Polymer, surface treatment agent, article, and method for producing article

Abstract

The present invention provides: a polymer which is capable of forming a surface layer that has excellent oil repellency; a surface treatment agent; an article which has a surface layer that is formed of the polymer; and a method for producing the article.　A polymer according to the present invention contains a repeating unit represented by formula (1), and has a specific reactive group such as -SiRa1 z1Ra11 3-z1 (wherein Ra1 represents a hydrolyzable group or the like, Ra11 represents a hydrocarbon group, and z1 represents an integer of 1 to 3). In formula (1), Rf represents -OCF3 or the like, n represents an integer of 1 or more, L1 represents a (1 + n)-valent organic group, L2 represents a single bond or an oxygen atom, and R1 and R2 each independently represent a hydrogen atom, an alkyl group, or (Rf)n-L1-. Formula (1) does not include a fluorine atom other than the fluorine atoms contained in Rf.

Description

Polymer, surface treatment agent, article, and method for manufacturing an article

[0001] The present invention relates to a polymer, a surface treatment agent, an article, and a method for manufacturing an article.

[0002] In various fields such as electric and electronic materials, semiconductor materials, optical materials, building materials, and automotive parts, a method of forming a surface layer on the surface of a member (substrate) is known for the purpose of suppressing the adhesion of dirt to the member to be used. For example, Patent Document 1 discloses a method of forming a surface treatment layer on chemically strengthened glass using a surface treatment agent containing a silane compound containing a fluorine atom and a solvent.

[0003] International Publication No. 2024 / 101404

[0004] In recent years, the required performance for the surface layer has been increasing, and in some applications, a surface layer with excellent oil repellency is required. When the present inventors evaluated the surface layer formed using the silane compound containing a fluorine atom as described in Patent Document 1, they found that there is room for improvement in the oil repellency of the surface layer.

[0005] The present invention has been made in view of the above problems, and an object thereof is to provide a polymer capable of forming a surface layer with excellent oil repellency, a surface treatment agent, an article having a surface layer formed from the compound, and a method for manufacturing the article.

[0006] As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following configuration. [1] A polymer containing a repeating unit represented by the following formula (1) and having a reactive group, wherein the reactive group is -Ar １ , -SR １０ , -NOR １０ , -C(=O)R １０ , -N(R １０ ), ２ , -N ＋ (R １０ ), ３ X ３ , -C≡N, -C(=NR １０ )-R １０ , -N ＋ ≡NX ３ , -N=N R １０ , -C(=O)OR１０ -C(=O)OX ２ , -C(=O)X ４ , -C(=O)OC(=O)R １０ , -OC(=O)-CH ２ =CH ２ -C (=O) OR １０ , -SO ２ R １０ , -SO ２ X ４ , -SO ３ H, -SO ３ X ２ , -P(=O)(-OR １０ ) ２ , -OP(=O)(-OR １０ ) ２ , -OP(=O)(-OR １０ ) (-OX ２ ), -N=C=O, -N=C=S, -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ , -SiH(R １０ ) ２ , -Si(-OC ２ H ４ - OCH ３ ) ３ , -Si[-N(CH ３ ) ２ ] ３ , -Si[-OSi(CH ３ ) ３ ] ３ -C≡C(R １０ ), -C(=O)N(R １０ ) ２ , -N(R １０ )C(=O)R １０ , -Si(R １０ ) ２ -O-Si(R １０ ) ３ , -NH-C(=O)R １０ , -C(=O)NHR １０ , -I, -Br, -B(OH) ２ , -N ３ , A polymer that is one of the following. However, R １０is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent, Ar １ is an aryl group which may have a substituent, X ２ is an alkali metal ion or an ammonium ion, X ３ is a halide ion, X ４ is a halogen atom, R ａ１ is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, R ａ１１ is a hydrocarbon group, z1 is an integer of 1 to 3, R １０ , R ａ１ or R ａ１１ When there are a plurality of them, the plurality of R １０ , R ａ１ or R ａ１１ may be the same as or different from each other. However, R ｆ is -OCF ３ , -SCF ３ , -SF ４ X １１ , -N(CF ３ )X １２ , -CHF ２ , -CH ２ F, -C ６ F ５ , or -C ８ F ７ is, X １１ is an alkyl group or a halogen atom, X １２ is an alkyl group or -CF ３ is, n is an integer of 1 or more, L １ is a (1 + n)-valent organic group, L ２ is a single bond or an oxygen atom, R １ and R ２ are each independently a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L １ -, R ｆ , L １ , or when there are a plurality of n, the plurality of R ｆ , L１ , or n may be the same or different from each other, and in formula (1) above, R ｆ It does not contain any fluorine atoms other than the fluorine atoms contained in [2] The polymer according to [1], wherein the repeating unit represented by formula (1) above includes the repeating unit represented by formula (1-1) below. However, R ｆ and n are R in formula (1) above, respectively. ｆ And is synonymous with n, L Ａ１ is -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ３１ C(=O)O- and -NR ３２ C(=O)NR ３３ A (1+n) valent hydrocarbon group which may have at least one group selected from the group consisting of -, R ３１ , R ３２ and R ３３ Each is independently a hydrogen atom or an alkyl group, and R Ａ１ and R Ａ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L Ａ１ - and R ｆ , L Ａ１ , or, in the case where there are multiple n, the multiple R ｆ , L Ａ１ , or n may be the same or different from each other, and in the above formula (1-1), R ｆ It does not contain any fluorine atoms other than the fluorine atoms contained in [1]. [3] The polymer according to [1], wherein the repeating unit represented by formula (1) above includes a repeating unit represented by the following formula (1-2). However, in equation (1-2), R ｆ and n are R in formula (1) above, respectively. ｆ And is synonymous with n, L Ｂ１ is -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ３１ C(=O)O- and -NR ３２ C(=O)NR ３３A (1+n) valent hydrocarbon group which may have at least one group selected from the group consisting of -, R ３１ , R ３２ and R ３３ Each is independently a hydrogen atom or an alkyl group, and R Ｂ１ and R Ｂ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L Ｂ１ - and R ｆ , L Ｂ１ , or, in the case where there are multiple n, the multiple R ｆ , L Ｂ１ , or n may be the same or different from each other, and in the above formula (1-2), R ｆ [4] A surface treatment agent comprising the polymer described in any of [1] to [3]. [5] The surface treatment agent according to [4], further comprising a liquid medium. [6] The surface treatment agent according to [4] or [5], which is an antifouling coating agent or a waterproof coating agent. [7] An article having a surface layer formed using the polymer described in any of [1] to [3] on the surface of a substrate. [8] The article according to [7], which is an optical component. [9] The article according to [7] or [8], which has the above surface layer on the surface of a component constituting the surface touched by a finger on a touch panel.

[10] A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent described in any of [4] to [6].

[11] A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the surface treatment agent described in any of [4] to [6].

[0007] According to the present invention, it is possible to provide a polymer capable of forming a surface layer with excellent oil-repellent properties, a surface treatment agent, an article having a surface layer formed from the compound, and a method for manufacturing the article.

[0008] This is a schematic cross-sectional view showing an example of an article of the present invention.

[0009] The meanings of terms used in this invention are as follows. In this specification, a repeating unit represented by formula (1) is referred to as unit 1. Repeating units represented by other formulas are also referred to accordingly. In this specification, when a compound or group is represented by a specific formula (X), the compound or group represented by formula (X) may be referred to as compound (X) or compound X, and group (X) or group X, respectively. Similarly, when a polymer is represented by a specific formula (X), the polymer represented by formula (X) may be referred to as polymer (X) or polymer X. "Fluoroalkyl group" is a general term encompassing both perfluoroalkyl groups and partial fluoroalkyl groups. "Perfluoroalkyl group" means a group in which all hydrogen atoms of the alkyl group are replaced with fluorine atoms. "Partial fluoroalkyl group" is an alkyl group in which one or more hydrogen atoms are replaced with fluorine atoms and which has one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group having one or more fluorine atoms. A fluoroalkylene group is also referred to accordingly. "Reactive silyl group" is a general term for hydrolyzable silyl groups and silanol groups (Si-OH), and "hydrolyzable silyl group" means a group that can form a silanol group through hydrolysis. "Organic group" means a hydrocarbon group that may have substituents and may have heteroatoms or other bonds in its carbon chain. "Hydrogen group" means an aliphatic hydrocarbon group (linear alkylene group, branched alkylene group, cycloalkylene group, etc.), an aromatic hydrocarbon group (phenylene group, etc.), or a group consisting of a combination thereof. "Surface layer" means a layer formed on the surface of the substrate. "Number average molecular weight" (Mn) and "weight average molecular weight" (Mw) are values ​​measured by size exclusion chromatography (gel permeation chromatography) using polystyrene as the standard substance. The "~" indicating a numerical range means that the values ​​written before and after it are included as the lower and upper limits. The bonding order in each divalent group is not limited unless otherwise specified. For example, L in formula (1-2) described later. Ｂ１ If is a (1+n) valent hydrocarbon group containing -C(=O)NH-, then the left bond of -C(=O)NH- is (R) of formula (1-2). ｆ )ｎ It may be located to the side, or the right-hand coupling is in equation (1-2) (R ｆ ) ｎ They may be located to the side. Furthermore, if identical symbols exist within a single chemical formula, these identical symbols may represent identical structures or different structures within a defined range. In this specification, "Me" may represent a methyl group and "Ph" may represent a phenyl group.

[0010] [Polymer 1] The polymer of the present invention is a polymer (hereinafter referred to as "Polymer 1") that contains unit 1 as described below and has a specific reactive group as described below.

[0011] Polymer 1 is a fluorine-containing group R containing a fluorine atom. ｆ It has multiple (see formula (1) described later) and also has specific reactive groups. When forming a surface layer using polymer 1, the specific reactive groups of polymer 1 are easily positioned on the substrate side, and the specific reactive groups are strongly chemically bonded to the substrate, so the resulting surface layer has excellent abrasion resistance. In addition, polymer 1 has fluorine-containing R ｆ By having multiple R ｆ This makes the surface more easily exposed, resulting in a surface layer with excellent oil-repellent properties.

[0012] Polymer 1 has at least one unit, and may have other repeating units. In polymer 1, the bonding positions of the specific reactive group include, for example, the ends of the main chain, the side chains of the other units, and both. The various components of polymer 1 will be described below.

[0013] <Unit 1> Unit 1 is a repeating unit represented by formula (1).

[0014]

[0015] In formula (1), R ｆ is, -OCF ３ , -SCF ３ , -SF ４ X １１ , -N(CF ３ ) X １２ ,-CHF ２ ien-CH ２ F, -C６ F ５ , or -C ８ F ７ X １１ X is an alkyl group or halogen atom. １２ is an alkyl group or -CF ３ And n is an integer greater than or equal to 1, L １ is an organic group with (1+n) valence, L ２ is a single bond or an oxygen atom, R １ and R ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L １ - and R ｆ , L １ , or, in the case where there are multiple n, the multiple R ｆ , L １ , or n may be the same or different from each other. In equation (1), R ｆ It does not contain any fluorine atoms other than those present in the fluorine atoms contained within.

[0016] R ｆ is, -OCF ３ , -SCF ３ , -SF ４ X １１ , -N(CF ３ ) X １２ ,-CHF ２ ien-CH ２ F, -C ６ F ５ , or -C ８ F ７ (In the formula, X １１ X is an alkyl group or halogen atom, １２ is an alkyl group or -CF ３ Therefore, -OCF is superior in terms of the oil-repellent properties of the surface layer. ３ , -SF ４ X １１ Preferably, -OCF ３ This is preferable. - SF ４ X １１ X in １１ X is an alkyl group or halogen atom. １１The number of carbon atoms in the alkyl group is preferably 1 to 8, and more preferably 1 to 4. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure. １１ Specific examples of halogen atoms in this include F, Cl, Br, and I, with F being preferred because it provides superior oil repellency to the surface layer. -N(CF ３ ) X １２ X in １２ is an alkyl group or -CF ３ That is. X １２ The number of carbon atoms in the alkyl group is preferably 1 to 8, and more preferably 1 to 4. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure. ｆ When there are multiple R ｆ They may be the same or different from one another.

[0017] n is an integer greater than or equal to 1, preferably 1 to 8, more preferably 1 to 4, and even more preferably 1 to 3.

[0018] L １ L is an organic group with (1+n) valency. １ The organic group in may have substituents, such as carbon-carbon atoms or L １ Examples include (1+n) valent hydrocarbon groups that may have a divalent group at the C-terminus and may have a branching nitrogen or silicon atom. Hydrocarbon groups include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Aliphatic hydrocarbon groups may be linear, branched, or cyclic. Substituents that the above organic group may have include Cl, Br, and I. Divalent groups that the above organic group may have include -O-, -S-, and -C(=O)NR ６ -, -NR ６ C(=O)-, -C(=O)-, -C(=O)O-, -OC(=O)-, -NR ６ C(=O)NR ６ -, -NR ６ C(=O)NR ６-, -C(=O)S-, -SC(=O)-, -S(=O) ２ NR ６ -, -NR ６ S (=O) ２ -, -S (=O) ２ O-, -OS (=O) ２ - are some examples. However, R ６ Each of these is independently either a hydrogen atom or an alkyl group.

[0019] Because of its superior oil-repellent properties on the surface layer, L １ The group is preferably represented by the following formula (L1). *-(Q １ ) ｔ１ -Z １ - (Q ２ -Z ２ ) ｔ２ -Q ３ (-**) ｎ ... (L1) However, Q １ and Q ２ Each of these is independently the aforementioned divalent group, Z １ and Z ２ Each of these is independently a hydrocarbon group, Q ３ is a single bond or a (1+n) valence base, t1 is 0 or 1, t2 is an integer from 0 to 12, * is the bond position with C in equation (1), and ** is R ｆ This is the connection point.

[0020] Q １ and Q ２ These are the divalent groups mentioned above, and among them -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, and -NR ３１ C(=O)O-, or -NR ３２ C(=O)NR ３３ - is preferable. Here R ３１ , R ３２ and R ３３ Each of these is independently either a hydrogen atom or an alkyl group. ３１ , R ３２ and R ３３The number of carbon atoms in the alkyl group is preferably 1 to 3. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a ring structure.

[0021] Z １ and Z ２ The hydrocarbon groups in this compound include arylene groups, linear or branched alkylene groups that may have a carbon-carbon double bond, and combinations thereof. Examples of arylene groups include phenylene groups and naphthylene groups, with phenylene groups being preferred. １ The alkylene group in is preferably having 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. ２ The alkylene group in this compound preferably has 1 to 20 carbon atoms, more preferably 1 to 6, and even more preferably 2 to 3. t2 is an integer from 0 to 12, preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1.

[0022] Q ３ is a (1+n) valence base. When n is 1, Q ３ It is a single bond. When n is 2 or greater, Q ３ A branched hydrocarbon group is preferred. The branching is a trivalent nitrogen atom (*-N(-**) ２ ), trivalent carbon atoms (*-CR ８ (-**) ２ ), tetravalent carbon atoms (*-C(-**) ３ ), trivalent silicon atom (*-SiR ９ (-**) ２ ), tetravalent silicon atom (*-Si(-**) ３ ), 3- to 6-valent ring structure residues, and combinations thereof are examples. However, R ８ R is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. ９ * is an alkyl group having 1 to 6 carbon atoms, and * is Z ２ The bonding position on the side, ** is R ｆ This indicates the side connection position. Q ３ A concrete example of this is *-N(-Z ３ -**) ２ , *-CR ８ (-Z４ -**) ２ , *-C(-Z ４ -**) ３ *-SiR ９ (-Z ３ -**) ２ , *-Si(-Z ３ -**) ３、 *-Ar(-Z ４ -**) ｎ２ These are some examples. However, Z ３ Z is an alkylene group having 1 to 6 carbon atoms. ４ is a single bond or an alkylene group having 1 to 6 carbon atoms, Ar is a (1+n2) valent residue of a benzene ring or naphthalene ring, n2 is an integer from 1 to 5, and * is Z ２ The bonding position is R. ｆ This indicates the bonding position.

[0023] The number of carbon atoms in the (1+n)-valent organic group is preferably 1 to 20. The number of carbon atoms in the (1+n)-valent organic group is preferably 1 to 3 or 8 to 20, from the viewpoint of superior fingerprint removal properties.

[0024] L ２ It is a single bond or an oxygen atom.

[0025] R １ and R ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L １ - is R １ and R ２ The number of carbon atoms in the alkyl group is preferably 1 to 20. If the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure. １ and R ２ (R ｆ ) ｎ -L １ - In R ｆ , n and L １ The definition is as stated above. R １ and R ２The hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0026] Polymer 1 may contain multiple units of only one type, or it may contain two or more types of units 1. The bonding order of the two or more types of units 1 is not limited and may be arranged randomly, alternately, or in blocks. Containing two or more types of units 1 means, for example, that within each unit 1, there are units 1 in which the chemical structure of at least one group is different from that of the others.

[0027] The content of unit 1 is preferably 50 to 100 mol%, and more preferably 80 to 100 mol%, relative to the total repeating units of polymer 1. If the content of unit 1 is above the lower limit of the above range, the oil repellency is better.

[0028] From the viewpoint of achieving superior effects of the present invention, unit 1 preferably includes at least one of unit 1-1 and unit 1-2, and more preferably is unit 1-1 or unit 1-2.

[0029] (Unit 1-1) Unit 1-1 is a repeating unit represented by formula (1-1).

[0030]

[0031] In formula (1-1), R ｆ and n are R in equation (1), respectively. ｆ And is synonymous with n, L Ａ１ is -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ３１ C(=O)O- and -NR ３２ C(=O)NR ３３ A (1+n) valent hydrocarbon group which may have at least one group selected from the group consisting of -, R ３１ , R ３２ and R ３３ Each is independently a hydrogen atom or an alkyl group, and R Ａ１ and R Ａ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -LＡ１ - and R ｆ , L Ａ１ , or when there are a plurality of n, the plurality of R ｆ , L Ａ１ , or n may be the same as or different from each other. In formula (1-1), R ｆ does not contain a fluorine atom other than the fluorine atoms contained in R

[0032] L Ａ１ is an optionally (1 + n)-valent hydrocarbon group having at least one group selected from the group consisting of -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ３１ C(=O)O-, and -NR ３２ C(=O)NR ３３ -. The (1 + n)-valent hydrocarbon group in L Ａ１ is preferably an aliphatic hydrocarbon group (which may be saturated or unsaturated, and may be linear, branched or cyclic), an aromatic hydrocarbon group, or a group combining these. From the viewpoint of more excellent oil repellency of the surface layer, an aliphatic hydrocarbon group is more preferable. The carbon number of the (1 + n)-valent hydrocarbon group is preferably 1 to 20. The carbon number of the (1 + n)-valent hydrocarbon group is preferably 1 to 3 or 8 to 20 from the viewpoint of more excellent fingerprint removability. R ３１ , R ３２ and R ３３ are defined as described for L １ in the above formula (1).

[0033] L Ａ１ The group at the position bonded to the carbon atom of the main chain in L Ａ１ (that is, the carbon atom bonded to R ２ in formula (1-1)) is preferably *-CH ２ -** or *-CH Ａ１ -O-** from the viewpoint of ease of synthesis. In the formula, * represents the bonding position with the carbon atom of the main chain (that is, the carbon atom bonded to R Ａ１ in formula (1-1)), and ** represents the residue of L ｆ or the bonding position with R

[0034] LＡ１ A specific example is *-(CH ２ ) ｎａ１ -**, *- (CH ２ ) ｎａ１ -O-CH(-CH ２ -**) ２ , *-(CH ２ ) ｎａ２ -O-(CH ２ ) ｎａ３ -C(-CH) ２ -**) ３ , *-(CH ２ ) ｎａ１ -CH (-CH ２ -**) ２ , *-(CH ２ ) ｎａ２ -O-(CH ２ ) ｎａ３ -** are listed. In the formula, * represents the carbon atoms of the main chain (i.e., R in formula (1-1)). Ａ１ This indicates the bond position with the carbon atom bonded to it, and ** represents R ｆ This represents the connection position, where na1 is an integer between 1 and 20, na2 and na3 are each independent integers of 1 or more, and the sum of na2 and na3 is between 2 and 20.

[0035] R Ａ１ and R Ａ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L Ａ１ - is R Ａ１ and R Ａ２ The number of carbon atoms in the alkyl group is preferably 1 to 20. If the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure. Ａ１ and R Ａ２ (R ｆ ) ｎ -L Ａ１ - In R ｆ , n and L Ａ１ The definition is as stated above.

[0036] When polymer 1 contains unit 1-1, polymer 1 may contain multiple units of only one type of unit 1-1, or it may contain two or more types of unit 1-1. The bonding order of the two or more types of unit 1-1 is not limited and may be arranged randomly, alternately, or in blocks. Containing two or more types of unit 1-1 means, for example, that there are units 1-1 in which the chemical structure of at least one group is different from that of the other.

[0037] A specific example of unit 1-1 is the repeating unit represented by the following formula.

[0038]

[0039] (Unit 1-2) Unit 1-2 is a repeating unit represented by equation (1-2).

[0040]

[0041] In formula (1-2), R ｆ and n are R in formula (1) above, respectively. ｆ And is synonymous with n, L Ｂ１ is -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ３１ C(=O)O- and -NR ３２ C(=O)NR ３３ A (1+n) valent hydrocarbon group which may have at least one group selected from the group consisting of -, R ３１ , R ３２ and R ３３ Each is independently a hydrogen atom or an alkyl group, and R Ｂ１ and R Ｂ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L Ｂ１ - and R ｆ , L Ｂ１ , or, in the case where there are multiple n, the multiple R ｆ , L Ｂ１ , or n may be the same or different from each other. In equation (1-2), R ｆ It does not contain any fluorine atoms other than those present in the fluorine atoms contained within.

[0042] L Ｂ１ is -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ３１ C(=O)O- and -NR ３２ C(=O)NR ３３ A (1+n) valent hydrocarbon group which may have at least one group selected from the group consisting of -. Ｂ１ The (1+n) valent hydrocarbon group in is preferably an aliphatic hydrocarbon group (which may be saturated or unsaturated, and may be linear, branched, or cyclic), an aromatic hydrocarbon group, or a combination thereof. Aliphatic hydrocarbon groups are more preferred because they provide superior oil repellency to the surface layer. The number of carbon atoms in the (1+n) valent hydrocarbon group is preferably 1 to 20. ３１ , R ３２ and R ３３ The definition of is L in equation (1) above. １ As explained above.

[0043] L Ｂ１ The carbon atoms in the main chain (i.e., R in formula (1-2)) Ｂ１ The group at the position that bonds with the carbon atom bonded to it is, from the standpoint of ease of synthesis, *-C(=O)O-** or *-CH ２ -** is preferable. Also, from the standpoint of liquid repellency, L Ｂ１ is -C(=O)O-, and R Ｂ１ is a hydrogen atom or an alkyl group, R Ｂ２ It is preferable that is a hydrogen atom and n is 2 or more. In the formula, * is a carbon atom of the main chain (i.e., R in formula (1-2)). Ｂ１ This indicates the bond position with the carbon atom bonded to it, and ** represents L Ｂ１ The residue or R ｆ This indicates the connection point with [the other element].

[0044] L Ｂ１ A concrete example is *-C(=O)O-(CH ２ ) ｎｂ１ -**, *-C(=O)O-(CH ２ ) ｎｂ１ -O-CH(-CH ２ -**) ２ , *-C(=O)O-(CH２ ) ｎｂ２ -O-(CH ２ ) ｎｂ３ -**, *-C(=O)O-(CH ２ ) ｎｂ２ -NR ３１ C(=O)O-(CH ２ ) ｎｂ３ -**, *- (CH ２ ) ｎｂ１ -**, *- (CH ２ ) ｎｂ２ -O-(CH ２ ) ｎｂ３ -**, *- (CH ２ ) ｎｂ１ -O-CH(-CH ２ -**) ２ , *-Ph １ - (**) ｎｂ４ These are examples. In the formula, * represents the carbon atoms of the main chain (i.e., R in formula (1-2)). Ｂ１ This indicates the bond position with the carbon atom bonded to it, and ** represents R ｆ This represents the connection position with, where nb1 is an integer from 1 to 20, nb2 and nb3 are each independent integers of 1 or more, and the sum of nb2 and nb3 is from 2 to 20, R ３１ As stated above, nb4 is an integer from 1 to 5, and Ph １ This is a phenylene group.

[0045] R Ｂ１ and R Ｂ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L Ｂ１ - is R Ｂ１ and R Ｂ２ The number of carbon atoms in the alkyl group is preferably 1 to 20. If the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure. Ｂ１ and R Ｂ２ (R ｆ ) ｎ -L Ｂ１ - In R ｆ , n and L Ｂ１ The definition is as stated above.

[0046] When polymer 1 contains units 1-2, polymer 1 may contain multiple units of only one type of unit 1-2, or it may contain two or more types of units 1-2. The bonding order of the two or more types of units 1-2 is not limited and may be arranged randomly, alternately, or in blocks. Containing two or more types of units 1-2 means, for example, that there are units 1-2 in which the chemical structure of at least one group is different from that of the other.

[0047] A specific example of unit 1-2 is the repeating unit represented by the following formula.

[0048]

[0049]

[0050]

[0051] <Specific Reactive Groups> The specific reactive group is -Ar １ ,-SR １０ , -NOR １０ , -C(=O)R １０ , -N(R １０ ) ２ , -N ＋ (R １０ ) ３ X ３ , -C≡N, -C(=NR １０ )-R １０ , -N ＋ ≡NX ３ -N=NR １０ , -C (=O) OR １０ -C(=O)OX ２ , -C(=O)X ４ , -C(=O)OC(=O)R １０ , -OC(=O)-CH ２ =CH ２ -C (=O) OR １０ , -SO ２ R １０ , -SO ２ X ４ , -SO ３ H, -SO ３ X ２ , -P(=O)(-OR １０ ) ２ , -OP(=O)(-OR １０ )２ , -OP(=O)(-OR １０ ) (-OX ２ ), -N=C=O, -N=C=S, -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ , -SiH(R １０ ) ２ , -Si(-OC ２ H ４ - OCH ３ ) ３ , -Si[-N(CH ３ ) ２ ] ３ , -Si[-OSi(CH ３ ) ３ ] ３ -C≡C(R １０ ), -C(=O)N(R １０ ) ２ , -N(R １０ )C(=O)R １０ , -Si(R １０ ) ２ -O-Si(R １０ ) ３ , -NH-C(=O)R １０ , -C(=O)NHR １０ , -I, -Br, -B(OH) ２ , -N ３ It is one of the following bases:

[0052]

[0053] However, R １０ Ar is a hydrogen atom, a C1-C6 alkyl group which may have substituents, or an aryl group which may have substituents. １ X is an aryl group which may have substituents, ２ X is an alkali metal ion or an ammonium ion. ３ X is a halide ion. ４ R is a halogen atom. ａ１ R is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. ａ１１ is a hydrocarbon group, z1 is an integer from 1 to 3, and R １０ , Rａ１ or R ａ１１ When there are multiple R １０ , R ａ１ or R ａ１１ They may be the same or different from one another.

[0054] Ar １ and R １０ The aryl group in this formula may be a phenyl group, a naphthyl group, etc., and may further have substituents. Substituents that the aryl group may have include fluorine atoms, halogen atoms such as chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and those similar to those exemplified as functionality-granting groups T. １０ The alkyl group in has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The alkyl group may have other substituents. Examples of substituents that the alkyl group may have include halogen atoms such as chlorine atoms, and those similar to those exemplified as the functional group T described later.

[0055] Polymer 1 having specific reactive groups such as N-hydroxyl groups, aldehyde groups, ketone groups, amino groups, quaternary ammonium groups, nitrile groups, imino groups, diazo groups, carboxyl groups, carboxylates, acid anhydride groups, sulfo groups, sulfonates, phosphate groups, phosphates, or boronic acid groups (hereinafter, these groups are referred to as "functionality-imparting groups T") is imparted with various properties such as acidity, alkalinity, and hydrophilicity by the functionality-imparting groups T, for example, by providing functions such as improved solubility in a specific solvent or improved adhesion to a specific substrate. Examples of counterions for quaternary ammonium groups include halide ions. Examples of counterions for carboxylates, sulfonates, and phosphates include alkali metal ions and ammonium ions. Furthermore, polymer 1 having an isocyanate group, isothiocyanate group, epoxy group, glycidyl group, oxetanyl group, or mercapto group as a specific reactive group can be combined with an epoxy curing agent to prepare a thermosetting or photocurable composition, and the cured coating obtained from this composition possesses both water-repellent and oil-repellent properties as well as hard-coat properties. The amide bond, ester bond, ether bond, thioether bond, siloxane bond, or urea bond in the specific reactive group is a bond that connects alkyl groups, fluoroalkyl groups, aryl groups, heteroaryl groups, etc., contained in the specific reactive group. It may also have other functional groups T via these bonds.

[0056] As for the specific reactive group contained in polymer 1, an amino group, a carboxyl group, or a mercapto group is preferred due to its excellent synthesis, chemical stability, and adhesion to the substrate.

[0057] Furthermore, when polymer 1 is used as a surface treatment agent to form a surface layer with excellent durability such as abrasion resistance, the specific reactive group is preferably a group having a reactive silyl group. As a group having a reactive silyl group, the group represented by the following formula (2) is preferred.

[0058] -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ (2)

[0059] In formula (2), Rａ１ R is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. ａ１１ is a hydrocarbon group, z1 is an integer from 1 to 3, and R ａ１ , or R ａ１１ If there are multiple R ａ１ , or R ａ１１ These may be the same or different.

[0060] R ａ１ If it is a hydroxyl group, it forms a silanol (Si-OH) group together with the Si atom. Hydrolyzable groups are groups that become hydroxyl groups through hydrolysis. The silanol group further reacts intermolecularly to form a Si-O-Si bond. The silanol group also undergoes a dehydration condensation reaction with the hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Polymer 1 has excellent abrasion resistance after surface layer formation because it has one or more specific reactive groups.

[0061] R ａ１ The hydrolyzable groups include alkoxy groups, aryloxy groups, alkenyloxy groups, halogen atoms, acyl groups, acyloxy groups, amino groups, isocyanate groups (-NCO), and -O-N=CR. ｒ ２ (R ｒ Examples of these groups independently include alkyl groups having 1 to 10 carbon atoms, alkylene oxide-modified alkoxy groups, etc. As the alkoxy group, alkoxy groups having 1 to 4 carbon atoms are preferred. As the acyl group, acyl groups having 1 to 6 carbon atoms are preferred. As the acyloxy group, acyloxy groups having 1 to 6 carbon atoms are preferred.

[0062] R ａ１ Examples of hydrolyzable groups in a group having a hydrolyzable group include the hydrolyzable groups exemplified above. A group having a hydrolyzable group is -O-L Ａ -L Ｂ This is preferable. L Ａ L is an alkylene group, Ｂ This is a hydrolyzable group. The number of carbon atoms in the alkylene group is preferably 1 to 10. Ｂ The hydrolyzable group represented by the above R ａ１This is synonymous with the hydrolyzable group in the above, and the preferred embodiment is also the same. A specific example of a group having a hydrolyzable group is -O-CH, which is also one of the alkylene oxide-modified alkoxy groups. ２ CH ２ - OCH ３ Examples include the following. Thus, the group having a hydrolyzable group may be an alkylene oxide-modified alkoxy group. The alkylene oxide-modified alkoxy group is -(O-R ４１ ) ｎ１１ -L ４１ A group represented by R is preferred. Here, R ４１ L is an alkylene group having 1 to 10 carbon atoms. ４１ R is an alkoxy group having 1 to 6 carbon atoms, and n11 is an integer from 1 to 6. Among them, R ４１ The alkylene group has 1 to 6 carbon atoms, and n11 is preferably 1.

[0063] R ａ１ From the standpoint of ease of synthesis, alkoxy groups having 1 to 4 carbon atoms, and the aforementioned -O-L Ａ -L Ｂ Alternatively, halogen atoms are preferred. ａ１ In this compound, the alkoxy group is preferably a C1-C4 alkoxy group because it provides excellent storage stability for polymer 1 and suppresses outgassing during the reaction. An ethoxy group is more preferable in terms of long-term storage stability, and a methoxy group is more preferable in terms of shortening the hydrolysis reaction time. Furthermore, a chlorine atom is preferred as the halogen atom.

[0064] R ａ１１ This is a hydrocarbon group. Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, alkenyl groups, and allyl groups, and alkyl groups are preferred from the viewpoint of ease of synthesis. Furthermore, from the viewpoint of ease of synthesis, 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.

[0065] In base 2, R ａ１ The number z1 can be 1 to 3, and from the viewpoint of excellent adhesion to the substrate, 2 or 3 is preferred, and 3 is more preferred. A specific example of group 2 is -Si(OCH ３ ) ３ , -Si(CH３ ) (OCH ３ ) ２ , -Si((CH ３ ) ２ (OCH ３ ), -Si(OCH ２ CH ３ ) ３ , -Si(OCH ２ CH ２ OCH ３ ) ３ , -SiCl ３ , -Si(OCOCH ３ ) ３ , -Si(NCO) ３ ,-Si(N(CH ３ ) ２ ) ３ -Si(OH) ３ One example is -Si(OCH) due to its ease of handling during manufacturing. ３ ) ３ , -Si(OCH ２ CH ３ ) ３ It is preferable.

[0066] The following structure is also a preferred embodiment of the specific reactive group. However, in the formula, R is the same as the R described above. １０ This represents a combination, and * indicates a bonding hand.

[0067]

[0068] The embodiments in which the specific reactive group is included in polymer 1 are not particularly limited, but examples include an embodiment in which polymer 1 includes repeating units having the specific reactive group (hereinafter referred to as "Embodiment X"), and an embodiment in which the specific reactive group is located at the end of a polymer chain containing unit 1 (hereinafter referred to as "Embodiment Y"). Embodiments X and Y will be described in detail below.

[0069] (Aspect X (Unit 2)) Aspect X is an aspect in which polymer 1 includes repeating units having a specific reactive group. The repeating unit having the specific reactive group is preferably unit 2.

[0070]

[0071] In formula (2), L Ｘ１ , L Ｘ２, R Ｘ１ , and R Ｘ２ These are L in equation (1), respectively. １ , L ２ , R １ , and R ２ It is synonymous with T Ｘ１ m1 is the specific reactive group mentioned above, and m1 is an integer greater than or equal to 1.

[0072] L Ｘ１ L in equation (1) １ This is synonymous with L. Ｘ１ A specific example is *-(CH ２ ) ｎｘ１ -**, *- (CH ２ ) ｎｘ２ -O-(CH ２ ) ｎｘ３ -**, *-C(=O)O-(CH ２ ) ｎｘ１ -**, *-C(=O)O-(CH ２ ) ｎｘ２ -OC(=O)NR ３１ - (CH ２ ) ｎｘ３ -**, *- (CH ２ ) ｎｘ２ -NR ３２ C(=O)NR ３３ - (CH ２ ) ｎｘ３ -**, *-OC(=O)NR ３１ - (CH ２ ) ｎｘ１ -** is an example. In the formula, * is a carbon atom of the main chain (i.e., R in formula (2)). Ｘ１ This indicates the bond position with the carbon atom bonded to it, and ** represents T Ｘ１ This represents the connection position with, where nx1 is an integer from 1 to 20, nx2 and nx3 are each independent integers of 1 or more, and the sum of nx2 and nx3 is from 2 to 20, R ３１ , R ３２ and R ３３ This is as stated above.

[0073] m1 is an integer greater than or equal to 1. From the viewpoint of ease of synthesis and ease of handling of polymer 1, m1 is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1 to 2.

[0074] If polymer 1 contains unit 2, the bonding order of unit 1 and unit 2 in polymer 1 is not limited and may be arranged randomly, alternately, or in blocks.

[0075] When polymer 1 contains unit 2, polymer 1 may contain multiple units of only one type of unit 2, or it may contain two or more types of unit 2. The bonding order of the two or more types of unit 2 is not limited and may be arranged randomly, alternately, or in blocks. Containing two or more types of unit 2 means, for example, that within unit 2, there exist units 2 in which the chemical structure of at least one group is different from that of the other units.

[0076] When polymer 1 contains unit 2, the content of unit 2 is preferably 1 to 50 mol%, and more preferably 1 to 20 mol%, relative to the total repeating units of polymer 1. If the content of unit 2 is above the lower limit of the above range, the abrasion resistance is better. If the content of unit 2 is below the upper limit of the above range, the oil repellency is better.

[0077] A concrete example of unit 2 is the repeating unit represented by the following formula.

[0078]

[0079]

[0080] (Aspect Y) Aspect Y is an aspect in which a specific reactive group is located at the end of a polymer chain containing unit 1. In this case, polymer 1 is preferably a polymer represented by formula (1Y), for example.

[0081] P Ｙ１ -L Ｙ１ - (T Ｙ１ ) ｍ２ (1Y)

[0082] In formula (1Y), P Ｙ１ This is a polymer chain containing unit 1, L Ｙ１ is a single bond or a (1+m2) valence group, T Ｙ１ L is the specific reactive group mentioned above. Ｙ１ If it is a single bond, then m2 is 1, L Ｙ１If is a (1 + m2) valence base, then m2 is an integer greater than or equal to 1.

[0083] P Ｙ１ This is a polymer chain containing unit 1. Ｙ１ In addition to unit 1, it may also include at least one of unit 2 (described above) and other units (described below). Ｙ１ If the combination includes unit 1, unit 2, and at least one of the other units, the order in which unit 1, unit 2, and at least one of the other units are combined is not limited and may be arranged randomly, alternately, or in blocks.

[0084] L Ｙ１ This is a single bond or a (1+m2) valence group. When m2 is 2 or more, the (1+m2) valence group is at least one branch point selected from the group consisting of C, N, Si, and a ring structure (hereinafter referred to as "branch point P"). ２ It is preferable to have the following:

[0085] Branch point P ２ As for the ring structure constituting the ring, from the standpoint of ease of synthesis and superior friction resistance, light resistance, and chemical resistance of the surface layer, one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 6-membered aromatic ring, a 5- to 6-membered heterocycle, and a fused ring consisting of two or more of these rings is preferred, and the ring structure shown in the following formula is more preferred. The ring structure may have substituents such as halogen atoms, alkyl groups (which may contain an etheric oxygen atom between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, and oxo groups (=O).

[0086]

[0087] L Ｙ１ This includes alkylene groups, hydroxyalkylene groups, alkoxyalkylene groups, carbonyl groups, amide bonds, ether bonds, thioether bonds, urea bonds, urethane bonds, carbonate bonds, ester bonds, and -SO ２ NR ２６ -, -Si(R ２６ ) ２ -, -OSi(R ２６ ) ２ -, and -Si(CH ３) ２ -Ph １ -Si(CH ３ ) ２ - A group comprising one or more selected from divalent organopolysiloxane residues (hereinafter referred to as "group B") １０ It is written as follows: ) It may have R ２６ This is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph １ This is a phenylene group. ２６ The number of carbon atoms in the alkyl group is preferably 1 to 3, and more preferably 1 to 2, from the standpoint of facilitating the production of polymer 1.

[0088] Examples of divalent organopolysiloxane residues include the group shown in the following formula. However, R in the following formula... ２７ R is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. ２７ The number of carbon atoms in the alkyl and alkoxy groups is preferably 1 to 10, and more preferably 1.

[0089]

[0090] L Ｙ１ (R in equation (1)) ｆ ) ｎ -L １ It may contain a group represented by -.

[0091] L Ｙ１ Preferred forms include one or more hydrocarbon groups, one or more hydrocarbon groups and one or more group B １０ A combination of one or more hydrocarbon groups and (R ｆ ) ｎ -L １ A combination with a group represented by -, one or more hydrocarbon groups and one or more groups B １０ and (R ｆ ) ｎ -L １ A combination with a group represented by -, one or more hydrocarbon groups and one or more branching points P ２ In combination with, one or more hydrocarbon groups and one or more branching points P ２ and one or more base B １０Examples of combinations include those with the above. Specific examples of hydrocarbon groups include aliphatic hydrocarbon groups (e.g., divalent aliphatic hydrocarbon groups such as alkylene groups and cycloalkylene groups) and aromatic hydrocarbon groups (e.g., divalent aromatic hydrocarbon groups such as phenylene groups). The number of carbon atoms in the hydrocarbon group is preferably 1 to 20. The number of carbon atoms in the hydrocarbon group may be 1 to 10, 1 to 6, or 1 to 4.

[0092] L Ｙ１ A specific example is *-(CH ２ ) ｎｃ１ -**, *- (CH ２ ) ｎｃ１ -C(-CH) ２ CH ２ CH ２ -**) ３ , *-CH(-**)-CH(Me)-C(=O)O-(CH ２ ) ｎｃ１ -OCF ３ *-CH ２ -CH(-**)-(CH ２ ) ｎｃ１ -OCF ３ , *-CH(-**)-CH ２ - (CH ２ ) ｎｃ１ -OCF ３ *-CH ２ -C(Me)(-CH ２ CH ２ CH ２ -**) ２ , *-O-(CH ２ ) ｎｃ１ -**, *-O-CH ２ -CH (-CH ２ CH ２ CH ２ -**) ２ , *-O-CH ２ -C(Me)(-CH ２ CH ２ CH ２ -**) ２ , *-O-CH ２ -C(-CH) ２ CH ２ CH ２ -**) ３ , *-O-(CH ２ )ｎｃ１ -C(=O)NH-CH ２ -CH (-CH ２ CH ２ CH ２ -**) ２ , *-(CH ２ ) ｎｃ１ -C(=O)NH-CH ２ -CH (-CH ２ CH ２ CH ２ -**) ２ , *-OC(=O)-C(-CH ２ CH ２ CH ２ -**) ３ Examples include: * is P Ｙ１ This indicates the connection position with T, where ** represents T Ｙ１ This represents the connection position, and nc1 is an integer between 1 and 20.

[0093] m2 is L Ｙ１ If it is a single bond, then it is 1, L Ｙ１ If it is a (1 + m²) valence linking group, then it is an integer greater than or equal to 1. Ｙ１ When the linking group is (1 + m2) valent, m2 is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3, from the viewpoint of ease of synthesis and ease of handling of the polymer.

[0094] A specific example of polymer 1Y is the polymer represented by the following formula.

[0095]

[0096]

[0097]

[0098] <Other units (unit 3)> Polymer 1 is R in formula (1) ｆ The material may include a repeating unit (hereinafter referred to as "other unit") that does not have the group represented by and a specific reactive group. The other unit is preferably unit 3.

[0099]

[0100] In formula (3), L Ｚ１is -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ４１ C(=O)O- and -NR ４２ C(=O)NR ４３ A monovalent hydrocarbon group which may have at least one group selected from the group consisting of - and may be substituted with -OH, L Ｚ２ L in equation (1) ２ This is synonymous with R Ｚ１ and R Ｚ２ Each of these is either a hydrogen atom or an alkyl group.

[0101] L Ｚ１ is -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ４１ C(=O)O- and -NR ４２ C(=O)NR ４３ A monovalent hydrocarbon group which may have at least one group selected from the group consisting of - and may be substituted with -OH. Ｚ１ The monovalent hydrocarbon group in is preferably an aliphatic hydrocarbon group (which may be saturated or unsaturated, and may be linear, branched, or cyclic), an aromatic hydrocarbon group, or a combination thereof. Aliphatic hydrocarbon groups are more preferred because they provide superior oil repellency to the surface layer. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 20. The number of carbon atoms in the monovalent hydrocarbon group may also be 1 to 10, 1 to 6, or 1 to 4. ４１ , R ４２ and R ４３ Each of these is independently either a hydrogen atom or an alkyl group. ４１ , R ４２ and R ４３ The number of carbon atoms in the alkyl group is preferably 1 to 6. If the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a ring structure.

[0102] L Ｚ１ A specific example is *-(CH ２ ) ｎｄ１ - OCH ３ , *-(CH ２) ｎｄ１ -CH=CH ２ *-CH ２ -O-(CH ２ ) ｎｄ１ - OCH ３ , *-(CH ２ ) ｎｄ２ -C(=O)NH-(CH ２ ) ｎｄ３ -CH ３ , *-C(=O)O-(CH ２ ) ｎｄ１ - OCH ３ , *-C(=O)O-(CH ２ ) ｎｄ２ -NR ４１ C(=O)O-(CH ２ ) ｎｄ３ -CH ３ , *-C(=O)O-(C ２ H ４ O) ｎｄ２ - (CH ２ ) ｎｄ３ -CH ３ , *-C(=O)O-(CH ２ ) ｎｄ１ -CH=CH ２ , *-C(=O)O-(CH ２ ) ｎｄ１ -OH, *- (CH ２ ) ｎｄ２ -CH=CH-(CH ２ ) ｎｄ３ -CH ３ These are examples. In the formula, * represents the carbon atoms of the main chain (i.e., R in formula (3)). Ｚ１ R represents the bond position with the carbon atom to which it is bonded, where nd1 is an integer from 1 to 20, nd2 and nd3 are each independent integers of 0 or more, and the sum of nd2 and nd3 is from 1 to 20. ４１ This is as stated above.

[0103] R Ｚ１ and R Ｚ２ Each of these is either a hydrogen atom or an alkyl group. Ｚ１ and R Ｚ２ The number of carbon atoms in the alkyl group is preferably 1 to 20. If the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a ring structure.

[0104] If polymer 1 contains other units, the bonding order of unit 1 and the other units in polymer 1 is not limited and may be random, alternating, or arranged in blocks.

[0105] If polymer 1 contains other units, polymer 1 may contain multiple units of only one type of other unit, or it may contain two or more types of other units. The bonding order of the two or more types of other units is not limited and may be random, alternating, or arranged in blocks. Containing two or more types of other units means, for example, that within unit 3, there exist units 3 in which the chemical structure of at least one group is different from that of the other units.

[0106] When polymer 1 contains unit 3, the content of unit 3 is preferably 1 to 30 mol%, and more preferably 1 to 10 mol%, relative to the total repeating units of polymer 1. If the content of unit 3 is above the lower limit of the above range, solubility is better. If the content of unit 3 is below the upper limit of the above range, oil repellency is better.

[0107] A concrete example of unit 3 is the repeating unit represented by the following formula.

[0108]

[0109] <Physical Properties, etc.> The number-average molecular weight (Mn) of polymer 1 is preferably 500 to 20,000, more preferably 500 to 10,000, and even more preferably 500 to 5,000. If Mn is above the lower limit of the above range, the abrasion resistance of the surface layer is better. If Mn is below the upper limit of the above range, the viscosity is easier to adjust within an appropriate range, and the solubility is improved, resulting in excellent handling during film formation.

[0110] [Surface Treatment Agent] The surface treatment agent of the present invention (hereinafter referred to as "this surface treatment agent") contains the polymer 1 described above. This surface treatment agent is suitable for applications where it is required that the water-repellent and oil-repellent properties of the surface layer not deteriorate even when repeatedly rubbed with fingers (abrasion resistance) and the ability to easily remove fingerprints adhering to the surface layer by wiping (fingerprint stain removal) be maintained for a long period of time, such as components that make up the surface that is touched by fingers on a touch panel, eyeglass lenses, and displays of wearable devices. Furthermore, because this surface treatment agent has excellent slip resistance, it is also suitable for use on glass-coated casings of portable devices such as smartphones and tablet terminals. This surface treatment agent is also suitable for use as an anti-fouling coating agent or a waterproof coating agent.

[0111] This surface treatment agent may further contain a liquid medium. In the following description, this surface treatment agent containing a liquid medium may be referred to as a coating solution. The coating solution may be a liquid, a solution, or a dispersion. The coating solution may contain polymer 1 and may contain impurities such as by-products generated in the manufacturing process of polymer 1. The concentration of polymer 1 in the coating solution is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass.

[0112] As the liquid medium, an organic solvent is preferred. The organic solvent may be a fluorine-containing organic solvent, a non-fluorine-containing organic solvent, or a mixture of both. Specific examples of fluorine-containing organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and hydrofluoroolefins (HFOs). As fluorinated alkanes, compounds having 4 to 8 carbon atoms are preferred. Specific examples of commercially available products include C ６ F １３ H (AGC Corporation, Asahi Clean® AC-2000), C ６ F １３ C ２ H ５ (Manufactured by AGC Corporation, Asahi Clean® AC-6000), C ２ F５ CHFCHFCF ３ (Chemours Bartrell® XF) is one example. Specific examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. As for fluoroalkyl ethers, compounds with 4 to 12 carbon atoms are preferred. A specific example of a commercially available product is CF ３ CH ２ OCF ２ CF ２ H (manufactured by AGC Corporation, Asahi Clean® AE-3000), C ４ F ９ OCH ３ (Manufactured by 3M, Novec® 7100), C ４ F ９ OC ２ H ５ (Manufactured by 3M, Novec® 7200), C ２ F ５ CF(OCH) ３ ) C ３ F ７ (Novec® 7300, manufactured by 3M) is one example. Specific examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. Specific examples of HFOs include 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) (Amorea® AS-300, manufactured by AGC). As non-fluorinated organic solvents, compounds consisting only of hydrogen and carbon atoms, and compounds consisting only of hydrogen, carbon, and oxygen atoms are preferred, and examples include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and glycol organic solvents.

[0113] Specific examples of hydrocarbon organic solvents include pentane, hexane, heptane, octane, hexadecane, isohexane, isooctane, isononane, cycloheptane, cyclohexane, bicyclohexyl, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.

[0114] Specific examples of alcoholic organic solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, diacetone alcohol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, and methylcyclohexanol.

[0115] Specific examples of ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and 3,3,5-trimethylcyclohexanone and isophorone.

[0116] Specific examples of ether-based organic solvents include diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane.

[0117] Specific examples of ester-based organic solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl acetate, propylene glycol dimethyl acetate, and ethylene glycol monoethyl ether acetate. Examples include tate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, γ-butyrolactone, triacetin, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

[0118] Specific examples of glycol-based organic solvents include ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol Examples include propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,3-butylene glycol, propylene glycol n-propyl ether, propylene glycol n-butyl ether, diethylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether pentane, triethylene glycol dimethyl ether, and polyethylene glycol dimethyl ether.

[0119] Other organic solvents include chlorinated organic solvents, nitrogen-containing compounds, sulfur-containing compounds, and siloxane compounds.

[0120] Specific examples of chlorinated organic solvents include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, and 1,2,3-trichloropropane.

[0121] Specific examples of nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

[0122] Specific examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.

[0123] Specific examples of siloxane compounds include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.

[0124] The coating liquid preferably contains 60 to 99.999% by mass of the liquid medium, more preferably 80 to 99.99% by mass, even more preferably 90 to 99.9% by mass, and particularly preferably 99 to 99.9% by mass.

[0125] The surface treatment agent may contain other components besides polymer 1 and the liquid medium, as long as they do not impair the effects of the disclosed herein. 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 surface treatment agent is preferably 10% by mass or less, and more preferably 1% by mass or less.

[0126] The total concentration of polymer 1 and other components in the coating solution (hereinafter referred to as "solids concentration") is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.01 to 10% by mass, and particularly preferably 0.01 to 1% by mass. The solids concentration of the coating solution is calculated from the mass of the coating solution before heating and the mass after heating in a convection dryer at 120°C for 4 hours.

[0127] [Article] The article of the present invention (hereinafter referred to as "the Article") has a surface layer formed from polymer 1 or the surface treatment agent on the surface of a substrate. An example of the Article will be described with reference to the drawings. Figure 1 is a schematic cross-sectional view showing a first article, which is an example of the Article. The first article is an article 20 having a substrate 12, a base layer 14, and a surface layer 22 in that order, wherein the base layer 14 contains an oxide containing silicon, and the surface layer 22 contains a condensate of polymer 1.

[0128] The material and shape of the base material 12 may be appropriately selected according to the intended use of the article 20. Examples of materials for the base material 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. Examples of base materials 12 that require water-repellent and oil-repellent properties include touch panel base materials, display base materials, and base materials that constitute the housing of electronic devices. Touch panel base materials and display base materials 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 touch panel base materials.

[0129] The base material 12 may have surface treatments such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment applied to the surface on which the underlayer 14 is provided. Surface treatment further improves the adhesion between the base material 12 and the underlayer 14, and as a result, the abrasion resistance of the surface layer 22 is further improved. Corona discharge treatment or plasma treatment is preferred as the surface treatment because it further improves the abrasion resistance of the surface layer 22.

[0130] The base layer 14 is a layer containing an oxide that includes at least silicon, and may also contain other elements. The presence of silicon oxide in the base layer 14 causes specific reactive groups of polymer 1 to undergo dehydration condensation, forming Si-O-Si bonds between the base layer 14 and the polymer, resulting in a surface layer 22 with superior abrasion resistance.

[0131] The silicon dioxide content in the base layer 14 is preferably 65% ​​by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass or more. If the silicon dioxide content is above the lower limit of the above range, sufficient Si-O-Si bonds are formed in the base layer 14, and the mechanical properties of the base layer 14 are sufficiently ensured. The silicon dioxide content is the remainder obtained by subtracting the total content of other elements (or the amount converted to oxides in the case of oxides) from the mass of the base layer 14.

[0132] From the standpoint of providing excellent durability of the surface layer 22, it is preferable that the oxide in the base layer 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. Including these elements strengthens the bond between the base layer 14 and the polymer 1, improving abrasion resistance.

[0133] When the base layer 14 contains one or more elements selected from iron, nickel, and chromium, the total content of these elements is preferably 10 to 1,100 ppm by mass, more preferably 50 to 1,100 ppm by mass, even more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass, relative to silicon oxide. When the base layer 14 contains one or more elements selected from aluminum and zirconium, the total content of these elements is preferably 10 to 2,500 ppm by mass, more preferably 15 to 2,000 ppm by mass, and even more preferably 20 to 1,000 ppm by mass. When the base layer 14 contains alkali metal elements, 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 base layer 14 contains platinum group elements, the total content of these elements is preferably 0.02 to 800 ppm by mass, more preferably 0.04 to 600 ppm by mass, and even more preferably 0.7 to 200 ppm by mass. Examples of platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium. When the base layer 14 contains one or more elements selected from boron and phosphorus, the total content of these elements is preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, as a ratio of the molar concentration of the total of boron and phosphorus to the molar concentration of silicon, from the viewpoint of excellent abrasion resistance of the surface layer 22. When the base layer 14 contains alkaline earth metal elements, the total content of these elements is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2, as a ratio of the molar concentration of the total alkaline earth metal elements to the molar concentration of silicon, from the viewpoint of excellent abrasion resistance of the surface layer 22. Examples of alkaline earth metal elements include calcium, strontium, barium, and magnesium.

[0134] To improve the adhesion of this surface treatment agent and enhance the water-repellent, oil-repellent, and abrasion-resistant properties of article 20, the base layer 14 is preferably a silicon oxide layer containing alkali metal atoms. In the silicon oxide layer, the average concentration of alkali metal atoms in the region at a depth of 0.1 to 0.3 nm from the surface in contact with the surface layer 22 is 2.0 × 10⁻¹⁴. １９ atoms / cm ３ The above is preferable. On the other hand, in order to sufficiently ensure the mechanical properties of the silicon oxide layer, the average value of the alkali metal atom concentration is 4.0 × 10 ２２ atoms / cm ３ The following is preferable:

[0135] The thickness of the base layer 14 is preferably 1 to 200 nm, and more preferably 2 to 20 nm. If the thickness of the base layer 14 is above the lower limit of the above range, the adhesive improvement effect of the base layer 14 is easily obtained. If the thickness of the base layer 14 is below the upper limit of the above range, the abrasion resistance of the base layer 14 itself will be increased. Methods for measuring the thickness of the base layer 14 include cross-sectional observation of the base layer 14 using an electron microscope (SEM, TEM, etc.), and methods using an optical interferometer, spectroscopic ellipsometer, step meter, etc.

[0136] Specific examples of methods for forming the underlayer 14 include a method of depositing a vapor deposition material having the desired underlayer 14 composition onto the surface of the substrate 12. One example of a vapor deposition method is the vacuum vapor deposition method. The vacuum vapor deposition method involves evaporating the vapor deposition material in a vacuum chamber and depositing it onto the surface of the substrate 12. The temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 100 to 3,000°C, and more preferably 500 to 3,000°C. The pressure during vapor deposition (for example, the absolute pressure in the chamber in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 1 Pa or less, and more preferably 0.1 Pa or less. When forming the underlayer 14 using a vapor deposition material, one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used. Examples of evaporation methods for the vapor deposition material include the resistance heating method, in which the vapor deposition material is melted and evaporated on a resistance heating boat made of high melting point metal, and the electron gun method, in which an electron beam is irradiated onto the vapor deposition material to directly heat the material, melt the surface, and evaporate it. As a method for evaporating the deposition material, the electron gun method is preferred because it allows for localized heating, enabling the evaporation of high-melting-point substances, and because the temperature is low in areas not exposed to the electron beam, eliminating the risk of reaction with the container or contamination by impurities. As the deposition material used in the electron gun method, molten granules or sintered bodies are preferred because they are less likely to scatter even if an airflow is generated.

[0137] The surface layer 22 on the base layer 14 contains a condensate of polymer 1. The condensate of polymer 1 includes a form in which hydrolyzable silyl groups in polymer 1 undergo hydrolysis to form silanol groups (Si-OH), and these silanol groups undergo intermolecular condensation to form Si-O-Si bonds, and a form in which silanol groups in polymer 1 undergo condensation with silanol groups or Si-OM groups (where M is an alkali metal element) on the surface of the base layer 14 to form Si-O-Si bonds. The surface layer 22 may also contain condensates of compounds other than polymer 1 contained in this surface treatment agent. The surface layer 22 may contain a polymer having reactive silyl groups in a state in which some or all of the reactive silyl groups of the polymer have undergone condensation.

[0138] The thickness of the surface layer 22 is preferably 1 to 100 nm, and more preferably 1 to 50 nm. If the thickness of the surface layer 22 is above the lower limit of the above range, the effect of the surface layer 22 can be sufficiently obtained. If the thickness of the surface layer 22 is below the upper limit of the above range, the utilization efficiency is high. The thickness of the surface layer 22 is the thickness obtained by an X-ray diffractometer for thin film analysis. The thickness of the surface layer 22 can be calculated from the vibration period of the interference pattern obtained by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis.

[0139] Another example of an article of the present invention is a second article. The second article 20 has a substrate 10 with a base layer and a surface layer 22 in that order, wherein the substrate 10 with the base layer contains a silicon-containing oxide and the surface layer 22 contains a condensate of polymer 1.

[0140] In the second article, since the substrate 10 with the underlayment has the same composition as the underlayment 14 in the first article, the surface layer 22 has excellent abrasion resistance even when the surface layer 22 is directly formed on the substrate 10 with the underlayment. The material of the substrate 10 with the underlayment in the second article can be any material having the same composition as the underlayment 14, and may be, for example, a glass substrate. The details of the material of the substrate 10 with the underlayment are the same as those of the substrate 12 and the underlayment 14, so the explanation is omitted here. Also, the composition of the surface layer 22 is the same as that of the first article, so the explanation is omitted here.

[0141] Specific examples of articles of the present invention include optical components, touch panels, anti-reflective films, anti-reflective glass, and SiO2 used as parts of the following products. ２ Examples include processed glass, tempered glass, sapphire glass, quartz substrates, and mold metals. Products include: car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio systems, gaming devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (endoscopes, etc.), photocopiers, 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.

[0142] [Method for Manufacturing Articles] The method for manufacturing articles of the present invention is to form a surface layer using polymer 1 or the surface treatment agent by a dry coating method or a wet coating method.

[0143] Polymer 1 and this surface treatment agent can be used directly in a dry coating method and are suitable for forming a surface layer with excellent adhesion by the dry coating method. Examples of dry coating methods include vacuum deposition, CVD, and sputtering. Vacuum deposition is preferably used because it suppresses the decomposition of the surface treatment agent and the equipment is simple. For vacuum deposition, a pellet-like material in which polymer 1, etc., is supported on a porous metal body made of a metal material such as iron or steel may be used. The pellet-like material on which polymer 1, etc., is supported can be manufactured by impregnating a porous metal body with a solution containing polymer 1 and drying it to remove the liquid medium.

[0144] This surface treatment agent (coating solution) containing a liquid medium can be suitably used in wet coating methods. Examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Bludget coating, and gravure coating.

[0145] To improve the abrasion resistance of the surface layer, operations to promote the reaction between polymer 1 and the substrate may be performed as needed. Such operations include heating, humidification, and light irradiation. For example, heating a substrate with a surface layer formed in a humid atmosphere can promote reactions such as the hydrolysis of hydrolyzable groups, the reaction between hydroxyl groups on the substrate surface and silanol groups, and the formation of siloxane bonds through the condensation reaction of silanol groups. After 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 onto the surface layer or wiping it with a cloth soaked in a solvent.

[0146] The present invention will be described in detail below with reference to examples. Of Examples 1 to 26, Examples 1 to 25 are examples, and Example 26 is a comparative example. However, the present invention is not limited to these examples.

[0147] [Example 1] <Synthesis of Compound A> Under a nitrogen atmosphere, 2-(5-bromopentyl)-oxirane (2.7 g) was dissolved in dry acetonitrile (15 mL). Trifluoromethyl nonafluoro-1-butanesulfonate (10 g) was added, and the mixture was cooled to -15°C. Then, silver fluoride (4.5 g) was added, and the mixture was stirred at 50°C for 15 hours. After the reaction, water and hexane were added to the mixture, and the organic phase was separated by liquid-liquid extraction. After drying the organic phase over magnesium sulfate, the solvent and low-boiling point components were removed by vacuum distillation. The resulting crude solution was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 2.2 g of Compound A. The structure of Compound A was confirmed from the following NMR data.

[0148]

[0149] (NMR spectrum of compound A) 1 H-NMR (400 MHz, CDCl3) δ 3.96 (t, J = 6.7 Hz, 2H), 2.93 -2.89 (m, 1H), 2.76(t, J = 4.5 Hz, 1H), 2.47 (dd, J = 4.9 Hz, 2.6 Hz, 1H), 1.74 - 1.67 (m, 2H), 1.56 - 1.43 (m, 6H). 19 F-NMR (376 MHz, CDCl3) δ-62.0.

[0150] <Synthesis of Polymer B> Under a nitrogen atmosphere, methyltriphenylphosphonium bromide (51 mg), compound A (300 mg), and dry toluene (1 mL) were added, and the mixture was cooled to -15°C. Then, a 1.0 M toluene solution of triisobutylaluminum (0.30 mL) was added, and the mixture was stirred at 0°C for 2 hours. A mixed solvent of water / methanol = 1 / 4 was added to the reaction solution to stop the reaction. Then, all volatile components were removed by distillation under reduced pressure. The crude product was extracted with dry dichloromethane (2 mL), and insoluble materials were filtered off with Celite. The low-boiling point components of the obtained filtrate were removed by distillation under reduced pressure, and further drying in a vacuum oven at 110°C yielded 250 mg of polymer B. Polymer B had Mn = 8,700 g / mol and Mw / Mn = 1.3.

[0151]

[0152] <Synthesis of Polymer C> Under a nitrogen atmosphere, polymer B (250 mg) was dissolved in dry tetrahydrofuran (THF, 1 mL), and sodium hydride (11 mg) dispersed in liquid paraffin was added. The mixture was stirred at 40°C for 30 minutes. Then, allyl bromide (35 mg) was added, and the mixture was stirred at 40°C for a further 3 days. The reaction was terminated by adding methanol (0.10 mL) dropwise, and the mixture was purified by silica gel column chromatography (developing solvent: dichloromethane) to obtain 200 mg of polymer C. Polymer C had Mn = 8,900 g / mol and Mw / Mn = 1.3.

[0153]

[0154] <Synthesis of Polymer 1A1> Polymer C (200 mg) dissolved in dichloromethane (1 mL) was mixed with a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 2.5 mg) and trimethoxysilane (27 mg), and the mixture was stirred at 25°C for 24 hours. By removing the solvent under reduced pressure, 210 mg of polymer 1A1 was obtained. Polymer 1A1 had Mn = 9,000 g / mol and Mw / Mn = 1.3.

[0155]

[0156] [Example 2] <Synthesis of Compound D> Under a nitrogen atmosphere, 10 g of 18-bromo-1-octadecene and 50 mL of dichloromethane were added to a round-bottom flask, and the solution was cooled to 0°C. Then, 8.9 g of metachloroperbenzoic acid (containing 30% water) was added, and the mixture was stirred for 15 hours while gradually increasing the temperature to 25°C. The reaction was stopped by adding saturated sodium sulfite aqueous solution to the reaction solution, and the organic phase was separated using hexane. The organic phase was washed with saturated brine, dried over magnesium sulfate, and then the solvent and low-boiling components were removed by distillation under reduced pressure to obtain 10 g of crude product containing compound D. The obtained crude product was used directly in the next step.

[0157]

[0158] <Synthesis of Compound E> Compound E was obtained using the same procedure as in the synthesis of Compound A, except that Compound D (5.0 g) was used instead of 2-(5-bromopentyl)-oxirane. The structure of Compound E was confirmed from the following NMR data.

[0159]

[0160] (NMR spectrum of compound E) 1 H-NMR (400 MHz, CDCl3) δ 3.94 (t, J = 6.7 Hz, 2H), 2.93 - 2.88 (m, 1H), 2.75 (t, J = 4.5 Hz, 1H), 2.46 (dd, J = 5.0 Hz, 2.4 Hz, 1H), 1.71 - 1.64 (m, 2H), 1.55 - 1.26 (m, 28H). 19 F-NMR (376 MHz, CDCl3) δ - 62.2.

[0161] <Synthesis of Polymer F> Polymer F was obtained in 260 mg using the same procedure as for the synthesis of polymer B, except that compound E (300 mg) was used instead of compound A. Polymer F had Mn = 12,000 g / mol and Mw / Mn = 1.4.

[0162]

[0163] <Synthesis of Polymer G> Polymer G was obtained using the same procedure as the synthesis of polymer C, except that polymer F (260 mg) was used instead of polymer B. Polymer G had Mn = 12,000 g / mol and Mw / Mn = 1.4.

[0164]

[0165] <Synthesis of Polymer 1A2> Polymer 1A2 was obtained using the same procedure as for the synthesis of Polymer 1A1, except that Polymer G (200 mg) was used instead of Polymer C. Polymer 1A2 had Mn = 12,000 g / mol and Mw / Mn = 1.4.

[0166]

[0167] [Example 3] <Synthesis of Polymer H> Under a nitrogen atmosphere, methyltriphenylphosphonium bromide (51 mg), compound A (300 mg), and dry toluene (1 mL) were added, and the mixture was cooled to -15°C. Then, a 1.0 M toluene solution of triisobutylaluminum (0.30 mL) was added, and the mixture was stirred at 0°C for 1 hour. Then, 1,2-epoxy-5-hexene (30 mg) was added, and the mixture was stirred at 25°C for a further 15 hours. A mixed solvent of water / methanol = 1 / 4 was added to the reaction solution to stop the reaction. Then, all volatile components were removed by distillation under reduced pressure. The crude product was extracted with dry dichloromethane, and insoluble materials were filtered off with Celite. The low-boiling point components of the obtained filtrate were removed by distillation under reduced pressure, and the mixture was further dried in a vacuum oven at 110°C to obtain 270 mg of polymer H, which is a block copolymer. Polymer H had Mn = 9,100 g / mol and Mw / Mn = 1.5. In the following equation, ma:mb = 5:1 (molar ratio).

[0168]

[0169] <Synthesis of Polymer 1A3> Using the same procedure as in the synthesis of Polymer 1A1, except that Polymer H (200 mg) was used instead of Polymer C, 220 mg of Polymer 1A3, a block copolymer, was obtained. Polymer 1A3 had Mn = 9,600 g / mol and Mw / Mn = 1.5. In the following formula, ma:mb = 5:1 (molar ratio).

[0170]

[0171] [Example 4] <Synthesis of Polymer J> Polymer J was obtained in 240 mg using the same procedure as in the synthesis of polymer B, except that 2-(5-trifluoromethyl)-oxirane (300 mg) was used instead of compound A. Polymer J had Mn = 5,200 g / mol and Mw / Mn = 1.3.

[0172]

[0173] <Synthesis of Polymer K> 200 mg of polymer K was obtained using the same procedure as in the synthesis of polymer C, except that polymer J (240 mg) was used instead of polymer B. Polymer K had Mn = 5,300 g / mol and Mw / Mn = 1.4.

[0174]

[0175] <Synthesis of Polymer 1A4> Polymer 1A4 was obtained using the same procedure as the synthesis of Polymer 1A1, except that Polymer K (200 mg) was used instead of Polymer C. Polymer 1A4 had Mn = 5,500 g / mol and Mw / Mn = 1.4.

[0176]

[0177] [Example 5] <Synthesis of Compound L> Under a nitrogen atmosphere, 2-phenyl-1,3-dioxan-5-ol (2.5 g) was mixed with dried dimethylformamide (50 mL) and 60% sodium hydride (dispersed in liquid paraffin, 1.4 g), and the mixture was stirred at 25°C for 10 minutes. Then, 18-bromo-1-octadecene (9.2 g) was added, and the mixture was stirred for a further 2 hours at 25°C. Next, water was added to the mixture to terminate the reaction, and ethyl acetate was added to separate the organic phase. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent and low-boiling components were removed by vacuum distillation. The resulting residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 6.0 g of compound L. The structure of compound L was confirmed from the following NMR data.

[0178]

[0179] (NMR spectrum of compound L) 1 H-NMR (400MHz, CDCl3) δ7.52 - 7.50 (m, 2H), 7.37 - 7.32 (m, 3H), 5.82 (ddt, J = 16.9 Hz, 10.3 Hz, 6.7 Hz, 2H), 5.55 (s, 1H), 5.02 - 4.91 (m, 1H), 4.34 (dd, J = 12.4 Hz, 1.2 Hz, 2H), 4.05 (dd, J = 12.4 Hz, 1.4 Hz, 2H), 3.55 (t, J = 6.9 Hz, 2H), 3.27 - 3.25 (m, 1H), 2.06 - 2.01 (m, 2H), 1.68 - 1.61 (m, 2H), 1.39 - 1.24 (m, 26H).

[0180] <Synthesis of Compound M> Compound L (6.0 g) was dispersed in methanol (100 mL), p-toluenesulfonic acid monohydrate (1.5 g) was added, and the mixture was stirred at 25°C for 6 hours. Next, saturated sodium bicarbonate aqueous solution was added to the mixture to terminate the reaction, and ethyl acetate was added to separate the organic phase. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent and low-boiling components were removed by vacuum distillation. The resulting residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 4.2 g of compound M. The structure of compound M was confirmed from the following NMR data.

[0181]

[0182] (NMR spectrum of compound M) 1H-NMR (400MHz, CDCl3) δ5.81 (ddt, J = 16.9 Hz, 10.3 Hz, 6.7 Hz, 2H), 5.02 - 4.91 (m, 1H), 3.80 - 3.65 (m, 4H), 3.57 (t, J = 6.7 Hz, 2H), 3.46 (quint, J = 5.0 Hz, 1H), 2.07 - 2.01 (m, 2H), 1.93 (d, J = 6.0 Hz, 2H), 1.63 - 1.56 (m, 2H), 1.39 - 1.25 (m, 26H).

[0183] <Synthesis of Compound N> Under a nitrogen atmosphere, Compound M (1.0 g), silver trifluoromethanesulfonate (7.2 g), cesium fluoride (6.4 g), Selectfluor® (registered trademark, manufactured by Tokyo Chemical Industry Co., Ltd., 19 g), 2-pyridine fluoride (2.4 mL), and dry toluene (30 mL) were added to a 100 mL flask in a glove box and stirred at 25°C for 10 minutes. Then, (trifluoromethyl)trimethylsilane (4.2 mL) was added dropwise over 5 minutes while stirring, and the mixture was stirred at 25°C for a further 15 hours. The precipitate formed after the reaction was filtered off using Celite, the residue was washed with hexane, and the low-boiling point components of the obtained filtrate were removed under reduced pressure. The obtained crude solution was purified by silica gel column chromatography (developing solvent: hexane) to obtain 400 mg of Compound N. The structure of Compound N was confirmed from the following NMR data.

[0184]

[0185] (NMR spectrum of compound N) 1 H-NMR (400MHz, CDCl3) δ5.81 (ddt, J = 17.2 Hz, 10.3 Hz, 6.7 Hz, 2H), 5.02 - 4.91 (m, 1H), 4.07 - 3.99 (m, 4H), 3.73 (quint, J = 5.0 Hz, 1H), 3.57 (t, J = 6.4 Hz, 2H), 2.06 - 2.01 (m, 2H), 1.61 - 1.52 (m, 2H), 1.39 - 1.22 (m, 26H). 19F-NMR (376MHz, CDCl3) δ-61.5.

[0186] <Synthesis of Compound P> Compound P was obtained in 360 mg using the same procedure as the synthesis of Compound D, except that Compound N (350 mg) was used instead of 18-bromo-1-octadecene. The structure of Compound P was confirmed from the following NMR data.

[0187]

[0188] (NMR spectrum of compound P) 1 H-NMR (400MHz, CDCl3) δ3.80 - 3.65 (m, 4H), 3.57 (t, J = 6.7 Hz, 2H), 3.46 (quint, J = 5.0 Hz, 1H), 2.93 - 2.88 (m, 1H), 2.75 (dd, J = 5.0 Hz, 4.2 Hz, 1H), 2.45 (dd, J = 5.0 Hz, 2.9 Hz, 1H), 1.93 (d, J = 6.0 Hz, 2H), 1.55 - 1.25 (m, 28H). 19 F-NMR (376MHz, CDCl3) δ-61.7.

[0189] <Synthesis of Polymer Q> Polymer Q was obtained in 260 mg using the same procedure as the synthesis of polymer B, except that compound P (300 mg) was used instead of compound A. Polymer Q had Mn = 13,000 g / mol and Mw / Mn = 1.2.

[0190]

[0191] <Synthesis of Polymer R> 200 mg of polymer R was obtained using the same procedure as the synthesis of polymer C, except that polymer Q (260 mg) was used instead of polymer B. Polymer R had Mn = 13,000 g / mol and Mw / Mn = 1.2.

[0192]

[0193] <Synthesis of Polymer 1A5> Polymer 1A5 was obtained using the same procedure as the synthesis of polymer 1A1, except that polymer R (200 mg) was used instead of polymer C. Polymer 1A5 had Mn = 13,000 g / mol and Mw / Mn = 1.3.

[0194]

[0195] [Example 6] <Synthesis of Compound S> Under a nitrogen atmosphere, pentaerythritol monobenzyl ether (1.0 g), silver trifluoromethanesulfonate (17 g), cesium fluoride (12 g), Selectfluor® (registered trademark, manufactured by Tokyo Chemical Industry Co., Ltd., 19 g), 2-pyridine fluoride (5.7 mL), and dry toluene (100 mL) were added to a flask in a glove box and stirred for 10 minutes. Then, (trifluoromethyl)trimethylsilane (9.8 mL) was added dropwise over 5 minutes while stirring, and the mixture was stirred at 23°C for 15 hours. The precipitate formed after the reaction was filtered off using Celite, the residue was washed with hexane, and the low-boiling point components of the obtained filtrate were removed under reduced pressure. The obtained crude solution was purified by silica gel column chromatography (developing solvent: hexane) to obtain 1.0 g of compound S. The structure of compound S was confirmed from the following NMR data.

[0196]

[0197] (NMR spectrum of compound S) 1 H-NMR (400MHz, CDCl3) δ 7.39 - 7.28 (m, 5H), 4.52 (s, 2H), 4.04 (s, 6H), 3.49 (s, 2H). 19 F-NMR (376MHz, CDCl3) δ-62.9.

[0198] <Synthesis of Compound T> Compound S (1.0 g) and methanol (15 mL) were added to a round-bottom flask and stirred until homogeneous. Next, 10% palladium-carbon (1.0 g) was added, and the gas in the flask was replaced with a hydrogen atmosphere using a balloon. After stirring the reaction suspension for 15 hours, the precipitate was removed by passing it through Celite. The low-boiling point components of the obtained filtrate were removed under reduced pressure, and the crude solution was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 760 mg of compound T. The structure of compound T was confirmed from the following NMR data.

[0199]

[0200] (NMR spectrum of compound T) 1 H-NMR (400MHz, CDCl3) δ4.05 (s, 6H), 3.74 (d, J = 5.0 Hz, 2H), 1.63 (t, J = 5.0 Hz, 1H). 19 F-NMR (376MHz, CDCl3) δ-62.9.

[0201] <Synthesis of Compound U> Under a nitrogen atmosphere, 270 mg of compound T was added to 10 mL of dried dimethylformamide and 110 mg of 60% sodium hydride (dispersed in liquid paraffin), and the mixture was stirred at 23°C for 10 minutes. Then, 980 mg of 18-iodo-1-octadecene was added, and the mixture was stirred at 23°C for a further 15 hours. Next, water was added to the mixture to terminate the reaction, and ethyl acetate was added to separate the organic phase. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent and low-boiling components were removed by vacuum distillation. The resulting crude solution was purified by silica gel column chromatography (developing solvent: hexane) to obtain 190 mg of compound U. The structure of compound U was confirmed from the following NMR data.

[0202]

[0203] (NMR spectrum of compound U) 1H-NMR (400MHz, CDCl3) δ 5.81 (ddt, J = 17.2 Hz, 10.3 Hz, 6.7 Hz, 2H), 5.02 - 4.91 (m, 1H), 4.02 (s, 6H), 3.43 - 3.40 (m, 4H), 2.07 - 2.01 (m, 2H), 1.56 - 1.51 (m, 2H), 1.39 - 1.26 (m, 26H). 19 F-NMR (376MHz, CDCl3) δ-61.6.

[0204] <Synthesis of Compound V> Compound V was obtained in 110 mg using the same procedure as the synthesis of Compound D, except that Compound U (100 mg) was used instead of 18-bromo-1-octadecene. The structure of Compound V was confirmed from the following NMR data.

[0205]

[0206] (NMR spectrum of compound V) 1 H-NMR (400MHz, CDCl3) δ4.02 (s, 6H), 3.43 - 3.40 (m, 4H), 2.93 - 2.88 (m, 1H),2.75 (dd, J = 5.0 Hz, 4.1 Hz, 1H), 2.46 (dd, J = 5.0 Hz, 2.9 Hz, 1H), 1.57 - 1.25 (m, 30H). 19 F-NMR (376MHz, CDCl3) δ-62.9.

[0207] <Synthesis of Polymer W> Polymer W was obtained in 80 mg using the same procedure as the synthesis of polymer B, except that compound V (100 mg) was used instead of compound A. Polymer W had Mn = 17,000 g / mol and Mw / Mn = 1.2.

[0208]

[0209] <Synthesis of Polymer X> Polymer X was obtained using the same procedure as in the synthesis of polymer C, except that polymer W (80 mg) was used instead of polymer B. Polymer X had Mn = 17,000 g / mol and Mw / Mn = 1.3.

[0210]

[0211] <Synthesis of Polymer 1A6> Polymer 1A6 was obtained using the same procedure as in the synthesis of Polymer 1A1, except that Polymer X (80 mg) was used instead of Polymer C. Polymer 1A6 had Mn = 17,000 g / mol and Mw / Mn = 1.3.

[0212]

[0213] [Example 7] <Synthesis of Compound Y> Under a nitrogen atmosphere, dimethyl malonate (3.0 g), dried dimethylformamide (50 mL), dried THF (50 mL), and 60% sodium hydride (dispersed in liquid paraffin, 0.75 g) were added and stirred at 23°C for 10 minutes. Then, 18-bromo-1-octadecene (5.0 g) was added and heated to 60°C and stirred for 5 hours. After that, water was added to the mixture to terminate the reaction, and ethyl acetate was added to separate the organic phase. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent and low-boiling components were removed by vacuum distillation. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 5.8 g of compound Y. The structure of compound Y was confirmed from the following NMR data.

[0214]

[0215] (NMR spectrum of compound Y) 1 H-NMR (400MHz, CDCl3) δ5.81 (ddt, J = 17.2Hz, 10.3Hz, 6.7Hz, 2H), 5.02 -4.91 (m, 1H), 3.74 (s, 6H) 3.36 (t, J=7.6 Hz, 1H), 2.06 - 2.01 (m, 2H), 1.92 - 1.86 (m, 2H), 1.39 - 1.25(m, 28H).

[0216] <Synthesis of Compound Z> Under a nitrogen atmosphere, lithium aluminum hydride (0.62 g) and dry THF (10 mL) were mixed, and the resulting suspension was cooled to 0°C. Next, compound Y (2.5 g) dissolved in dry THF (15 mL) was added dropwise, and the mixture was stirred at 0°C for 15 minutes. Then, the temperature was raised to 23°C and the mixture was stirred for a further 2 hours. After the reaction, the reaction mixture was cooled again to 0°C, and the reaction was terminated by adding saturated sodium sulfate aqueous solution dropwise. The resulting precipitate was filtered off using Celite, the residue was washed with THF, and the low-boiling point components of the obtained filtrate were removed under reduced pressure. The obtained solid was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 1.5 g of compound Z. The structure of compound Z was confirmed from the following NMR data.

[0217]

[0218] (NMR spectrum of compound Z) 1 H-NMR (400MHz, CDCl3) δ5.82 (ddt, J = 16.9 Hz, 10.3 Hz, 6.7 Hz, 2H), 5.02 - 4.91 (m, 1H), 3.85 - 3.80 (m, 2H), 3.69 - 3.63 (m, 2H), 2.11 (t, J = 5.5 Hz, 2H), 2.06 - 2.01 (m, 2H), 1.81 - 1.74 (m, 1H), 1.39 - 1.21 (m, 30H).

[0219] <Synthesis of Compound AA> Compound AA was obtained in 400 mg using the same procedure as the synthesis of Compound N, except that Compound Z (1.5 g) was used instead of Compound M. The structure of Compound AA was confirmed from the following NMR data.

[0220]

[0221] (NMR spectrum of compound AA) 1H-NMR (400MHz, CDCl3) δ5.82 (ddt, J = 16.9 Hz, 10.3 Hz, 6.7 Hz, 2H), 5.02 - 4.91 (m, 1H), 3.99 (dd, J = 9.8 Hz, 4.5 Hz, 2H), 3.95 (dd, J = 9.8 Hz, 6.2 Hz, 2H), 2.06 - 2.01 (m, 3H), 1.41 - 1.26 (m, 30H). 19 F-NMR (376MHz, CDCl3) δ-61.1.

[0222] <Synthesis of Compound AB> Compound AB was obtained in 280 mg using the same procedure as the synthesis of Compound D, except that Compound AA (400 mg) was used instead of 18-bromo-1-octadecene. The structure of Compound AB was confirmed from the following NMR data.

[0223]

[0224] (NMR spectrum of compound AB) 1 H-NMR (400MHz, CDCl3) δ3.99 (dd, J = 9.8 Hz, 5.0 Hz, 2H), 3.95 (dd, J = 9.8 Hz, 6.2 Hz, 2H),2.93 - 2.88 (m, 1H), 2.75 (dd, J = 5.0 Hz, 4.1 Hz, 1H), 2.46 (dd, J = 5.0 Hz, 2.9 Hz), 2.07 - 1.99 (m, 1H), 1.53 - 1.26 (m, 32H). 19 F-NMR (376MHz, CDCl3) δ-61.1.

[0225] <Synthesis of Polymer AC> 180 mg of polymer AC was obtained using the same procedure as for the synthesis of polymer B, except that compound AB (200 mg) was used instead of compound A. Polymer AC had Mn = 12,000 g / mol and Mw / Mn = 1.3.

[0226]

[0227] <Synthesis of Polymer AD> 140 mg of polymer AD was obtained using the same procedure as the synthesis of polymer C, except that polymer AC (180 mg) was used instead of polymer B. Polymer AD had Mn = 12,000 g / mol and Mw / Mn = 1.3.

[0228]

[0229] <Synthesis of Polymer 1A7> Polymer 1A7 was obtained in 140 mg using the same procedure as the synthesis of polymer 1A1, except that polymer AD (140 mg) was used instead of polymer C. Polymer 1A7 had Mn = 13,000 g / mol and Mw / Mn = 1.3.

[0230]

[0231] [Example 8] <Synthesis of Polymer AE> In the synthesis procedure for polymer H, 320 mg of polymer AE, a block copolymer, was obtained by the same procedure, except that compound E (300 mg) was used instead of compound A. Polymer AE had Mn = 15,000 g / mol and Mw / Mn = 1.3. In the following formula, ma:mb = 5:1 (molar ratio).

[0232]

[0233] <Synthesis of Polymer 1A8> Polymer 1A8 was obtained in 350 mg using the same procedure as the synthesis of polymer 1A1, except that polymer AE (320 mg) was used instead of polymer C. Polymer 1A8 had Mn = 17,000 g / mol and Mw / Mn = 1.3. In the following formula, ma:mb = 5:1 (molar ratio).

[0234]

[0235] [Example 9] <Synthesis of Polymer AF> Under a nitrogen atmosphere, polymer J (200 mg) was dissolved in dry THF (1 mL), and liquid paraffin-dispersed sodium hydride (10 mg) was added. The mixture was stirred at 40°C for 30 minutes. Then, 4-(chloromethyl)-4-(2-propen-1-yl)-1,6-heptadiene (50 mg) was added, and the mixture was stirred at 65°C for 3 days. The reaction was terminated by adding methanol (0.10 mL) dropwise, and the mixture was purified by silica gel column chromatography (developing solvent: dichloromethane) to obtain 120 mg of polymer AF. Polymer AF had Mn = 5,500 g / mol and Mw / Mn = 1.4.

[0236]

[0237] <Synthesis of Polymer 1A9> Polymer 1A9 was obtained in 130 mg using the same procedure as the synthesis of polymer 1A1, except that polymer AF (120 mg) was used instead of polymer C. Polymer 1A9 had Mn = 5,700 g / mol and Mw / Mn = 1.4.

[0238]

[0239] [Example 10] <Synthesis of Polymer 1A10> Under a nitrogen atmosphere, 200 mg of 2-(trifluoromethoxy)ethyl methacrylate, 35 mg of 3-(trimethoxysilyl)propyl 2-bromoisobutyrate, 230 mg of 4,4'-dinonyl-2,2'-bipyridyl, and 25 mg of copper(I) chloride were added to 1 mL of dry dimethylformamide. The mixture was then stirred at 60°C for 4 hours. After the reaction, dry methanol was added to the crude solution, and the resulting precipitate was filtered off and dried under reduced pressure to obtain 190 mg of polymer 1A10. Polymer 1A10 had Mn = 2,500 g / mol and Mw / Mn = 1.3.

[0240]

[0241] [Example 11] <Synthesis of Compound AG> Compound T (2.0 g), triethylamine (1.8 g), and 4-dimethylaminopyridine (14 mg) were dissolved in dry tetrahydrofuran (5 mL). The mixture was then reacted at 25°C for 3 hours. After the reaction, water and hexane were added to the solution and liquid-liquid extraction was performed to separate the organic phase. The organic phase was dried over magnesium sulfate, and the solvent and low-boiling point components were removed by vacuum distillation. The resulting crude solution was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 2.2 g of Compound AG. The structure of Compound AG was confirmed from the following NMR data.

[0242]

[0243] (NMR spectrum of compound AG) 1 H-NMR (400MHz, CDCl3) δ6.12 - 6.10 (m, 1H), 5.66 - 5.64 (m, 1H), 4.25 (s, 2H), 4.06 (s, 6H), 1.97 - 1.96 (m, 3H). 19 F-NMR (376MHz, CDCl3) δ- 61.8.

[0244] <Synthesis of Polymer 1A11> Polymer 1A11 was obtained in 170 mg using the same procedure as for the synthesis of polymer 1A10, except that compound AG (200 mg) was used instead of 2-(trifluoromethoxy)ethyl methacrylate. Polymer 1A11 had Mn = 5,000 g / mol and Mw / Mn = 1.4.

[0245]

[0246] [Example 12] <Synthesis of Polymer 1A12> Polymer 1A11 was dissolved in dry tetrahydrofuran (1 mL) in a flask, and triethylamine (50 mg) and 10% palladium carbon (10 mg) were added. The gas in the flask was replaced with a hydrogen atmosphere using a balloon. After stirring the reaction suspension for 4 hours, dry methanol was added to the crude solution, the resulting precipitate was filtered off, and dried under reduced pressure to obtain 150 mg of polymer 1A12. Polymer 1A12 is M ｎ The values ​​were 5,000 g / mol and Mw / Mn = 1.3.

[0247]

[0248] [Example 13] <Synthesis of Compound AH> Under a nitrogen atmosphere, 17-octadecen-1-ol (700 mg) and triethylamine (530 mg) were dissolved in dry tetrahydrofuran (5 mL). Then, 2-bromoisobrityl bromide (900 mg) was added dropwise, and the mixture was stirred at 25°C for 30 minutes. After the reaction, water and hexane were added to the solution, and the organic phase was separated by liquid-liquid extraction. After drying the organic phase over magnesium sulfate, the solvent and low-boiling point components were removed by reduced pressure distillation. The resulting crude solution was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 900 mg of compound AH. The structure of compound AH was confirmed from the following NMR data.

[0249]

[0250] (NMR spectrum of compound AH) 1 H-NMR (400MHz, CDCl3) δ5.81 (ddt, J = 17.2 Hz, 10.3 Hz, 6.7 Hz, 2H), 5.02 - 4.91 (m, 1H), 4.17 (t, J = 6.4 Hz, 2H), 2.07 - 2.02 (m, 2H), 1.94 (s, 6H), 1.72 - 1.65 (m, 2H), 1.40 - 1.26 (m, 26H).

[0251] <Synthesis of Compound AJ> Compound AH (900 mg) was dissolved in dichloromethane (1 mL). To this, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 27 mg), aniline (2 mg), and trimethoxysilane (400 mg) were added, and the mixture was stirred at 25°C for 15 hours. By removing the solvent under reduced pressure, 1.2 g of compound AJ was obtained. The structure of compound AJ was confirmed from the following NMR data.

[0252]

[0253] (NMR spectrum of compound AJ) 1H-NMR (400MHz, CDCl3) δ4.16 (t, J = 6.4 Hz, 2H), 3.57 (s, 9H), 1.94 (s, 6H), 1.72 - 1.65 (m, 2H), 1.40 - 1.24 (m, 30H), 0.66 - 0.62 (m, 2H).

[0254] <Synthesis of Polymer 1A13> Polymer 1A13 was obtained in 180 mg using the same procedure as for the synthesis of polymer 1A10, except that compound AG (200 mg) was used instead of 2-(trifluoromethoxy)ethyl methacrylate and compound AJ (26 mg) was used instead of 3-(trimethoxysilyl)propyl 2-bromoisobutyrate. Polymer 1A13 had Mn = 5,500 g / mol and Mw / Mn = 1.3.

[0255]

[0256] [Example 14] <Synthesis of compound AK> Compound AK was obtained by the same procedure as in the synthesis of compound AH, except that 2,2-di-2-propen-1-yl-4-penten-1-ol (2.0 g) was used instead of 17-octadecen-1-ol. The structure of compound AK was confirmed from the following NMR data.

[0257]

[0258] (NMR spectrum of compound AK) 1 H-NMR (400MHz, CDCl3) δ5.86 - 5.76 (m, 3H), 5.13 - 5.07 (m, 6H), 3.92 (s, 2H), 2.10 (d, J = 7.6 Hz, 6H), 1.95 (s, 6H).

[0259] <Synthesis of Compound AL> Compound AK (500 mg) was dissolved in dry toluene (1 mL). To this, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 61 mg), aniline (2 mg), and trimethoxysilane (870 mg) were added, and the mixture was stirred at 100°C for 48 hours. By removing the solvent under reduced pressure, 1.1 g of compound AL was obtained. The structure of compound AL was confirmed from the following NMR data.

[0260]

[0261] (NMR spectrum of compound AL) 1 H-NMR (400MHz, CDCl3) δ3.91 (s, 2H), 3.56 (s, 27H), 1.93 (s, 6H), 1.43 - 1.20 (m, 12H), 0.62 - 0.56 (m, 6H).

[0262] <Synthesis of Polymer 1A14> Polymer 1A14 was obtained in 150 mg using the same procedure as for the synthesis of polymer 1A10, except that compound AG (200 mg) was used instead of 2-(trifluoromethoxy)ethyl methacrylate and compound AL (33 mg) was used instead of 3-(trimethoxysilyl)propyl 2-bromoisobutyrate. Polymer 1A14 had Mn = 5,900 g / mol and Mw / Mn = 1.5.

[0263]

[0264] [Example 15] <Synthesis of Polymer 1A15> Under a nitrogen atmosphere, compound AG (200 mg), compound AL (67 mg), 4,4'-dinonyl-2,2'-bipyridyl (230 mg), and copper(I) chloride (24 mg) were added to dry dimethylformamide (1 mL). The mixture was then stirred at 60°C for 4 hours. After the reaction, dry methanol was added to the crude solution, and the resulting precipitate was filtered off and dried under reduced pressure to obtain 140 mg of polymer 1A15. Polymer 1A15 had Mn = 3,000 g / mol and Mw / Mn = 1.7.

[0265]

[0266] [Example 16] <Synthesis of Polymer 1A16> Under a nitrogen atmosphere, compound AG (200 mg), compound AL (6.7 mg), 4,4'-dinonyl-2,2'-bipyridyl (23 mg), and copper(I) chloride (2.4 mg) were added to dry dimethylformamide (1 mL). The mixture was then stirred at 60°C for 4 hours. After the reaction, dry methanol was added to the crude solution, and the resulting precipitate was filtered off and dried under reduced pressure to obtain 190 mg of polymer 1A16. Polymer 1A16 had Mn = 22,000 g / mol and Mw / Mn = 1.1.

[0267]

[0268] [Example 17] <Synthesis of Polymer 1A17> Under a nitrogen atmosphere, compound AG (200 mg), ethyl 2-bromoisobutyrate (10 mg), 4,4'-dinonyl-2,2'-bipyridyl (110 mg), and copper(I) chloride (12 mg) were added to dry dimethylformamide (1 mL). The mixture was then stirred at 60°C for 4 hours. After the reaction, dry methanol was added to the crude solution, the resulting precipitate was filtered off, and dried under reduced pressure. The obtained polymer was then dispersed again in dry dimethylformamide (1 mL), and 3-(trimethoxysilyl)propyl methacrylate (50 mg), 4,4'-dinonyl-2,2'-bipyridyl (110 mg), and copper(I) chloride (12 mg) were added. The mixture was then stirred at 60°C for 4 hours. After the reaction, dry methanol was added to the crude solution, the resulting precipitate was filtered off, and dried under reduced pressure to obtain 210 mg of polymer 1A17, which is a block copolymer. Polymer 1A17 had Mn = 6,000 g / mol and Mw / Mn = 1.4. The molar ratio of ma:mb in the polymer was 3:2.

[0269]

[0270] [Example 18] <Synthesis of Compound AM> Compound AM was obtained in 470 mg using the same procedure as in the synthesis of Compound N, except that 2-benzyloxy-1,3-propanediol (2.0 g) was used instead of Compound M. The structure of Compound AM was confirmed from the following NMR data.

[0271]

[0272] (NMR spectrum of compound AM) 1 H-NMR (400MHz, CDCl3) δ7.40 - 7.30 (m, 5H), 4.68 (s, 2H), 4.10 - 4.02 (m, 4H), 3.87 (quint, J = 5.0 Hz, 1H). 19 F-NMR (376MHz, CDCl3) δ-61.2.

[0273] <Synthesis of Compound AN> Compound AM (470 mg) and tetrahydrofuran (10 mL) were added to a round-bottom flask and stirred until homogeneous. Next, 10% palladium carbon (1.0 g) was added, and the gas in the flask was replaced with a hydrogen atmosphere using a balloon. After stirring the reaction suspension for 1 hour, the precipitate was removed by passing it through Celite to obtain a tetrahydrofuran solution of compound AN (0.14 M, 11 mL).

[0274]

[0275] <Synthesis of Compound AP> Compound AP was obtained in 320 mg using the same procedure as the synthesis of compound AG, except that a tetrahydrofuran solution of compound AN (0.14 M, 11 mL) was used instead of compound T. The structure of compound AP was confirmed from the following NMR data.

[0276]

[0277] (NMR spectrum of compound AP) 1 H-NMR (400MHz, CDCl3) δ6.20 - 6.19 (m, 1H), 5.69 - 5.67 (m, 1H), 5.27 (quint, J = 4.8 Hz, 1H), 4.20 (d, J = 5.0 Hz, 4H), 1.97 - 1.96 (m, 3H). 19 F-NMR (376MHz, CDCl3) δ-61.4.

[0278] <Synthesis of Polymer 1A18> Polymer 1A18 was obtained in 140 mg using the same procedure as the synthesis of polymer 1A10, except that compound AP (200 mg) was used instead of 2-(trifluoromethoxy)ethyl methacrylate. Polymer 1A18 had Mn = 3,400 g / mol and Mw / Mn = 1.2.

[0279]

[0280] [Example 19] <Synthesis of Polymer 1A19> 140 mg of Polymer 1A19 was obtained using the same procedure as for the synthesis of Polymer 1A10, except that 4-(trifluoromethoxy)styrene (200 mg) was used instead of 2-(trifluoromethoxy)ethyl methacrylate. Polymer 1A19 had Mn = 2,000 g / mol and Mw / Mn = 1.3.

[0281]

[0282] [Example 20] <Synthesis of Polymer 1A20> Under a nitrogen atmosphere, polymer 1A14 (100 mg), 4,4'-dinonyl-2,2'-bipyridyl (57 mg), and copper(I) chloride (6 mg) were added to dry dimethylformamide (0.5 mL). The mixture was stirred at 120°C for 15 hours. After the reaction, dry methanol was added to the crude solution, and the resulting precipitate was filtered off and dried under reduced pressure to obtain 95 mg of polymer 1A20. Polymer 1A20 had Mn = 9,700 g / mol and Mw / Mn = 1.8.

[0283]

[0284] [Example 21] <Synthesis of Compound AQ> Under a nitrogen atmosphere, 4-(aminomethyl)hepta-1,6-diene (3.7 g) was dissolved in dry tetrahydrofuran (20 mL). Then, 2-bromoisobrityl bromide (3.0 g) was added dropwise, and the mixture was stirred at 25°C for 1 hour. After the reaction, water and hexane were added to the solution and liquid-liquid extraction was performed to separate the organic phase. After drying the organic phase over magnesium sulfate, the solvent and low-boiling point components were removed by vacuum distillation. The resulting crude solution was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 3.2 g of compound AQ. The structure of compound AQ was confirmed from the following NMR data.

[0285]

[0286] (NMR spectrum of compound AQ) 1 H-NMR (400MHz, CDCl3) δ5.84 - 5.74 (m, 2H), 5.46 (s, 1H), 5.08 - 5.03 (m, 4H), 3.22 (t, J = 6.2 Hz, 2H), 2.11 - 2.04 (m, 4H), 1.95 (s, 6H), 1.77 - 1.69 (m, 1H).

[0287] <Synthesis of Compound AR> The synthesis procedure for compound AL was the same as for compound AK, except that compound AQ (1.0 g) was used instead. 1.9 g of compound AR was obtained using this procedure. The structure of compound AR was confirmed from the following NMR data.

[0288]

[0289] (NMR spectrum of compound AR) 1 H-NMR (400MHz, CDCl3) δ5.49 (s, 1H), 3.58 (s, 18H), 3.18 (t, J = 5.7 Hz, 2H), 1.95 (s, 6H), 1.52 - 1.28 (m, 9H), 0.65 - 0.61 (m, 4H).

[0290] <Synthesis of Polymer 1A21> Under a nitrogen atmosphere, compound AP (200 mg), compound AR (33 mg), 4,4'-dinonyl-2,2'-bipyridyl (150 mg), and copper(I) chloride (16 mg) were added to dry dimethylformamide (1 mL). The mixture was then stirred at 80°C for 15 hours. After the reaction, dry methanol was added to the crude solution, and the resulting precipitate was filtered off and dried under reduced pressure to obtain 220 mg of polymer 1A21. Polymer 1A21 had Mn = 5,900 g / mol and Mw / Mn = 1.4.

[0291]

[0292] [Example 22] <Synthesis of Compound AS> Compound T (1.0 g) and triethylamine (0.60 g) were dissolved in dry tetrahydrofuran (20 mL). Then, acryloyl chloride (0.40 g) was added and the mixture was reacted at 25°C for 3 hours. After the reaction, water and hexane were added to the solution and liquid-liquid extraction was performed to separate the organic phase. After drying the organic phase over magnesium sulfate, the solvent and low-boiling point components were removed by vacuum distillation. The resulting crude solution was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 1.1 g of compound AS. The structure of compound AS was confirmed from the following NMR data.

[0293]

[0294] (NMR spectrum of compound AS) 1 H-NMR (400MHz, CDCl3) δ6.43 - 6.35 (m, 1H), 6.19 - 6.01 (m, 1H), 5.82 - 5.75(m, 1H), 4.18 (s, 2H), 4.06 (s, 6H). 19 F-NMR (376MHz, CDCl3) δ- 61.6.

[0295] <Synthesis of Polymer 1A22> Polymer 1A22 was obtained in 260 mg using the same procedure as for the synthesis of polymer 1A10, except that compound AS (400 mg) was used instead of 2-(trifluoromethoxy)ethyl methacrylate and compound AJ (26 mg) was used instead of 3-(trimethoxysilyl)propyl 2-bromoisobutyrate. Polymer 1A22 had Mn = 6,500 g / mol and Mw / Mn = 1.5.

[0296]

[0297] [Example 23] <Synthesis of Polymer 1A23> Under a nitrogen atmosphere, compound AS (250 mg) and compound AJ (10 mg) were dissolved in dry dimethyl sulfoxide (0.50 mL). Then, copper(I) bromide (0.18 mg) and tris(2-(dimethylamino)ethyl)amine (1.8 mg) were added and the mixture was stirred at room temperature for 15 hours. After the reaction, dry methanol was added to the crude solution, the resulting precipitate was filtered off, and dried under reduced pressure to obtain 200 mg of polymer 1A23. Polymer 1A23 had Mn = 2,800 g / mol and Mw / Mn = 1.6.

[0298]

[0299] [Example 24] <Synthesis of Polymer 1A24> 93 mg of polymer 1A24 was obtained in the same manner as in the synthesis procedure for polymer 1A12, except that polymer 1A23 (100 mg) was used instead of polymer 1A11. Polymer 1A24 had Mn = 2,600 g / mol and Mw / Mn = 1.5.

[0300]

[0301] [Example 25] <Synthesis of compound AT> 2.0 g of compound AT was obtained by referring to Journal of Medical Chemistry (2024), 67, 15131-15147.

[0302]

[0303] <Synthesis of Compound AU> Under a nitrogen atmosphere, compound AS (500 mg) and compound AT (33 mg) were dissolved in dry dimethyl sulfoxide (0.50 mL). Then, copper(I) bromide (0.18 mg) and tris(2-(dimethylamino)ethyl)amine (1.8 mg) were added, and the mixture was stirred at room temperature for 15 hours. After the reaction, dry methanol was added to the crude solution, and the resulting precipitate was filtered off and dried under reduced pressure to obtain 420 mg of polymer AU. Polymer AU had Mn = 4,000 g / mol and Mw / Mn = 1.2.

[0304]

[0305] <Synthesis of Compound AV> 380 mg of polymer AV was obtained in the same manner as the synthesis procedure for polymer 1A12, except that polymer AU was used instead of polymer 1A11. Polymer AV had Mn = 3,400 g / mol and Mw / Mn = 1.2.

[0306]

[0307] <Synthesis of Compound AW> Under a nitrogen atmosphere, thionyl chloride (100 mg) was added to polymer AV (380 mg) and the mixture was stirred at 80°C for 18 hours. The volatile components were then removed by vacuum distillation to obtain the corresponding acid chloride. Next, methylene chloride (1.0 mL) and 2,2-diallylpent-4-ene-1-amine (150 mg) were added to the same vessel and the mixture was stirred at room temperature for 1 hour. After the reaction, hydrochloric acid and hexane were added for extraction, and the low-boiling point components were removed by vacuum distillation to obtain polymer AW (390 mg). Polymer AW had Mn = 3,700 g / mol and Mw / Mn = 1.3.

[0308]

[0309] <Synthesis of Polymer 1A25> 400 mg of polymer 1A25 was obtained using the same procedure as for the synthesis of polymer C, except that polymer AW (390 mg) was used instead of polymer B. Polymer 1A25 had Mn = 4,300 g / mol and Mw / Mn = 1.4.

[0310]

[0311] [Example 26] Compound (9) described in International Publication No. 2024 / 101404 was used as compound C1-1.

[0312]

[0313] [Manufacturing of Articles] 30 g of silicon dioxide was placed as a deposition source in the copper hearth inside a vacuum deposition apparatus (VTR-350M, manufactured by ULVAC, Inc.). A glass substrate was placed inside the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was 5 × 10 －３ The chamber was evacuated until the pressure was below Pa. The hearth was heated to approximately 2,000°C, and silicon dioxide was vacuum-deposited onto the surface of the substrate to prepare a substrate with a silicon dioxide layer approximately 20 nm thick. The substrate with the silicon dioxide layer was placed on the sample stage of a spray coater (API-90RS, manufactured by Apiros Co., Ltd.) with the silicon dioxide layer facing the surface. Next, 13 g of a heptane solution containing 0.2% by mass of the polymer obtained in each example was put into a syringe in the spray coater and spray-coated at an atomization pressure of 130 kPa, a nozzle-to-sample surface distance of 50 mm, and a scanning speed of 300 mm / second (wet coating method). Subsequently, the substrate with the silicon dioxide layer coated on the surface was heat-treated at 140°C for 30 minutes to obtain an evaluation sample (article) in which the substrate, silicon dioxide layer, and surface layer were stacked in this order.

[0314] [Evaluation] The following evaluations were conducted using the obtained items. The results of the evaluation tests are shown in Table 1.

[0315] <Oil Repellency> Approximately 2 μL of oleic acid was dropped onto the surface layer of an object, and the initial oil contact angle (oleic acid contact angle) was measured using a contact angle measuring device (product name "DM-500", manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five locations on the surface layer, and the average value was calculated to evaluate the oil repellency of the surface layer. The 2θ method was used to calculate the oil contact angle. The evaluation criteria are as follows: A: Average oil contact angle is 62 degrees or higher. B: Average oil contact angle is 50 degrees or higher and less than 62 degrees. C: Average oil contact angle is less than 50 degrees.

[0316] <Fingerprint Removal Test> A 1 kg weight equipped with a 2 cm diameter red rubber stopper to serve as the fingerprint stamp portion was prepared. Next, 70 μL of artificial fingerprint solution (manufactured by Isekyu Co., Ltd.) was dropped onto a cloth, and the fingerprint stamp was left in the solution for 1 minute. To remove excess artificial fingerprint solution from the fingerprint stamp, it was left in a new cloth for 20 seconds. After that, an article with a surface treatment layer was placed on a hot plate heated to 23°C, and the fingerprint stamp was pressed against the surface treatment layer. The article with the artificial fingerprint solution attached was placed in a sliding device (product name "HHS-2000", manufactured by Shinto Kagaku Co., Ltd.). A wiping cloth (Savina Minimax, manufactured by KB Seiren Co., Ltd.) was attached to a flat indenter with an area of ​​1 cm square using double-sided tape, and placed in the sliding device. With a load of 100 g, the attached artificial fingerprint solution was wiped off the surface treatment layer in one direction with the wiping cloth. The haze was measured on the wiped area using a haze meter (product name "NDH7000SP", manufactured by Nippon Denshoku Industries Co., Ltd.). The evaluation criteria were as follows: A: Haze value less than 0.1%. B: Haze value 0.1% or more and less than 0.5%. C: Haze value 0.5% or more.

[0317]

[0318] As shown in Table 1, the polymers obtained in Examples 1 to 25 were confirmed to be able to form a surface layer with excellent oil repellency. Furthermore, a comparison of Examples 1 to 25 confirmed that the polymers obtained in Examples 11 to 18 and Examples 20 to 25 were able to form a surface layer with even better oil repellency.

[0319] Articles having a surface layer containing polymer 1 are, for example, optical articles, touch panels, anti-reflective films, anti-reflective glass, and SiO2 used as parts of the following products. ２It is useful as processed glass, tempered glass, sapphire glass, quartz substrates, mold metals, etc. Products: Car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (endoscopes, etc.), photocopiers, 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.

[0320] This application claims priority based on Japanese Patent Application No. 2024-184286, filed on 18 October 2024, and Japanese Patent Application No. 2025-078584, filed on 9 May 2025, and incorporates all of their disclosures herein.

[0321] 10 Substrate with undercoat 12 Substrate 14 Undercoat 20 Article 22 Surface layer

Claims

1. A polymer containing a repeating unit represented by the following formula (1) and having a reactive group, wherein the reactive group is -Ar ３ , ３ , ２ , ２ , ３ , ３ , ３ , ２ , ２ , -SR １０ , -NOR １０ , -C(=O)R １０ , -N(R １０ ), ２ , -N ＋ (R １０ ), ３ X ３ , -C≡N, -C(=NR １０ )-R １０ , -N ＋ ≡NX ３ , -N = NR １０ , -C(=O)OR １０ , -C(=O)OX ２ , -C(=O)X ４ , -C(=O)OC(=O)R １０ , -O-C(=O)-CH ２ =CH ２ -C(=O)OR １０ , -SO ２ R １０ , -SO ２ X ４ , -SO ３ , -SO ３ X ２ , -P(=O)(-OR １０ ), ２ , -O-P(=O)(-OR １０ ), <​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​), -C(=O)N(R １０ ), ２ , -N(R １０ ), -C(=O)R １０ , -Si(R １０ ), ２ , -O - Si(R １０ ), ３ , -NH - C(=O)R １０ , -C(=O)NH R １０ , -I, -Br, -B(OH) ２ , -N ３ , A polymer which is any one of the following. However, R １０ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent, Ar １ is an aryl group which may have a substituent, X ２ is an alkali metal ion or an ammonium ion, X ３ is a halide ion, X ４ is a halogen atom, R ａ１ is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, R ａ１１ is a hydrocarbon group, z1 is an integer from 1 to 3, R １０ , R ａ１ or R ａ１１ When there are a plurality of them, the plurality of R １０ , R ａ１ or R ａ１１ may be the same as or different from each other. However, R ｆ is -OCF ３ , -SCF ３ , -SF ４ X １１ , or -N(CF ３ )X １２ , -CHF ２ , -CH ２ F, -C ６ F ５ , or -C ８ F ７ and X １１ is an alkyl group or a halogen atom, X １２ is an alkyl group or -CF ３ where n is an integer of 1 or more, and L １ is a (1 + n)-valent organic group, and L ２ is a single bond or an oxygen atom, and R １ and R ２ are each independently a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L １ -, and R ｆ , L １ , or when there are a plurality of n, the plurality of R ｆ , L １ , or n may be the same as or different from each other. In the formula (1), R ｆ does not contain a fluorine atom other than the fluorine atom contained in 2. The polymer according to claim 1, wherein the repeating unit represented by formula (1) includes a repeating unit represented by the following formula (1-1). However, R ｆ and n are R in formula (1) above, respectively. ｆ And is synonymous with n, L Ａ１ -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ３１ C(=O)O- and -NR ３２ C(=O)NR ３３ A (1+n) valent hydrocarbon group which may have at least one group selected from the group consisting of -, R ３１ , R ３２ and R ３３ Each is independently a hydrogen atom or an alkyl group, and R Ａ１ and R Ａ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L Ａ１ - and R ｆ , L Ａ１ , or, in the case where there are multiple n, the multiple R ｆ , L Ａ１ , or n may be the same or different from each other, and in formula (1-1) above, R ｆ It does not contain any fluorine atoms other than those present in the fluorine atoms contained within.

3. The polymer according to claim 1, wherein the repeating unit represented by formula (1) includes a repeating unit represented by the following formula (1-2). However, in equation (1-2), R ｆ and n are R in formula (1) above, respectively. ｆ And is synonymous with n, L Ｂ１ -O-, -C(=O)-, -C(=O)NH-, -C(=O)O-, -NR ３１ C(=O)O- and -NR ３２ C(=O)NR ３３ A (1+n) valent hydrocarbon group which may have at least one group selected from the group consisting of -, R ３１ , R ３２ and R ３３ Each is independently a hydrogen atom or an alkyl group, and R Ｂ１ and R Ｂ２ Each of these independently comprises a hydrogen atom, an alkyl group, or (R ｆ ) ｎ -L Ｂ１ - and R ｆ , L Ｂ１ , or, in the case where there are multiple n, the multiple R ｆ , L Ｂ１ , or n may be the same or different from each other, and in formula (1-2) above, R ｆ It does not contain any fluorine atoms other than those present in the fluorine atoms contained within.

4. A surface treatment agent comprising the polymer described in any one of claims 1 to 3.

5. The surface treatment agent according to claim 4, further comprising a liquid medium.

6. The surface treatment agent according to claim 4, which is an antifouling coating agent or a waterproof coating agent.

7. The surface treatment agent according to claim 5, which is an antifouling coating agent or a waterproof coating agent.

8. An article having a surface layer formed using the polymer described in any one of claims 1 to 3 on the surface of a substrate.

9. The article according to claim 8, which is an optical component.

10. The article according to claim 8, wherein the surface layer is provided on the surface of a component that constitutes the surface of a touch panel that is touched by a finger.

11. A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent described in claim 4.

12. A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent described in claim 5.

13. A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the surface treatment agent described in claim 5.

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