Compound, composition, surface treatment agent, coating liquid, article, and method for manufacturing article

Abstract

Provided are a compound that can form a surface layer excelling in wear resistance, a composition, a surface treatment agent, a coating liquid, an article having a surface layer with excellent wear resistance, and a method for manufacturing the article. The compound comprises a fluoropolyether chain and a group represented by formula (g1).　(g1): *-Rg1-Tg1 In formula (g1), Rg1 is an alkylene group which may have an etheric oxygen atom between carbon atoms and in which the atom having the bond denoted by * may be an etheric oxygen atom, and has a carbon chain in which nine or more carbon atoms are linked. Tg1 is -SiRa1 z1Ra2 3-z1, and the other symbols are as described in the specification.

Description

Compound, composition, surface treatment agent, coating liquid, article, and method for manufacturing article

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

[0002] Fluorine-containing ether compounds having a perfluoropolyether chain and a hydrolyzable silyl group are suitable for use as surface treatment agents because they 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 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) must be maintained for a long period of time, such as for components constituting the surfaces of touch panels that are touched by fingers, eyeglass lenses, and displays of wearable devices.

[0003] For example, Patent Document 1 proposes a surface treatment agent containing a specific fluorine-containing silane compound that provides water repellency, oil repellency, etc. and forms a durable surface treatment layer.

[0004] International Publication No. 2021 / 010105

[0005] The present invention aims to provide a compound, composition, surface treatment agent, and coating liquid that can form a surface layer with excellent abrasion resistance, as well as an article having a surface layer with excellent abrasion resistance and a method for producing the article.

[0006] The present invention provides a compound, 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

[12] .

[0007] [1] A compound having a fluoropolyether chain and a group represented by the following formula (g1): *-R ｇ１ -T ｇ１ ... (g1) where R ｇ１ is an alkylene group in which the atom having the bond * may be an ethereal oxygen atom, or which may have an ethereal oxygen atom between carbon atoms, and which has a carbon chain in which 9 or more carbon atoms are linked; T ｇ１ is -SiR ａ１ｚ１ R ａ２ ３－ｚ１ 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 ａ２ is a non-hydrolyzable group, and R ａ２ If there are multiple R ａ２ may be the same or different, z1 is an integer of 1 to 3, and * is a bond bonded to the fluoropolyether chain directly or via a linking group. [2] The R ｇ１ is a group represented by the following formula (g2): *-(O) ａ１ -R ｇ９ -** ... (g2) where R ｇ９ represents an alkylene group having 9 or more carbon atoms, a1 represents 0 or 1, * represents a bond bonded to the fluoropolyether chain directly or via a linking group, and ** represents T in formula (g1). ｇ１ [3] The R ｇ９ is an alkylene group having 11 or more carbon atoms. ｇ９ is an alkylene group having 19 or less carbon atoms. [5] The compound of [2] or [3]. ｇ９ The compound according to any one of [2] to [4], wherein the alkylene group in the formula is a linear alkylene group. [6] The compound according to any one of [1] to [5], wherein the alkylene group in the formula is a linear alkylene group. [R ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ ] ｊ -L １ - (R １１ -T １１ ) ｘ１ ... (A1) (T ３１ -R ３１ ) ｘ３ -L ３ -R ３ - (OR ｆ１２ ) ｙ２ -O-R ２ -L ２- (R ２１ -T ２１ ) ｘ２ ... (A2) Q １ [-(OR ｆ１３ ) ｙ３ -O-R ４ -L ４ - (R ４１ -T ４１ ) ｘ４ ] ｒ１ ... (A3) However, R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms, and R ｆ１ If there are multiple R ｆ１ may be the same or different, 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 R １ If there are multiple R １ may be the same or different, L １ is a single bond or a j+x monovalent group which may contain N, O, S, or Si and may have a branch point, and R １ and R １１ 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 a hydroxyl group or an oxo group (═O), １１ Is, L １ The atom bonded to R may be an ethereal oxygen atom, and an alkylene group may have an ethereal oxygen atom between carbon atoms, １１ If there are multiple R １１ may be the same or different, provided that R １１ At least one of the carbon atoms in the carbon chain is 9 or more carbon atoms; １１ is -SiR ａ１１ ｚ１１ R ａ１２ ３－ｚ１１ And T １１ If there are multiple T １１may be the same or different, R ａ１１ is a hydroxyl group or a hydrolyzable group, and R ａ１１ If there are multiple R ａ１１ may be the same or different, R ａ１２ is a non-hydrolyzable group, and R ａ１２ If there are multiple R ａ１２ may be the same or different from each other, j is an integer of 1 or more, z11 is an integer of 1 to 3, x1 is an integer of 1 or more, y1 is an integer of 1 or more, and when there are multiple y1's, the multiple y1's may be the same or different from each other, 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 and R ３ are each independently an alkylene group or a fluoroalkylene group; 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 ２１ The atoms bonded to L are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (═O), 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 ３１ 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 a hydroxyl group or an oxo group (═O), ２１ Is, L ２ The atom adjacent to R may be an ethereal oxygen atom, and an alkylene group may have an ethereal oxygen atom between carbon atoms, ２１ If there are multiple R ２１ may be the same or different, R ３１ Is, L ３The atom adjacent to R may be an ethereal oxygen atom, and an alkylene group may have an ethereal oxygen atom between carbon atoms, ３１ If there are multiple R ３１ may be the same or different, provided that R ２１ and R ３１ At least one of the carbon atoms in the carbon chain is 9 or more carbon atoms; ２１ and T ３１ are each independently —SiR ａ２１ ｚ２１ R ａ２２ ３－ｚ２１ And T ２１ or T ３１ If there are multiple T ２１ and T ３１ may be the same or different from each other independently, R ａ２１ is a hydroxyl group or a hydrolyzable group, and R ａ２１ If there are multiple R ａ２１ may be the same or different, R ａ２２ is a non-hydrolyzable group, and R ａ２２ If there are multiple R ａ２２ may be the same or different, z21 is an integer of 1 to 3, x2 and x3 are each independently an integer of 1 or more, y2 is an integer of 1 or more, Q １ is a 1-valent group having a branch point, 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 ４ are each independently an alkylene group or a fluoroalkylene group, and R ４ If there are multiple R ４ may be the same or different, 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 ４１The atoms bonded to L are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O), ４ If there are multiple L ４ may be the same or different, R ４１ Is, L ４ The atom adjacent to R may be an ethereal oxygen atom, and an alkylene group may have an ethereal oxygen atom between carbon atoms, ４１ If there are multiple R １１ may be the same or different, provided that R ４１ At least one of the carbon atoms in the carbon chain is 9 or more carbon atoms; ４１ is -SiR ａ４１ ｚ４１ R ａ４２ ３－ｚ４１ And T ４１ If there are multiple T ４１ may be the same or different, R ａ４１ is a hydroxyl group or a hydrolyzable group, and R ａ４１ If there are multiple R ａ４１ may be the same or different, R ａ４２ is a non-hydrolyzable group, and R ａ４２ If there are multiple R ａ４２may be the same or different, z41 is an integer of 1 to 3, x41 is an integer of 1 or greater, and when there are multiple x41, the multiple x41 may be the same or different, y3 is an integer of 1 or greater, and when there are multiple y3, the multiple y3 may be the same or different, and r1 is 3 or 4. [7] A composition containing any of the compounds [1] to [6] and another fluorine-containing compound. [8] A surface treatment agent containing any of the compounds [1] to [6] or the composition [7]. [9] A coating liquid containing any of the compounds [1] to [6] or the composition [7] and a liquid medium.

[10] An article having a surface layer formed on the surface of a substrate from any of the compounds [1] to [6], the composition [7], or the surface treatment agent [8].

[11] A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the compound according to any one of [1] to [6], the composition of [7], the surface treatment agent of [8], or the coating liquid of [9].

[12] A compound having a fluoropolyether chain and a group represented by the following formula (g2): *-R ｇ２ -CH=CH ２ ... (g2) where R ｇ２ represents an alkylene group in which the atom having the bond * may be an ethereal oxygen atom or which may have an ethereal oxygen atom between carbon atoms, and which may be formed independently or in the form of -CH=CH ２ In combination with the above, a carbon chain of 9 or more carbon atoms is formed, and * is a bond that is bonded to the fluoropolyether chain directly or via a linking group.

[0008] The present invention provides a compound, composition, surface treatment agent, and coating liquid that can form a surface layer with excellent abrasion resistance, as well as an article having a surface layer with excellent abrasion resistance and a method for producing the article.

[0009] 1 is a schematic cross-sectional view showing an example of an article of the present invention.

[0010] In this specification, a group represented by formula (g1) may be referred to as group (g1). A compound represented by formula (A1) may be referred to as compound (A1). Compounds represented by other formulas may also be referred to as such. A fluoroalkyl group is a collective term that includes perfluoroalkyl groups and partial fluoroalkyl groups. A perfluoroalkyl group refers to a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms. A partial fluoroalkyl group refers to an alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms and which also has one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group having one or more fluorine atoms. A "reactive silyl group" is a collective term for hydrolyzable silyl groups and silanol groups (Si—OH), and a "hydrolyzable silyl group" refers to a group that can form a silanol group by hydrolysis. An "organic group" refers to a hydrocarbon group that may have a substituent and may have a heteroatom or other bond in the carbon chain. The term "hydrocarbon group" refers to a group consisting of carbon atoms and hydrogen atoms, and includes aliphatic hydrocarbon groups (straight-chain alkylene groups, branched alkylene groups, cycloalkylene groups, etc.), aromatic hydrocarbon groups (phenylene groups, etc.), and groups consisting of combinations thereof. The term "surface layer" refers to a layer formed on the surface of a substrate. The "molecular weight" of a fluoropolyether chain is １ H-NMR and １９ The number average molecular weight is calculated by F-NMR to determine the number (average value) of oxyfluoroalkylene units based on the terminal groups. The range of values ​​indicated by "to" means that the values ​​before and after it are included as the lower and upper limits.

[0011] [Compound] The compound of the present invention (hereinafter also referred to as the present compound) is characterized by having a fluoropolyether chain and a group represented by the following formula (g1): *-R ｇ１ -T ｇ１ ... (g1) where R ｇ１ is an alkylene group in which the atom having the bond * may be an ethereal oxygen atom, or which may have an ethereal oxygen atom between carbon atoms, and which has a carbon chain in which 9 or more carbon atoms are linked; T ｇ１ is -SiRａ１ ｚ１ R ａ２ ３－ｚ１ 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 ａ２ is a non-hydrolyzable group, and R ａ２ If there are multiple R ａ２ may be the same or different, z1 is an integer of 1 to 3, and * is a bond that is bonded to the fluoropolyether chain directly or via a linking group.

[0012] Because this compound has a fluoropolyether chain, the surface layer obtained using this compound has excellent water and oil repellency and fingerprint stain removability. This compound has a reactive silyl group. This reactive silyl group is strongly chemically bonded to the substrate, so the resulting surface layer has excellent durability, such as abrasion resistance. In this compound, the group (g1) has a carbon chain connecting 9 or more carbon atoms. By having this carbon chain relatively close to the reactive silyl group, intermolecular interactions between the carbon chains are more likely to occur, making it easier for the molecules to be aligned and arranged during surface layer formation, and it is believed that this compound is more densely arranged in the surface layer. As a result, it is believed that wear resistance in particular is improved.

[0013] The fluoropolyether chain is a group having two or more oxyfluoroalkylene units. The oxyfluoroalkylene units include the OR ｆ１１ The fluoropolyether chain includes the following [R ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １]. The fluoropolyether chain may have hydrogen atoms. From the viewpoint of achieving superior abrasion resistance and fingerprint stain removability of the surface layer, the proportion of fluorine atoms in the fluoropolyether chain represented by the following mathematical formula (I) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, i.e., a perfluoropolyether chain. If the fluorine atoms are 60% or more, the amount of fluorine in the fluoropolyether chain increases, further improving the smoothness and fingerprint removability. Mathematical formula (I): Proportion of fluorine atoms (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} × 100

[0014] The molecular weight per fluoropolyether chain is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, and even more preferably 3,000 to 10,000, from the viewpoint of achieving both fingerprint removability and slip resistance of the surface layer. If the molecular weight of the fluoropolyether chain is 2,000 or more, the flexibility of the fluoropolyether chain is improved and the amount of fluorine in the molecule is increased, thereby further improving finger slip resistance and fingerprint removability. On the other hand, if the molecular weight of the fluoropolyether chain is 20,000 or less, the surface layer will have better abrasion resistance.

[0015] R ｇ１ is an alkylene group in which the atom having the bond * may be an ethereal oxygen atom, or which may have an ethereal oxygen atom between carbon atoms, and which has a carbon chain of 9 or more carbon atoms. ｇ１ The alkylene group in may be linear or may have a branched and / or cyclic structure. In view of the ease with which the present compound is densely arranged when forming a surface layer, an alkylene group having a methylene group as a linear or branched chain is preferred, and a linear alkylene group is more preferred. The term "having a carbon chain in which 9 or more carbon atoms are linked" means that R ｇ１ It indicates that an alkylene group having 9 or more carbon atoms is contained therein. In the case of an alkylene group having a branched and / or cyclic structure, the carbon atoms of the branched and cyclic structures are also included. Specifically, for example, -CH ２ CH ２ CH(-CH ２ CH ３ )-CH２ CH ２ CH ２ CH ２ - has a carbon chain with nine carbon atoms, including the branched carbon atoms. The number of carbon atoms constituting the carbon chain is preferably 11 or more from the viewpoint of abrasion resistance as a surface layer. There is no particular upper limit, but the number of carbon atoms is preferably 19 or less from the viewpoint of superior water and oil repellency and fingerprint stain removability.

[0016] R ｇ１ In the alkylene group in the formula (I), the atom adjacent to * may be an ethereal oxygen atom, or an ethereal oxygen atom may be present between carbon atoms. ｇ１ can be expressed by the following formula (g4): *-(O) ａ１ - (R ｇ４ O) ａ２ -R ｇ４ -** ... (g4) where R ｇ４ is an alkylene group having one or more carbon atoms, and ｇ４ may be the same or different, provided that R ｇ４ at least one of the groups is an alkylene group having 9 or more carbon atoms, a1 is 0 or 1, a2 is an integer of 0 or more, * is a bond bonded to the fluoropolyether chain directly or via a linking group, and ** is T in formula (g1). ｇ１ is the bond that bonds to

[0017] When a1 is 0, the atom having the bond * is a carbon atom, and when a1 is 1, the atom having the bond * is an oxygen atom. In this compound, a1 may be either 0 or 1, and may be appropriately selected from the viewpoint of synthesis, etc. a2 is R ｇ４ R is the number of repetitions of O, and from the viewpoint of durability as a surface layer, it is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1. ｇ４ At least one of R may be an alkylene group having 9 or more carbon atoms. ｇ４ When there are a plurality of R groups, it is preferable that only one of them is an alkylene group having 9 or more carbon atoms. ｇ４is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms.

[0018] R ｇ１ is more preferably a group represented by the following formula (g2) in that the surface layer has better water and oil repellency and fingerprint stain removability, and is also excellent in durability such as abrasion resistance. When an alkylene group having 9 or more carbon atoms is adjacent to a hydrolyzable silyl group, the abrasion resistance of the surface layer is further improved. *-(O) ａ１ -R ｇ９ -** ... (g2) where R ｇ９ represents an alkylene group having 9 or more carbon atoms, and a1, *, and ** are the same as in formula (g4).

[0019] R ｇ９ The alkylene group in R may be linear or may have a branched and / or cyclic structure. A linear alkylene group is preferred in that the present compound is easily arranged densely when forming a surface layer. ｇ９ The number of carbon atoms in the alkylene group in the formula (I) may be 9 or more, and from the viewpoint of abrasion resistance as a surface layer, it is preferably 11 or more. There is no particular upper limit, but from the viewpoint of superior water and oil repellency and fingerprint stain removability, the number of carbon atoms is preferably 19 or less.

[0020] T ｇ１ is -SiR ａ１ ｚ１ R ａ２ ３－ｚ１ where R ａ１ is a hydroxyl group or a hydrolyzable group, and R ａ１ If there are multiple R ａ１ may be the same or different, R ａ２ is a non-hydrolyzable group, and R ａ２ If there are multiple R ａ２ may be the same or different, and z1 is an integer of 1 to 3.

[0021] R ａ１is a hydroxyl group, it forms a silanol (Si-OH) group together with the Si atom. Also, a hydrolyzable group is a group that becomes a hydroxyl group (i.e., a silanol group) through a hydrolysis reaction. The silanol group further reacts with other molecules to form a Si-O-Si bond. Furthermore, the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). This compound is T ｇ１ By containing one or more of the above, the surface layer has excellent abrasion resistance after formation.

[0022] 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.

[0023] 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 alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred, as it provides excellent storage stability for the compound and suppresses outgassing during the reaction, an ethoxy group is particularly preferred from the standpoint of long-term storage stability, and a methoxy group is particularly preferred from the standpoint of shortening the hydrolysis reaction time. Also, as the halogen atom, a chlorine atom is particularly preferred.

[0024] R ａ２ Examples of the non-hydrolyzable group include a hydrogen atom or a monovalent hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group, and the hydrocarbon group may be substituted with fluorine. From the standpoint of ease of production, the hydrocarbon group is preferably an alkyl group. 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.

[0025] z1 may be an integer of 1 to 3, and from the viewpoint of adhesion to the substrate, it is preferably 2 or 3, and more preferably 3. ｇ１Specific examples of -Si(OCH ３ ) ３ , -SiCH ３ (OCH ３ ) ２ , -Si(OCH ２ CH ３ ) ３ , -SiCl ３ , -Si(OCOCH ３ ) ３ , —Si(NCO) ３ , -Si(OCH ２ CF ３ ) ３ From the viewpoint of ease of handling in production, -Si(OCH ３ ) ３ is particularly preferred. ｇ１ If there are multiple T ｇ１ may be the same or different.

[0026] In the present compound, the fluoropolyether chain and the group (g1) are bonded directly or via a linking group. Examples of the linking group include a divalent or higher group, and more specifically, examples of the linking group include the group L １ Examples include groups described in the above. The number of fluoropolyether chains in one molecule of the present compound may be one or two or more. From the viewpoint of ease of synthesis, the number of fluoropolyether chains in one molecule is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. The number of groups (g1) in one molecule of the present compound may be one or two or more. From the viewpoint of achieving both abrasion resistance and water and oil repellency, the number of groups (g1) is preferably 1 to 32, more preferably 1 to 18, and even more preferably 2 to 12. When there are multiple fluoropolyether chains, the multiple fluoropolyether chains may be the same or different. When there are multiple groups (g1), the groups (g1) may be the same or different, but from the viewpoint of abrasion resistance, it is preferable that all of the groups (g1) are groups represented by formula (g2), and further, R ｇ９ It is preferable that the number of carbon atoms of the alkylene groups in

[0027] The present compound may be any compound as long as it satisfies the above-mentioned constitution. In terms of ease of synthesis and ease of handling of the compound, among others, a compound represented by the following formula (A1), (A2) or (A3) is preferred. [R ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ ] ｊ -L １ - (R １１ -T １１ ) ｘ１ ... (A1) (T ３１ -R ３１ ) ｘ３ -L ３ -R ３ - (OR ｆ１２ ) ｙ２ -O-R ２ -L ２ - (R ２１ -T ２１ ) ｘ２ ... (A2) Q １ [-(OR ｆ１３ ) ｙ３ -O-R ４ -L ４ - (R ４１ -T ４１ ) ｘ４ ] ｒ１ ... (A3) However, R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms, and R ｆ１ If there are multiple R ｆ１ may be the same or different, 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 R １ If there are multiple R １ may be the same or different, L １ is a single bond or a j+x monovalent group which may contain N, O, S, or Si and may have a branch point, and R １ and R １１Atoms 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 a hydroxyl group or an oxo group (═O), １１ Is, L １ The atom bonded to R may be an ethereal oxygen atom, and an alkylene group may have an ethereal oxygen atom between carbon atoms, １１ If there are multiple R １１ may be the same or different, provided that R １１ At least one of the carbon atoms in the carbon chain is 9 or more carbon atoms; １１ is -SiR ａ１１ ｚ１１ R ａ１２ ３－ｚ１１ And T １１ If there are multiple T １１ may be the same or different, R ａ１１ is a hydroxyl group or a hydrolyzable group, and R ａ１１ If there are multiple R ａ１１ may be the same or different, R ａ１２ is a non-hydrolyzable group, and R ａ１２ If there are multiple R ａ１２ may be the same or different from each other, j is an integer of 1 or more, z11 is an integer of 1 to 3, x1 is an integer of 1 or more, y1 is an integer of 1 or more, and when there are multiple y1's, the multiple y1's may be the same or different from each other, 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 and R ３ are each independently an alkylene group or a fluoroalkylene group; 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 ２１The atoms bonded to L are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (═O), 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 ３１ 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 a hydroxyl group or an oxo group (═O), ２１ Is, L ２ The atom adjacent to R may be an ethereal oxygen atom, and an alkylene group may have an ethereal oxygen atom between carbon atoms, ２１ If there are multiple R ２１ may be the same or different, R ３１ Is, L ３ The atom adjacent to R may be an ethereal oxygen atom, and an alkylene group may have an ethereal oxygen atom between carbon atoms, ３１ If there are multiple R ３１ may be the same or different, provided that R ２１ and R ３１ At least one of the carbon atoms in the carbon chain is 9 or more carbon atoms; ２１ and T ３１ are each independently —SiR ａ２１ ｚ２１ R ａ２２ ３－ｚ２１ And T ２１ or T ３１ If there are multiple T ２１ and T ３１ may be the same or different from each other independently, R ａ２１ is a hydroxyl group or a hydrolyzable group, and R ａ２１ If there are multiple R ａ２１ may be the same or different, R ａ２２ is a non-hydrolyzable group, and R ａ２２ If there are multiple R ａ２２may be the same or different, z21 is an integer of 1 to 3, x2 and x3 are each independently an integer of 1 or more, y2 is an integer of 1 or more, Q １ is a 1-valent group having a branch point, 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 ４ are each independently an alkylene group or a fluoroalkylene group, and R ４ If there are multiple R ４ may be the same or different, 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 ４１ The atoms bonded to L are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O), ４ If there are multiple L ４ may be the same or different, R ４１ Is, L ４ The atom adjacent to R may be an ethereal oxygen atom, and an alkylene group may have an ethereal oxygen atom between carbon atoms, ４１ If there are multiple R １１ may be the same or different, provided that R ４１ At least one of the carbon atoms in the carbon chain is 9 or more carbon atoms; ４１ is -SiR ａ４１ ｚ４１ R ａ４２ ３－ｚ４１ And T ４１ If there are multiple T ４１ may be the same or different, R ａ４１ is a hydroxyl group or a hydrolyzable group, and R ａ４１ If there are multiple R ａ４１ may be the same or different, R ａ４２is a non-hydrolyzable group, and R ａ４２ If there are multiple R ａ４２ may be the same or different from each other, z41 is an integer of 1 to 3, x41 is an integer of 1 or greater, and when there are multiple x41s, the multiple x41s may be the same or different from each other, y3 is an integer of 1 or greater, and when there are multiple y3s, the multiple y3s may be the same or different from each other, and r1 is 3 or 4. The structure of each compound will be explained below, but symbols having similar structures will be indicated as such and can be read interchangeably for reference as appropriate.

[0028] <Compound (A1)> Compound (A1) has a structure represented by the following formula (A1): [R ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ ] ｊ -L １ - (R １１ -T １１ ) ｘ１ ...(A1) where each symbol in formula (A1) is as defined above.

[0029] R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms. The fluoroalkyl group may be linear or may have a branched and / or cyclic structure. From the viewpoint of abrasion resistance, a linear fluoroalkyl group is preferred, and from the viewpoint of ease of synthesis, the fluoroalkyl group preferably has 1 to 6 carbon atoms.

[0030] 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 represents a fluoropolyether chain, and y1 may be an integer of 1 or more, preferably 1 to 200.

[0031] (OR ｆ１１ ) ｙ１ Preferably, the compound has a structure represented by the following formula (G11): -[(OG ｆ１ )ｍ１ (OG ｆ２ ) ｍ２ (OG ｆ３ ) ｍ３ (OG ｆ４ ) ｍ４ (OG ｆ５ ) ｍ５ (OG ｆ６ ) ｍ６ ] - Formula (G11) 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 ) ~ (OG ｆ６ The bonding order of m1 to m6 in formula (G11) is arbitrary. ｆ１ ) ~ (OG ｆ６ ) and does not represent the arrangement. For example, (OG ｆ５ ) ｍ５ (OG ｆ５ ) is m5, and (OG ｆ５ ) ｍ５ Similarly, it does not represent the block arrangement structure of (OG ｆ１ ) ~ (OG ｆ６ The order of the units does not represent the bonding order of the units. The fluoroalkylene group having 3 to 6 carbon atoms may be a linear fluoroalkylene group or a fluoroalkylene group having a branched or cyclic structure.

[0032] G ｆ１ Specific examples of the group include -CF ２ -, -CHF-. ｆ２ Specific examples of the group include -CF ２ CF２ -1, -CHFCF ２ -1, -CHFCHF-, -CH ２ CF ２ -1, -CH ２ CHF- etc. can be mentioned. G ｆ３ As a specific example of, -CF ２ CF ２ CF ２ -1, -CF ２ CHFCF ２ -1, -CF ２ CH ２ CF ２ -1, -CHFCF ２ CF ２ -1, -CHFCHFCF ２ -1, -CHFCHFCHF-, -CHFCH ２ CF ２ -1, -CH ２ CF ２ CF ２ -1, -CH ２ CHFCF ２ -1, -CH ２ CH ２ CF ２ -1, -CH ２ CF ２ CHF-, -CH ２ CHFCHF-, -CH ２ CH<{ ２ CHF-, -CF(CF ３ )-CF ２ -1, -CF(CHF ２ )-CF ２ -1, -CF(CH ２ F)-CF ２ -1, -CF(CH ３ )-CF ２ -1, -CF(CF ３ )-CHF-, -CF(CHF ２ )-CHF-, -CF(CH ２ F)-CHF-, -CF(CH ３ )-CHF-, -CF(CF ３ )-CH ２ -1, -CF(CHF ２ )-CH ２ -1, -CF(CH ２ F)-CH ２ -1, -CF(CH ３ )-CH２ -, -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 [[ID=3)]]F) -CH ２ - etc. are mentioned. G ｆ４ Specific examples of G include, -CF ２ CF ２ CF ２ CF ２ -, -CHFCF (Note: There seems to be a mistake in the original text where the closing parenthesis is missing. Assuming it should be -CHF(CF ２ CF ２ CF ２ -, -CH ２ )]]CF ２ CF ２ CF ２ -, -CF ２ CHFCF ２ CF ２ -, -CHFCHFCF ２ CF ２ -, -CH ２ CHFCF ２ CF ２ -, -CF ２ CH ２ CF ２ CF ２ -, -CHFCH ２ CF ２ CF ２ -, -CH ２ CH ２ CF ２ CF ２ -, -CHFCF ２ CHFCF ２ [[ID=]03]]-, -CH ２ CF ２ CHFCF It should be noted that there are some possible errors or unclear parts in the original text, especially in the chemical formula expressions. The translation is done as accurately as possible based on the given text.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 CH ２ CHF-, -cycloC ４ F ６ - etc. can be mentioned. G ｆ５ As a specific example of G, -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 ２ CF ２ CF ２ CF ２ CF ２ -, -CF ２ CF ２ CHFCHFCF ２ CF ２ -, -CHFCF ２ CF ２ CF ２ CF ２ CF ２ -, -CHFCHFCHFCHFCHFCHF-, -CHFCF ２ CF ２ CF ２ CF ２ CH ２ -, -CH ２ CF ２ CF ２ CF ２ CF ２ CH ２ -, -cycloC ６ F １０ -, etc. Here, -cycloC ４ F ６- means a perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group. ５ F ８ - means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,3-diyl group. ６ F １０ "-" means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0033] (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 (G11).

[0034] 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.

[0035] The fluoropolyether chain (OR ｆ１１ ) ｙ１ The proportion of fluorine atoms in the fluoropolyether chain (OR) [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, from the viewpoint of excellent water and oil repellency and fingerprint removability. ｆ１１ ) ｙ１ From the viewpoint of abrasion resistance, the molecular weight of the portion is preferably from 2,000 to 20,000, more preferably from 2,500 to 15,000, and even more preferably from 3,000 to 10,000.

[0036] R １ is an alkylene group or a fluoroalkylene group. １ The alkylene group and fluoroalkylene group in R may be linear or may have a branched and / or cyclic structure. From the viewpoint of ease of synthesis, a linear or branched alkylene group or fluoroalkylene group is preferred, and a linear or branched alkylene group or fluoroalkylene group having a methylene group or fluoromethylene group is more preferred. １ The number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3. １ Is, L １ When is a single bond, R １１ In this case, R １ R in １１ is bonded to at least one fluorine atom or fluoroalkyl group.

[0037] j represents the number of fluoropolyether chains in one molecule and may be an integer of 1 or more, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.

[0038] R １１ -T １１ is a group corresponding to the group (g1), and R １１ -T １１ If there are multiple １１ -T １１ At least one of the R in the group (g1) is a group represented by the group (g1). ｇ１ R corresponding to １１ is R in the group (g1). ｇ１ The same applies to the preferred embodiments, except that "having a bond *" does not mean "L １ This should be read as "bonded to." １ When is a single bond, R １１ is R １ directly binds to

[0039] R ｇ１ Different R １１ The alkylene group in １ The atom bonded to R may be an ethereal oxygen atom, or an alkylene group which may have an ethereal oxygen atom between carbon atoms, and which does not have a carbon chain connecting 9 or more carbon atoms. １１ is preferably a group represented by the following formula (g5): *-(O) ａ３ - (R ｇ５ O) ａ４ -R ｇ５ -** ... (g5) where R ｇ５ is an alkylene group having 1 to 8 carbon atoms, and a plurality of R ｇ５ may be the same or different, a3 is 0 or 1, a4 is an integer of 0 or more, * is L １ is the bond to be bonded, and ** is T １１ is the bond that bonds to

[0040] When a3 is 0, the atom having the bond * is a carbon atom, and when a3 is 1, the atom having the bond * is an oxygen atom. In this compound, a3 may be either 0 or 1, and may be appropriately selected from the viewpoint of synthesis, etc. a4 is R ｇ５ R is the number of repetitions of O, and from the viewpoint of durability as a surface layer, it is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1. ｇ４ The alkylene group may be a linear or branched alkylene group having 1 to 8 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. The alkylene group is also preferably a linear alkylene group.

[0041] R ｇ１ Different R １１ is more preferably a group represented by the following formula (g3) in that the surface layer has better water and oil repellency and fingerprint stain removability, and is also excellent in durability such as abrasion resistance: *-(O) ａ３ -R ｇ３ -** ... (g3) where R ｇ３ represents an alkylene group having 1 to 8 carbon atoms, and a3, *, and ** are the same as in formula (g5).

[0042] T １１ and T １１ R that constitutes ａ１１ , R ａ１２ , z11 are the T ｇ１ , R ａ１ , R ａ２ , z1, and the preferred embodiments are also the same.

[0043] x1 is R in one molecule １１ -T １１ It is sufficient if it is an integer of 1 or more, and it is preferably 1 to 32, more preferably 1 to 18, and even more preferably 2 to 12.

[0044] L １ is a single bond or a j+x monovalent group which may contain N, O, S, or Si and may have a branch point, and R １ and R １１The 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 a hydroxyl group or an oxo group (=O). １ and R １１ The atoms bonded to may be the same atom or different atoms.

[0045] 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 １１ ...(A1') Here, each symbol in formula (A1') is the same as in formula (A1).

[0046] L １ When L is a trivalent or higher valent group, １ is at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and a (j+x1)-valent organopolysiloxane residue. １ ").

[0047] N is the branch point P １ If so, the branch point P １ For example, *-N(-**) ２ or (*-) ２ It is expressed as N-**, where * is R １ is a bond on the side, and ** is R １１ C is the branch point P １ If so, the branch point P １ For example, *-C(-**) ３ , (*-) ２ C (-**) ２ , (*-) ３ C-**, *-CR ２９ (-**) ２ , or (*-) ２ CR ２９ -**, where * is R １ is a bond on the side, and ** is R １１ side bond, R ２９is a monovalent group, and examples thereof include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group. １ If so, the branch point P １ For example, *-Si(-**) ３ , (*-) ２ Si(-**) ２ , (*-) ３ Si-**, *-SiR ２９ (-**) ２ , or (*-) ２ SiR ２９ -**, where * is R １ is a bond on the side, and ** is R １１ side bond, R ２９ is a monovalent group, and examples thereof include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.

[0048] 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).

[0049]

[0050] 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.

[0051]

[0052] Divalent or higher L １ is -C(O)N(R ２６) -, -N(R ２６ )C(O)-, -C(O)O-, -OC(O)-, -C(O)-, -O-, -N(R ２６ )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N(R ２６ ) -, -SO ２ N (R ２６ ) -, -N(R ２６ ) SO ２ -, -Si(R ２６ ) ２ -, -OSi(R ２６ ) ２ -, -Si(CH ３ ) ２ -Ph-Si(CH ３ ) ２ - and at least one bond selected from the group consisting of divalent organopolysiloxane residues (hereinafter referred to as "bond B １ "). 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.

[0053] 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.

[0054]

[0055] 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.

[0056] 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 the divalent L １ Specific examples of B include a single bond, one or more bonds B １ (For example, *-B １ -**, *-B １ -R ２８ -B １ -**), etc. However, R ２８ is a single bond or a divalent organic group, * is R １ is a bond on the side, and ** is R １１ It is the connecting hand on the side.

[0057] Trivalent or higher L １ is R １ and R １１ are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O). １ and R １１ The atoms 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{(*-) ｊ P １ (-**) ｘ１}, {(*-) ｊ P １ -R ２８ -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, * is R １ is a bond on the side, and ** is R １１ It is the connecting hand on the side.

[0058] The above R ２８ Examples of the divalent organic group in the formula (I) include hydrocarbon groups such as divalent aliphatic hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups) and divalent aromatic hydrocarbon groups (e.g., phenylene groups), and the hydrocarbon groups may have a bond B between carbon atoms. １ The divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0059] Said L １ As the group, a group represented by any one of the following formulae (L1) to (L7) is preferred in terms of ease of production of the present compound.

[0060] (-A １ -) ｄ５ C (R ｅ２ ) ４－ｄ５―ｄ６ (-Q ２２ -) ｄ６ Formula (L2) (-A ２ -) ｄ７ N(-Q ２３ -) ３－ｄ７ Formula (L3) (-A ３ -) ｄ８ Z １ (-Q ２４ -) ｄ９ Formula (L4) (-A ２ -) ｄ１０ Si(R ｅ３ ) ４－ｄ１０－ｄ１１ (-Q ２５ -) ｄ１１ Formula (L5) -A １ -Q ２６ - Formula (L6) -A １ -CH(-Q ２２ -)-Si(Rｅ３ ) ３－ｄ１２ (-Q ２５ -) ｄ１２ Formula (L7) In formulas (L1) to (L7), 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 Side is R １１ where A １ is a single bond, -B ３ -, -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)-, -CO(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 A ３ Z to which １ If the atom in is a carbon atom, A １ and A ３ Z to which １ If the atom in is a nitrogen atom, A ２ and Q １１ represents a single bond, —O—, an alkylene group, or —C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. ｅ６ -, -C(O)-, -NR ｅ６ - or -O-, ２２ is a single bond, -B ３-, -R ３０ -B ３ -or-B ２ -R ３０ -B ３ - and Q ２３ is a single bond or -R ３０ -B ３ - and Q ２４ Is, Q ２４ Z to which １ If the atom in is a carbon atom, Q ２２ and Q ２４ Z to which １ When the atom in is a nitrogen atom, Q ２３ and Q ２５ is a single bond or -R ３０ -B ３ - and Q ２６ is a single bond or -R ３０ -B ３ - and Z １ A ３ has a carbon atom or nitrogen atom to which Q is directly bonded, ２４ is a group having a (d8+d9)-valent ring structure having a carbon atom or a nitrogen atom to which R is directly bonded, ｅ１ is a hydrogen atom or an alkyl group, R ｅ２ is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, and R ｅ３ is an alkyl group, and R ｅ６ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1+d2 is an integer of 1 to 3, d3 is an integer of 0 to 3, d4 is an integer of 0 to 3, and d3+d4 is an integer of 1 to 3, d1+d3 is an integer of 1 to 5, d2+d4 is an integer of 1 to 5, d5 is an integer of 1 to 3, d6 is an integer of 1 to 3, and d5+d6 is an integer of 2 to 4, d7 is 1 or 2, d8 is an integer of 1 or more, d9 is an integer of 1 or more, d10 is an integer of 1 to 3, d11 is an integer of 1 to 3, and d10+d11 is an integer of 2 to 4, and d12 is an integer of 1 to 3. ２ and B ３ The orientation of the does not matter.１ If there are multiple A １ may be the same or different. ２ , A ３ , Q ２２ , Q ２３ , Q ２４ , Q ２５ , R ｅ１ , R ｅ２ , R ｅ３ Also, d1+d3, d5, d7, d8, and d10 are j, and d2+d4, d6, 3-d7, d9, d11, and 1+d12 are x1.

[0061] R ３０ 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. １ The ring structure in １ and preferred forms are also the same.

[0062] 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 portion of the acyloxy group in 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, and from the viewpoint of further improving the abrasion resistance and fingerprint removability of the surface layer, d8 is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of further improving the abrasion resistance and fingerprint removability of the surface layer, and from the viewpoint of further improving the abrasion resistance and fingerprint removability of the surface layer.

[0063] Said L １ Other examples of the group include groups represented by any of the following formulae (L11) to (L17).

[0064] (-A １ -) ｄ５ C (R ｅ２ ) ４－ｄ５―ｄ６ (-Q ２２ -G) ｄ６ Formula (L12) (-A ２ -) ｄ７ N(-Q ２３ -G) ３－ｄ７ Formula (L13) (-A ３ -) ｄ８ Z １ (-Q ２４ -G) ｄ９ Formula (L14) (-A ２ -) ｄ１０ Si(R ｅ３ ) ４－ｄ１０－ｄ１１ (-Q ２５ -G) ｄ１１ Formula (L15) -A １ -Q ２６ -G Formula (L16) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -G) ｄ１２ Formula (L17)

[0065] However, in the formulas (L11) to (L17), 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 Side is R １１ G is the following group (G21), and L １ The two or more Gs in the formula (L1) may be the same or different. The symbols other than G are the same as those in the formula (L1) to the formula (L7). ５１ ) ３－ｋ (-Q ３ -) ｋ Formula (G21) where, in formula (G21), the Si side is Q ２２ , Q２３ , Q ２４ , Q ２５ or Q ２６ Connect to Q ３ Side is R １１ Connect to R ５１ is an alkyl group. ３ is a single bond or -R ５２ -B ３ - and R ５２ represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. ３２ -, -C(O)-, -NR ３２ - or -O- containing group, or -(OSi(R ２２ ) ２ ) ｐ１１ -O-, and two or more Q ３ may be the same or different. k is 2 or 3. R ３２ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. ２２ is an alkyl group, a phenyl group, or an alkoxy group, and two R ２２ may be the same or different. p11 is an integer of 0 to 5, and when p11 is 2 or more, there are 2 or more (OSi(R ２２ ) ２ ) may be the same or different.

[0066] Q ３ and R ５２ The number of carbon atoms in the alkylene groups R 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. ５１ 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. ２２In 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. p11 is preferably 0 or 1.

[0067] Examples of the compound (A1) include the following.

[0068]

[0069]

[0070]

[0071]

[0072] However, Rf ２ are each independently [R ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ ] or [R ｆ１ - (OR ｆ１１ ) ｙ１ -O-], and T is T １１ is the same as:

[0073] <Compound (A2)> Compound (A2) has a structure represented by the following formula (A2): (T ３１ -R ３１ ) ｘ３ -L ３ -R ３ - (OR ｆ１２ ) ｙ２ -O-R ２ -L ２ - (R ２１ -T ２１ ) ｘ２ ...(A2) where each symbol in formula (A2) is as defined above.

[0074] R ｆ１２ , and (OR ｆ１２ ) ｙ２ is the R ｆ１１ AND (OR ｆ１１ ) ｙ１ The same applies to the preferred embodiments. ２ and R ３ are each independently the R １ The same applies to the preferred embodiments.

[0075] R ２１ -T ２１ and T ３１ -R ３１ At least one of the R in the group (g1) is a group represented by the formula (g1). ｇ１ R corresponding to ２１ and R ３１ are each independently the R ｇ１ The same applies to the preferred embodiments, except that "having a bond *" is replaced by "L ２ "L ３ This should be read as "bonded to." ２ When is a single bond, R ２１ is R ２ It is directly bonded to L ３ When is a single bond, R ３１ is R ３ directly bonded to R ｇ１ Different R ２１ and R ３１ The alkylene group in R １１ The same applies to the preferred embodiments as well. ２１ and T ３１ are each independently the T ｇ１ The same applies to the preferred embodiments. ２１ or T ３１ R that constitutes ａ２１ , R ａ２２ , z21 each independently represent the R ａ１ , R ａ２ , z1, and preferred embodiments are also the same. x2 and x3 are each independently the same as x1, and preferred embodiments are also the same.

[0076] L ２ and L ３ are each independently the L １ The same as when j is 1. For example, L ２ and L ３ When T is a single bond, the compound (A2) is represented by the following formula (A2'): ３１ -R ３１ -R ３ - (OR ｆ１２ ) ｙ２ -O-R２ -L ２ -R ２１ -T ２１ ...(A2') Here, each symbol in formula (A2') is the same as in formula (A2).

[0077] L ２ or L ３ When L is a trivalent or higher valent group, ２ or L ３ 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+x2)- or (1+x3)-valent organopolysiloxane residue. ２ ").

[0078] N is the branch point P ２ If so, the branch point P ２ For example, *-N(-**) ２ where * is R ２ or R ３ is a bond on the side, and ** is R ２１ or R ３１ C is the branch point P ２ If so, the branch point P ２ For example, *-C(-**) ３ , or *-CR ２９ (-**) ２ where * is R ２ or R ３ is a bond on the side, and ** is R ２１ or R ３１ side bond, R ２９ is a monovalent group, and examples thereof include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group. ２ If so, the branch point P ２ For example, *-Si(-**) ３ , or *-SiR ２９ (-**) ２ where * is R 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.

[0079] Branch point P ２ The ring structure and organopolysiloxane residue constituting the branch point P １ The preferred embodiments are also the same as those of the above. ２ or L ３ Each independently represents the bond B １ Bond B １ The embodiments are as described above, and the preferred embodiments are also the same.

[0080] Divalent L ２ or L ３ is R ２ and R ２１ , or R ３ and R ３１ are each independently an N, O, S, or Si atom or a carbon atom having an oxo group (=O). ２ and R ２１ , or R ３ and R ３１ The atoms adjacent to each bond B １ It is a constituent element of the divalent L ２ or L ３ Specific examples of B include a single bond, one or more bonds B １ (For example, *-B １ -**, *-B １ -R ２８ -B １ -**), etc. However, R ２８ is a single bond or a divalent organic group, * is R １ is a bond on the side, and ** is R １１ It is the connecting hand on the side.

[0081] Trivalent or higher L ２ or L ３ is R ２ and R ２１ , or R ３ and R ３１ are each independently an N, O, S, or Si atom, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group (=O). ２ and R ２１ , or R ３ and R ３１ The atoms adjacent to each bond B１ Or branch point P ２ It is a constituent element of trivalent or higher L ２ or L ３ As a specific example of ２ (For example, {*-P ２ (-**) ｘ}, {*-P １ -R ２８ -P １ -** ｘ１ etc.), one or more branch points P ２ and one or more bonds B １ and combinations (for example, *-B １ -R ２８ -P １ (-**) ｘ}, {*-B １ -R ２８ -P １ (-R ２８ -B １ -**) ｘ}, etc., where x is L ２ In the case of x2, L ３ In the case of R, it is x3. ２８ is a single bond or a divalent organic group, * is R １ is a bond on the side, and ** is R １１ The R ２８ The embodiments are as described above, and the preferred embodiments are also the same.

[0082] Said L ２ or L ３ As the groups, from the viewpoint of ease of production of the present compound, groups each independently represented by any one of the following formulae (L21) to (L27) are preferred.

[0083] -A １ -C(R ｅ２ ) ４－ｄ６ (-Q ２２ -) ｄ６ Formula (L22) -A ２ -N(-Q ２３ -) ２ Formula (L23) -A ３ -Z １ (-Q ２４ -) ｄ９Formula (L24) -A ２ -Si(R ｅ３ ) ４－ｄ１１ (-Q ２５ -) ｄ１１ Formula (L25) -A １ -Q ２６ - Formula (L26) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -) ｄ１２ Formula (L27) In formulas (L21) to (L27), A １ , A ２ or A ３ The side is formula R ２ or R ３ Connect with Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ Side is R ２１ or R ３１ where A １ , A ２ , A ３ , Q １１ , Q ２２ , Q ２３ , Q ２４ , Q ２５ , Q ２６ , R ｅ１ , R ｅ２ R ｅ３ , R ｅ６ is the above L １ The same applies to the preferred embodiments as those described in the above. １ A ３ has a carbon atom or nitrogen atom to which Q is directly bonded, ２４is a group having a (1+d9)-valent ring structure having a carbon atom or a nitrogen atom to which is directly bonded, d2 is an integer of 0 to 3, d4 is an integer of 0 to 3, d2+d4 is an integer of 1 to 5, d6 is an integer of 1 to 3, d9 is an integer of 1 or more, d11 is an integer of 1 to 3, and d12 is an integer of 1 to 3. Note that d2+d4, d6, d9, d11, and 1+d12 are x2 or x3. d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, in terms of ease of production of the present compound and further excellent abrasion resistance and fingerprint removability of the surface layer.

[0084] Said L ２ or L ３ Other examples of the group include groups represented by any of the following formulae (L31) to (L37).

[0085] -A １ -C(R ｅ２ ) ４－ｄ６ (-Q ２２ -G) ｄ６ Formula (L32) -A ２ -N(-Q ２３ -G) ２ Formula (L33) -A ３ -Z １ (-Q ２４ -G) ｄ９ Formula (L34) -A ２ -Si(R ｅ３ ) ４－ｄ１１ (-Q ２５ -G) ｄ１１ Formula (L35) -A １ -Q ２６ -G Formula (L36) -A １ -CH(-Q ２２ -G)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -G) ｄ１２ Formula (L37)

[0086] However, in formulas (L31) to (L37), A １ , A ２ or A ３The side is the R of the formula ２ or R ３ Connect with Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ Side is R ２１ or R ３１ G is the group (G21), and preferred embodiments are also the same. The symbols other than G are the same as the symbols in formulae (L21) to (L27), and preferred embodiments are also the same.

[0087] Examples of the compound (A2) include the following.

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096] However, Rf ３ are each independently [R ３ - (OR ｆ１２ ) ｙ２ -O-R ２ ] or [(OR ｆ１２ ) ｙ２ -O], and T is T ２１ or T ３１ is the same as:

[0097] <Compound (A3)> Compound (A3) has a structure represented by the following formula (A3): Q １ [-(OR ｆ１３ ) ｙ３ -O-R ４ -L ４ - (R ４１ -T ４１ ) ｘ４ ]ｒ１ ...(A3) where each symbol in formula (A3) is as described above.

[0098] R ｆ１３ , and (OR ｆ１３ ) ｙ３ is the R ｆ１１ AND (OR ｆ１１ ) ｙ１ The same applies to the preferred embodiments. ４ is the R １ The same applies to the preferred embodiments.

[0099] R ４１ -T ４１ At least one of the R in the group (g1) corresponds to the group (g1). ｇ１ R corresponding to ４１ is the R ｇ１ The same applies to the preferred embodiments, except that "having a bond *" does not mean "L ４ This should be read as "bonded to." ４ When is a single bond, R ４１ is R ４ directly bonded to R ｇ１ Different R ４１ The alkylene group in R １１ The same applies to the preferred embodiments as well. ４１ and T ４１ R that constitutes ａ４１ , R ａ４２ , z41 are the above-mentioned T ｇ１ , R ａ１ , R ａ２ , z1 are the same as z1, and preferred embodiments are also the same. x4 is the same as x1, and preferred embodiments are also the same. L ４ Is, L ２ or L ３ The same applies to the preferred embodiments.

[0100] Q １ is an r1-valent group having a branch point, and r1 is preferably 3 or 4.

[0101] Q １ The branch point P that constitutes ３Examples of the branch point P include N, C, Si, and a ring structure. ３ may be one or may have two or more.

[0102] N is the branch point P ３ If so, the branch point P ３ For example, N(-*) ３ , N.R. ２９ (-*) ２ C is the branch point P ３ If so, the branch point P ３ For example, C(-*) ４ , C.R. ２９ (-*) ３ , C(R ２９ ) ２ (-*) ２ Si is the branch point P ３ If so, the branch point P ３ For example, Si(-*) ４ , SiR ２９ (-*) ３ , Si(R ２９ ) ２ (-*) ２ However, * indicates OR. ｆ１３ side bond, R ２９ is a monovalent group. ２９ Examples of the alkyl group include a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, and R ４１ -T ４１ and fluoropolyether chains that do not have

[0103] Branch point P ３ The ring structure constituting the １ The substituents of the ring structure may be the same as those described above, and may further include a fluorine atom, a fluoroalkyl group, R ４１ -T ４１ It may have a fluoropolyether chain that does not have the formula:

[0104] Q １ As the group, a group represented by any one of the following formulae (Q1) to (Q6) is preferred in terms of ease of production of the present compound.

[0105] C (-A１１ -) ｄ２３ (R ｅ１２ ) ４－ｄ２３ Formula (Q2) N(-A １２ -) ３ Formula (Q3) Z １ (-A １３ -) ｄ２４ Formula (Q4) Si(-A １２ -) ｄ２５ (R ｅ１３ ) ４－ｄ２５ Formula (Q5) CH(-A １１ -) ２ -Si(R ｅ１３ ) ３－ｄ２６ (-A １１ -) ｄ２６ Formula (Q6) However, in formulas (Q1) to (Q6), A １１ (OR ｆ１３ ) where A １１ is a single bond, -R ４０ -, -B １３ -R ４０ - and R ４０ represents an alkylene group, a fluoroalkylene group, or an alkylene group or fluoroalkylene group having two or more carbon atoms, with —C(O)NR between carbon atoms. ｅ１６ -, -C(O)-, -CO(O)-, -NR ｅ１６ - or -O-, and B １３ is -C(O)NR ｅ１６ -, -C(O)-, -NR ｅ１６ - or -O-, A １２ is a single bond or -R ４０ - and A １３ A １３ Z to which １ If the atom in is a carbon atom, A １１ and A １３ Z to which １ If the atom in is a nitrogen atom, A １２ and Z １ A １３ is a group having a 1-valent ring structure having a carbon atom or a nitrogen atom to which Q is directly bonded, ５２represents a single bond, —O—, an alkylene group, a fluoroalkylene group, or an alkylene group or fluoroalkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. ｅ１６ -, -C(O)-, -NR ｅ１６ - or -O-, R ｅ１１ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, R ４１ -T ４１ or a fluoropolyether chain having no -Q in the range of r1 being 3 to 4. ５２ -C(R ｅ１１ ) ３－ｄ２１ (-A １１ -) ｄ２１ is a group having a repeating structure of R ｅ１２ is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, or R ４１ -T ４１ is a fluoropolyether chain having no R ｅ１３ is an alkyl group or a fluoroalkyl group, R ｅ１６ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, or a phenyl group which may be substituted with fluorine, d21 is an integer of 0 to 3, d22 is an integer of 0 to 3, and d21+d22 is an integer of 3 to 4, d3 is an integer of 0 to 3, d4 is an integer of 0 to 3, and d3+d4 is an integer of 1 to 3, d23 is 3 or 4, d24 is 3 or 4, d25 is 3 or 4, and d26 is 1 or 2. Note that, B １３ The orientation of the does not matter. １１ If there are multiple A １ may be the same or different. １２ , A １３ , R ｅ１１ , R ｅ１２ , R ｅ１３ The same is true for .

[0106] R ４０The number of carbon atoms in the alkylene group or fluoroalkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of the 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. １ Examples of the ring structure in the formula (I) include the ring structures described above, and the preferred forms are also the same.

[0107] R ｅ１１ , R ｅ１２ or R ｅ１３ The number of carbon atoms in the alkyl group or fluoroalkylene group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the present compound.

[0108] Examples of the compound (A3) include the following.

[0109]

[0110]

[0111]

[0112]

[0113] However, Rf ４ are each independently [-(OR ｆ１３ ) ｙ３ -O-R ４ -] ｒ１ , or [-(OR ｆ１３ ) ｙ３ -O-] ｒ１ and T is T ４１ is the same as:

[0114] Further, specific examples of the present compound include the following compounds.

[0115] However, R ｆ２２ are each independently [R ｆ１ - (OR ｆ１１ ) ｙ１ ] and T is T ｇ１ is the same as:

[0116] More specific examples of the present compound include the following compounds.

[0117] Here, m and n each independently represent an integer of 1 or more.

[0118] <Method for Producing the Present Compound> The method for producing the present compound is not particularly limited, but from the viewpoint of ease of production, a method of subjecting the following compound (B) to a hydrosilylation reaction with the following compound (C1) is preferred. The above group (g1) is obtained by the hydrosilylation reaction of the following group (g2) with the following compound (C1).

[0119] (Compound (B)) A compound having a fluoropolyether chain and a group represented by the following formula (g2): *-R ｇ２ -CH=CH ２ ... (g2) where R ｇ２ represents an alkylene group in which the atom having the bond * may be an ethereal oxygen atom or which may have an ethereal oxygen atom between carbon atoms, and which may be formed independently or in the form of -CH=CH ２ In combination with the above, a carbon chain of 9 or more carbon atoms is formed, and * is a bond that is bonded to the fluoropolyether chain directly or via a linking group.

[0120] HSiR ａ１ ｚ１ R ａ２ ３－ｚ１ ... (C1) where R ａ１ , R ａ２ and Z1 are the same as those in the group (g1), and preferred embodiments are also the same.

[0121] From the viewpoint of ease of synthesis and ease of handling of the compound, the compound (B) is preferably a compound represented by the following formula (B1), (B2) or (B3): ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ ] ｊ -L １- (R ｇ１２ -CH=CH ２ ) ｘ１ ...(B1) (CH ２ =CH-R ｇ１２ ) ｘ３ -L ３ -R ３ - (OR ｆ１２ ) ｙ２ -O-R ２ -L ２ - (R ｇ１２ -CH=CH ２ ) ｘ２ ... (B2) Q １ [-(OR ｆ１３ ) ｙ３ -O-R ４ -L ４ - (R ｇ１２ -CH=CH ２ ) ｘ４ ] ｒ１ ... (B3) where R in the molecule ｇ１２ At least one of them is R ｇ２ and other R ｇ１２ is alone or -CH=CH ２ The other symbols are as described above, and the preferred embodiments are also as described above.

[0122] Compound (B) can be obtained, for example, by changing the raw material in a known synthesis method to the following compound (E), etc. Specifically, for example, a method of introducing the following compound (E) into a precursor of compound (B) (for example, the following compounds (D1) to (D3)) can be mentioned. [R ｆ１ - (OR ｆ１１ ) ｙ１ -O-R １ ] ｊ -L １ - (E １ ) ｘ１ ... (D1) (E １ ) ｘ３ -L ３ -R ３ - (OR ｆ１２ ) ｙ２ -O-R ２ -L ２ - (E １ ) ｘ２... (D2) Q １ [-(OR ｆ１３ ) ｙ３ -O-R ４ -L ４ - (E １ ) ｘ４ ] ｒ１ ... (D3) E ２ -R ｇ２ -CH=CH ２ ... (E) However, E １ is -OH, -OR, -C(O)-X, -I, -NH ２ , or -CH=CH ２ X is a halogen atom, an alkoxy group, a hydroxyl group, or an amino group; R is an alkyl group; and E ２ is -OH, -OR, -C(O)-X, -I, -NH ２ , or -CH=CH ２ And E １ The substituent capable of addition reaction is selected depending on the above. The other symbols are as described above.

[0123] The synthesis method of compounds (D1) to (D3), and the addition reaction of a compound corresponding to compound (E), for example, the method described in WO 2009 / 008380, the method described in WO 2013 / 121984, the method described in WO 2013 / 121986, the method described in WO 2015 / 087902, the method described in Patent Document 1, the method described in WO 2017 / 038832, the method described in WO 2018 / 143433, the method described in the specification of Japanese Patent Application No. 2017-104731, the method described in WO 2021 / 060537, the method described in WO 2021 / 054417, and the like.

[0124] [Composition] The composition of the present invention (hereinafter also referred to as the present composition) is a composition containing the compound according to the present invention, a fluorine-containing compound other than the present compound, and at least one of the impurities described below. Examples of impurities include compounds that are unavoidable in the production of the present compound and other fluorine-containing compounds. Note that the present composition does not contain a liquid medium described below.

[0125] 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.

[0126] 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.

[0127] 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 Japanese Patent Application Laid-Open No. 2015-199906, Japanese Patent Application Laid-Open No. 2016-204656, Japanese Patent Application Laid-Open No. 2016-210854, and Japanese Patent Application Laid-Open No. 2016-222859Fluorine-containing ether compounds described in WO 2018 / 216630, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 039186, WO 2019 / 044479, JP 2019-44158 A, WO 2019 / 044479, and WO 2019 / 163282. Commercially available fluorine-containing compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., the SURECO AF series such as SURECO (registered trademark) 2101S manufactured by AGC Inc., and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0128] The proportion of the present compound 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 present composition contains other fluorine-containing compounds, the proportion of the other fluorine-containing compounds relative to the total of the present compound and the 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 proportion of the present compound and the other fluorine-containing compounds in the composition is preferably 80% by mass or more, more preferably 85% by mass or more. When the contents of the present compound and the other fluorine-containing compounds are within the above ranges, the surface layer has excellent water and oil repellency, abrasion resistance, fingerprint smear removability, lubricity, and appearance. The present composition and the present compound are suitable as surface treatment agents for forming a surface layer that imparts water and oil repellency, abrasion resistance, and fingerprint smear removability to a substrate surface.

[0129] [Coating Liquid] The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present compound or 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 compound or the present composition, and may also contain impurities such as by-products generated in the production process of the present compound. The concentration of the present compound or 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.

[0130] 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.

[0131] 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.

[0132] In addition to the present compound or composition and the liquid medium, the present 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 present coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.

[0133] The total concentration of the present compound and other components or 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.

[0134] [Article] Fig. 1 is a schematic cross-sectional view showing an example of the 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 compound.

[0135] 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.

[0136] 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.

[0137] The underlayer 14 is a layer containing an oxide containing at least silicon, and may further contain other elements. When the underlayer 14 contains silicon oxide, T of the present compound undergoes dehydration condensation, forming Si—O—Si bonds between the underlayer 14 and the underlayer 14, thereby forming a surface layer 22 with excellent wear resistance.

[0138] 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.

[0139] 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 compound, improving wear resistance.

[0140] 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.

[0141] From the viewpoint of improving the adhesiveness of the compound 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:

[0142] 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.

[0143] 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.

[0144] The surface layer 22 on the underlayer 14 contains a condensate of the present compound. Condensates of the present compound include those in which a hydrolyzable silyl group in the present compound undergoes a hydrolysis reaction to form a silanol group (Si—OH), which then undergoes an intermolecular condensation reaction to form an Si—O—Si bond, and those in which a silanol group in the present compound undergoes a condensation reaction 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 present compound. 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.

[0145] 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.

[0146] The second article of the present invention is an article 20 having a substrate 10 with an undercoat layer and a surface layer 22 in this order, wherein the substrate 10 with an undercoat layer contains an oxide containing silicon, and the surface layer 22 contains a condensate of the present compound.

[0147] 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.

[0148] [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 fluorine-containing compound, the fluorine-containing compound-containing composition, or the coating liquid.

[0149] The present compound and composition can be used directly in a dry coating method. The present compound and composition 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 because it suppresses decomposition of the present compound and because the equipment is simple. For vacuum deposition, a pellet-shaped substance in which the present compound is supported on a porous metal body made of a metal material such as iron or steel may be used. The pellet-shaped substance in which the present compound is supported can be produced by impregnating a porous metal body with a solution of the present compound, drying it, and removing the liquid medium. The present coating liquid can be used as the solution of the present compound.

[0150] The present coating liquid can be suitably used for wet coating methods such as spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0151] To improve the abrasion resistance of the surface layer, an operation to promote the reaction between the present compound and the substrate may be performed as necessary. Examples of such an operation include heating, humidification, and light irradiation. For example, the substrate on which the surface layer is formed can be heated in a humid atmosphere to promote reactions such as the hydrolysis reaction of hydrolyzable groups, the reaction between hydroxyl groups on the surface of the substrate and silanol groups, and the formation of siloxane bonds through the condensation reaction of silanol groups. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as needed. Specific methods include, for example, pouring a solvent over the surface layer or wiping it off with a cloth soaked in the solvent.

[0152] 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 1 to 16 and 19 to 24 are working examples, and Examples 17 to 18 are comparative examples.

[0153] [Example 1] Synthesis of Compound I <Synthesis Example 1-1> The following compound (1-1) was obtained according to the methods described in (Example 1-1) to (Example 1-4) of WO 2018 / 216630.

[0154] However, the average of p1 is 21 and the average of q1 is 20.

[0155] Synthesis Example 1-2 Into a reaction vessel, 40.0 g of the compound (1-1), 80.0 g of 1,3-bis(trifluoromethyl)benzene, and undec-10-enylmagnesium bromide (CH ２ =CH(CH ２ ) ９ 6.1 g of methylparaben-MgBr and 20 g of tetrahydrofuran (THF) were added and stirred at room temperature under a nitrogen atmosphere. After the reaction was completed, 1N hydrochloric acid was added, and the organic phase was recovered, followed by filtration. The recovered organic phase was concentrated using an evaporator and subjected to silica gel column chromatography. 39.1 g of compound (1-2) was obtained.

[0156]

[0157] Synthesis Example 1-3 Into a reaction vessel purged with nitrogen, 5.0 g of the compound (1-2), 5.0 g of 1,3-bis(trifluoromethyl)benzene, 0.15 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.28 g of the above and 0.04 g of dimethyl sulfoxide (DMSO) were added and stirred at 40° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 4.8 g of the following compound I.

[0158] However, the average of p1 is 21 and the average of q1 is 20.

[0159] Example 2 Synthesis of Compound II Synthesis Example 2-1 5.0 g of the compound (1-2), 15 g of 1,3-bis(trifluoromethyl)benzene, and 5.0 g of 1,1,1-triacetoxy-1,1-dihydro-1,2-benzoiodoxol-3-(1H)-one were placed in a reaction vessel and stirred under a nitrogen atmosphere at 40° C. After completion of the reaction, methanol was added and the organic phase (1,3-bis(trifluoromethyl)benzene phase) was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 4.5 g of compound (2-1).

[0160] However, the average of p2 is 21 and the average of q2 is 20.

[0161] Synthesis Example 2-2 Into a reaction vessel purged with nitrogen, 3.0 g of the compound (2-1), 3.0 g of 1,3-bis(trifluoromethyl)benzene, 0.09 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.17 g of the above and 0.03 g of DMSO were added and stirred at 40° C. After the reaction was completed, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 3.0 g of the following compound II.

[0162] However, the average of p2 is 21 and the average of q2 is 20.

[0163] Example 3 Synthesis of Compound III Synthesis Example 3-1 A reaction vessel was charged with 20 g of dehydrated acetonitrile, 200 g of dehydrated THF, 46.97 g of lithium diisopropylamide, and 11-bromo-1-undecene (CH ２ =CH(CH ２ ) ９ 102.25 g of (-Br) was added and stirred under a nitrogen atmosphere at about -70°C. After completion of the reaction, hydrochloric acid was added and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 58.8 g of compound (3-1).

[0164]

[0165] Synthesis Example 3-2 10.3 g of lithium aluminum hydride and 105 g of dehydrated THF were placed in a reaction vessel and stirred at 0° C. under a nitrogen atmosphere. Then, 10.5 g of the compound (3-1) was added, and the mixture was stirred at 0° C. under a nitrogen atmosphere. After completion of the reaction, water and 1N sodium hydroxide were added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 8.7 g of compound (3-2).

[0166]

[0167] Synthesis Example 3-3 The following compound (3-3) was obtained according to the methods of (Example 6-1) to (Example 6-4) of WO 2013 / 121984.

[0168] However, the average of p3 is 13.

[0169] Synthesis Example 3-4 50.0 g of the compound (3-3), 50.0 g of 1,3-bis(trifluoromethyl)benzene, and 5.2 g of the compound (3-2) were placed in a reaction vessel and stirred under a nitrogen atmosphere at 60° C. After completion of the reaction, the mixture was washed, concentrated using an evaporator, and subjected to silica gel column chromatography to obtain 35.7 g of compound (3-4).

[0170]

[0171] Synthesis Example 3-5 Into a reaction vessel purged with nitrogen, 5.0 g of the compound (3-4), 5.0 g of 1,3-bis(trifluoromethyl)benzene, 0.15 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.25 g of the above and 0.04 g of DMSO were added and stirred at 40° C. After the reaction was completed, the solvent and the like were distilled off under reduced pressure, and the resulting mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 4.9 g of the following compound III.

[0172] However, the average of p3 is 13.

[0173] [Example 4] Synthesis of Compound IV <Synthesis Example 4-1> Compound (4-1) was synthesized with reference to Synthesis Example 7 of WO 2021 / 010105.

[0174] However, the average of p4 is 22.

[0175] Synthesis Example 4-2 Into a reaction vessel, 6.4 g of the compound (4-1), 6.4 g of 1,3-bis(trifluoromethyl)benzene, NH[(CH ２ ) ８ CH=CH ２ ] ２ The mixture was stirred under a nitrogen atmosphere at 40° C. After the reaction was completed, methanol was added, and the organic phase was concentrated with an evaporator and subjected to silica gel column chromatography to obtain 4.8 g of compound (4-2).

[0176]

[0177] Synthesis Example 4-3 Into a reaction vessel purged with nitrogen, 5.5 g of the compound (4-2), 5.5 g of 1,3-bis(trifluoromethyl)benzene, 0.22 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.63 g of the above and 0.05 g of DMSO were added and stirred at 40° C. After the reaction was completed, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 5.7 g of the following compound IV.

[0178] However, the average of p4 is 22.

[0179] [Example 5] Synthesis of Compound V <Synthesis Example 5-1> In a reaction vessel, 10.0 g of the compound (1-2), 11-bromo-1-undecene (CH ２ =CH(CH ２ ) ９2.7 g of 1,3-bis(trifluoromethyl)benzene (5-4) and 0.03 g of tetrabutylammonium iodide were added and stirred. Next, 0.6 g of potassium hydroxide was added, and the mixture was stirred at 70°C under a nitrogen atmosphere. After completion of the reaction, acetone was added, and the 1,3-bis(trifluoromethyl)benzene phase was concentrated using an evaporator and subjected to silica gel column chromatography to obtain 7.4 g of compound (5-1).

[0180] However, the average of p5 is 21 and the average of q5 is 20.

[0181] Synthesis Example 5-2 Into a reaction vessel purged with nitrogen, 5.0 g of the compound (5-1), 5.0 g of 1,3-bis(trifluoromethyl)benzene, 0.20 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.54 g of the above and 0.04 g of DMSO were added and stirred at 40° C. After the reaction was completed, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 5.2 g of the following compound V.

[0182] However, the average of p5 is 21 and the average of q5 is 20.

[0183] [Example 6] Synthesis of Compound VI <Synthesis Example 6-1> 2.1 g of methyl cyanoacetate and 11-bromo-1-undecene (CH ２ =CH(CH ２ ) ９ 11.9 g of toluene (6-Br), 11.2 g of potassium carbonate, and 52.5 g of N,N-dimethylformamide (DMF) were added and stirred at 85° C. under a nitrogen atmosphere. After completion of the reaction, hydrochloric acid was added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator to obtain 8.1 g of compound (6-1).

[0184]

[0185] Synthesis Example 6-2 A reaction vessel was charged with 8.1 g of the compound (6-1), 24.3 g of DMSO, 3.0 g of lithium chloride, and 4.7 g of water, and the mixture was stirred under a nitrogen atmosphere at 180° C. After completion of the reaction, hydrochloric acid was added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 6.2 g of compound (6-2).

[0186]

[0187] Synthesis Example 6-3 3.0 g of lithium aluminum hydride and 27.0 g of dehydrated THF were placed in a reaction vessel and stirred at 0° C. under a nitrogen atmosphere. Then, 5.4 g of the compound (6-2) was added, and the mixture was stirred at 0° C. under a nitrogen atmosphere. After completion of the reaction, water and 1N sodium hydroxide were added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 4.3 g of compound (6-3).

[0188]

[0189] Synthesis Example 6-4 15 g of the compound (3-3), 15 g of 1,3-bis(trifluoromethyl)benzene, and 2.8 g of the compound (6-3) were placed in a reaction vessel and stirred under a nitrogen atmosphere at 60° C. After completion of the reaction, the mixture was washed, concentrated using an evaporator, and subjected to silica gel column chromatography to obtain 11.4 g of compound (6-4).

[0190] However, the average of p6 is 13.

[0191] Synthesis Example 6-5 Into a reaction vessel purged with nitrogen, 5.0 g of the compound (6-4), 5.0 g of 1,3-bis(trifluoromethyl)benzene, 0.21 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.48 g of the above and 0.04 g of DMSO were added and stirred at 40° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 5.1 g of the following compound VI.

[0192] However, the average of p6 is 13.

[0193] [Example 7] Synthesis of Compound VII <Synthesis Example 7-1> 2.0 g of dimethyl malonate and 11-bromo-1-undecene (CH ２ =CH(CH ２ ) ９ 10.6 g of (-Br), 8.4 g of potassium carbonate, and 50.0 g of DMF were added and stirred at 85° C. under a nitrogen atmosphere. After completion of the reaction, hydrochloric acid was added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator to obtain 6.1 g of compound (7-1).

[0194]

[0195] Synthesis Example 7-2 6.1 g of the compound (7-1), 24.4 g of DMSO, 2.4 g of lithium chloride, and 3.27 g of water were placed in a reaction vessel and stirred under a nitrogen atmosphere at 180° C. After completion of the reaction, hydrochloric acid was added and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 4.0 g of compound (7-2).

[0196]

[0197] Synthesis Example 7-3 A reaction vessel was charged with 2.9 g of the compound (7-2), 52.98 g of ethanol, and 8.6 g of potassium hydroxide, and the mixture was stirred under a nitrogen atmosphere at 120° C. After completion of the reaction, hydrochloric acid was added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 2.5 g of compound (7-3).

[0198]

[0199] Synthesis Example 7-4: 2.5 g of the compound (7-3), 25 g of dichloromethane, 2.6 g of oxalyl chloride, and 0.04 g of DMF were placed in a reaction vessel and stirred at room temperature under a nitrogen atmosphere. After completion of the reaction, the mixture was concentrated using an evaporator to obtain 2.6 g of compound (7-4).

[0200]

[0201] <Synthesis Example 7-5> The following compound (7-5) was obtained according to the methods of (Example 1-1) to (Example 1-3) of WO 2021 / 131960.

[0202] However, the average of p7 is 13.

[0203] Synthesis Example 7-6 10.0 g of the compound (7-5), 1.6 g of the compound (7-4), and 10 g of 1,3-bis(trifluoromethyl)benzene were placed in a reaction vessel and stirred under a nitrogen atmosphere at 40° C. After completion of the reaction, the mixture was concentrated using an evaporator and subjected to silica gel column chromatography to obtain 5.2 g of compound (7-6).

[0204]

[0205] Synthesis Example 7-7 Into a reaction vessel purged with nitrogen, 2.0 g of the compound (7-6), 2.0 g of 1,3-bis(trifluoromethyl)benzene, 0.09 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.19 g of and 0.02 g of DMSO were added and stirred at 40° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 2.0 g of the following compound VII.

[0206] However, the average of p7 is 13.

[0207] Example 8 Synthesis of Compound VIII Synthesis Example 8-1 0.5 g of lithium aluminum hydride and 5 g of dehydrated THF were placed in a reaction vessel and stirred at 0°C under a nitrogen atmosphere. Next, 1.0 g of the compound (7-2) was added, and the mixture was stirred at 0°C under a nitrogen atmosphere. After completion of the reaction, water and 1 M sodium hydroxide were added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 0.8 g of compound (8-1).

[0208]

[0209] Synthesis Example 8-2 The following compound (8-2) was obtained according to the method described in Example 6 of WO 2013 / 121984. ３ -O-(CF ２ CF ２ O-CF ２ CF ２ CF ２ CF ２ O) ｐ８ (CF ２ CF ２ O) -CF ２ CF ２ CF ２ -C(O)OCH ３ ...Equation (8-2) However, the average of p8 is 13.

[0210] Synthesis Example 8-3: 10.0 g of the compound (8-2) and 10 g of 1,3-bistrifluoromethylbenzene were placed in a reaction vessel, and then 450 mg of triethylsilane and 10 mg of trispentafluorophenylborane were added. After stirring at room temperature, low-boiling components were distilled off to obtain 10.3 g of a mixture of the following compounds (8-3a) and (8-3b).

[0211]

[0212] Synthesis Example 8-4: 5.0 g of a mixture of the above compounds (8-3a) and (8-3b) and 10 g of 1,3-bistrifluoromethylbenzene were placed in a reaction vessel, and then 5.0 g of methanol and 2.5 g of concentrated sulfuric acid were added. After stirring at 60°C, extraction was performed using AC-6000. The solvent was distilled off to obtain 4.9 g of a mixture of the following compounds (8-4a) and (8-4b).

[0213]

[0214] Synthesis Example 8-5 4.9 g of a mixture of the above compounds (8-4a) and (8-4b) was placed in a vacuum constant temperature dryer and concentrated under reduced pressure at 100° C. for 16 hours, thereby obtaining 4.8 g of the following compound (8-5).

[0215]

[0216] Synthesis Example 8-6 4.5 g of the compound (8-5), 0.56 g of the compound (8-1), and 10 g of 1,3-bis(trifluoromethyl)benzene were placed in a reaction vessel and stirred at 80° C. under a nitrogen atmosphere, and then 0.94 g of bis(2-methoxyethyl)aminosulfur trifluoride was added and the mixture was further stirred at 80° C. After completion of the reaction, the mixture was concentrated using an evaporator and subjected to silica gel column chromatography to obtain 3.6 g of compound (8-6).

[0217]

[0218] Synthesis Example 8-7 Into a reaction vessel purged with nitrogen, 1.5 g of the compound (8-6), 1.5 g of 1,3-bis(trifluoromethyl)benzene, 0.06 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.15 g of the above and 0.01 g of aniline were added and stirred at 40° C. After the reaction was completed, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 1.6 g of the following compound VIII.

[0219] However, the average of p8 is 13.

[0220] [Example 9] Synthesis of Compound IX <Synthesis Example 9-1> 0.50 g of methyl cyanoacetate, 18-bromo-1-octadecene (CH ２ =CH(CH ２ ) １６ 4.2 g of N,N-dimethylformamide (4.2 g of HCl-Br), 2.8 g of potassium carbonate, and 20 g of N,N-dimethylformamide (DMF) were added and stirred at 85° C. under a nitrogen atmosphere. After completion of the reaction, hydrochloric acid was added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator to obtain 3.0 g of compound (9-1).

[0221]

[0222] Synthesis Example 9-2 A reaction vessel was charged with 3.0 g of the compound (9-1), 30.0 g of DMSO, 0.74 g of lithium chloride, and 5.0 g of water, and the mixture was stirred under a nitrogen atmosphere at 180° C. After completion of the reaction, hydrochloric acid was added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 2.5 g of compound (9-2).

[0223]

[0224] Synthesis Example 9-3 0.91 g of lithium aluminum hydride and 26.0 g of dehydrated THF were placed in a reaction vessel and stirred at 0° C. under a nitrogen atmosphere. Then, 2.6 g of the compound (9-2) was placed in the reaction vessel and stirred at 0° C. under a nitrogen atmosphere. After the reaction was completed, water and 1 M sodium hydroxide were added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 2.3 g of compound (9-3).

[0225]

[0226] Synthesis Example 9-4 10.0 g of the compound (3-3), 10 g of 1,3-bis(trifluoromethyl)benzene, and 2.9 g of the compound (9-3) were placed in a reaction vessel and stirred under a nitrogen atmosphere at 60° C. After completion of the reaction, the mixture was washed, concentrated using an evaporator, and subjected to silica gel column chromatography to obtain 6.1 g of compound (9-4).

[0227] However, the average of p9 is 13.

[0228] Synthesis Example 9-5 Into a reaction vessel purged with nitrogen, 2.0 g of the compound (9-4), 2.0 g of 1,3-bis(trifluoromethyl)benzene, 0.09 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.19 g of the above and 0.01 g of DMSO were added and stirred at 40° C. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 2.1 g of the following compound IX.

[0229] However, the average of p9 is 13.

[0230] Example 10 Synthesis of Compound X Synthesis Example 10-1 A reaction vessel was charged with 5.2 g of dehydrated acetonitrile, 52 g of dehydrated THF, 67.9 g of lithium diisopropylamide, and 11-bromo-1-undecene (CH ２ =CH(CH ２ ) ９ 147.7 g of (-Br) was added and stirred under a nitrogen atmosphere at about -70°C. After completion of the reaction, hydrochloric acid was added and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 45.3 g of compound (10-1).

[0231]

[0232] Synthesis Example 10-2 1.91 g of lithium aluminum hydride and 50 g of dehydrated THF were placed in a reaction vessel and stirred at 0° C. under a nitrogen atmosphere. Then, 5.0 g of the compound (10-1) was added, and the mixture was stirred at 0° C. under a nitrogen atmosphere. After completion of the reaction, water and 1 M sodium hydroxide were added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 3.1 g of compound (10-2).

[0233]

[0234] Synthesis Example 10-3 9.0 g of the compound (3-3), 9.0 g of 1,3-bis(trifluoromethyl)benzene, and 2.4 g of the compound (10-2) were placed in a reaction vessel and stirred under a nitrogen atmosphere at 60° C. After completion of the reaction, the mixture was washed, concentrated using an evaporator, and subjected to silica gel column chromatography to obtain 6.0 g of compound (10-3).

[0235] However, the average of p10 is 13.

[0236] Synthesis Example 10-4 Into a reaction vessel purged with nitrogen, 3.0 g of the compound (10-3), 3.0 g of 1,3-bis(trifluoromethyl)benzene, 0.15 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.42 g of the above and 0.02 g of DMSO were added and stirred at 40° C. After the reaction was completed, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 3.1 g of the following compound X.

[0237] However, the average of p10 is 13.

[0238] Example 11 Synthesis of Compound XI Synthesis Example 11-1 A reaction vessel was charged with 4.0 g of the compound (6-3), 40.0 g of dehydrated THF, 3.1 g of lithium diisopropylamide, and 11-bromo-1-undecene (CH ２ =CH(CH ２ ) ９ 6.8 g of HCl (-Br) was added and stirred under a nitrogen atmosphere at about -70°C. After completion of the reaction, hydrochloric acid was added and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 4.1 g of compound (11-1).

[0239]

[0240] Synthesis Example 11-2 1.56 g of lithium aluminum hydride and 41.0 g of dehydrated THF were placed in a reaction vessel and stirred at 0° C. under a nitrogen atmosphere. Then, 4.1 g of the compound (11-1) was placed in the reaction vessel and stirred at 0° C. under a nitrogen atmosphere. After the reaction was completed, water and 1 M sodium hydroxide were added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 3.1 g of compound (11-2).

[0241]

[0242] Synthesis Example 11-3 9.0 g of the compound (1-1), 9.0 g of 1,3-bis(trifluoromethyl)benzene, and 2.7 g of the compound (11-2) were placed in a reaction vessel and stirred under a nitrogen atmosphere at 60° C. After completion of the reaction, the mixture was washed, concentrated using an evaporator, and subjected to silica gel column chromatography to obtain 6.1 g of compound (11-3).

[0243] However, the average of p11 is 21 and the average of q11 is 20.

[0244] Synthesis Example 11-4 Into a reaction vessel purged with nitrogen, 2.5 g of the compound (11-3), 2.5 g of 1,3-bis(trifluoromethyl)benzene, 0.13 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.39 g of the above and 0.02 g of DMSO were added and stirred at 40° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 2.6 g of the following compound XI.

[0245] However, the average of p11 is 21 and the average of q11 is 20.

[0246] Example 12 Synthesis of Compound XII Synthesis Example 12-1 A reaction vessel was charged with 2.0 g of the compound (7-2), 20.0 g of dehydrated THF, 6.6 mL of 2.0 M lithium diisopropylamide (THF solution), and 11-bromo-1-undecene (CH ２ =CH(CH ２ ) ９ 3.1 g of HCl (-Br) was added and stirred under a nitrogen atmosphere at about -70°C. After completion of the reaction, hydrochloric acid was added and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 2.1 g of compound (12-1).

[0247]

[0248] Synthesis Example 12-2 A reaction vessel was charged with 2.1 g of the compound (12-1), 27.4 g of ethanol, and 4.4 g of potassium hydroxide, and the mixture was stirred under a nitrogen atmosphere at 120° C. After completion of the reaction, hydrochloric acid was added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 1.8 g of compound (12-2).

[0249]

[0250] Synthesis Example 12-3: 1.8 g of the compound (12-2), 18 g of dichloromethane, 1.3 g of oxalyl chloride, and 0.01 g of DMF were placed in a reaction vessel and stirred at room temperature under a nitrogen atmosphere. After completion of the reaction, the mixture was concentrated using an evaporator to obtain 1.8 g of compound (12-3).

[0251]

[0252] Synthesis Example 12-4 The following compound (12-4) was obtained with reference to the production process for compound (D) in WO 2018 / 143433.

[0253] However, the average of p12 is 28 and the average of q12 is 19.

[0254] Synthesis Example 12-5 7.0 g of the compound (12-4), 7.0 g of AC-6000, 0.4 g of triethylamine, 0.2 g of 4-dimethylaminopyridine, and 1.8 g of the compound (12-3) were placed in a reaction vessel and stirred under a nitrogen atmosphere at 40° C. After completion of the reaction, the mixture was purified by silica gel chromatography to obtain 5.9 g of compound (12-5).

[0255]

[0256] Synthesis Example 12-6 Into a reaction vessel purged with nitrogen, 5.0 g of the compound (12-5), 5.0 g of 1,3-bis(trifluoromethyl)benzene, 0.23 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3%), and HSi(OCH ３ ) ３0.78 g of the above and 0.1 g of aniline were added and stirred at 40° C. After the reaction was completed, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 5.2 g of the following compound XII.

[0257] However, the average of p12 is 28 and the average of q12 is 19.

[0258] Example 13 Synthesis of Compound XIII <Synthesis Example 13-1> The following compound (13-1) was obtained with reference to Synthesis Example 12 of JP-A No. 2014-218639.

[0259] However, the average of p13 is 21 and the average of q13 is 20.

[0260] Synthesis Example 13-2 Into a reaction vessel, 5.0 g of the compound (13-1), 5.0 g of 1,3-bis(trifluoromethyl)benzene, and undec-10-enylmagnesium bromide (CH ２ =CH(CH ２ ) ９ 1.5 g of HCl (-MgBr) was added and stirred at room temperature under a nitrogen atmosphere. After the reaction was completed, methanol was added and the organic phase was recovered, followed by addition of silica gel and recovery of the organic phase by filtration. The recovered organic phase was concentrated using an evaporator and subjected to silica gel column chromatography to obtain 4.4 g of compound (13-2).

[0261]

[0262] Synthesis Example 13-3 Into a reaction vessel purged with nitrogen, 2.0 g of the compound (13-2), 2.0 g of 1,3-bis(trifluoromethyl)benzene, 0.2 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH ３ ) ３ 0.33 g of the above and 0.02 g of DMSO were added and stirred at 40° C. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 2.0 g of the following compound XIII.

[0263] However, the average of p13 is 21 and the average of q13 is 20.

[0264] Example 14 Synthesis of Compound XIV Synthesis Example 14-1 0.89 g of lithium aluminum hydride and 25 g of dehydrated THF were placed in a reaction vessel and stirred at 0°C under a nitrogen atmosphere. Then, 2.5 g of the compound (12-1) was added, and the mixture was stirred at 0°C under a nitrogen atmosphere. After completion of the reaction, water and 1 M sodium hydroxide were added, and the organic phase was recovered. The recovered organic phase was then concentrated using an evaporator and subjected to silica gel column chromatography to obtain 2.0 g of compound (14-1).

[0265]

[0266] Synthesis Example 14-2 Using the above compound (14-1), the following compound (14-2) was obtained with reference to the methods of Examples 1 to 4 of WO 2021 / 054413.

[0267]

[0268] The following compound (12-4B) was obtained using compound (12-4) according to the method of Synthesis Example 2 of WO 2021 / 054413.

[0269] However, the average of p14 is 28 and the average of q14 is 19.

[0270] Synthesis Example 14-3 A reaction vessel was charged with 5.0 g of the compound (12-4B), 3.0 g of the compound (14-2), 5.0 g of 1,3-bis(trifluoromethyl)benzene, 0.08 g of 1-phenyl-1-propyne, and CuCl ２ The mixture was stirred under a nitrogen atmosphere at 60° C. After the reaction was completed, the mixture was concentrated with an evaporator and purified by silica gel chromatography to obtain 4.1 g of compound (14-3).

[0271] However, the average of p14 is 28 and the average of q14 is 19.

[0272] Synthesis Example 14-4 Into a reaction vessel purged with nitrogen, 3.0 g of the compound (12-5), 3.0 g of 1,3-bis(trifluoromethyl)benzene, 0.18 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3%), and HSi(OCH ３ ) ３ 0.46 g of the above and 0.03 g of aniline were added and stirred at 40° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 3.2 g of the following compound XIV.

[0273] However, the average of p14 is 28 and the average of q14 is 19.

[0274] Example 15 Synthesis of Compound XV Synthesis Example 15-1 The following compound (15-1) was obtained according to the method of Example 7 of WO 2013 / 121984.

[0275] However, the average of p15 is 13.

[0276] In addition, the following compound (15-1B) was obtained using the compound (15-1) according to the method of Synthesis Example 2 of WO 2021 / 054413.

[0277] However, the average of p15 is 13.

[0278] In addition, the following compound (14-2B) was obtained by referring to the methods of Examples 1 to 4 of WO 2021 / 054413.

[0279]

[0280] Synthesis Example 15-2 Into a reaction vessel, 10 g of the compound (15-1B), 4.6 g of the compound (14-2B), 10.0 g of 1,3-bis(trifluoromethyl)benzene, 0.16 g of 1-phenyl-1-propyne, and CuCl ２ The mixture was stirred under a nitrogen atmosphere at 60° C. After the reaction was completed, the mixture was concentrated with an evaporator and purified by silica gel chromatography to obtain 4.1 g of compound (15-2).

[0281]

[0282] Synthesis Example 15-3 Into a reaction vessel purged with nitrogen, 2.0 g of the compound (15-2), 2.0 g of AC-6000, 0.12 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3%), and HSi(OCH ３ ) ３ 0.28 g of the above and 0.02 g of aniline were added and stirred at 40° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 2.1 g of the following compound XV.

[0283] However, the average of p15 is 13.

[0284] [Example 16] Synthesis of Compound XVI <Synthesis Example 16-1> The following compound (16-1) was obtained with reference to the method of Synthesis Example 9-2 of WO 2020 / 166488.

[0285] However, the average of p16 is 21 and the average of q16 is 23.

[0286] Synthesis Example 16-2: 20 g of the compound (16-1), 5.9 g of the compound (10-2), and 20.0 g of 1,3-bis(trifluoromethyl)benzene were placed in a reaction vessel and stirred at room temperature under a nitrogen atmosphere. After completion of the reaction, the mixture was concentrated using an evaporator and purified by silica gel chromatography to obtain 13.9 g of compound (16-2).

[0287]

[0288] Synthesis Example 16-3 Into a reaction vessel purged with nitrogen, 10.0 g of the compound (16-2), 0.9 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3%), HSi(OCH ３ ) ３ 2.1 g of the above, 0.18 g of aniline, and 10.0 g of AC-6000 were added and stirred at 40° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 11.2 g of the following compound XVI.

[0289] However, the average of p16 is 21 and the average of q16 is 23.

[0290] [Example 17] The following compound described in WO 2021 / 010105 was prepared.

[0291] However, the average of p17 is 22.

[0292] Example 18 The following compound described in JP 2014-218639 A was prepared.

[0293]

[0294] Example 19 Synthesis of Compound XIX Synthesis Example 19-1 Dimethyl malonate (2.0 g), 11-bromo-1-undecene (9.1 g), potassium carbonate (8.4 g), and dimethylformamide (50 g) were added and stirred at 85°C. After cooling to room temperature, aqueous hydrochloric acid was added, and the mixture was extracted with dichloromethane. The solvent was distilled off to obtain 8.15 g of the following compound (19-1).

[0295]

[0296] NMR spectrum of compound (19-1) １ H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92-5.74 (m, 2H), 5.13-4.90 (m, 4H), 3.7 (s, 6H), 1.95-2.20 (m, 4H), 1.90-1.0 (m, 32H)

[0297] Synthesis Example 19-2 Dimethyl sulfoxide (30 g) was added to the compound (19-1) (8.15 g) and stirred, and then water (5 g) and lithium chloride (2.9 g) were added. The temperature was raised to 180°C and the mixture was heated and stirred. After cooling to room temperature, the mixture was extracted with dichloromethane, the solvent was distilled off, and the mixture was subjected to flash column chromatography using silica gel (developing solvent: ethyl acetate / hexane) to obtain 4.3 g of compound (19-2).

[0298]

[0299] NMR spectrum of compound (19-2) １H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92 to 5.74 (m, 2H), 5.13 to 4.90 (m, 4H), 3.7 (s, 3H), 2.21 to 2.42 (m, 1H), 1.95 to 2.20 (m, 4H), 1.90 to 1.0 (m, 32H)

[0300] Synthesis Example 19-3 The compound (19-2) (1.0 g) was dissolved in THF (10 mL), and a THF solution of lithium diisopropylamide (1.6 mL, 3.17 mmol) was added thereto, followed by stirring at −70° C. for 15 minutes. 11-Bromo-1-undecene (0.92 g) was then added thereto, followed by stirring overnight at room temperature. Hydrochloric acid was then added thereto, and the mixture was extracted with dichloromethane and evaporated to obtain 1.23 g of the following compound (19-3).

[0301]

[0302] NMR spectrum of compound (19-3) １ H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92-5.74 (m, 3H), 5.13-4.90 (m, 6H), 3.55-3.72 (s, 3H), 1.95-2.20 (m, 6H), 1.90-1.0 (m, 48H)

[0303] Synthesis Example 19-4 The compound (19-3) (1.23 g) was dissolved in THF and cooled to 0° C. A THF solution of lithium aluminum hydride (5 mL, 5 mmol) was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and the mixture was subjected to flash column chromatography using silica gel (developing solvent: ethyl acetate / hexane) to obtain 1.0 g of the following compound (19-4).

[0304]

[0305] NMR spectrum of compound (19-4) １ H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92-5.74 (m, 3H), 5.13-4.90 (m, 6H), 3.28-3.45 (s, 2H), 1.95-2.20 (m, 6H), 1.90-1.0 (m, 48H)

[0306] Synthesis Example 19-5 The following compound (19-5) was obtained according to the method described in Example 6 of WO 2013 / 121984. ３ -O-(CF ２ CF ２ O-CF ２ CF ２ CF ２ CF ２ O) ｘ１９ (CF ２ CF ２ O) -CF ２ CF ２ CF ２ -C(O)OCH ３ ...Equation (19-5) Number of units x 19 average value: 14

[0307] Synthesis Example 19-6 Using the above compound (19-5), the following compound (19-6) was obtained according to the methods of Synthesis Examples 8 to 10 described in Examples of WO 2021 / 251396.

[0308] Average number of units p19: 14

[0309] Synthesis Example 19-7 1,3-bistrifluoromethylbenzene (10 g) was added to the compound (19-6) (5.0 g), and then the compound (19-4) (0.74 g) was added. After stirring at room temperature for 1 hour, bis(2-methoxyethyl)aminosulfur trifluoride (0.95 g) was added. The mixture was heated to 80°C and stirred for 1 hour, and then methanol was added and extracted with AC6000. The solvent was distilled off, and column chromatography using silica gel (developing solvent: AC6000) was performed to obtain 4.8 g of the following compound (19-7).

[0310] Average number of units p19: 14

[0311] NMR spectrum of compound (19-7) １ H-NMR (400MHz, Chloroform-d) δ (ppm): 5.82 to 5.65 (m, 3H), 5.65 to 5.35 (1H), 5.0 to 4.75 (m, 6H), 4.00 to 3.40 (2H), 2.1 to 1.85 (m, 6H), 1.60 to 1.00 (48H)１９ F-NMR (376MHz, Chloroform-d) δ (ppm): -55.3, -82.8, -88.0, -90.2, -125.2, -141.8

[0312] Synthesis Example 19-8 AC6000 (1.0 g), the above compound (19-7) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (200 mg) were added and stirred at 40° C., and then the solvent was distilled off under reduced pressure, thereby obtaining 0.52 g of the following fluorinated ether compound XIX.

[0313] Average number of units p19: 14

[0314] NMR spectrum of compound XIX １ H-NMR (400MHz, Chloroform-d) δ (ppm): 5.65-5.35 (1H), 4.01-3.38 (29H), 1.81-1.03 (m, 60H), 0.73-0.63 (6H) １９ F-NMR (376MHz, Chloroform-d) δ (ppm): -55.3, -82.8, -88.0, -90.2, -125.2, -141.8

[0315] Example 20 Synthesis of Compound XX Synthesis Example 20-1 The compound (19-3) (1.0 g) was dissolved in THF (10 mL), and a THF solution of lithium diisopropylamide (1.6 mL, 3.17 mmol) was added, followed by stirring at −70° C. for 15 minutes. Then, iodomethane (1.0 g) was added, and the mixture was stirred overnight at room temperature. Hydrochloric acid was then added, followed by extraction with dichloromethane and evaporation, yielding 0.95 g of the following compound (20-1).

[0316]

[0317] NMR spectrum of compound (20-1) １H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92 to 5.70 (m, 2H), 5.13 to 4.90 (m, 4H), 3.55 to 3.72 (s, 3H), 1.90 to 2.20 (m, 4H), 1.90 to 1.20 (m, 32H), 1.00 to 1.20 (s, 3H)

[0318] Synthesis Example 20-2 The compound (20-1) (0.95 g) was dissolved in THF and cooled to 0° C. A THF solution of lithium aluminum hydride (5 mL, 5 mmol) was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and the mixture was subjected to flash column chromatography using silica gel (developing solvent: ethyl acetate / hexane) to obtain 0.83 g of the following compound (20-2).

[0319]

[0320] NMR spectrum of compound (20-2) １ H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92 to 5.74 (m, 2H), 5.13 to 4.90 (m, 4H), 3.28 to 3.48 (s, 2H), 1.95 to 2.20 (m, 4H), 1.90 to 1.20 (m, 32H), 1.00 to 1.20 (s, 3H)

[0321] Synthesis Example 20-3 The above compound (20-2) (0.83 g) was dissolved in acetonitrile, and carbon tetrachloride (0.63 g) and triphenylphosphine (1.08 g) were added thereto, followed by stirring for 3 hours at 60° C. After filtration, the solvent was distilled off, and the residue was subjected to flash column chromatography using silica gel (developing solvent: ethyl acetate / hexane), to obtain 0.73 g of the following compound (20-3).

[0322]

[0323] NMR spectrum of compound (20-3) １H-NMR (400MHz, Chloroform-d) δ (ppm): 5.92 to 5.74 (m, 2H), 5.13 to 4.90 (m, 4H), 3.34 to 3.52 (s, 2H), 1.95 to 2.20 (m, 4H), 1.90 to 1.20 (m, 32H), 1.00 to 1.20 (s, 3H)

[0324] Synthesis Example 20-4 The above compound (20-3) (0.45 g) was dissolved in THF (0.46 g), and a THF solution of isopropyl magnesium chloride (12 wt %, 0.052 g) and magnesium (0.031 g) were added, followed by stirring at 60° C. for 24 hours. Thereafter, 1,3-bistrifluoromethylbenzene (10 mL), copper chloride (0.0047 g), and the following compound (20-4) (1.1 g) were added, followed by stirring at 60° C. for 24 hours. Thereafter, hydrochloric acid was added, and the mixture was extracted with 1,3-bistrifluoromethylbenzene. After distillation, the mixture was subjected to flash column chromatography using silica gel (developing solvent: AE-3000 / hexane) to obtain 0.53 g of the following compound (20-5).

[0325] Average number of units p20: 14 Average number of units p20: 14

[0326] Synthesis Example 20-5 AC6000 (1.0 g), the above compound (20-5) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (200 mg) were added and stirred at 40° C. for 24 hours, and then the solvent was distilled off under reduced pressure, thereby obtaining 0.52 g of the following fluorinated ether compound (XX).

[0327] Average number of units p20: 14 １ H-NMR (400MHz, Chloroform-d) δ (ppm): 4.01-3.38 (18H), 2.20-2.0 (m, 2H), 1.90-1.10 (m, 44H), 0.98-0.82 (s, 3H), 0.80-0.72 (t, 4H)

[0328] Example 21 Synthesis of Compound XXI Synthesis Example 21-1 3.0 g of malononitrile, 22.3 g of 11-bromo-1-undecene, 25.1 g of potassium carbonate, and 30.1 g of N,N-dimethylformamide were placed in a reaction vessel and stirred at 80°C for 2 hours, after which the organic layer was recovered by filter filtration. The recovered organic layer was evaporated under reduced pressure, dissolved in dichloromethane, and washed with water. The organic layer was recovered and evaporated under reduced pressure, and then purified by silica gel chromatography to obtain 15.3 g of compound (21-1).

[0329]

[0330] Synthesis Example 21-2 A reaction vessel was charged with 15.0 g of compound (21-1), 3.1 g of lithium aluminum hydride, and 75.2 g of tetrahydrofuran, and the mixture was stirred at 40° C. for 2 hours, followed by the addition of t-butyl methyl ether, water, and a 12% aqueous solution of sodium hydroxide to quench the reaction. The solution was recovered by filtration, and the recovered solution was evaporated under reduced pressure and then purified by silica gel chromatography to obtain 10.6 g of compound (21-2).

[0331]

[0332] Synthesis Example 21-3 Into a reaction vessel were placed 5.0 g of the compound (3-3) obtained in Synthesis Example 3-3 and 0.7 g of the compound (21-2), and the mixture was stirred at 130°C for 90 hours. The mixture was then purified by silica gel chromatography to obtain 2.9 g of the compound (21-3).

[0333] The average p21 is 13.

[0334] Synthesis Example 21-4 Into a reaction vessel were placed 1.0 g of compound (21-3), 2.0 g of AC-6000, 0.032 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3%), and 0.032 g of HSi(OCH ３ ) ３ The mixture was stirred at 40° C. for 2 hours, and then evaporated under reduced pressure to obtain 1.0 g of Compound XXI.

[0335] The average p21 is 13.

[0336] [Example 22] Synthesis of Compound XXII <Synthesis Example 22-1> Using compound (8-1) obtained in Synthesis Example 8-1 above, compound (22-1) was obtained by referring to the methods of Examples 1 and 2 of WO 2021 / 054413.

[0337]

[0338] Synthesis Example 22-2 In the above Synthesis Example 1-2, the compound (1-1) was converted into the compound (3-3) obtained in the above Synthesis Example 3-3 by the addition of undec-10-enylmagnesium bromide (CH ２ =CH(CH ２ ) ９ Compound (22-2) was obtained in the same manner as in Synthesis Example 1-2 above, except that compound (22-1) was used instead of compound (22-1).

[0339] The average p22 is 13.

[0340] Synthesis Example 22-3 Compound (22-3) was obtained in the same manner as in Synthesis Example 5-1 above, except that compound (1-2) in Synthesis Example 5-1 was changed to compound (22-2).

[0341] The average p22 is 13.

[0342] Synthesis Example 22-4 Compound XXII was obtained in the same manner as in Synthesis Example 5-2, except that compound (5-1) in Synthesis Example 5-2 was changed to compound (22-3).

[0343] The average p22 is 13.

[0344] Example 23 Synthesis of Compound XXIII Synthesis Example 23-1 2.0 g of compound (6-2) obtained in Synthesis Example 6-2 above and 7.6 g of tetrahydrofuran were placed in a reaction vessel and cooled to 0°C. 3.4 g of lithium diisopropylamide (2 M tetrahydrofuran solution) was added and stirred for 30 minutes, after which 2.7 g of diethylene glycol 2-bromoethyl methyl ether was added and stirred at room temperature. After completion of the reaction, hydrochloric acid was added, and the organic phase was recovered, which was then distilled off under reduced pressure. Silica gel column chromatography was performed to obtain 2.2 g of compound (23-1).

[0345]

[0346] Synthesis Example 23-2 A reaction vessel was charged with 2.2 g of compound (23-1), 0.34 g of lithium aluminum hydride, and 11.0 g of tetrahydrofuran, and the mixture was stirred at 40° C. for 1 hour, and then tert-butyl methyl ether, water, and a 12% aqueous solution of sodium hydroxide were added to quench the reaction. The solution was recovered by filtration, and the recovered solution was evaporated under reduced pressure and then purified by silica gel chromatography to obtain 1.6 g of compound (23-2).

[0347]

[0348] Synthesis Example 23-3 Into a reaction vessel were placed 1.5 g of the compound (3-3) obtained in Synthesis Example 3-3 above, 0.33 g of the compound (23-2), and 0.75 g of AC-2000, and the mixture was stirred at 40° C. for 16 hours. The mixture was then purified by silica gel chromatography to obtain 1.2 g of the compound (23-3).

[0349] The average p23 is 13.

[0350] Synthesis Example 23-4 Into a reaction vessel were placed 1.0 g of compound (23-3), 2.0 g of AC-6000, 0.032 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3%), and 1.0 g of HSi(OCH ３ ) ３ The mixture was stirred at 40° C. for 2 hours, and then evaporated under reduced pressure to obtain 1.0 g of Compound XXIII.

[0351] The average p23 is 13.

[0352] Example 24 Synthesis of Compound XXIV Synthesis Example 24-1 Compound (24-1) was obtained according to the methods described in Examples 2 and 3 of WO 2022 / 186266.

[0353] The weight average molecular weight Mw is 4,500.

[0354] Synthesis Example 24-2 7 g of compound (24-1), 0.23 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%), 7 g of 1,3-bis(trifluoromethyl)benzene, and 1.05 g of trichlorosilane were added and stirred at room temperature for 2 hours, and then evaporated under reduced pressure to obtain 7.1 g of compound (24-2).

[0355]

[0356] Synthesis Example 24-3 7 g of compound (24-2), Undec-10-enylmagnesium bromide (CH ２ =CH(CH ２ ) ９ 4.4 g of 1,3-bis(trifluoromethyl)benzene (MgBr) and 14 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 60°C for 12 hours, and then 1N hydrochloric acid was added, and the organic layer was recovered. The organic layer recovered by filtration was then distilled off under reduced pressure, to obtain 5.4 g of compound (24-3).

[0357]

[0358] Synthesis Example 24-4 1 g of compound (24-3), 0.05 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%), 0.02 g of DMSO, 3 g of 1,3-bis(trifluoromethyl)benzene, and 0.14 g of trimethoxysilane were added and stirred at 40° C. for 2 hours, followed by evaporation under reduced pressure to obtain 1 g of compound XXIV.

[0359]

[0360] [Production and Evaluation of Articles] Substrates were surface-treated using each of the compounds in Examples 1 to 24 to obtain articles having a surface layer. The surface treatment method used for each example was the dry coating method and wet coating method described below. Chemically strengthened glass was used as the substrate. The obtained articles were evaluated using the following methods. The results are shown in Table 1.

[0361] Dry coating was carried out using a vacuum deposition apparatus (VTR-350M, manufactured by ULVAC) (vacuum deposition method). 0.5 g of each of the compounds in Examples 1 to 24 was placed in a molybdenum boat in the vacuum deposition apparatus, and the interior 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 AE-3000 to obtain an article having a surface layer on the surface of the substrate.

[0362] (Wet coating method) Each of the compounds of Examples 1 to 24 and C as a liquid 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, left 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 AE-3000 to obtain an article having a surface layer on the surface of the substrate.

[0363] (Evaluation Method) <Contact Angle Measurement Method> The contact angle of approximately 2 μL of distilled water or n-hexadecane placed on the surface of the surface layer was measured using a contact angle measurement device (DMo-701, 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.

[0364] <Initial Contact Angle> The initial water contact angle and initial n-hexadecane contact angle of the surface layer were measured by the above-mentioned measurement method. The evaluation criteria are as follows. Initial water contact angle: A (Excellent): 110 degrees or more B (Good): 100 degrees or more and less than 110 degrees C (Fail): Less than 100 degrees Initial n-hexadecane contact angle: A (Excellent): 66 degrees or more B (Good): 60 degrees or more and less than 66 degrees C (Fail): Less than 60 degrees.

[0365] <Abrasion Resistance> 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 the elastomer at a pressure of 49 kPa and a speed of 320 cm / min, and the water contact angle was measured every 1000 reciprocations. The water contact angle of the surface layer was measured. Table 1 shows the number of times at which 90% of the initial contact angle was maintained. Note that the measurement was performed up to 15000 reciprocations, and if the water contact angle after 15000 reciprocations maintained 90% or more of the initial contact angle, it is recorded as 15000 in the table.

[0366] <Fingerprint Stain Removal Ability> An artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) was applied to the flat surface of a silicone rubber stopper, and then excess oil was wiped off with a nonwoven fabric (Bengot (registered trademark) M-3, manufactured by Asahi Kasei Corporation) to prepare a fingerprint stamp. The fingerprint stamp was placed on the surface layer and pressed against it with a load of 9.8 N for 10 seconds. The haze of the area where the fingerprint was attached was measured with a haze meter and recorded as the initial value. The area where the fingerprint was attached was wiped with a load of 2.5 N using a reciprocating traverse tester (manufactured by KNT Corporation) equipped with tissue paper. The haze value was measured for each wiping stroke, and the number of wipes required to reduce the haze to 10% or less of the initial value was counted. The fewer the number of wipes required, the easier it was to remove fingerprint stains and the better the fingerprint wiping ability. The evaluation criteria are as follows: A (Excellent): 3 or fewer wipes B (Good): 4 to 5 wipes C (Fair) : 6 to 8 wipes D (Not acceptable): 9 or more wipes

[0367]

[0368] It was shown that all of the compounds I to XVI and compounds XIX to XXIV, which have a fluoropolyether chain and a group (g1), are superior to the compounds XVII to XVIII, particularly in terms of abrasion resistance.

[0369] Examples of articles having a surface layer containing the present compound include optical articles used as parts of the following products, touch panels, anti-reflection films, anti-reflection glass, SiO ２ Useful as treated glass, tempered glass, sapphire glass, quartz substrates, mold metal, etc. Products: car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), copiers, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.

[0370] This application claims priority based on Japanese Patent Application No. 2021-178306, filed on October 29, 2021, the disclosure of which is incorporated herein in its entirety.

[0371] 10: Base material with undercoat layer, 12: Base material, 14: Undercoat layer, 20: Article, 22: Surface layer

Claims

1. A compound having a fluoropolyether chain and a group represented by the following formula (g1). * - R ｇ１ - T ｇ１ ... (g1) However, R ｇ１ is an alkylene group in which the atom having the bond * may be an ether oxygen atom and may have an ether oxygen atom between carbon-carbon atoms, and has a carbon chain to which 9 or more carbon atoms are linked, T ｇ１ is -SiR ａ１ ｚ１ R ａ２ ３－ｚ１ and R ａ１ is a hydroxyl group or a hydrolyzable group, and when there are a plurality of R ａ１ s, the plurality of R ａ１ s may be the same as or different from each other, R ａ２ is a non-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. z1 is an integer from 1 to 3, * is a bond that is bonded to the fluoropolyether chain directly or via a linking group.

2. said R ｇ１ The compound according to claim 1, wherein R is a group represented by the following formula (g2). *-(O) ａ１ -R ｇ９ -**...(g2) However, R ｇ９ is an alkylene group having 9 or more carbon atoms, a1 is 0 or 1, * is a bond that is bonded to the fluoropolyether chain directly or via a linking group, ** is a bond that binds to T in formula (g1). ｇ１ is a bond that binds to

3. Said R ｇ９ The compound according to claim 2, wherein R is an alkylene group having 11 or more carbon atoms.

4. Said R ｇ９ The compound according to claim 2, wherein R is an alkylene group having 19 or less carbon atoms.

5. The compound according to claim 3, wherein Rg9 is an alkylene group having 19 or fewer carbon atoms.

6. The R ｇ９ The compound according to claim 2, wherein the alkylene group in

7. The compound according to claim 3, wherein the alkylene group in Rg9 is a linear alkylene group.

8. The compound according to claim 4, wherein the alkylene group in Rg9 is a linear alkylene group.

9. The compound according to any one of claims 1 to 8, represented by the following formula (A1), formula (A2) or formula (A3). [R ｆ１ -(OR ｆ１１ ) ｙ１ -O-R １ ｊ -L １ -(R １１ -T １１ ) ｘ１ ...(A1)​ (T ３１ - R ３１ ) ｘ３ - L ３ - R ３ - (OR ｆ１２ ) ｙ２ - O - R ２ - L ２ - (R ２１ - T ２１ ) ｘ２ ・・・(A2) Q １ [-(OR ｆ１３ ) ｙ３ -O-R ４ -L ４ [-(R ４１ -T ４１ ) ｘ４ ｒ１ ...(A3)​ However, R ｆ１ is a fluoroalkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ｆ１ s, the plurality of Rs ｆ１ may be the same as or different from each other R ｆ１１ is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of R ｆ１１ , the plurality of R ｆ１１ may be the same as or different from each other, R １ is an alkylene group or a fluoroalkylene group, and when there are a plurality of R １ s, the plurality of R １ s may be the same as or different from each other. L １ is a j + x1-valent group which may have a single bond or contain N, O, S, Si, and may have a branching point, where the １ atoms bonded to R １１ and R are each independently an N, O, S, Si atom, a carbon atom forming a branching point, a carbon atom having a hydroxyl group or an oxo group (=O). R １１ is an alkylene group in which the atom bonding to L １ may be an ether oxygen atom and may have an ether 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, provided that at least one of R １１ has a carbon chain to which 9 or more carbon atoms are linked. T １１ is -SiR ａ１１ ｚ１１ R ａ１２ ３－ｚ１１ and when there are a plurality of Ts １１ the plurality of Ts １１ may be the same as or different from each other R ａ１１ is a hydroxyl group or a 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. R ａ１２ is a non-hydrolyzable group, and when there are a plurality of Rs ａ１２ the plurality of Rs ａ１２ may be the same as or different from each other j is an integer of 1 or more, z11 is an integer from 1 to 3, x1 is an integer of 1 or more, y1 is an integer of 1 or more. When there are a plurality of y1, the plurality of y1 may be the same as or different from each other, 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 and R ３ each independently represents 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, and the ２ atoms bonded to R ２１ and R are each independently an N, O, S, Si atom, a carbon atom forming a branching point, a carbon atom having a hydroxyl group or an oxo group (=O). 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 R ３ and R ３１ are each independently an N, O, S, Si atom, a carbon atom forming a branching point, a carbon atom having a hydroxyl group or an oxo group (=O). R ２１ is an alkylene group in which the atom adjacent to L ２ may be an ether oxygen atom and may have an ether oxygen atom between carbon-carbon atoms. When there are a plurality of R ２１ the plurality of R ２１ may be the same as or different from each other. R ３１ is an alkylene group in which the atom adjacent to L ３ may be an ether oxygen atom, or may have an ether oxygen atom between carbon-carbon atoms, and when there are a plurality of R ３１ s, the plurality of R ３１ s may be the same as or different from each other, provided that at least one of R ２１ and R ３１ has a carbon chain to which 9 or more carbon atoms are linked. T ２１ and T ３１ each independently is -SiR ａ２１ ｚ２１ R ａ２２ ３－ｚ２１ wherein, T ２１ or T ３１ when there are a plurality of them, the plurality of Ts ２１ and T ３１ may each independently be the same as or different from each other, R ａ２１ is a hydroxyl group or a hydrolyzable group, and when there are a plurality of R ａ２１ s, the plurality of Rs ａ２１ may be the same as or different from each other, R ａ２２ is a non-hydrolyzable group, and when there are a plurality of R ａ２２ s, the plurality of R ａ２２ s may be the same as or different from each other. z21 is an integer from 1 to 3, x2 and x3 are each independently an integer of 1 or more, y2 is an integer of 1 or more, Q １ is an r1-valent group having a branch point, 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 ４ is, independently of each other, an alkylene group or a fluoroalkylene group, and when there are a plurality of R ４ the plurality of R ４ may be the same as or different from each other 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, where R ４ and R ４１ are each independently an atom that binds to N, O, S, Si atoms, a carbon atom constituting a branching point, a carbon atom having a hydroxyl group or an oxo group (=O), and when there are a plurality of L ４ the plurality of L ４ may be the same as or different from each other. R ４１ is an alkylene group in which the atom adjacent to L ４ may be an ether oxygen atom, or may have an ether oxygen atom between carbon-carbon atoms, and when there are a plurality of R ４１ s, the plurality of R41s may be the same as or different from each other, provided that at least one of the R ４１ s has a carbon chain to which 9 or more carbon atoms are linked. T ４１ is -SiR ａ４１ ｚ４１ R ａ４２ ３－ｚ４１ and when there are a plurality of Ts, the plurality of Ts ４１ may be the same as or different from each other, ４１ ​ R ａ４１ is a hydroxyl group or a hydrolyzable group, and when there are a plurality of R ａ４１ s, the plurality of Rs ａ４１ may be the same as or different from each other R ａ４２ is a non-hydrolyzable group, and when there are a plurality of R ａ４２ , the plurality of R ａ４２ may be the same as or different from each other. z41 is an integer from 1 to 3, x41 is an integer of 1 or more. When there are a plurality of x41, the plurality of x41 may be the same as or different from each other, y3 is an integer of 1 or more. When there are a plurality of y3, the plurality of y3 may be the same as or different from each other, r1 is 3 or 4.

10. A composition containing the compound according to any one of claims 1 to 8 and another fluorine-containing compound.

11. A surface treatment agent containing the compound according to any one of claims 1 to 8, or a composition containing the compound according to any one of claims 1 to 8 and another fluorine-containing compound.

12. A coating liquid containing the compound according to any one of claims 1 to 8, or a composition containing the compound according to any one of claims 1 to 8 and another fluorine-containing compound, and a liquid medium.

13. An article having a surface layer formed from the compound according to any one of claims 1 to 8, a composition containing the compound according to any one of claims 1 to 8 and another fluorine-containing compound, or a surface treatment agent containing the compound or the composition, on the surface of a substrate.

14. A method for manufacturing an article, comprising forming a surface layer by a dry coating method or a wet coating method using a compound according to any one of claims 1 to 8, a composition containing the compound according to any one of claims 1 to 8 and another fluorine-containing compound, a surface treatment agent containing the compound or the composition, or a coating liquid containing the compound or the composition and a liquid medium.

15. A compound having a fluoropolyether chain and a group represented by the following formula (g2). *-R ｇ２ -CH=CH ２ ...(g2) However, R ｇ２ is an alkylene group in which the atom having the bond * may be an ether oxygen atom and which may have an ether oxygen atom between carbon-carbon atoms, and which has a carbon chain in which nine or more carbon atoms are linked alone or together with -CH=CH ２ and has a carbon chain in which nine or more carbon atoms are linked together, * is a bond that binds directly to the fluoropolyether chain or via a linking group.

Images