Composition, surface treatment agent, coating liquid, article, and method for producing article

Abstract

A purpose is to provide: a composition having excellent abrasion resistance; a surface treatment agent; a coating liquid; an article having a surface layer with excellent abrasion resistance; and a method for producing the article.　A composition that contains two or more selected from compounds represented by formula (A1), compounds represented by formula (A2), compounds represented by formula (B1), and compounds represented by formula (B2) and satisfies (I)-(III). Ｒｆ１－（ＯＲｆ１１）ｙ１－Ｏ－Ｒ１－Ｌ１－（Ｒ１１－Ｔ１）ｘ１　…（Ａ１） Ｒｆ２－（ＯＲｆ１２）ｙ２－Ｏ－Ｒ２－Ｌ２－（Ｒ１２－Ｔ２）ｘ２　…（Ａ２） （Ｔ３－Ｒ１３）ｘ３－Ｌ３－Ｒ３－（ＯＲｆ１３）ｙ３－Ｏ－Ｒ２３－Ｌ１３－（Ｒ３３－Ｔ１３）ｘ１３　…（Ｂ１） （Ｔ４－Ｒ１４）ｘ４－Ｌ４－Ｒ４－（ＯＲｆ１４）ｙ４－Ｏ－Ｒ２４－Ｌ１４－（Ｒ３４－Ｔ１４）ｘ１４　…（Ｂ２）Where, each symbol in the formulas is as described in the specification.

Description

Composition, surface treatment agent, coating liquid, article, and method for manufacturing article

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

[0002] Fluorine-containing ether compounds have excellent properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency, and are used in a wide variety of fields, including electrical and electronic materials, semiconductor materials, optical materials, and surface treatment agents.

[0003] For example, a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group is suitable for use as a surface treatment agent because it can form a surface layer on the surface of a substrate that exhibits high lubricity, water and oil repellency, etc. Surface treatment agents containing fluorine-containing ether compounds are used in applications where it is required that the performance of the surface layer not easily reduced in water and oil repellency even when rubbed repeatedly with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability) be maintained for a long period of time, such as surface treatment agents for components constituting the surfaces of touch panels that are touched by fingers, eyeglass lenses, and displays of wearable devices.

[0004] As a fluorine-containing ether compound capable of forming a surface layer having excellent abrasion resistance on the surface of a substrate, a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group has been proposed (Patent Document 1).

[0005] International Publication No. 2018 / 143433

[0006] As described above, fluorine-containing ether compounds are useful as surface treatment agents for imparting the above-mentioned various physical properties, and there is an increasing demand for fluorine-containing ether compounds that can be used in a variety of environments. The present inventors have conducted studies with the aim of further improving friction resistance.

[0007] An object of the present invention is to provide a composition having excellent abrasion resistance, a surface treatment agent, a coating liquid, an article having a surface layer having excellent abrasion resistance, and a method for producing the same.

[0008] The present invention provides a composition, a surface treatment agent, a coating liquid, an article, and a method for producing an article, each having the following constitutions [1] to

[10] . [1] A composition containing two or more compounds selected from a compound represented by the following formula (A1), a compound represented by the following formula (A2), a compound represented by the following formula (B1), and a compound represented by the following formula (B2), and satisfying the following (I) to (III): R ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ -L １ - (R １１ -T １ ) ｘ１ ... (A1) R ｆ２ - (OR ｆ１２ ) ｙ２ -O-R ２ -L ２ - (R １２ -T ２ ) ｘ２ ... (A2) (T ３ -R １３ ) ｘ３ -L ３ -R ３ - (OR ｆ１３ ) ｙ３ -O-R ２３ -L １３ - (R ３３ -T １３ ) ｘ１３ ... (B1) (T ４ -R １４ ) ｘ４ -L ４ -R ４ - (OR ｆ１４ ) ｙ４ -O-R ２４ -L １４ - (R ３４ -T １４ ) ｘ１４ ... (B2) where R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms, and R ｆ１１ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１１ If there are multiple R ｆ１１ may be the same or different, R １ is an alkylene group or a fluoroalkylene group, and L１ is a single bond or a 1+x1-valent group which may have N, O, S, or Si and may have a branch point, and R １ and R １１ Atoms bonded to R are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (═O), １１ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １１ If there are multiple R １１ may be the same or different, T １ is -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ x1 is an integer of 1 or more, and 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 ａ１１ is a non-hydrolyzable group, and R ａ１１ If there are multiple R ａ１１ may be the same or different from each other, z1 is an integer of 0 to 3, and when x1 is 2 or more, multiple z1 in a molecule may be the same or different from each other, provided that at least one of z1 is an integer of 1 to 3, y1 is an integer of 1 or more, R ｆ２ is a fluoroalkyl group having 1 to 20 carbon atoms, and R ｆ１２ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１２ If there are multiple R ｆ１２ may be the same or different, R ２ is an alkylene group or a fluoroalkylene group, and L ２ is a single bond or a 1+x divalent group which may have N, O, S, or Si and may have a branch point, and R ２ and R １２ Atoms bonded to R are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (═O),１２ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １２ If there are multiple R １２ may be the same or different, T ２ is -SiR ａ２ ｚ２ R ａ１２ ３－ｚ２ x2 is an integer of 1 or more, and R ａ２ is a hydroxyl group or a hydrolyzable group, and R ａ２ If there are multiple R ａ２ 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 from each other, z2 is an integer of 0 to 3, and when x2 is 2 or more, multiple z2's in a molecule may be the same or different from each other, provided that at least one of z2's is an integer of 1 to 3, y2 is an integer of 1 or more, R ｆ１３ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１３ If there are multiple R ｆ１３ may be the same or different, R ３ is an alkylene group or a fluoroalkylene group, R ２３ is an alkylene group or a fluoroalkylene group, and L ３ is a single bond or a 1+x trivalent group which may have N, O, S, or Si and may have a branch point, and R ３ and R １３ The atom bonded to L is an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １３ is a single bond or a 1+x13-valent group which may have N, O, S, or Si and may have a branch point, and R ２３ and R ３３ The atom bonded to R is an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １３is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １３ If there are multiple R １３ may be the same or different, R ３３ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R ３３ If there are multiple R ３３ may be the same or different, T ３ and T １３ are each independently —SiR ａ３ ｚ３ R ａ１３ ３－ｚ３ x3 and x13 each independently represent an integer of 1 or more; R ａ３ is a hydroxyl group or a hydrolyzable group, and R ａ３ If there are multiple R ａ３ may be the same or different, R ａ１３ is a non-hydrolyzable group, and R ａ１３ If there are multiple R ａ１３ may be the same or different from each other, z3 is an integer of 0 to 3, and multiple z3's in a molecule may be the same or different from each other, provided that at least one of z3's is an integer of 1 to 3, y3 is an integer of 1 or more, R ｆ１４ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１４ If there are multiple R ｆ１４ may be the same or different, R ４ is an alkylene group or a fluoroalkylene group, R ２４ is an alkylene group or a fluoroalkylene group, and L ４ is a single bond or a 1+x tetravalent group which may have N, O, S, or Si and may have a branch point, and R ４ and R １４ The atom bonded to L is an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １４is a single bond or a 1+x14-valent group which may have N, O, S, or Si and may have a branch point, and R ２４ and R ３４ The atom bonded to R is an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １４ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １４ If there are multiple R １４ may be the same or different, R ３４ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R ３４ If there are multiple R ３４ may be the same or different, T ４ and T １４ are each independently —SiR ａ４ ｚ４ R ａ１４ ３－ｚ４ x4 and x14 each independently represent an integer of 1 or more; R ａ４ is a hydroxyl group or a hydrolyzable group, and R ａ４ If there are multiple R ａ４ may be the same or different, R ａ１４ is a non-hydrolyzable group, and R ａ１４ If there are multiple R ａ１４ may be the same or different from each other, z4 is an integer of 0 to 3, and a plurality of z4s in a molecule may be the same or different from each other, provided that at least one of z4s is an integer of 1 to 3, and y4 is an integer of 1 or more, (I) When a compound represented by formula (A1) and a compound represented by formula (A2) are contained, -O-R in formula (A1) １ -L １ -R １１ The chain length a1 of -O-R in formula (A2) ２ -L ２ -R １２ - The chain lengths a2 of T are different from each other, １ and T ２(II) In the case where a compound represented by formula (B1) and a compound represented by formula (B2) are contained, -R in formula (B1) １３ -L ３ -R ３ The chain length b1 of —O— and —O—R ２３ -L １３ -R ３３ A set of chain lengths b11 of - and -R in formula (B2) １４ -L ４ -R ４ The chain length b2 of —O— and —O—R ２４ -L １４ -R ３４ (III) In cases other than (I) and (II), the chain length a1 or the chain length a2 is different from either the chain length b1 or the chain length b11, or different from either the chain length b2 or the chain length b12. [2] The composition according to [1], which contains a compound represented by formula (A1) and a compound represented by formula (A2), or a compound represented by formula (B1) and a compound represented by formula (B2). [3] R ｆ１ and R ｆ２ The composition of [2], wherein L １ and L ２ are the same, or L ３ and L ４ are the same, and L １３ and L １４ The composition according to [2] to [3], wherein R １ , R ２ , R ３ , R ４ , R ２３ and R ２４ are each independently represented by the following formula (C): *-(CR ４１ ２ ) ａ - (CH ２ ) ｂ -** ... Formula (C) where R ４１are each independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, provided that two R ４１ at least one of the groups is a fluorine atom or a fluoroalkyl group, a is an integer of 0 to 6, b is an integer of 0 to 10, a+b is an integer of 1 to 16, * is a bond to O, and ** is L １ , L ２ , L ３ , L ４ , L １３ , or L １４ [6] R １ a + b in R ２ a+b in R are different values, or ３ a + b in R ４ a+b in ２３ a + b in R ２４ The composition of [5], wherein a+b have different values. [7] A surface treatment agent comprising any of the compositions of [1] to [6]. [8] A coating liquid comprising any of the compositions of [1] to [6] and a liquid medium. [9] An article having a surface layer formed on the surface of a substrate from any of the compositions of [1] to [6] or the surface treatment agent according to [7].

[10] A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using any of the compositions of [1] to [6], the surface treatment agent of [7], or the coating liquid of [8].

[0009] According to the present invention, it is possible to provide a composition having excellent abrasion resistance, a surface treatment agent, a coating liquid, an article having a surface layer having excellent abrasion resistance, and a method for producing the same.

[0010] 1 is a schematic cross-sectional view showing an example of an article of the present invention.

[0011] In this specification, a compound represented by formula (A1) will be referred to as compound (A1). Compounds represented by other formulae will 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 contains one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group containing one or more fluorine atoms. A "reactive silyl group" is a collective term for hydrolyzable silyl groups and silanol groups (Si—OH), and a "hydrolyzable silyl group" refers to a group that can form a silanol group through 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. A "hydrocarbon group" refers to an aliphatic hydrocarbon group (e.g., a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group), an aromatic hydrocarbon group (e.g., a phenylene group), or a group consisting of a combination thereof. The term "surface layer" refers to a layer formed on the surface of a substrate. １ -L １ -R １１ The chain length a1 of R ｆ１１ and T １ represents the number of atoms constituting the carbon chain which may have a heteroatom connecting the two, and when the carbon chain has a ring structure, it is the shortest (R ｆ１１ and T １ The "molecular weight" of a polyfluoropolyether chain is expressed as follows: 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.

[0012] [Composition] The composition of the present invention is characterized by containing two or more compounds selected from the group consisting of a compound represented by the following formula (A1), a compound represented by the following formula (A2), a compound represented by the following formula (B1), and a compound represented by the following formula (B2), and satisfying the following (I) to (III): ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ -L １ - (R １１ -T １ ) ｘ１ ... (A1) R ｆ２ - (OR ｆ１２ ) ｙ２ -O-R ２ -L ２ - (R １２ -T ２ ) ｘ２ ... (A2) (T ３ -R １３ ) ｘ３ -L ３ -R ３ - (OR ｆ１３ ) ｙ３ -O-R ２３ -L １３ - (R ３３ -T １３ ) ｘ１３ ... (B1) (T ４ -R １４ ) ｘ４ -L ４ -R ４ - (OR ｆ１４ ) ｙ４ -O-R ２４ -L １４ - (R ３４ -T １４ ) ｘ１４ ... (B2) where R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms, and R ｆ１１ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１１ If there are multiple R ｆ１１ may be the same or different, R １ is an alkylene group or a fluoroalkylene group, and L １is a single bond or a 1+x1-valent group which may have N, O, S, or Si and may have a branch point, and R １ and R １１ Atoms bonded to R are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (═O), １１ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １１ If there are multiple R １１ may be the same or different, T １ is -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ x1 is an integer of 1 or more, and 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 ａ１１ is a non-hydrolyzable group, and R ａ１１ If there are multiple R ａ１１ may be the same or different from each other, z1 is an integer of 0 to 3, and when x1 is 2 or more, multiple z1 in a molecule may be the same or different from each other, provided that at least one of z1 is an integer of 1 to 3, y1 is an integer of 1 or more, R ｆ２ is a fluoroalkyl group having 1 to 20 carbon atoms, and R ｆ１２ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１２ If there are multiple R ｆ１２ may be the same or different, R ２ is an alkylene group or a fluoroalkylene group, and L ２ is a single bond or a 1+x divalent group which may have N, O, S, or Si and may have a branch point, and R ２ and R １２ Atoms bonded to R are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (═O), １２is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １２ If there are multiple R １２ may be the same or different, T ２ is -SiR ａ２ ｚ２ R ａ１２ ３－ｚ２ x2 is an integer of 1 or more, and R ａ２ is a hydroxyl group or a hydrolyzable group, and R ａ２ If there are multiple R ａ２ 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 from each other, z2 is an integer of 0 to 3, and when x2 is 2 or more, multiple z2's in a molecule may be the same or different from each other, provided that at least one of z2's is an integer of 1 to 3, y2 is an integer of 1 or more, R ｆ１３ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１３ If there are multiple R ｆ１３ may be the same or different, R ３ is an alkylene group or a fluoroalkylene group, R ２３ is an alkylene group or a fluoroalkylene group, and L ３ is a single bond or a 1+x trivalent group which may have N, O, S, or Si and may have a branch point, and R ３ and R １３ The atom bonded to L is an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １３ is a single bond or a 1+x13-valent group which may have N, O, S, or Si and may have a branch point, and R ２３ and R ３３ The atom bonded to R is an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １３is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １３ If there are multiple R １３ may be the same or different, R ３３ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R ３３ If there are multiple R ３３ may be the same or different, T ３ and T １３ are each independently —SiR ａ３ ｚ３ R ａ１３ ３－ｚ３ x3 and x13 each independently represent an integer of 1 or more; R ａ３ is a hydroxyl group or a hydrolyzable group, and R ａ３ If there are multiple R ａ３ may be the same or different, R ａ１３ is a non-hydrolyzable group, and R ａ１３ If there are multiple R ａ１３ may be the same or different from each other, z3 is an integer of 0 to 3, and multiple z3's in a molecule may be the same or different from each other, provided that at least one of z3's is an integer of 1 to 3, y3 is an integer of 1 or more, R ｆ１４ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１４ If there are multiple R ｆ１４ may be the same or different, R ４ is an alkylene group or a fluoroalkylene group, R ２４ is an alkylene group or a fluoroalkylene group, and L ４ is a single bond or a 1+x tetravalent group which may have N, O, S, or Si and may have a branch point, and R ４ and R １４ The atom bonded to L is an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １４is a single bond or a 1+x14-valent group which may have N, O, S, or Si and may have a branch point, and R ２４ and R ３４ The atom bonded to R is an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), １４ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １４ If there are multiple R １４ may be the same or different, R ３４ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R ３４ If there are multiple R ３４ may be the same or different, T ４ and T １４ are each independently —SiR ａ４ ｚ４ R ａ１４ ３－ｚ４ x4 and x14 each independently represent an integer of 1 or more; R ａ４ is a hydroxyl group or a hydrolyzable group, and R ａ４ If there are multiple R ａ４ may be the same or different, R ａ１４ is a non-hydrolyzable group, and R ａ１４ If there are multiple R ａ１４ may be the same or different from each other, z4 is an integer of 0 to 3, and a plurality of z4s in a molecule may be the same or different from each other, provided that at least one of z4s is an integer of 1 to 3, and y4 is an integer of 1 or more, (I) When a compound represented by formula (A1) and a compound represented by formula (A2) are contained, -O-R in formula (A1) １ -L １ -R １１ The chain length a1 of -O-R in formula (A2) ２ -L ２ -R １２ - The chain lengths a2 of T are different from each other, １ and T ２(II) In the case where a compound represented by formula (B1) and a compound represented by formula (B2) are contained, -R in formula (B1) １３ -L ３ -R ３ The chain length b1 of —O— and —O—R ２３ -L １３ -R ３３ A set of chain lengths b11 of - and -R in formula (B2) １４ -L ４ -R ４ The chain length b2 of —O— and —O—R ２４ -L １４ -R ３４ (III) In cases other than (I) and (II), the chain length a1 or the chain length a2 is different from either the chain length b1 or the chain length b11, or different from either the chain length b2 or the chain length b12.

[0013] Compounds A1 and A2 roughly have a structure of "polyfluoropolyether chain-linking group-reactive silyl group." Compounds B1 and B2 roughly have a structure of "reactive silyl group-linking group-polyfluoropolyether chain-linking group-reactive silyl group." The reactive silyl group forms a strong chemical bond with the substrate, so the surface layer formed using these compounds has excellent abrasion resistance. Furthermore, because this compound has a polyfluoropolyether chain, the surface layer has excellent fingerprint stain removal properties.

[0014] The present composition uses a combination of two or more compounds from the above compounds, each having a different length between the polyfluoropolyether chain and the reactive silyl group, i.e., the chain length of the linking group. This allows the composition to adapt to the micro-irregularities on the substrate surface and bond firmly. Furthermore, since the present composition contains the long-chain compound and the short-chain compound, the reduced friction resistance caused by the long-chain compound can be compensated for by the friction resistance of the short-chain compound, resulting in excellent friction resistance. As described above, the present composition has excellent friction resistance and is useful as a surface treatment agent capable of forming a surface layer with excellent friction resistance.

[0015] <Compound (A1)> R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms. The fluoroalkyl group may be linear or branched. 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.

[0016] R ｆ１１ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１１ If there are multiple R ｆ１１ may be the same or different. (OR ｆ１１ ) ｙ１ is a polyfluoropolyether chain, and y1 is an integer of 1 or more.

[0017] (OR ｆ１１ ) ｙ１ The polyfluoropolyether chain in the formula (G1) preferably has a structure represented by the following formula (G1): ｆ１ ) ｍ１ (OG ｆ２ ) ｍ２ (OG ｆ３ ) ｍ３ (OG ｆ４ ) ｍ４ (OG ｆ５ ) ｍ５ (OG ｆ６ ) ｍ６ ] - Formula (G1) where 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, ｆ６ is 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 1 to 200. ｆ１ ) ~ (OGｆ６ The bonding order of m1 to m6 in formula (G1) 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 respective 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.

[0018] 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 -, -CH ２ CF ２ CF ２ -, -CH ２ CHFCF ２ -, -CH ２ CH ２ CF ２ -, -CH２ 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)−CH<00,00477>-, etc. G ｆ４ Specific examples of G include,−CF ２ CF ２ CF ２ CF ２ −,−CHFCF ２ CF２ 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 -、-CH ２ CH ２ CH ２ CF ２ -、-CHFCH ２ CH ２ CHF-、-CH ２ CH ２ CH２ CHF-, -cycloC ４ F ６ - and others. ｆ５ Specific examples of the group include -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 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 ２ CF ２ CH ２ -, -cycloC ５ F ８ - and others. ｆ６ Specific examples of the group include -CF ２ CF ２CF 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.

[0019] (OR ｆ１１ ) ｙ１ In particular, it is preferable that the compound has a structure represented by the following formula (G2) to formula (G4) because it has excellent water and oil repellency, abrasion resistance, and fingerprint stain removal properties. ｆ１ ) ｍ１ - (OG ｆ２ ) ｍ２ Formula (G2) (OG ｆ２ ) ｍ２ - (OG ｆ４) ｍ４ Formula (G3) (OG ｆ３ ) ｍ３ Formula (G4) Here, the symbols in formulas (G2) to (G4) are the same as those in formula (G1).

[0020] In formula (G2) and formula (G3), (OG ｆ１ ) and (OG ｆ２ ), (OG ｆ２ ) and (OG ｆ４ ) can be bonded in any order. For example, in formula (G2), ｆ１ ) and (OG ｆ２ ) may be alternated, and (OG ｆ１ ) and (OG ｆ２ ) may be arranged in blocks or randomly. The same applies to formula (G3). In formula (G2), m1 is preferably 1 to 30, more preferably 1 to 20. Furthermore, m2 is preferably 1 to 30, more preferably 1 to 20. In formula (G3), m2 is preferably 1 to 30, more preferably 1 to 20. Furthermore, m4 is preferably 1 to 30, more preferably 1 to 20. In formula (G4), m3 is preferably 1 to 30, more preferably 1 to 20.

[0021] The polyfluoropolyether chain (OR ｆ１１ ) ｙ１ The proportion of fluorine atoms in the polyfluoropolyether chain (OR) [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 40% or more, more preferably 50% or more, and even more preferably 60% 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 200 to 30,000, more preferably from 600 to 25,000, and even more preferably from 1,000 to 20,000.

[0022] R １ is an alkylene group or a fluoroalkylene group. １The alkylene group and fluoroalkylene group in R are preferably linear from the viewpoint of ease of synthesis. The number of carbon atoms is preferably 1 to 16, and more preferably 1 to 12. In addition, from the viewpoint of ease of synthesis, １ Is, L １ or R １１ (L １ is a single bond) is preferably an alkylene group or fluoroalkylene group in which the carbon atom bonded to the alkyl group is bonded to two hydrogen atoms, or a fluoroalkylene group having 1 to 3 carbon atoms.

[0023] Also R １ is preferably a group represented by the following formula (C) in terms of ease of adjusting the chain length: ４１ ２ ) ａ - (CH ２ ) ｂ -** ... Formula (C) where R ４１ are each independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and two R ４１ At least one of the R ４１ may be the same or different, a is an integer of 0 to 6, b is an integer of 0 to 10, a+b is an integer of 1 to 16, * is a bond to O, ** is L １ It is a combination of.

[0024] In formula (C), (CR ４１ ２ ) ａ - (CH ２ ) ｂ indicates the bond order, and when a and b are 1 or more, CR ４１ ２ The block is (OR ｆ１１ ) ｙ１ -O side, and CH ２ The block is L １ Placed on the side. ４１ The fluoroalkyl group in R preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. ４１Among these, a is preferably a fluorine atom or a fluoroalkyl group having 1 to 3 carbon atoms, and more preferably a fluorine atom. a may be an integer of 0 to 6, preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. b may be an integer of 0 to 10, preferably 1 to 8, and more preferably 1 to 6.

[0025] R １ A preferred example of the group is —CF ２ -, -CF ２ CF ２ -, -CF ２ CH ２ -, -CF ２ CF ２ CF ２ -, -CF ２ CF ２ CH ２ -, -CF ２ CF ２ CF ２ CH ２ -, -CF ２ CH ２ CH ２ CH ２ -, -CF ２ CF ２ CF ２ CH ２ CH ２ -, -CF ２ CH ２ CH ２ CH ２ CH ２ CH ２ -, -CF ２ CF ２ CF ２ CH ２ CH ２ CH ２ CH ２ -, -CF ２ CF ２ CF ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ - and others.

[0026] L １is a single bond or a 1+x1-valent group which may have 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 an N, O, S, or Si atom, 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.

[0027] L １ When R in formula (A1) is a single bond, １ and R １１ is directly bonded, and the compound (A1) is represented by the following formula (A1′): ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ -R １１ -T １ ...(A1') Here, each symbol in formula (A1') is the same as in formula (A1).

[0028] 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 (1+x1)-valent organopolysiloxane residue. １ ").

[0029] N is the branch point P １ If so, the branch point P １ For example, *-N(-**) ２ where * is R １ is a bond on the side, and ** is R １１ C is the branch point P １ If so, the branch point P １ For example, *-C(-**) ３ or *-CR ２９ (-**) ２ 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 or *-SiR ２９ (-**) ２ 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.

[0030] Branch point P １ From the viewpoints of ease of production of the present compound and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer, the ring structure constituting the formula (I) is preferably one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings, and particularly preferably a ring structure represented by the following formula: The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an etheric oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group (═O).

[0031]

[0032] 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.

[0033]

[0034] 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 (R２６ ) -, -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 "). 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 present compound.

[0035] Examples of the divalent organopolysiloxane residue include groups of the following formula: ２７ is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. ２７ The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 carbon atom.

[0036]

[0037] Join B １ As the group, —C(O)NR is preferred in terms of ease of production of the present compound. 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.

[0038] Trivalent or higher L １ is R １ and R １１are each independently an N, O, S, or Si atom, 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 １ As a specific example of １ (For example, {*-P １ (-**) ｘ１}), 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. However, R ２８ is a single bond or a divalent organic group, and * is R １ is a bond on the side, and ** is R １１ It is the connecting hand on the side.

[0039] Also, divalent L １ As for R １ and R １１ are each independently an N, O, S, or Si atom 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 divalent or higher 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, and * is R １ is a bond on the side, and ** is R １１ It is the connecting hand on the side.

[0040] The above R ２８ Examples of the divalent organic group in the formula include a divalent aliphatic hydrocarbon group (such as an alkylene group or a cycloalkylene group) and a divalent aromatic hydrocarbon group (such as a phenylene group), and the hydrocarbon group having two or more carbon atoms has a bond B between its carbon atom and its carbon atom. 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.

[0041] Said L １ As the group, a group represented by any one of the following formulae (Q1) to (Q7) is preferred in terms of ease of production of the present compound.

[0042] -A １ -C(R ｅ２ ) ３－ｇ３ (-Q ２２ -) ｇ３ Formula (Q2) -A ２ -N(-Q ２３ -) ２ Formula (Q3) -A ３ -Z １ (-Q ２４ -) ｇ４ Formula (Q4) -A ２ -Si(R ｅ３ ) ３－ｇ３ (-Q ２５ -) ｇ３ Formula (Q5) -A １ -Q ２６ - Formula (Q6) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｇ５ (-Q ２５ -) ｇ５ Formula (Q7) In the formulas (Q1) to (Q7), A １ , A ２ or A ３ side is R of formula (A1) １ Connect with Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６The side (R １１ -T １ ) ｘ１ where A １ is a single bond, -B ２ -, -B ３ -R ３０ - or -B ３ -R ３０ -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 -NR ｅ６ - and A ２ is a single bond or -B ３ -R ３０ - and A ３ Is A ３ Z to which １ When the atom in is a carbon atom, A １ and A ３ Z to which １ When 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 ２ -, -R ３０ -B ３ -or-B ２ -R ３０ -B ３ - and Q ２２ If there are two or more, there are two or more Q ２２ may be the same or different, and Q ２３ is a single bond or -R ３０ -B ３ - and two Q２３ may be the same or different, 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 ２４ If there are two or more, there are two or more Q ２４ may be the same or different, and Q ２５ is a single bond or -R ３０ -B ３ - and Q ２５ If there are two or more, there are two or more Q ２５ may be the same or different, 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 (g4+1)-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, and R ｅ１ When there are two or more R ｅ１ may be the same or different, R ｅ２ is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, and R ｅ３ is an alkyl group, and R ｅ６ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, g1 is an integer from 0 to 3, g2 is an integer from 0 to 3, and g1+g2 is an integer from 1 to 6, g3 is an integer from 1 to 3, g4 is an integer of 1 or more, and g5 is an integer from 1 to 3. Note that g1+g2=x1, g3=x1, g4=x1, and g5=x1.

[0043] R ３０The 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 present compound and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.

[0044] Z １ The ring structure in １ The preferred embodiments are also the same. １ The ring structure in ２４ is directly bonded, for example, an alkylene group is linked to the ring structure, and Q is ２４ are never connected.

[0045] 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 present compound. ｅ２ The number of carbon atoms in the alkyl group moiety of the acyloxy 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. g4 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of ease of production of the compound and further improved abrasion resistance and fingerprint removability of the surface layer.

[0046] Said L １ Other examples of the group include groups represented by any of the following formulae (Q11) to (Q17).

[0047] -A １ -C(R ｅ２ ) ３－ｇ３ (-Q ２２ -G) ｇ３ Formula (Q12) -A ２ -N(-Q ２３ -G) ２ Formula (Q13) -A ３ -Z １ (-Q ２４ -G) ｇ４Formula (Q14) -A ２ -Si(R ｅ３ ) ３－ｇ３ (-Q ２５ -G) ｇ３ Formula (Q15) -A １ -Q ２６ -G Formula (Q16) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｇ５ (-Q ２５ -G) ｇ５ Formula (Q17)

[0048] However, in formulas (Q11) to (Q17), A １ , A ２ or A ３ side is R of formula (A1) １ Connect with Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ The side (R １１ -T １ ) ｘ１ G is the following group g3, and L １ The two or more Gs in the formula (Q1) may be the same or different. The symbols other than G are the same as those in the formula (Q1) to the formula (Q7). ２１ ) ３－ｋ (-Q ３ -) ｋ Formula g3 However, in formula g3, the Si side is Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ Connect to Q ３ The side (R １１ -T １ ) ｘ１ 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 ) ｐ -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. p is an integer of 0 to 5, and when p is 2 or more, there are two or more (OSi(R ２２ ) ２ ) may be the same or different.

[0049] 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 present compound 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 present compound. 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 present compound. ２２ In view of excellent storage stability of the present compound, 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. p is preferably 0 or 1.

[0050] Furthermore, in the present invention, L １ is the branch point P １ It is preferable that the L is composed only of N atoms, C atoms, and Si atoms, and more preferable that the L is composed of N atoms, C atoms, and Si atoms. １ By selecting these as the copolymer, the effect of the difference in chain length on the abrasion resistance is more significantly exhibited.

[0051] R １１is an alkylene group or an alkylene group having an etheric oxygen atom between carbon atoms, and R １１ If there are multiple R １１ may be the same or different from each other.

[0052] R １１ The alkylene group in R which may have an etheric oxygen atom is preferably a linear one. The number of carbon atoms in the alkylene group is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8. １１ is preferably an alkylene group having no etheric oxygen atom. In the present invention, from the viewpoint of the effect of the difference in chain length on the abrasion resistance, it is preferable that R １１ If there are multiple R １１ are preferably the same.

[0053] T １ is -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ However, 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 ａ１１ is a non-hydrolyzable group, and R ａ１１ If there are multiple R ａ１１ may be the same or different. z1 is an integer of 0 to 3, and when x1 is 2 or more, multiple z1s in a molecule may be the same or different, provided that at least one of z1 is an integer of 1 to 3.

[0054] R ａ１ is a hydroxyl group, it forms a silanol (Si-OH) group together with the Si atom. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. The silanol group further reacts with other molecules to form a Si-O-Si bond. The silanol group also undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). This compound (A1) is T １By containing one or more of the above, the surface layer has excellent abrasion resistance after formation.

[0055] 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.

[0056] R ａ１ In view of ease of production of the present compound, R is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. ａ１ In terms of the excellent storage stability of the compound and the suppression of outgassing during the reaction, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, an ethoxy group is particularly preferred from the viewpoint of long-term storage stability, and a methoxy group is particularly preferred from the viewpoint of shortening the hydrolysis reaction time. Furthermore, as the halogen atom, a chlorine atom is particularly preferred.

[0057] R ａ１１ 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.

[0058] One T １ Inside R ａ１ The number z1 is an integer from 0 to 3. However, if there is no T １ When only one T is present, z1 is an integer of 1 to 3. １ When there are multiple z1's, at least one of the multiple z1's is an integer of 1 to 3. In terms of adhesion to the substrate, even when there are multiple z1's, each z1 is preferably 1 to 3, more preferably 2 or 3, and even more preferably 3. T １ Specific examples of -Si(OCH ３ ) ３ , -SiCH３ (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 is particularly preferred.

[0059] T in one molecule of compound (A1) １ The number x1 may be 1 to 20, and from the viewpoints of ease of synthesis and ease of handling of the compound (A1), x1 is preferably 1 to 12, more preferably 1 to 6. １ If there is a T １ may have the same structure as each other or may have different structures.

[0060] <Compound (A2)> Compound (A2) is a compound represented by the following formula (A2): ｆ２ - (OR ｆ１２ ) ｙ２ -O-R ２ -L ２ - (R １２ -T ２ ) ｘ２ ...(A2) where each symbol in the formula is as defined above.

[0061] The compound (A2) and the compound (A1) are represented by the formula (A1) -O-R １ -L １ -R １１ The chain length a1 of -O-R in formula (A2) ２ -L ２ -R １２ The difference is that the chain length a2 of R is different from that of R. Except for this, the embodiment of compound (A2) is the same as that of compound (A1). ｆ２ , R ｆ１２ , y2, R ２ , L ２ , R １２ , T ２The embodiments of x1 and x2 are, in this order, R ｆ１ , R ｆ１１ , y1, R １ , L １ , R １１ , T １ , and x1, respectively, and can be appropriately interpreted and applied, and the same applies to preferred embodiments.

[0062] A preferred combination of the compound (A1) and the compound (A2) when the compound (A1) and the compound (A2) are used in combination will be described below. ｆ１ and R ｆ２ It is preferable that R have the same structure as each other in order to further improve the abrasion resistance. ｆ１１ and R ｆ１２ It is preferable that the basic structure of R ｆ１１ is a structure represented by the formula (G2), R ｆ１２ The structure represented by the formula (G2) is also preferred. However, the numbers of repeating units m1 and m2 may be the same or different. ｆ１ ) and (OG ｆ２ ) may be bonded in the same order or different orders. In the surface layer obtained from this composition, the reactive silyl groups are arranged on the substrate side, and the polyfluoropolyether chains are arranged on the surface opposite to the substrate. The polyfluoropolyether chains contain many ether bonds, are relatively flexible, and are presumed to move flexibly against friction. In the present invention, the linking group to the reactive silyl group (in the case of compound (A1), R １ -L １ -R １１ It is presumed that the abrasion resistance is improved by using two or more compounds with different lengths (chain lengths), and the difference in polyfluoroether is the basic structure (fluoroalkylene R ｆ１１ It is assumed that it is sufficient if the length of the formula (G3) and the formula (G4) match. ｆ１１ is a structure represented by the formula (G3), R ｆ１２ is preferably a structure represented by the formula (G3), and R ｆ１１ is a structure represented by the formula (G4), R ｆ１２The structure represented by the formula (G4) is also preferred. However, the numbers of repeating units m2 to m4 may be the same or different. ｆ２ ) and (OG ｆ４ The bonding order of L) may be the same or different. １ and L ２ It is preferable that R have the same structure as each other in order to further improve the abrasion resistance. １ and R ２ are each preferably a structure represented by the formula (C), and R １ a + b in R ２ It is more preferable that a+b in the above formula (1) and (2) have different values. That is, the difference between the chain length a1 of the compound (A1) and the chain length a2 of the compound (A2) is １ and R ２ It is preferable that the difference in length between the two is caused by the difference in length between the two. １ and T ２ may be the same or different, but are preferably the same. Also, x1 and x2 may be the same or different, but are preferably the same.

[0063] <Compound (B1)> Compound (B1) is a compound represented by the following formula (B1): (T ３ -R １３ ) ｘ３ -L ３ -R ３ - (OR ｆ１３ ) ｙ３ -O-R ２３ -L １３ - (R ３３ -T １３ ) ｘ１３ ...(B1) where each symbol in the formula is as defined above.

[0064] The compound (B1) differs from the compound (A1) in that reactive silyl groups are arranged on both sides of the polyfluoropolyether chain. １３ -L ３ -R ３ The chain length b1 of —O— and —O—R ２３ -L １３ -R ３The chain lengths b11 of the compound (B1) are different from one another. Except for these points, the embodiment of the compound (B1) is the same as that of the compound (A1). That is, in the compound (B1), １３ , T ３ , x3, L ３ , R ３ , R ｆ１３ , y3, R ２３ , L １３ , R ３３ , T １３ The embodiments of x13 and x14 are, in this order, R １１ , T １ , x1, L １ , R １ , R ｆ１ , y1, R １ , L １ , R １１ , T １ , and x1, respectively, and can be appropriately interpreted and applied, and the same applies to preferred embodiments.

[0065] In addition, L in compound (B1) ３ and L １３ Preferably, R have the same structure. ３ and R ２３ Preferably, R have the same structure. １３ and R ３３ Preferably, T ３ and T １３ may be the same or different, but are preferably the same. Also, x3 and x13 are preferably the same.

[0066] A preferred combination of the compound (A1) and the compound (B1) when the compound (A1) and the compound (B1) are used in combination will be described below. ｆ１１ and R ｆ１３ It is preferable that the basic structure of R ｆ１１ is a structure represented by the formula (G2), R ｆ１３ The structure represented by the formula (G2) is also preferred. However, the numbers of repeating units m1 and m2 may be the same or different. ｆ１ ) and (OG ｆ２The same applies to the case of formula (G3) and formula (G4), and the bonding order of R ｆ１１ is a structure represented by the formula (G3), R ｆ１３ is preferably a structure represented by the formula (G3), and R ｆ１１ is a structure represented by the formula (G4), R ｆ１３ The structure represented by the formula (G4) is also preferred. However, the numbers of repeating units m2 to m4 may be the same or different. ｆ２ ) and (OG ｆ４ The bonding order of L) may be the same or different. １ , L ３ and L １３ It is preferable that R have the same structure as each other in order to further improve the abrasion resistance. １ , R ３ , R ２３ are preferably the structures represented by the formula (C), and R １ a + b in R ３ or R ２３ In other words, the difference between the chain length a1 of the compound (A1) and at least one of the chain lengths b1 and b11 of the compound (B1) is such that R １ and R ３ or R ２３ It is preferable that the difference in length between R ３ and R ２３ When R have the same structure, the chain length a1 is different from both the chain length b1 and the chain length b11. １１ , R １３ and R ３３ Preferably, T １ , T ３ and T １３ may be the same or different, but are preferably the same. Also, x1, x3 and x13 may be the same or different, but are preferably the same.

[0067] <Compound (B2)> Compound (B2) is a compound represented by the following formula (B2): (T ４ -R １４ ) ｘ４-L ４ -R ４ - (OR ｆ１４ ) ｙ４ -O-R ２４ -L １４ - (R ３４ -T １４ ) ｘ１４ ...(B2) where each symbol in the formula is as defined above.

[0068] The compound (B2) and the compound (B1) are represented by the formula (B1) represented by -R １３ -L ３ -R ３ The chain length b1 of —O— and —O—R ２３ -L １３ -R ３３ -R in formula (B2) １４ -L ４ -R ４ The chain length b2 of —O— and —O—R ２４ -L １４ -R ３４ At least one pair of the chain lengths b12 of - is different from each other. Except for this point, the embodiment of the compound (B2) is the same as that of the compound (B1). That is, R １４ , T ４ , x4, L ４ , R ４ , R ｆ１４ , y4, R ２４ , L １４ , R ３４ , T １４ and x14 are, in this order, R １３ , T ３ , x3, L ３ , R ３ , R ｆ１３ , y3, R ２３ , L １３ , R ３３ , T １３ , and x13, respectively, and can be applied by appropriately replacing the readings, and preferred embodiments are also the same, specifically as explained for the compound (A1) and the compound (B1).

[0069] A preferred combination of the compound (B1) and the compound (B2) when the compound (B1) and the compound (B2) are used in combination will be described below. ｆ１３ and R ｆ１４ It is preferable that the basic structure of R ｆ１３ is a structure represented by the formula (G2), R ｆ１４ The structure represented by the formula (G2) is also preferred. However, the numbers of repeating units m1 and m2 may be the same or different. ｆ１ ) and (OG ｆ２ The same applies to the case of formula (G3) and formula (G4), and the bonding order of R ｆ１３ is a structure represented by the formula (G3), R ｆ１４ is preferably a structure represented by the formula (G3), and R ｆ１３ is a structure represented by the formula (G4), R ｆ１４ The structure represented by the formula (G4) is also preferred. However, the numbers of repeating units m2 to m4 may be the same or different. ｆ２ ) and (OG ｆ４ The bonding order of L) may be the same or different. ３ , L １３ , L ４ and L １４ It is preferable that R have the same structure as each other in order to further improve the abrasion resistance. ３ , R ２３ , R ４ and R ２４ are preferably the structures represented by the formula (C), and R ３ a + b in R ４ a+b in ２３ a + b in R ２４ It is preferable that a+b in R ３ The value of a + b and R ２３ The values ​​of a+b in ４ The value of a + b and R ２４ The values ​​of a+b in ３ The value of a + b and R ４In other words, the difference between the chain lengths b1 and b11 of the compound (B1) and the chain lengths b2 and b12 of the compound (B2) is preferably ３ , R ２３ , R ４ and R ２４ It is preferable that the difference in length between R １３ , R ３３ , R １４ and R ３４ Preferably, T ３ , T １３ , T ３ and T １３ may be the same or different, but are preferably the same. Also, x3, x13, x4 and x14 may be the same or different, but are preferably the same.

[0070] The molecular weights of compounds (A1), (A2), (B1), and (B2) are preferably 500 to 100,000, and more preferably 1,000 to 20,000. Furthermore, the molecular weight distribution (Mw / Mn) of the compounds in the composition is preferably 1.0 to 2.0, and more preferably 1.0 to 1.3. When the molecular weight and molecular weight distribution are within these ranges, the composition has the advantages of low viscosity, few evaporating components, and excellent uniformity when dissolved in a solvent. The molecular weight and molecular weight distribution of the compounds can be measured by gel permeation chromatography, and are values ​​calculated in terms of polystyrene.

[0071] The present composition contains two or more compounds selected from the above-mentioned compounds (A1), (A2), (B1), and (B2), and satisfies the following (I) to (III), and therefore has particularly excellent abrasion resistance. (I) When the composition contains a compound represented by formula (A1) and a compound represented by formula (A2), -O-R in formula (A1) １ -L １ -R １１ The chain length a1 of -O-R in formula (A2) ２ -L ２ -R １２ - The chain lengths a2 of T are different from each other, １ and T ２(II) In the case where a compound represented by formula (B1) and a compound represented by formula (B2) are contained, -R in formula (B1) is different from each other in at least one pair of a1 and a2. １３ -L ３ -R ３ The chain length b1 of —O— and —O—R ２３ -L １３ -R ３３ A set of chain lengths b11 of - and -R in formula (B2) １４ -L ４ -R ４ The chain length b2 of —O— and —O—R ２４ -L １４ -R ３４ (III) In cases other than (I) and (II), the chain length a1 or the chain length a2 is different from either the chain length b1 or the chain length b11, or different from either the chain length b2 or the chain length b12.

[0072] A specific method for determining the chain length a1 of compound (A1) is as follows: ｆ１１ and T １ "-O-R" which connects １ -L １ -R １１ -" represents the number of constituent atoms. When the carbon chain has a ring structure, it represents the number of constituent atoms of the shortest carbon chain. There are x1 atoms of chain length a1. For example, in the case of the following compound (A1-10), R １ is CF ２ CH ２ and L １ is C(-) ３ and R １１ There are three identical CH ２ CH ２ CH ２ Therefore, there are three chain lengths a1, all of which are 7. In this case, the set of chain lengths a1 is also written as (7, 7, 7).

[0073] The numbers of repeating units m10 and n10 are each independently 1 to 200.

[0074] The chain length a2 of compound (A2) is also determined in the same manner. ｆ１２ and T ２ "-O-R" which connects ２ -L ２ -R １２ When the carbon chain has a ring structure, the number of constituent atoms of the shortest carbon chain is represented by a2. There are x2 atoms of the chain length a2. For example, in the case of the following compound (A2-10), R ２ is CF ２ CF ２ CH ２ and L ２ is C(-) ３ and R １２ There are three identical CH ２ CH ２ CH ２ Therefore, there are three chain lengths a2, all of which are 8. In this case, the set of chain lengths a2 is also written as (8, 8, 8).

[0075] The numbers of repeating units m11 and n11 are each independently 1 to 200.

[0076] When the chain lengths a1 and a2 are the same, as in the combination of compound (A1-10) and compound (A2-10), the chain lengths a1 and a2 are compared in descending order of length, and if at least one pair is different, it is determined that the above condition (I) is satisfied. Specifically, the set of chain lengths a1 (7,7,7) and the set of chain lengths a2 (8,8,8) are compared in descending order of length. In this case, all three pairs are different, that is, at least one pair is different from each other, and therefore it is determined that the above condition (I) is satisfied.

[0077] Similarly, T １ Compound (A1-11) having two T ２ It will be explained that the combination of the compound (A2-11) having two of the above groups satisfies (I). The numbers of repeating units m12 and n12 are each independently 1 to 200. The numbers of repeating units m13 and n13 are each independently 1 to 200.

[0078] The set of chain lengths a1 of compound (A1-11) is (7,7), and the set of chain lengths a2 of compound (A2-11) is (8,8). Therefore, when the set of chain lengths a1 (7,7) and the set of chain lengths a2 (8,8) are compared in order of length, all of the two sets are different, that is, at least one set is different from the other, and therefore it is determined that the above condition (I) is satisfied.

[0079] In the combination of compound (A1-10) and compound (A2-11), when the set of chain lengths a1 (7,7,7) of compound (A1-10) and the set of chain lengths a2 (8,8) of compound (A2-11) are compared in order of length, the two sets are different, that is, at least one set is different from the other, and therefore it is determined that the above condition (I) is satisfied.

[0080] Furthermore, in the combination of compound (A1-10) and compound (A1-11), when the set of chain lengths (7,7,7) of compound (A1-10) and the set of chain lengths (7,7) of compound (A1-11) are compared in order of increasing length, no mutually different sets exist, and therefore it is determined that the combination does not satisfy the above condition (I).

[0081] Regarding (II), the method for determining each chain length is the same as described above. A set having the longest of the sets of chain lengths b1 and b11 of compound (B1) (for example, the set of chain length b1) is compared with a set having the longest of the sets of chain lengths b2 and b12 of compound (B2) (for example, the set of chain length b2), and if at least one pair differs, the above (II) is satisfied. If the sets having the longest pairs match, the other sets (for example, chain length b11 and chain length b12) are compared. If the comparisons are made in order of length and at least one pair differs, the above (II) is satisfied. Even when the numbers are different, the comparisons are made in order of length, and if at least one pair differs, the above (II) is satisfied.

[0082] The determination method of (II) will be specifically explained below using the compound (B1-10) and the compound (B2-10). The numbers of repeating units m14 and n14 are each independently 1 to 200. The numbers of repeating units m15 and n15 each independently range from 1 to 200.

[0083] The chain length b1 of the compound (B1-10) is "-R １３ -L ３ -R ３ The chain length b11 represents the number of atoms constituting "-O-R ２３ -L １３ -R ３３ When the carbon chain has a ring structure, the number of constituent atoms of the shortest carbon chain is represented. ３ is CF ２ CH ２ CH ２ CH ２ and L ３ is C(-) ３ and R １３ There are three identical CH ２ CH ２ CH ２ Therefore, there are three chain lengths b1, all of which are 9. In this case, the set of chain lengths b1 is also described as (9,9,9). ２３ is CF ２ CH ２ CH ２ CH ２ and L １３ is C(-) ３ and R ３３ There are three identical CH ２ CH ２ CH ２ Therefore, there are three chain lengths b11, all of which are 9. In this case, the set of chain lengths b11 is also written as (9, 9, 9).

[0084] The chain length b2 of the compound (B2-10) is "-R １４ -L ４ -R ４ The chain length b12 represents the number of atoms constituting "-O-R ２４ -L １４ -R ３４ When the carbon chain has a ring structure, the number of atoms constituting the shortest carbon chain is represented. ４ is CF ２ CH ２CH ２ CH ２ CH ２ CH ２ and L ４ is C(-) ３ and R １４ There are three identical CH ２ CH ２ CH ２ Therefore, there are three chain lengths b2, all of which are 11. In this case, the set of chain lengths b2 is also described as (11, 11, 11). ２４ is CF ２ CH ２ CH ２ CH ２ CH ２ CH ２ and L １４ is C(-) ３ and R ３４ There are three identical CH ２ CH ２ CH ２ Therefore, there are three chain lengths b12, all of which are 11. In this case, the set of chain lengths b12 is also written as (11, 11, 11).

[0085] The set of chain lengths b1 of compound (B1-10) is (9,9,9), and the set of chain lengths b11 is (9,9,9). The set of chain lengths b2 of compound (B2-10) is (11,11,11), and the set of chain lengths b12 is (11,11,11). When the set having the longest of the sets of chain lengths b1 and b11 (in this case, since both are the same length, it is assumed to be chain length b1) is compared with the set having the longest of the chain lengths b2 and b12 (in this case, since both are the same length, it is assumed to be chain length b2), in order of length, all three sets are different, that is, at least one set is different from the other, and therefore it is determined that the above condition (II) is satisfied.

[0086] Similarly, T ３ and T １３ Compound (B1-11) having two of each of T ４ and T １４ It will be explained that the combination of the compound (B2-11) having two of each of the following groups satisfies the above (II). The numbers of repeating units m16 and n16 are each independently 1 to 200. The numbers of repeating units m17 and n17 are each independently 1 to 200.

[0087] The set of chain lengths b1 of compound (B1-11) is (9,9), and the set of chain lengths b11 is (9,9). The set of chain lengths b2 of compound (B2-11) is (11,11), and the set of chain lengths b12 is (11,11). Therefore, when the set having the longest of the set of chain lengths b1 and b11 (in this case, since both are the same length, it is assumed to be chain length b1) is compared with the set having the longest of the set of chain lengths b2 and b12 (in this case, since both are the same length, it is assumed to be chain length b2), in order of length, all of the two sets are different, that is, at least one set is different from the other, and therefore it is determined that the above condition (II) is satisfied.

[0088] In the combination of compound (B1-10) and compound (B2-11), when the set (9,9,9) of chain length b1 of compound (B1-10) and the set (9,9,9) of chain length b11 (in this case, since both are the same length, this is provisionally designated as chain length b1) are compared with the set (11,11) of chain length b2 of compound (B2-11) and the set (11,11) of chain length b12 (in this case, since both are the same length, this is provisionally designated as chain length b2) in order of length, the two sets are different, that is, at least one set is different from the other, and therefore it is determined that the above condition (II) is satisfied.

[0089] Furthermore, in the case of the combination of compound (B1-10) and compound (B1-11), when the set of chain lengths (9,9,9) including the longest one among the sets of chain lengths of compound (B1-10) and the set of chain lengths (9,9) including the longest one among the sets of chain lengths of compound (B1-11) are compared in order of length, no mutually different pairs exist, and therefore it is determined that the combination does not satisfy the above condition (II).

[0090] Regarding (III), for example, when compound (A1) and compound (B1) are used in combination, a set of chain lengths a1 is compared with a set of chain lengths b1, and a set of chain lengths a1 is compared with a set of chain lengths b11. The comparison is made in order of length, and if at least one pair is different, the above (III) is satisfied. Even when the number of chains is different, the comparison is made in order of length, and if at least one pair is different, the above (III) is satisfied.

[0091] For example, when compound (A1-10) and compound (B1-10) are combined, the set of chain lengths a1 (7,7,7) is compared with the set of chain lengths b1 (9,9,9), and the set of chain lengths a1 (7,7,7) is compared with the set of chain lengths b11 (9,9,9). In this case, at least one pair is different in the comparison between the set of chain lengths a1 and the set of chain lengths b1 and b11, and therefore it is determined that the above condition (III) is satisfied.

[0092] Of the present compositions, a composition containing at least the compound (A1) and the compound (A2) or a composition containing at least the compound (B1) and the compound (B2) is preferred, and a composition containing at least the compound (A1) and the compound (A2) is more preferred.

[0093] When two of the compounds (A1), (A2), (B1), and (B2) are combined, the mass ratio thereof is preferably 5:95 to 95:5. When the compounds (A1) and (A2) are combined, the mass ratio thereof is preferably 5:95 to 95:5. When the compounds (B1) and (B2) are combined, the mass ratio thereof is preferably 5:95 to 95:5.

[0094] The manufacturing method of each compound in the present composition may be appropriately selected from conventionally known methods. For example, compound (A1) and compound (B1) can be synthesized with reference to International Publication No. WO 2017 / 038830 and International Publication No. WO 2021 / 054413. For example, compound (A1) and compound (A2) can be separately produced by using raw materials with different carbon chain lengths. Although the manufacturing method is not limited to these methods, these methods can produce the present compound in high yield. The present composition is obtained by mixing the synthesized compound (A1) and compound (A2). The same applies to compound (B1) and the like.

[0095] The composition may further contain other compounds as long as the effects of the present invention are achieved. Examples of such other compounds include compounds produced as by-products during the production of compound (A1) or the like.

[0096] Specific examples of the present composition include the combinations of the following compounds. For example, a combination of compounds where the number following compound (A1-) is the same as the number following compound (A2-), such as the combination of compound (A1-12) and compound (A2-12), is preferred. Similarly, a combination of compounds where the number following compound (B1-) is the same as the number following compound (B2-), such as the combination of compound (B1-12) and compound (B2-12), is preferred. The numbers of repeating units m20 to m47, n20 to n29, n34 to n41, n44 to n47, l26 to l29, l40, and l41 each independently represent 1 to 200. In addition, although the above example illustrates a combination of two types, the present composition may contain three or more types of compounds selected from the present compounds.

[0097] The present composition may contain at least one of the following fluorine-containing compounds other than the above-mentioned compounds (A1), (A2), (B1), and (B2), and the following impurities. Examples of impurities include compounds that are unavoidable in the production of the present compounds and other fluorine-containing compounds. The present composition does not contain the liquid medium described below.

[0098] Examples of the other fluorine-containing compounds include fluorine-containing compounds produced as by-products during the production process of the present compound (hereinafter also referred to as by-product fluorine-containing compounds), known fluorine-containing compounds used for the same purposes as the present compound, etc. As the other fluorine-containing compounds, compounds that are unlikely to deteriorate the properties of the present compound are preferred. In order to fully exhibit the properties of the present compound, the content of the other fluorine-containing compounds is preferably less than 50% by mass, more preferably less than 30% by mass, and even more preferably less than 10% by mass, of the total amount of the present composition.

[0099] Examples of by-product fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of the present compound. When the present composition contains a by-product fluorine-containing compound, the purification step for removing the by-product fluorine-containing compound or reducing the amount of the by-product fluorine-containing compound can be simplified.

[0100] Examples of known fluorine-containing compounds include those 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 / 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, and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0101] The total content of compounds (A1), (A2), (B1), and (B2) in the composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. When the composition contains other fluorine-containing compounds, the ratio of the other fluorine-containing compounds to the total of compounds (A1), (A2), (B1), (B2), and other fluorine-containing compounds in the composition is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. The total content of compounds (A1), (A2), (B1), (B2), and other fluorine-containing compounds in the composition is preferably 80% by mass or more, more preferably 85% by mass or more. When the content of compounds (A1), (A2), (B1), (B2), and other fluorine-containing compounds is within the above range, the surface layer has excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

[0102] [Surface Treatment Agent] A surface treatment agent containing the present composition (hereinafter also referred to as the present surface treatment agent) is suitable for use in applications where it is required that the performance of preventing a decrease in water and oil repellency even when the surface layer is repeatedly rubbed with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability) be maintained for a long period of time, such as for components constituting the surfaces of touch panels that are touched with fingers, eyeglass lenses, and displays of wearable devices.

[0103] [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 generated in the production process of the present composition. The concentration of the present composition in the present coating liquid is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass.

[0104] 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.

[0105] Examples of fluorine-based organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. The fluorinated alkanes are preferably compounds having 4 to 8 carbon atoms. Commercially available products include, for example, 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. Examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. Preferred fluoroalkyl ethers are compounds having 4 to 12 carbon atoms. Commercially available products include, for example, 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), C４ 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 Corporation). Fluorinated alkylamines include, for example, perfluorotripropylamine and perfluorotributylamine. Fluoroalcohols include, for example, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. Non-fluorinated organic solvents are preferably compounds consisting of only hydrogen atoms and carbon atoms, and compounds consisting of only hydrogen atoms, carbon atoms, and oxygen atoms, and examples of such non-fluorinated organic solvents include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents. The coating liquid preferably contains 75 to 99.999% by mass of the liquid medium, more preferably 85 to 99.99% by mass, and particularly preferably 90 to 99.9% by mass.

[0106] 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.

[0107] The total concentration of the present composition and other components in the present coating liquid (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.

[0108] [Article] Figure 1 is a schematic cross-sectional view showing an example of an article of the present invention. The first article of the present invention is an article 20 having a substrate 12, an underlayer 14, and a surface layer 22 in this order, in which the underlayer 14 contains a silicon-containing oxide and the surface layer 22 contains a condensate of the present composition.

[0109] The material and shape of the substrate 12 in the first article may be appropriately selected depending on the application of the article 20. Examples of materials for the substrate 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. In particular, examples of substrates 12 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 in accordance with JIS R3106:1998 (ISO 9050:1990) is 25% or more. Glass or transparent resin is preferred as the material for the touch panel substrate.

[0110] The substrate 12 may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment on the surface on which the underlayer 14 is to be formed. The surface that has been subjected to the surface treatment further improves the adhesion between the substrate 12 and the underlayer 14, and as a result, further improves the abrasion resistance of the surface layer 22. As the surface treatment, corona discharge treatment or plasma treatment is preferred because it further improves the abrasion resistance of the surface layer 22.

[0111] The underlayer 14 is a layer containing at least an oxide containing silicon, and may further contain other elements. When the underlayer 14 contains silicon oxide, the T １ is dehydrated and condensed to form Si—O—Si bonds with the underlayer 14, forming a surface layer 22 with excellent abrasion resistance.

[0112] The content of silicon oxide in the underlayer 14 may be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. When the content of silicon oxide is equal to or greater than the lower limit of the above range, Si—O—Si bonds are sufficiently formed in the underlayer 14, and the mechanical properties of the underlayer 14 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 14.

[0113] From the viewpoint of durability of the surface layer 22, it is preferable that the oxide in the underlayer 14 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. The inclusion of these elements strengthens the bond between the underlayer 14 and the present composition, improving wear resistance.

[0114] When the underlayer 14 contains one or more elements selected from iron, nickel, and chromium, the total content of these elements relative to silicon oxide is preferably 10 to 1100 ppm by mass, more preferably 50 to 1100 ppm by mass, even more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass. When the underlayer 14 contains one or more elements selected from aluminum and zirconium, the total content of these elements is preferably 10 to 2500 ppm by mass, more preferably 15 to 2000 ppm by mass, and even more preferably 20 to 1000 ppm by mass. When the underlayer 14 contains an alkali metal element, the total content of these elements is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and even more preferably 1.0 to 10% by mass. Examples of alkali metal elements include lithium, sodium, potassium, rubidium, and cesium. When the underlayer 14 contains platinum group elements, the total content thereof is preferably 0.02 mass ppm to 800 mass ppm, more preferably 0.04 mass ppm to 600 mass ppm, and even more preferably 0.7 mass ppm to 200 mass ppm. Examples of platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium. When the underlayer 14 contains one or more elements selected from boron and phosphorus, the total content thereof is preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, in terms of the ratio of the molar concentration of the sum of boron and phosphorus to the molar concentration of silicon, from the viewpoint of the wear resistance of the surface layer 22. When the underlayer 14 contains alkaline earth metal elements, the total content thereof, expressed as the ratio of the molar concentration of the total alkaline earth metal elements to the molar concentration of silicon, is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2, from the viewpoint of the wear resistance of the surface layer 22. Examples of alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

[0115] From the viewpoint of improving the adhesiveness of the composition and improving the water / oil repellency and abrasion resistance of the article 20, the underlayer 14 is preferably a silicon oxide layer containing alkali metal atoms. In particular, in the silicon oxide layer, the average concentration of alkali metal atoms in a region 0.1 to 0.3 nm deep from the surface in contact with the surface layer 22 is preferably 2.0×10 １９ atoms / cm ３ On the other hand, in order to ensure sufficient mechanical properties of the silicon oxide layer, the average concentration of the alkali metal atoms is preferably 4.0×10 or more. ２２ atoms / cm ３ It is preferable that:

[0116] The thickness of the underlayer 14 is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm. If the thickness of the underlayer 14 is at least the lower limit of the above range, the underlayer 14 is likely to sufficiently improve adhesion. If the thickness of the underlayer 14 is at most the upper limit of the above range, the underlayer 14 itself will have high abrasion resistance. Methods for measuring the thickness of the underlayer 14 include a method of observing the cross section of the underlayer 14 using an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a profilometer, etc.

[0117] The underlayer 14 can be formed, for example, by depositing a deposition material having a desired composition for the underlayer 14 on the surface of the substrate 12. One example of the deposition method is vacuum deposition. Vacuum deposition is a method in which the deposition material is evaporated in a vacuum chamber and attached to the surface of the substrate 12. The temperature during deposition (for example, when using a vacuum deposition device, the temperature of the boat on which the deposition material is placed) is preferably 100 to 3000°C, and particularly preferably 500 to 3000°C. The pressure during deposition (for example, when using a vacuum deposition apparatus, the absolute pressure in a tank in which the deposition material is placed is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less. When forming the underlayer 14 using a deposition material, one deposition material may be used, or two or more deposition materials containing different elements may be used. 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 the deposition material is irradiated with an electron beam 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 be heated locally and therefore high-melting-point substances can be evaporated, and because areas not irradiated by the electron beam are at low temperatures, there is no risk of reaction with the container or the inclusion of impurities. The deposition material used in the electron gun method is preferably a molten granular or sintered material because it is less likely to scatter even when an air current is generated.

[0118] The surface layer 22 on the underlayer 14 contains a condensate of a compound contained in the present composition. Condensates of the present compound include those formed by hydrolysis of a hydrolyzable silyl group in a compound contained in the present composition to form a silanol group (Si—OH), which then undergoes an intermolecular condensation reaction to form an Si—O—Si bond, and those formed by condensation of a silanol group in the present compound with a silanol group or a Si—OM group (where M is an alkali metal element) on the surface of the underlayer 14 to form an Si—O—Si bond. The surface layer 22 may also contain a condensate of a fluorine-containing compound other than the compound contained in the present composition. That is, the surface layer 22 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.

[0119] The thickness of the surface layer 22 is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. When the thickness of the surface layer 22 is equal to or greater than the lower limit of the above range, the effect of the surface layer 22 can be sufficiently obtained. When the thickness of the surface layer 22 is equal to or less than the upper limit of the above range, the utilization efficiency is high. The thickness of the surface layer 22 is a thickness obtained using an X-ray diffractometer for thin film analysis. The thickness of the surface layer 22 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.

[0120] The second article of the present invention is an article 20 having, in this order, a substrate 10 with an undercoat layer and a surface layer 22, in which the substrate 10 with an undercoat layer contains an oxide containing silicon, and the surface layer 22 contains a condensate of the present composition.

[0121] In the second article, the base layer-attached substrate 10 has the same composition as the base layer 14 in the first article, and therefore the surface layer 22 has excellent abrasion resistance even when the surface layer 22 is formed directly on the base layer-attached substrate 10. The material of the base layer-attached substrate 10 in the second article may be any material as long as it has the composition of the base layer 14, and may be, for example, a glass substrate. Details of the material of the base layer-attached substrate 10 are the same as the materials of the substrate 12 and the base layer 14, and therefore will not be described here. The configuration of the surface layer 22 is also the same as that of the first article, and therefore will not be described here.

[0122] [Method for Producing an Article] The method for producing an article according to the present invention is a method for forming a surface layer by a dry coating method or a wet coating method using the composition, the surface treatment agent, or the coating liquid.

[0123] The present composition and the present surface treatment agent can be used directly in a dry coating method. Furthermore, the present composition and the present surface treatment agent are 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 in terms of preventing decomposition of the present composition and the simplicity of the equipment.

[0124] 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 and then drying it to remove the liquid medium. The solution of the present composition can be the present coating liquid.

[0125] The present surface treatment agent and the present coating liquid can be suitably used in 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.

[0126] To improve the abrasion resistance of the surface layer, an operation to promote the reaction between the composition and the substrate may be performed as needed. 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 moist 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, for example, pouring a solvent over the surface layer or wiping it off with a cloth soaked in the solvent.

[0127] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following, "%" means "% by mass" unless otherwise specified. Examples 2 to 9 and 11 are examples, and Examples 1 and 10 are comparative examples.

[0128] [Synthesis Example 1] The following compound (A1-1) was obtained according to the synthesis method for compound (B) in Synthesis Example 2 of WO 2018 / 143433. ３ -O-(CF ２ CF ２ O) ２０ (CF ２ O) １６ -CF２ CONHCH ２ C(CH ２ CH ２ CH ２ Si(OCH ３ ) ３ ) ３ ...Formula (A1-1)

[0129] [Synthesis Example 2] In the synthesis of compound (B) in Synthesis Example 2 of WO 2018 / 143433, CF ３ O (CF ２ CF ２ O) ２０ (CF ２ O) １６ CF ２ COOCH ３ Instead of CF ３ O (CF ２ CF ２ O) ２０ (CF ２ O) １６ CF ２ CH ２ COOCH ３ The following compound (A2-1) was obtained using the above method. The average values ​​of the numbers of repeating units m50 and n50 are 20 and 16, respectively.

[0130] In addition, CF ３ O (CF ２ CF ２ O) ２０ (CF ２ O) １６ CF ２ CH ２ COOCH ３ With reference to the following literature, the raw material was CF ３ O (CF ２ CF ２ O) ２０ (CF ２ O) １６ CF ２ It was synthesized by changing the compound to I. Example 11 of WO 2013 / 121984, Journal of Fluorine Chemistry (1988), 41(2), 173-183, and JP 2015-096545 A.

[0131] [Synthesis Example 3] The following compound (A1-2) was obtained according to the synthesis method of compound (VIII) in Example 21 of WO 2021 / 054413. The average number of repeating units m51 is 12.

[0132] [Synthesis Example 4] In the synthesis method of compound (VIII) of Example 21 of WO 2021 / 054413, the compound of [Chemical Formula 16] was used instead of the compound of [Chemical Formula 33] of Synthesis Example 11, and the compound was synthesized in the same manner as compound (VII) to obtain the following compound (A2-2). The average number of repeating units m52 is 12.

[0133] [Synthesis Example 5] The following compound (A1-3) was obtained according to the synthesis method for compound (1C-1) in Example 3 of WO 2017 / 038832. The average number of repeating units m53 is 13.

[0134] Synthesis Example 6 In the synthesis of compound (1C-1) in Example 3 of WO 2017 / 038832, CF was used instead of compound (15C-1). ３ O-(CF ２ CF ２ OCF ２ CF ２ CF ２ CF ２ O) １３ -CF ２ CF ２ -O-CF ２ CF ２ CF ２ -CH ２ CH ２ OH was used to obtain the following compound (A2-3). The average number of repeating units m54 is 13.

[0135] In addition, the above CF ３ O-(CF ２ CF ２ OCF ２ CF ２ CF ２ CF ２ O) １３ -CF ２ CF ２ -O-CF ２ CF２ CF ２ -CH ２ CH ２ OH was synthesized with reference to the following literature: Example 11 of WO 2013 / 121984, Journal of Fluorine Chemistry (1988), 41(2), 173-183.

[0136] [Synthesis Example 7] The following compound (A1-4) was obtained according to the synthesis method for compound (H) in Synthesis Example 8 of WO 2018 / 079743. The average values ​​of the numbers of repeating units m55 and n55 are 20 and 16, respectively.

[0137] [Synthesis Example 8] In addition, in the synthesis of compound (H) in Synthesis Example 8 of WO 2018 / 079743, CF ３ (CF ２ CF ２ ) ２０ (CF ２ O) １６ CF ２ CH ２ CH=CH ２ Instead of CF ３ (CF ２ CF ２ ) ２０ (CF ２ O) １６ CF ２ CH ２ CH ２ CH ２ CH=CH ２ The following compound (A2-4) was obtained by the same synthesis method as in the case of compound (H). The average numbers of repeating units m56 and n56 are 20 and 16, respectively.

[0138] [Synthesis Example 9] In the synthesis of compound (VIII) in Example 21 of WO 2021 / 054413, compound (B1-6) was used instead of compound (B1-2) to obtain the following compound (B1-1). The average numbers of repeating units m57 and n57 are 22 and 25, respectively.

[0139] [Synthesis Example 10] The following compound (B2-1) was obtained according to the synthesis method of compound (VIII) in Example 21 of WO 2021 / 054413. The average numbers of repeating units m58 and n58 are 22 and 25, respectively.

[0140] [Synthesis Example 11] In the synthesis of compound (B) of WO 2018 / 143433, NH ２ CH ２ C(CH ２ CH=CH ２ ) ３ Instead of NH ２ CH ２ CH ２ C(CH ２ CH=CH ２ ) ３ The following compound (A2-5) was obtained using the above method. The average numbers of repeating units m59 and n59 are 20 and 16, respectively.

[0141] In addition, NH ２ CH ２ CH ２ C(CH ２ CH=CH ２ ) ３ was synthesized with reference to the following literature: Synthesis Example 3-1 of WO 2021 / 059981, Tetrahedron Letters (2015), 56(23), 3658-3661.

[0142] Examples 1 to 11 The compounds synthesized in the above synthesis examples were mixed in the mass ratios shown in Table 1 to obtain compositions of Examples 1 to 11.

[0143] [Production and Evaluation of Articles] Substrates were surface-treated using the compositions obtained by the above-mentioned production methods to obtain articles. The surface treatment methods used in each example were the dry coating method and the wet coating method described below. Chemically strengthened glass was used as the substrate. The obtained articles were evaluated by the following methods. The results are shown in the table.

[0144] Dry coating was carried out using a vacuum deposition apparatus (VTR350M, manufactured by ULVAC) (vacuum deposition method). 0.5 g of each compound was placed in a molybdenum boat in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was heated to 1×10 －３ The chamber was evacuated to a pressure of 10 Pa or less. The boat on which the compound was placed was heated at a temperature increase rate of 10°C / min or less, and when the deposition rate measured by a quartz crystal oscillator film thickness meter exceeded 1 nm / sec, the shutter was opened to start film formation on the surface of the substrate. When the film thickness reached approximately 50 nm, the shutter was closed to terminate film formation on the surface of the substrate. The substrate on which the compound had been deposited was heat-treated at 200°C for 30 minutes and washed with dichloropentafluoropropane (AK-225, manufactured by AGC) to obtain an article having a surface layer on the surface of the substrate.

[0145] [Wet Coating Method] Each composition and C as a medium ４ F ９ O.C. ２ H ５ (Novec (registered trademark) 7200, manufactured by 3M Company) was mixed to prepare a coating solution with a solids concentration of 0.05%. A substrate was dipped into the coating solution, allowed to stand for 30 minutes, and then pulled out (dip coating method). The coating film was dried at 200°C for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.

[0146] (Evaluation Method) <Method for Measuring 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. The 2θ method was used to calculate the contact angle.

[0147] <Initial Contact Angle> The initial water contact angle of the surface layer was measured by the above-mentioned measurement method. The evaluation criteria are as follows: A (Good): 115 degrees or more. B (Fair): 105 degrees or more and less than 115 degrees. C (Unacceptable): Less than 105 degrees.

[0148] <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 reciprocate steel wool Bonstar (#0000) 10,000 times at a pressure of 98.07 kPa and a speed of 320 cm / min, and the water contact angle was then measured using the method described above. 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 (Good): The change in water contact angle after 15,000 reciprocating cycles is 10 degrees or less. C (Fail): The change in water contact angle after 15,000 reciprocating cycles is more than 10 degrees.

[0149]

[0150] As shown in Table 1, it was clear that the surface layer formed using the present composition had excellent abrasion resistance.

[0151] This application claims priority based on Japanese Patent Application No. 2021-185049, filed on November 12, 2021, the entire disclosure of which is incorporated herein by reference.

[0152] 10: Base material with undercoat layer, 12: Base material, 14: Undercoat layer, 20: Article, 22: Surface layer

Claims

1. A composition containing two or more selected from the compound represented by the following formula (A1), the compound represented by the following formula (A2), the compound represented by the following formula (B1), and the compound represented by the following formula (B2), and satisfying the following (I) to (III). R ｆ１ -(OR ｆ１１ ) ｙ１ -O-R １ -L １ -(R １１ -T １ ) ｘ１ ...(A1) R ｆ２ -(OR ｆ１２ ) ｙ２ -O-R ２ -L ２ -(R １２ -T ２ ) ｘ２ ...(A2) (T ３ -R １３ ) ｘ３ -L ３ -R ３ -(OR ｆ１３ ) ｙ３ -O-R ２３ -L １３ -(R ３３ -T １３ ) ｘ１３ ・・・(B1) (T ４ - R １４ ) ｘ４ - L ４ - R ４ - (OR ｆ１４ ) ｙ４ - O - R ２４ - L １４ - (R ３４ - T １４ ) ｘ１４ ・・・(B2) However, R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１１ is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of R ｆ１１ s, the plurality of R ｆ１１ s may be the same as or different from each other. R １ is an alkylene group or a fluoroalkylene group, L １ is a 1 + x1-valent group which may have a single bond or contain N, O, S, Si, and may have a branching point, where the １ and １１ atoms bonded to R and R are each independently an N, O, S, Si atom, a carbon atom forming a branching point, or a carbon atom having an oxo group (=O). R １１ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon-carbon atoms, and when there are a plurality of R １１ the plurality of R １１ may be the same as or different from each other, T １ is -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ and x1 is an integer of 1 or more, R ａ１ is a hydroxyl group or a hydrolyzable group, and when there are a plurality of Rs ａ１ where there are a plurality of Rs ａ１ may be the same as or different from each other R ａ１１ is a non-hydrolyzable group, and when there are a plurality of R ａ１１ , the plurality of R ａ１１ may be the same as or different from each other. z1 is an integer from 0 to 3. When x1 is 2 or more, a plurality of z1 in the molecule may be the same or different from each other. However, at least one of z1 is an integer from 1 to 3, y1 is an integer of 1 or more, R ｆ２ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１２ is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of R ｆ１２ s, the plurality of R ｆ１２ s may be the same as or different from each other. R ２ is an alkylene group or a fluoroalkylene group, L ２ is a 1 + x divalent group which may have a single bond or contain N, O, S, Si and may have a branching point, where the ２ and １２ atoms bonded to R are each independently an N, O, S, Si atom, a carbon atom forming a branching point, or a carbon atom having an oxo group (=O). R １２ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon-carbon atoms, and when there are a plurality of R １２ the plurality of R １２ may be the same as or different from each other. T ２ is -SiR ａ２ ｚ２ R ａ１２ ３－ｚ２ and x2 is an integer of 1 or more, R ａ２ is a hydroxyl group or a hydrolyzable group, and when there are a plurality of R ａ２ s, the plurality of Rs ａ２ may be the same as or different from each other. R ａ１２ is a non-hydrolyzable group, and when there are a plurality of R ａ１２ , the plurality of R ａ１２ may be the same as or different from each other. z2 is an integer from 0 to 3. When x2 is 2 or more, a plurality of z2 in the molecule may be the same or different from each other. However, at least one of z2 is an integer from 1 to 3, y2 is an integer of 1 or more, R ｆ１３ is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of R ｆ１３ , the plurality of R ｆ１３ may be the same as or different from each other. R ３ is an alkylene group or a fluoroalkylene group, R ２３ is an alkylene group or a fluoroalkylene group, L ３ is a 1 + x trivalent group which may have a single bond or contain N, O, S, Si and may have a branching point, where the atoms bonded to ３ R １３ and R are N, O, S, Si atoms, carbon atoms forming a branching point, or carbon atoms having an oxo group (=O). L １３ is a 1 + x trivalent group which may have a single bond or contain N, O, S, Si and may have a branching point, where the atoms ２３ bonded to R ３３ and R are N, O, S, Si atoms, carbon atoms forming a branching point, or carbon atoms having an oxo group (=O). R １３ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon-carbon atoms, and when there are a plurality of Rs １３ the plurality of Rs １３ may be the same as or different from each other R ３３ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon-carbon atoms, and when there are a plurality of R ３３ the plurality of R ３３ may be the same as or different from each other. T ３ and T １３ are each independently, -SiR ａ３ ｚ３ R ａ１３ ３－ｚ３ wherein x3 and x13 are each independently an integer of 1 or more, R ａ３ is a hydroxyl group or a hydrolyzable group, and when there are a plurality of R ａ３ , the plurality of R ａ３ may be the same as or different from each other. R ａ１３ is a non-hydrolyzable group, and when there are a plurality of R ａ１３ , the plurality of R ａ１３ may be the same as or different from each other. z3 is an integer from 0 to 3. A plurality of z3 in the molecule may be the same or different from each other. However, at least one of z3 is an integer from 1 to 3, y3 is an integer of 1 or more, R ｆ１４ is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of Rs ｆ１４ the plurality of Rs ｆ１４ may be the same as or different from each other R ４ is an alkylene group or a fluoroalkylene group, R ２４ is an alkylene group or a fluoroalkylene group, L ４ is a 1 + x tetravalent group which may have a single bond or contain N, O, S, Si and may have a branching point, and the atoms ４ bonded to R １４ and R are N, O, S, Si atoms, carbon atoms constituting the branching point, or carbon atoms having an oxo group (=O). L １４ is a 1 + x tetravalent group which may have a single bond or contain N, O, S, Si and may have a branching point, where the atoms ２４ bonded to R ３４ and R are N, O, S, Si atoms, carbon atoms forming a branching point, or carbon atoms having an oxo group (=O). R １４ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon-carbon atoms, where R １４ when there are a plurality of them, the plurality of Rs １４ may be the same as or different from each other, R ３４ is an alkylene group or an alkylene group having an etheric oxygen atom between carbon-carbon atoms, and when there are a plurality of Rs ３４ the plurality of Rs ３４ may be the same as or different from each other T ４ and T １４ are each independently, -SiR ａ４ ｚ４ R ａ１４ ３－ｚ４ wherein x4 and x14 are each independently an integer of 1 or more, R ａ４ is a hydroxyl group or a hydrolyzable group, and when there are a plurality of R ａ４ s, the plurality of Rs ａ４ may be the same as or different from each other, R ａ１４ is a non-hydrolyzable group, and when there are a plurality of R ａ１４ , the plurality of R ａ１４ may be the same as or different from each other. z4 is an integer from 0 to 3. A plurality of z4 in the molecule may be the same or different from each other. However, at least one of z4 is an integer from 1 to 3, y4 is an integer of 1 or more, (I) When containing the compound represented by formula (A1) and the compound represented by formula (A2), -O-R in formula (A1) １ -L １ -R １１ - and the chain length a1 of -O-R in formula (A2) ２ -L ２ -R １２ wherein the chain lengths a2 of - are different from each other However, T １ and T ２ If there are a plurality of them, at least one set of the plurality of chain lengths a1 and chain length a2 are different from each other. (II) When containing the compound represented by formula (B1) and the compound represented by formula (B2), -R in formula (B1) １３ -L ３ -R ３ The chain length b1 of -O-, -O-R ２３ -L １３ -R ３３ The set of chain lengths b11 of -, and -R in formula (B2) １４ -L ４ -R ４ The chain length b2 of -O- and the chain length b12 of -O-R ２４ -L １４ -R ３４ At least one set of the chain lengths b12 and b2 is different from each other. (III) In cases other than the above (I) and (II), The chain length a1 or the chain length a2 is different from either the chain length b1 or the chain length b11, or either the chain length b2 or the chain length b12.

2. The composition according to claim 1, containing the compound represented by the formula (A1) and the compound represented by the formula (A2), or containing the compound represented by the formula (B1) and the compound represented by the formula (B2).

3. R ｆ１ and R ｆ２ are the same, the composition according to claim 2.

4. L １ and L ２ are the same, or, L ３ and L ４ are the same, and L １３ and L １４ are the same The composition according to claim 2.

5. R １ 、R ２ 、R ３ 、R ４ 、R ２３ and R ２４ are each independently the composition according to any one of claims 1 to 4, represented by the following formula (C). *-(CR ４１ ２ ) ａ -(CH ２ ) ｂ -**... Formula (C) However, R ４１ each independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, provided that at least one of two Rs bonded to one carbon atom ４１ is a fluorine atom or a fluoroalkyl group, and a plurality of Rs ４１ may be the same or different a is an integer from 0 to 6, b is an integer from 0 to 10, a + b is an integer from 1 to 16, * is a bond with O, ** is L １ L ２ L ３ L ４ L １３ or L １４ and is a linking hand therewith.

6. R １ the a + b in ２ the a + b in is a different value, or R ３ The a + b in, and R ４ The a + b in is a different value, and R ２３ The a + b in, and R ２４ The a + b in is a different value The composition according to claim 5.

7. A surface treatment agent containing the composition according to any one of claims 1 to 4.

8. A surface treatment agent containing the composition according to claim 5.

9. A surface treatment agent comprising the composition according to claim 6.

10. A coating liquid comprising the composition according to any one of claims 1 to 4 and a liquid medium.

11. A coating liquid comprising the composition according to claim 5 and a liquid medium.

12. A coating liquid comprising the composition according to claim 6 and a liquid medium.

13. An article having, on the surface of a substrate, a surface layer formed from the composition according to any one of claims 1 to 4 or a surface treatment agent comprising the composition according to any one of claims 1 to 4.

14. An article having, on the surface of a substrate, a surface layer formed from the composition according to claim 5 or a surface treatment agent comprising the composition according to claim 5.

15. An article having, on the surface of a substrate, a surface layer formed from the composition according to claim 6 or a surface treatment agent comprising the composition according to claim 6.

16. A method for manufacturing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the composition according to any one of claims 1 to 4, a surface treatment agent comprising the composition according to any one of claims 1 to 4, or a coating liquid comprising the composition according to any one of claims 1 to 4 and a liquid medium.

17. A method for manufacturing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the composition according to claim 5, a surface treatment agent comprising the composition according to claim 5, or a coating liquid comprising the composition according to claim 5 and a liquid medium.

18. A method for manufacturing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the composition according to claim 6, a surface treatment agent comprising the composition according to claim 6, or a coating liquid comprising the composition according to claim 6 and a liquid medium.

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