133] Examples of the compound (1-3) include the following: ｆ３ (OCF ２ ) ｍ３１ ・(OCF ２ CF ２ ) ｍ３２ -O-R ４ is.

[0134]

[0135]

[0136]

[0137]

[0138] The total content of the compound (G11) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, based on the total mass of the composition, from the viewpoint of more excellent lubricity of the surface layer. The content of the compound (G11) is preferably 99.9 mass% or less, more preferably 99.5 mass% or less, based on the total mass of the composition.

[0139] (Compound A and Compound B) This composition contains two or more compounds selected from the above-mentioned compound (G11). From among these, compound A having the largest m31 / m32 = M and compound B having the smallest M are determined. Specifically, first, each compound is separated by liquid chromatography to separate each compound in this composition. Next, for each separated compound, (OCF ２ ) and (OCF ２ CF ２ ) １９The ratio M in each compound is determined by F-NMR. Based on the value of the ratio M for each compound thus determined, the compound having the largest ratio M is designated as compound A, and the compound having the smallest ratio M is designated as compound B. When the raw materials for the composition are available, the ratio M may be determined from the raw materials.

[0140] M of the compound A (=M Ａ ) and M (=M) of the compound B Ｂ ) and the ratio (M Ａ / M Ｂ By combining a compound having a M of 1.35 or more, a surface layer having excellent lubricity can be formed. Ａ / M Ｂ From the viewpoint of lubricity, M is preferably 1.50 or more, more preferably 2.00 or more, and even more preferably 4.00 or more. Ａ / M Ｂ The upper limit is not particularly limited, but is usually 30 or less, preferably 20 or less, and more preferably 10 or less.

[0141] M Ａ The value of is not particularly limited, but from the viewpoint of lubricity, it is preferably 1.00 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. Furthermore, from the viewpoint of superior abrasion resistance of the surface layer, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Ｂ Although the value of M is not particularly limited, it is preferably less than 1.00, more preferably 0.98 or less, and even more preferably 0.95 or less, from the viewpoint of lubricity. Ａ is 1.00 or more, and M Ｂ is preferably less than 1.00. In this case, the fluoropolyether chain of compound A is (OCF ２ ) ratio is high, and the fluoropolyether chain of compound B is (OCF ２ CF ２ ) ratio is high, which makes it easier for the position of the ether bond to shift, making stacking less likely to occur and further improving lubricity. Ａ and M Ｂ The absolute value of the difference between is preferably 1 to 8, more preferably 1.5 to 7, and even more preferably 2 to 6, in that the lubricity of the surface layer is better.

[0142] The content of compound A and compound B in the composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, based on the total mass of the composition. When compound A and compound B are contained in an amount of 0.1 mass% or more, respectively, lubricity is further improved. The upper limit of the content of compound A and compound B is not particularly limited, but is preferably 99.9 mass% or less, more preferably 99.5 mass% or less, based on the total mass of the composition. However, the total content of compound A and compound B is 100 mass% or less, based on the total amount of the composition.

[0143] Furthermore, regarding the ratio of compound A to compound B, from the viewpoint of lubricity, the mass ratio (A / B) of the content of compound A to the content of compound B is preferably 0.01 to 100, more preferably 5 to 80, and even more preferably 10 to 70. When the mass ratio is equal to or greater than the lower limit, the abrasion resistance is superior, and when the mass ratio is equal to or less than the upper limit, the lubricity is superior.

[0144] The compounds A and B are not particularly limited in structure except for the structure (G11) in that they have a fluoropolyether chain and a reactive silyl group. １ N, C or Si has a branch point P １ Among them, compound A and compound B are preferably compounds each independently having the structure of formula (1-1), and among them, L １ is more preferably the formula (L2), the formula (L3) or the formula (L5), and furthermore, A １ and A ２ is a single bond, -B ３ -R ３０ - or -R ３３ - is preferred. The same applies to compounds (1-2) and (1-3). Examples of a combination of compounds in which compound A and compound B are both represented by formula (1-1) include a combination of compounds having different structures such as structures 1 to 4 below, and a combination of compounds having the same structure but different fluoropolyether chains. Structure 1: Formula (1-1) where L １ is formula (L2), d6 is 3, and A １Ga-B ３ -R ３０ - and B ３ -C(O)NR ｅ６ - and R ３０ is an alkylene group; Structure 2: Compounds represented by formula (1-1) where L １ is formula (L3), and A ２ is —C(O)—; Structure 3: Compounds represented by formula (1-1) in which L １ is formula (L5), d11 is 2, and R ｅ３ is a hydroxyl group, and A ２ is a single bond or -R ３３ -, Structure 4: A compound represented by formula (1-1) in which L １ is formula (L5), d11 is 3, and A ２ is a single bond or -R ３３ A compound in which:

[0145] Examples of Structure 1 include the following compounds. Examples of Structure 2 include the following compounds: Examples of Structure 3 include the following structures: Examples of Structure 4 include the following structure: Examples of combinations of Structure 1 and Structure 2 include combinations of Structure 1 and Structure 3, combinations of Structure 1 and Structure 4, combinations of Structure 2 and Structure 3, combinations of Structure 2 and Structure 4, and combinations of Structure 3 and Structure 4.

[0146] Compound A and compound B preferably have similar chemical structures except for the different number of repeating units in the fluoropolyether chain, from the viewpoint of providing a surface layer with superior abrasion resistance and / or water and oil repellency. Specifically, a first embodiment in which compound A and compound B are both a combination of compounds represented by formula (1-1), a second embodiment in which both are a combination of compounds represented by formula (1-2), and a third embodiment in which both are a combination of compounds represented by formula (1-3) are preferred. Among these, the first embodiment is preferred from the viewpoint of providing a surface layer with superior abrasion resistance and / or water and oil repellency, and further, a combination of compound A and compound B with L １ A combination of compounds in which the formulas are the same is more preferred.

[0147] <Other Components> The present composition may contain at least one of a fluorine-containing compound other than the above-mentioned fluorine-containing ether compound and the following impurities. Examples of impurities include compounds that are unavoidable in the production of the above-mentioned fluorine-containing ether compound and other fluorine-containing compounds. The present composition does not contain a liquid medium described below.

[0148] Examples of the other fluorine-containing compound include a fluorine-containing compound produced as a by-product in the production process of the above-mentioned fluorine-containing ether compound (hereinafter also referred to as a "by-product fluorine-containing compound"), a known fluorine-containing compound used for the same purpose as the above-mentioned fluorine-containing ether compound, etc. As the other fluorine-containing compound, a compound that is unlikely to deteriorate the properties of the above-mentioned fluorine-containing ether compound is preferred.

[0149] Examples of by-product fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of the above-mentioned fluorine-containing ether compounds. When the present composition contains by-product fluorine-containing compounds, the purification step for removing the by-product fluorine-containing compounds or reducing the amount of the by-product fluorine-containing compounds can be simplified.

[0150] Examples of known fluorine-containing compounds include compounds described in the following documents: perfluoropolyether-modified aminosilanes described in JP 11-029585 A, silicon-containing organic fluorine-containing polymers described in JP 2874715 A, organosilicon compounds described in JP 2000-144097 A, perfluoropolyether-modified aminosilanes described in JP 2000-327772 A, fluorinated siloxanes described in JP 2002-506887 A, organosilicon compounds described in JP 2008-534696 A, fluorinated modified hydrogen-containing polymers described in JP 4138936 A, compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064, and JP 2014-070163 A, Organosilicon compounds 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; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP 2014-080473 A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437, WO 2018 / 079743, and WO 2018 / 143433; 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 ether compounds described in WO 2018 / 216630, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 039186, WO 2019 / 044479, JP 2019-44158 A, WO 2019 / 044479, and WO 2019 / 163282. Commercially available fluorine-containing compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., the SURECO AF series such as SURECO (registered trademark) 2101S manufactured by AGC Inc., and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0151] When the present composition contains the other fluorine-containing compound described above, the content of the other fluorine-containing compound is preferably less than 50 mass%, more preferably less than 30 mass%, and even more preferably less than 10 mass%, relative to the total mass of the present composition, in order to fully exhibit the properties of the fluorine-containing ether compound.

[0152] <Method for Producing the Composition> The method for producing the composition of the present invention (hereinafter also referred to as the present production method) is a method for producing a composition containing two or more fluorinated ether compounds having a fluoropolyether chain and a reactive silyl group, wherein a first compound among the fluorinated ether compounds has a fluoropolyether chain having a structure represented by the following formula (G1), and a second compound among the fluorinated ether compounds has a fluoropolyether chain having a structure represented by the following formula (G2), m11 in the following formula (G1) is different from m21 in the following formula (G2), and / or m12 in the following formula (G1) is different from m22 in the following formula (G2), and the first compound and the second compound are mixed together. (OCF ２ ) ｍ１１ ・(OCF ２ CF ２ ) ｍ１２ ...(G1) (OCF ２ ) ｍ２１ ・(OCF ２ CF ２ )ｍ２２ In formula (G1), m11 is (OCF ２ m12 means the average number of (OCF ２ CF ２ In formula (G2), m21 represents the average number of (OCF ２ m22 means the average number of (OCF ２ CF ２ ) and is a positive number of 2 or more.

[0153] According to the present production method, the present composition can be conveniently produced by mixing the first compound, the second compound, and other fluorine-containing compounds as needed.

[0154] (First Compound) The first compound is one of the fluorine-containing ether compounds used as raw materials for the composition, and has the reactive silyl group and a fluoropolyether chain having the following structure (G1): (OCF ２ ) ｍ１１ ・(OCF ２ CF ２ ) ｍ１２ ...(G1) where m11 is the (OCF ２ m12 means the average number of (OCF ２ CF ２ ) and is a positive number of 2 or more. The first compound is a raw material compound of the present composition, and may be a single compound or a composition containing two or more kinds of fluorinated ether compounds.

[0155] In formula (G1), (OCF ２ ) and (OCF ２ CF ２ ) may be bonded in any order. For example, in formula (G1), ２ ) and (OCF ２ CF ２ ) may be alternately arranged, and (OCF ２) and (OCF ２ CF ２ ) may be arranged in blocks or randomly. m11 is a positive number of 2 or more, preferably a positive number from 2 to 100, more preferably a positive number from 3 to 80, and still more preferably a positive number from 4 to 60. m12 is a positive number of 2 or more, preferably a positive number from 2 to 100, more preferably a positive number from 3 to 80, and still more preferably a positive number from 4 to 60. The value of m11 / m12 is preferably 1.0 to 10.0, more preferably 1.5 to 8.0, and still more preferably 2.0 to 6.0.

[0156] (OCF ２ ) and the average number of (OCF ２ CF ２ ) is the average number of １９ It is measured by F-NMR.

[0157] The fluoropolyether chain in the first compound is (OCF ２ ) and (OCF ２ CF ２ ) in the above formula (f2) (hereinafter, also referred to as "other oxyfluoroalkylene units"). Specific examples of other oxyfluoroalkylene units include (OG ｆ１ ) ｍ１ (However, G ｆ１ Ga-CF ２ - Except when ｆ２ ) ｍ２ (However, G ｆ２ Ga-CF ２ CF ２ - Except when ｆ３ ) ｍ３ , (OG ｆ４ ) ｍ４ , (OG ｆ５ ) ｍ５ , (OG ｆ６ ) ｍ６ Examples include: ｆ１ ~G ｆ６ The definitions of m1 to m6 are as described above.

[0158] The first compound may be any compound as long as it satisfies the above-mentioned constitution. In terms of ease of synthesis and ease of handling of the compound, among others, it is preferable to use a compound represented by the following formula (1-1), (1-2) or (1-3): [R ｆ１ -(OCF ２ ) ｍ１１ ・(OCF ２ CF ２ ) ｍ１２ -O-R １ ] ｊ -L １ - (R １１ -T １１ ) ｘ１ ...(1-1) (T ３１ -R ３１ ) ｘ３ -L ３ -R ３ -(OCF ２ ) ｍ１１ ・(OCF ２ CF ２ ) ｍ１２ -O-R ２ -L ２ - (R ２１ -T ２１ ) ｘ２ ... (1-2) Q １ [-(OCF ２ ) ｍ１１ ・(OCF ２ CF ２ ) ｍ１２ -O-R ４ -L ４ - (R ４１ -T ４１ ) ｘ４ ] ｒ１ ... (1-3) However, (OCF ２ ) ｍ１１ and (OCF ２ CF ２ ) ｍ１２ is the same as in the formula (G1), and the other symbols are the same as in the formula (G11).

[0159] The content of the first compound is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, based on the total mass of the composition, from the viewpoint of more excellent lubricity of the surface layer. The content of the first compound is preferably 99.9 mass% or less, more preferably 99.5 mass% or less, based on the total mass of the composition.

[0160] (Second Compound) The second compound is one of the above-mentioned fluorine-containing ether compounds, and has the above-mentioned reactive silyl group and a fluoropolyether chain having the following structure (G2): (OCF ２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ ...(G2) where m21 is the (OCF ２ m22 means the average number of (OCF ２ CF ２ ) and is a positive number of 2 or more. The second compound is a raw material compound of the present composition, and may be a single compound or a composition containing two or more kinds of fluorine-containing ether compounds.

[0161] In this production method, m11 in formula (G1) and m21 in formula (G2) are different, and / or m12 in formula (G1) and m22 in formula (G2) are different. When m11 and m21 are different, m12 and m22 may be the same or different, and when m12 and m22 are different, m11 and m21 may be the same or different.

[0162] In formula (G2), (OCF ２ ) and (OCF ２ CF ２ ) can be bonded in any order. For example, in formula (G2), ２ ) and (OCF ２ CF ２ ) may be alternately arranged, and (OCF ２ ) and (OCF ２ CF ２) may be arranged in blocks or randomly. m21 is a positive number of 2 or more, preferably a positive number from 2 to 100, more preferably a positive number from 3 to 80, and still more preferably a positive number from 4 to 60. m22 is a positive number of 2 or more, preferably a positive number from 2 to 100, more preferably a positive number from 3 to 80, and still more preferably a positive number from 4 to 60. The value of m21 / m22 is preferably 1.0 to 10.0, more preferably 1.5 to 8.0, and still more preferably 2.0 to 6.0.

[0163] In the second compound (OCF ２ ) and the average number of (OCF ２ CF ２ The average number of hydroxyl groups is measured in the same manner as for the primary compound.

[0164] The fluoropolyether chain in the second compound may contain other oxyfluoroalkylene units as described above.

[0165] In order to obtain a more excellent lubricity of the surface layer, it is preferable that the first compound and the second compound have at least different values ​​of m11 / m12 in formula (G1) and m21 / m22 in formula (G2). The absolute value of the difference between m11 / m12 and m21 / m22 is preferably 1 to 8, more preferably 1.5 to 7, and even more preferably 2 to 6, in order to obtain a more excellent lubricity of the surface layer.

[0166] The second compound may be any compound as long as it satisfies the above-mentioned constitution. In terms of ease of synthesis and ease of handling of the compound, it is preferable that the second compound is a compound represented by the following formula (2-1), (2-2), or (2-3): [R ｆ２ -(OCF ２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ -O-R ５ ] ｊ１ -L ５ - (R １２ -T １２ ) ｘ１１ ...(2-1) (T ３２ -R ３２ ) ｘ１３ -L ７ -R７ -(OCF ２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ -O-R ６ -L ６ - (R ２２ -T ２２ ) ｘ１２ ... (2-2) Q ２ [-(OCF ２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ -O-R ８ -L ８ - (R ４２ -T ４２ ) ｘ１４ ] ｒ２ ... (2-3) However, (OCF ２ ) ｍ２１ and (OCF ２ CF ２ ) ｍ２２ is the same as in the formula (G2), and the other symbols are the same as in the formula (G11).

[0167] The content of the second compound is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, based on the total mass of the composition, from the viewpoint of more excellent lubricity of the surface layer. The content of the second compound is preferably 99.9 mass% or less, more preferably 99.5 mass% or less, based on the total mass of the composition.

[0168] When the value of m11 / m12 in the above formula (G1) is smaller than the value of m21 / m22 in the above formula (G2), the mass ratio of the content of the first compound to the content of the second compound (content of the first compound / content of the second compound) is preferably 0.01 to 100, more preferably 5 to 80, and even more preferably 10 to 70. When the above mass ratio is equal to or greater than the lower limit, the friction resistance is superior, and when the above mass ratio is equal to or less than the upper limit, the lubricity is superior.

[0169] In this production method, in order to prepare the present composition which is likely to form a surface layer excellent in lubricity, the compound constituting the first compound with the largest m11 / m12 = M is compared with the compound constituting the second compound with the largest m21 / m22 = M, and when the compound with the larger M value is designated as compound A, the M (= M) of compound A is Ａ ) is preferably 1.00 or more.

[0170] In this production method, in order to prepare the present composition which is likely to form a surface layer excellent in lubricity, a compound constituting the first compound and having the smallest m11 / m12 = M is compared with a compound constituting the second compound and the compound having the smallest m21 / m22 = M is designated as compound B, and the M (= M) of compound B is determined. Ｂ ) is preferably less than 1.00.

[0171] In the present production method, from the viewpoint of preparing the present composition which is likely to form a surface layer having excellent lubricity, it is preferable that the first compound includes the compound A and the second compound includes the compound B.

[0172] In addition, in order to prepare the present composition which can easily form a surface layer having excellent lubricity, Ａ and the aforementioned M Ｂ The ratio is preferably 1.35 or more, more preferably 1.50 or more, even more preferably 2.00 or more, and particularly preferably 4.00 or more.

[0173] [Coating Liquid] The coating liquid of the present invention (hereinafter also referred to as "the present coating liquid") contains the present composition and a liquid medium. The present coating liquid may be in a liquid state, and may be a solution or a dispersion. The present coating liquid may contain the present composition, and may also contain impurities such as by-products produced in the production process of the fluorinated ether compound.

[0174] The content of the present composition is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass, based on the total mass of the present coating liquid.

[0175] The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or a mixture of both.

[0176] Specific examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. Specific examples of the fluorinated alkanes are preferably compounds having 4 to 8 carbon atoms. Commercially available products include C ６ F １３ H (manufactured by AGC, Asahiklin (registered trademark) AC-2000), C ６ F １３ C ２ H ５ (AGC, Asahiklin (registered trademark) AC-6000), C ２ F ５ CHFCHFCF ３ (Vertrel (registered trademark) XF, manufactured by Chemours) and the like. Specific examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. As the fluoroalkyl ether, compounds having 4 to 12 carbon atoms are preferred. Commercially available products include CF ３ CH ２ OCF ２ CF ２ H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C ４ F ９ OCH ３ (3M Novec (registered trademark) 7100), C ４ F ９ O.C. ２ H ５ (3M Novec (registered trademark) 7200), C ２ F ５ CF (OCH ３ ) C ３ F ７(Novec (registered trademark) 7300, manufactured by 3M Company) and the like. 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. As the non-fluorinated organic solvent, compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms are preferred, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents.

[0177] The coating liquid preferably contains 60 to 99.999 mass %, more preferably 85 to 99.99 mass %, and even more preferably 90 to 99.9 mass %, of the liquid medium.

[0178] In addition to the composition and the liquid medium, the coating liquid may contain other components as long as the effects of the present invention are not impaired. Examples of other components include known additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups. The content of other components in the coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.

[0179] The total concentration of the present composition and other components (hereinafter also referred to as "solids concentration") is preferably 0.001 to 40 mass%, more preferably 0.01 to 20 mass%, even more preferably 0.01 to 10 mass%, and particularly preferably 0.01 to 1 mass%. The solids concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120°C.

[0180] [Article] The article of the present invention (hereinafter also referred to as "the article") has a substrate and a surface layer disposed on the substrate, and preferably has an underlayer between the substrate and the surface layer. The surface layer is a layer formed from the composition of the present invention or the coating liquid of the present invention, and contains a condensate of the above-mentioned fluorinated ether compound.

[0181] The material and shape of the substrate may be appropriately selected depending on the application of the article. Examples of the substrate material include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. In particular, substrates that require water and oil repellency include substrates for touch panels, substrates for displays, and substrates that constitute the housings of electronic devices. Touch panel substrates and display substrates are translucent. "Translucent" means that the normal incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. Glass or transparent resin is preferred as the material for the touch panel substrate.

[0182] The substrate may be one that has been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment on the surface on which the undercoat layer is to be formed. The surface that has been subjected to the surface treatment further improves the adhesion between the substrate and the undercoat layer, and as a result, the abrasion resistance of the surface layer is further improved. As the surface treatment, corona discharge treatment or plasma treatment is preferred in terms of further improving the abrasion resistance of the surface layer.

[0183] The underlayer is preferably a layer containing a silicon-containing oxide (preferably silicon oxide), and may further contain other elements. When the underlayer contains silicon oxide, the reactive silyl groups of the fluorine-containing ether compound undergo dehydration condensation to form Si—O—Si bonds between the underlayer and the underlayer, resulting in the formation of a surface layer with excellent abrasion resistance.

[0184] The content of silicon oxide in the underlayer is preferably 65% ​​by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass or more. When the content of silicon oxide is equal to or greater than the lower limit, Si—O—Si bonds are sufficiently formed in the underlayer, and the mechanical properties of the underlayer are sufficiently ensured. The content of silicon oxide is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxide) from the mass of the underlayer.

[0185] From the viewpoint of the durability of the surface layer, it is preferable that the oxide in the underlayer further contains one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. By containing these elements, the bond between the underlayer and the fluorine-containing ether compound is strengthened, thereby improving the abrasion resistance.

[0186] The thickness of the underlayer is preferably 1 to 200 nm, more preferably 2 to 20 nm. If the thickness of the underlayer is equal to or greater than the lower limit, the underlayer is likely to have a sufficient effect of improving adhesion. If the thickness of the underlayer is equal to or less than the upper limit, the abrasion resistance of the underlayer itself is increased. Methods for measuring the thickness of the underlayer include a method of observing the cross section of the underlayer using an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step gauge, etc.

[0187] Examples of methods for forming the underlayer include a method of depositing a deposition material having a desired composition for the underlayer on the surface of a substrate. Vacuum deposition is an example of a deposition method. The deposition material is evaporated in a vacuum chamber and attached to the surface of the substrate. The temperature during deposition (e.g., the temperature of the boat in which the deposition material is placed when using a vacuum deposition apparatus) is preferably 100 to 3000°C, more preferably 250 to 3000°C. The pressure during deposition (e.g., the absolute pressure in the chamber in which the deposition material is placed when using a vacuum deposition apparatus) is preferably 1 Pa or less, more preferably 0.1 Pa or less. When forming the underlayer using a deposition material, a single deposition material may be used, or two or more deposition materials containing different elements may be used. Examples of methods for evaporating the deposition material include a resistance heating method in which the deposition material is melted and evaporated on a resistance heating boat made of a high-melting-point metal, and an electron gun method in which an electron beam is irradiated onto the deposition material to directly heat the deposition material and melt and evaporate the surface. The electron gun method is preferred as a method for evaporating the deposition material because it can evaporate high-melting-point substances because it can heat locally, and because areas not irradiated by the electron beam are at low temperatures, there is no risk of reaction with the container or contamination with impurities. The deposition material used in the electron gun method is preferably a molten granular material or a sintered material because it is less likely to scatter even when an air current is generated.

[0188] The surface layer contains a condensate of the above-mentioned fluorine-containing ether compound. The condensate of the fluorine-containing ether compound includes a structure in which a silanol group (Si—OH) is formed by the hydrolysis reaction of a hydrolyzable silyl group in the fluorine-containing ether compound, and the silanol group undergoes an intermolecular condensation reaction to form an Si—O—Si bond, and a structure in which a silanol group in the fluorine-containing ether compound undergoes a condensation reaction with a silanol group or Si—OM group (wherein M is an alkali metal element) on the surface of the substrate or underlayer to form an Si—O—Si bond. The surface layer may also contain a condensate of a fluorine-containing compound other than a fluorine-containing ether compound. That is, the surface layer contains a fluorine-containing compound having a reactive silyl group in a state in which some or all of the reactive silyl groups of the fluorine-containing compound have undergone a condensation reaction.

[0189] The thickness of the surface layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. If the thickness of the surface layer is equal to or greater than the lower limit, the effect of the surface layer can be sufficiently obtained. If 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 is the thickness obtained using an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the oscillation period of the interference pattern obtained by X-ray reflectivity method using an X-ray diffractometer for thin film analysis.

[0190] The article is preferably a touch panel. In this case, the surface layer is preferably formed on the surface of a member that constitutes the surface of the touch panel that is touched by a finger.

[0191] [Method for Producing an Article] The method for producing the present article is a method for forming a surface layer on a substrate by a dry coating method or a wet coating method using the present composition or the present coating liquid.

[0192] The present composition can be used directly in a dry coating method. The present composition is suitable for forming a surface layer with excellent adhesion by a dry coating method. Examples of dry coating methods include vacuum deposition, CVD, and sputtering. Vacuum deposition is preferred because it suppresses decomposition of the fluorinated ether compound and because the equipment is simple. For vacuum deposition, a pellet-shaped material in which the present composition is supported on a porous metal body made of a metal material such as iron or steel may be used. The pellet-shaped material supporting the present composition can be produced by impregnating a porous metal body with a solution of the present composition, drying it, and removing the liquid medium. The present coating liquid can be used as the solution of the present composition.

[0193] The present coating liquid can be suitably used for wet coating methods such as 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.

[0194] In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the fluorine-containing ether compound and the substrate (or underlayer) may be carried out as necessary. Examples of such an operation include heating, humidification, and light irradiation. For example, the substrate on which the surface layer has been formed can be heated in a humid atmosphere to promote reactions such as the hydrolysis reaction of hydrolyzable groups, the reaction between hydroxyl groups on the surface of the substrate and silanol groups, and the formation of siloxane bonds through the condensation reaction of silanol groups. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as needed. Specific methods include pouring a solvent over the surface layer and wiping with a cloth soaked in the solvent.

[0195] The present invention will be described in detail below with reference to examples. Examples 1 to 9 and 15 to 17 are working examples, and Examples 10 to 14 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.

[0196] [Production of Compound X1] Compound X1 was obtained in the same manner as in Synthesis Example 15 of Japanese Patent No. 5761305. ３ -(OCF ２ ) １６ ・(OCF ２ CF ２ ) １５ -OCF ２ CH ２ -OCH ２ CH ２ CH ２ -Si[CH ２ CH ２ CH ２ -Si(OCH ３ ) ３ ] ３ ...(X1) In formula (X1), (OCF ２ ) and (OCF ２ CF ２ ) are the values ​​in parentheses of (OCF ２ ) and (OCF ２ CF ２ ) means the average number of

[0197] (OCF in compound X1 ２ ) and (OCF ２ CF ２ ) is the average number of １９ It was determined by F-NMR.

[0198] In addition, by liquid chromatography, (OCF ２ ) and (OCF ２ CF ２ ) are separated, and for each of the separated compounds, (OCF ２ ) and (OCF ２ CF ２ ) １９ The proportion M in each compound was determined by F-NMR. The maximum and minimum values ​​of the proportion M in the compounds constituting compound X1 are shown in Table 1.

[0199] [Preparation of Compounds X2 to X6] (OCF ２ ) and (OCF ２ CF ２Compounds X2 to X6 were obtained in the same manner as in the production of Compound X1, except that the perfluoropolyether-modified allyloxy compound used as the raw material was changed so that the average number of CF ３ -(OCF ２ ) １８ ・(OCF ２ CF ２ ) １４ -OCF ２ CH ２ -OCH ２ CH ２ CH ２ -Si[CH ２ CH ２ CH ２ -Si(OCH ３ ) ３ ] ３ ... (X2) CF ３ -(OCF ２ ) １７ ・(OCF ２ CF ２ ) １４ -OCF ２ CH ２ -OCH ２ CH ２ CH ２ -Si[CH ２ CH ２ CH ２ -Si(OCH ３ ) ３ ] ３ ... (X3) CF ３ -(OCF ２ ) ２４ ・(OCF ２ CF ２ ) １１ -OCF ２ CH ２ -OCH ２ CH ２ CH ２ -Si[CH ２ CH ２ CH ２ -Si(OCH ３ ) ３ ] ３ ... (X4) CF ３ -(OCF ２ ) ３０ ・(OCF ２ CF２ ) ７ -OCF ２ CH ２ -OCH ２ CH ２ CH ２ -Si[CH ２ CH ２ CH ２ -Si(OCH ３ ) ３ ] ３ ... (X5) CF ３ -(OCF ２ ) １４ ・(OCF ２ CF ２ ) １７ -OCF ２ CH ２ -OCH ２ CH ２ CH ２ -Si[CH ２ CH ２ CH ２ -Si(OCH ３ ) ３ ] ３ ...(X6) In formulas (X2) to (X6), (OCF ２ ) and (OCF ２ CF ２ ) are the values ​​in parentheses for compounds X2 to X6 (OCF ２ ) and (OCF ２ CF ２ ) means the average number of

[0200] Compound Y1 was obtained in the same manner as described in Example 1 of JP 2015-199906 A. ３ -(OCF ２ ) １６ ・(OCF ２ CF ２ ) １８ -OCF ２ -C(OH)[CH ２ CH ２ CH ２ -Si(OCH ３ ) ３ ] ２ ...(Y1) In formula (Y1), (OCF ２ ) and (OCF ２ CF ２) are the values ​​in parentheses of (OCF ２ ) and (OCF ２ CF ２ ) means the average number of

[0201] (OCF in Compounds X2 to X6 and Compound Y1 ２ ) and (OCF ２ CF ２ The average number of the moieties was determined in the same manner as for compound X1. The maximum and minimum values ​​of the ratio M in compounds X2 to X6 and compound Y1 were also determined in the same manner as for compound X1.

[0202]

[0203] In Table 1, "mA" represents the amount of each compound (OCF ２ ) in each compound, and "mB" indicates the average number of ２ CF ２ ) means the average number of

[0204] [Production of Compositions 1 to 11] Fluorine-containing ether compounds were mixed so as to have the compositions shown in Table 2, thereby obtaining compositions 1 to 11.

[0205]

[0206] [Examples 1 to 8 and Examples 15 to 17] A substrate (alkali-free glass (Eagle XG: product name, manufactured by Corning, 50 mm x 50 mm, thickness 0.5 mm)) was placed in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was heated to 5 × 10 －３ The pressure was evacuated to a pressure of 100 Pa or less. A deposition vessel containing each composition listed in Table 3 was heated to 300°C by resistance heating at a distance of 1000 mm so as to face one main surface of the substrate, and the composition was vacuum-deposited. Film formation was terminated when the thickness of the composition on the substrate reached 10 nm. Thereafter, the substrate on which the composition had been deposited was heated at a temperature of 200°C for 30 minutes (post-treatment) to obtain a substrate (article) with a surface layer.

[0207] [Example 9] A mixture of the composition shown in Table 1 and C as a liquid medium ４ F ９ O.C. ２ H ５(Novec-7200: product name, manufactured by 3M) was mixed to prepare a coating solution in which the content of the composition in the coating agent was 0.1% by mass. Alkali-free glass (Eagle XG: product name, manufactured by Corning Incorporated, 50 mm x 50 mm, thickness 0.5 mm) was prepared as the substrate. One main surface of the substrate was spray-coated with the coating agent at a coating rate of 6.0 g / sec using a Nordson sprayer, and the coating film formed on the substrate was then dried at 120°C for 10 minutes to obtain a substrate (article) with a surface layer. The thickness of the surface layer was 10 nm.

[0208] Examples 10 to 12 Substrates (articles) with surface layers were obtained in the same manner as in Examples 1 to 8, except that the compounds shown in Table 1 were used instead of the compositions.

[0209] Examples 13 and 14 Substrates (articles) with a surface layer were obtained in the same manner as in Example 9, except that the compounds shown in Table 1 were used instead of the composition.

[0210] The substrates with surface layers of Examples 1 to 17 were subjected to the following evaluation tests.

[0211] <Initial Water Contact Angle> The contact angle of approximately 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different points on the surface of the surface layer, and the average value was calculated to obtain the initial contact angle. The 2θ method was used to calculate the contact angle. Based on the obtained initial contact angle value, water repellency was evaluated according to the following evaluation criteria: A (Excellent): 115 degrees or more. B (Good): 110 degrees or more and less than 115 degrees. C (Fair): 100 degrees or more and less than 110 degrees. D (Fail): Less than 100 degrees.

[0212] <Abrasion Resistance (Steel Wool)> For the surface layer, a reciprocating traverse tester (manufactured by KNT Corporation) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) to measure the water contact angle after steel wool Bonstar (#0000) was reciprocated 10,000 times at a pressure of 98.07 kPa and a speed of 320 cm / min. The smaller the decrease in water repellency (water contact angle) after abrasion, the smaller the decrease in performance due to friction, indicating excellent abrasion resistance. The evaluation criteria are as follows: A (Excellent): The change in water contact angle after 10,000 reciprocating cycles is 2 degrees or less. B (Good): The change in water contact angle after 10,000 reciprocating cycles is more than 2 degrees and less than 5 degrees. C (Acceptable): The change in water contact angle after 10,000 reciprocating cycles is more than 5 degrees and less than 10 degrees. D (Fail): The change in water contact angle after 10,000 reciprocating cycles is more than 10 degrees.

[0213] <Abrasion Resistance (Eraser)> For the surface layer, a reciprocating traverse tester (manufactured by KNT Corporation) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) to measure the water contact angle after a Rubber Eraser (manufactured by Minoan Co., Ltd.) was reciprocated 30,000 times at a load of 4.9 N and a speed of 60 revolutions per minute (rpm). The smaller the decrease in water repellency (water contact angle) after abrasion, the smaller the decrease in performance due to friction, and the more excellent the abrasion resistance. The evaluation criteria are as follows: A (Excellent): The change in water contact angle after 10,000 reciprocating cycles is 2 degrees or less. B (Good): The change in water contact angle after 10,000 reciprocating cycles is more than 2 degrees and less than 5 degrees. C (Acceptable): The change in water contact angle after 10,000 reciprocating cycles is more than 5 degrees and less than 10 degrees. D (Fail): The change in water contact angle after 10,000 reciprocating cycles is more than 10 degrees.

[0214] <Lubricity> The dynamic friction coefficient of the surface layer against artificial skin (PBZ13001, manufactured by Idemitsu Technofine Co., Ltd.) was measured using a load-varying friction and wear testing system (HHS2000, manufactured by Shinto Scientific Co., Ltd.) under conditions of a contact area of ​​3 cm × 3 cm and a load of 0.98 N. The smaller the dynamic friction coefficient, the better the lubricity.

[0215]

[0216] As shown in Table 3, (OCF ２ ) and (OCF ２ CF ２ ) in different ratios, (OCF２ Compound A with the highest ratio of (OCF ２ CF ２ ) ratio of compound A is the highest, and ２ ) and (OCF ２ CF ２ ) ratio M Ａ and Compound B (OCF ２ ) and (OCF ２ CF ２ ) ratio M Ｂ Ratio to (M Ａ / M Ｂ It was confirmed that when the coefficient of dynamic friction was 1.35 or more, the coefficient of dynamic friction was low and a surface layer with excellent lubricity could be formed (Examples 1 to 9 and Examples 15 to 17).

[0217] This application claims priority based on Japanese Patent Application No. 2022-442, filed on January 5, 2022, the disclosure of which is incorporated herein in its entirety by reference.

Claims

1. A composition comprising two or more fluorinated ether compounds having a fluoropolyether chain and a reactive silyl group, wherein at least two of the fluorinated ether compounds have a fluoropolyether chain containing a structure represented by the following formula (G11), when the fluorinated ether compound having the largest m31 / m32 = M is compound A and the fluorinated ether compound having the smallest M is compound B, M(=M of the compound A Ａ ) and M(=M of the compound B Ｂ ) with a ratio (M Ａ / M Ｂ ) of 1.35 or more, a composition. (OCF ２ ) ｍ３１ ・ (OCF ２ CF ２ ) ｍ３２ ・・・ (G11) in formula (G11), m31 means the number of (OCF ２ ), which is an integer greater than or equal to 2, m32 means the number of (OCF ２ CF ２ ), and is an integer of 2 or more.

2. The above-mentioned M Ａ The composition according to claim 1, wherein M is 1.00 or more.

3. The above-mentioned M Ｂ The composition according to claim 1 or 2, wherein M is less than 1.

00.

4. The above-mentioned M Ａ / M Ｂ is 1.50 or more, and the composition according to claim 1 or 2.

5. The above-mentioned M Ａ / M Ｂ is 2.00 or more, and the composition according to claim 1 or 2.

6. The above-mentioned M Ａ / M Ｂ is 4.00 or more, the composition according to claim 1 or 2.

7. The composition according to claim 1 or 2, wherein the contents of the compound A and the compound B are each 0.1% by mass or more based on the total mass of the composition.

8. The composition according to claim 1 or 2, wherein the mass ratio of the content of the compound A to the content of the compound B is 0.01 to 100.

9. A method for producing a composition comprising two or more fluorinated ether compounds having a fluoropolyether chain and a reactive silyl group, wherein among the fluorinated ether compounds, the first compound has a fluoropolyether chain having a structure represented by the following formula (G1), wherein among the fluorinated ether compounds, the second compound has a fluoropolyether chain having a structure represented by the following formula (G2), m11 in the following formula (G1) is different from m21 in the following formula (G2), and / or m12 in the following formula (G1) is different from m22 in the following formula (G2), and mixing the first compound and the second compound, a method for producing a composition. (OCF ２ ) ｍ１１ - (OCF ２ CF ２ ) ｍ１２ ··· (G1) (OCF ２ ) ｍ２１ ・ (OCF ２ CF ２ ) ｍ２２ ・・・ (G2) In formula (G1), m11 means the average number of (OCF ２ ) in the first compound, and is a positive number of 2 or more. m12 means the average number of (OCF ２ CF ２ ) in the first compound, and is a positive number of 2 or more. In formula (G2), m21 means the average number of (OCF ２ ) in the second compound, and is a positive number of 2 or more. m22 means the average number of (OCF ２ CF ２ ) in the second compound, and is a positive number of 2 or more.

10. Among the compounds constituting the first compound, the compound having the largest m11 / m12 = M, and among the compounds constituting the second compound, the compound having the largest m21 / m22 = M, when the compound having the larger value of M is designated as compound A, The M(=M Ａ ) of the compound A is 1.00 or more, and the method for producing the composition according to claim 9.

11. Among the compounds constituting the first compound, the compound having the smallest m11 / m12 = M, and among the compounds constituting the second compound, the compound having the smallest m21 / m22 = M, when the compound having the smaller value of M is designated as compound B, The M(=M Ｂ ) of the compound B is less than 1.00, and the method for producing the composition according to claim 9 or 10.

12. the first compound contains the compound A, the second compound contains the compound B, a method for producing the composition according to claim 11.

13. The aforementioned M Ａ / M Ｂ is 1.35 or more, and a method for producing the composition according to claim 12.

14. Said M Ａ / M Ｂ is 1.50 or more, The method for producing a composition according to claim 12.

15. The above-mentioned M Ａ / M Ｂ is 2.00 or more, and the method for producing the composition according to claim 12.

16. The aforementioned M Ａ / M Ｂ is 4.00 or more, the method for producing a composition according to claim 12.

17. The method for producing the composition according to claim 12, wherein the contents of the first compound and the second compound are each 0.1% by mass or more based on the total mass of the composition.

18. The method for producing the composition according to claim 12, wherein the mass ratio of the content of the first compound to the content of the second compound is 0.01 to 100.

19. A coating liquid comprising the composition according to claim 1 or 2 and a liquid medium.

20. An article having a surface layer formed from the composition according to claim 1 or 2, or a coating liquid comprising the composition according to claim 1 or 2 and a liquid medium, on a substrate.

21. The article according to claim 20, wherein the article is a touch panel and the surface layer is provided on the surface of a member constituting the surface touched by a finger of the touch panel.

22. A method for producing an article, characterized in that a surface layer is formed on a substrate by a dry coating method or a wet coating method using the composition according to claim 1 or 2, or a coating liquid comprising the composition according to claim 1 or 2 and a liquid medium.