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

Abstract

Provided are: a compound capable of forming a surface layer having excellent oil repellency; a surface treatment agent; an article having a surface layer formed from the compound; and a method for producing the article. A compound according to the present invention is represented by (Rf1-L2) y1-L3-R1-L1-(R2-T1) x1. In the formula, Rf1 is a fluorine-containing group such as a perfluoroalkyl group, L2 is a single bond or a divalent linking group, L3 is a 1 + y1-valent organopolysiloxane residue, R1 is a single bond, a fluoroalkylene group, an alkylene group, or an alkylene group having an etheric oxygen atom, L1 is a single bond or a 1 + x1-valent group, R2 is an alkylene group, or an alkylene group having an etheric oxygen atom, T1 is a reactive group, y1 is an integer of 1 or more, and x1 is an integer of 1-10.

Description

Technical Field

[0001] This invention relates to compounds, surface treatment agents, articles, and methods for manufacturing articles. Background Technology

[0002] In a wide variety of fields such as electrical and electronic materials, semiconductor materials, optical materials, building materials, and automotive parts, methods for forming a surface layer on the surface of a component (substrate) are known in order to inhibit the adhesion of stains to the components used.

[0003] For example, Patent Document 1 discloses a method for forming an organic thin film on the surface of a substrate using a composition comprising n-octadecyltrimethoxysilane as an organosilicon compound.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2008 / 016029 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] In recent years, the performance requirements for surface layers have become more stringent, with a need for surface layers with excellent oil repellency depending on their intended use. The inventors evaluated a surface layer formed using the organosilicon compound described in Patent Document 1 and found that there is room for improvement in the oil repellency of the surface layer.

[0009] The present invention was made in view of the above-mentioned problems, the problem of which is to provide a compound capable of forming a surface layer with excellent oil repellency, a surface treatment agent, an article having a surface layer formed by the compound, and a method for manufacturing the article.

[0010] Solution for solving the problem

[0011] The inventors have conducted in-depth research on the above-mentioned problems and found that the above-mentioned problems can be solved by the following configuration.

[0012] [1] The compound shown in formula (1) below.

[0013] (R f1 -L 2 ) y1 -L 3 -R 1 -L 1 -(R 2 -T 1 ) x1 …(1)

[0014] in,

[0015] Rf1 The selection is based on perfluoroalkyl groups, -C(X) 10 )F2、-C(X 10 -2F, -SF5, -OCF3, -SCF3, fluorovinyl, fluoroacetylene, -NX 11 X 12 Fluorine-containing groups in the group consisting of monovalent cyclic hydrocarbon groups containing fluorine atoms and monovalent heterocyclic groups containing fluorine atoms, X 10 For H, Cl, Br, or I, X 11 It is a fluoroalkyl group, X 12 It is an alkyl or fluoroalkyl group.

[0016] L 2 It is a single bond or a divalent linker.

[0017] L 3 It consists of organopolysiloxane residues with a valence of 1+y1.

[0018] R 1 It is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms and an ether-like oxygen atom.

[0019] L 1 It is a single bond or a 1+x1 valence group.

[0020] R 2 It is an alkylene group, or an alkylene group having an ether-like oxygen atom.

[0021] T 1 It is a reactive group.

[0022] y1 is an integer greater than or equal to 1.

[0023] x1 is an integer from 1 to 10.

[0024] There are multiple R f1 L 2 R 2 T 1 or X 10 In the case of the multiple Rs that exist f1 L 2 R 2 T 1 or X 10 Choose whether they are the same or different from each other.

[0025] [2] According to the compound described above [1], wherein the compound represented by the above formula (1) is the compound represented by the following formula (1-1).

[0026] R f1 -L 2 -SiR 11 R12 -O-(SiR 13 R 14 -O) z11 -SiR 15 R 16 -R 1 -L 1 -(R 2 -T 1 ) x1 …(1-1)

[0027] in,

[0028] R 11 and R 12 Each is independently an alkyl or R f1 -L 2 -,

[0029] R 13 R 14 R 15 and R 16 Each is independently an alkyl group.

[0030] R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1,

[0031] z11 is an integer greater than or equal to 1.

[0032] There are multiple R 13 R 14 R 2 or T 1 In the case of the multiple Rs that exist 13 R 14 R 2 or T 1 Choose whether they are the same or different from each other.

[0033] [3] According to the compound described above [1], wherein the compound represented by the above formula (1) is the compound represented by the following formula (1-2).

[0034] SiR 21 R 22 R 23 -O-(SiR 24 R 25-O) z21 -(SiR 26 R 27 -O) z22 -SiR 28 R 29 -R 1 -L 1 -(R 2 -T 1 )x1…(1-2)

[0035] in,

[0036] R 21 R 22 and R 23 Each is independently an alkyl or R f1 -L 2 -,

[0037] R 24 For R f1 -L 2 -,

[0038] R 25 alkyl or R f1 -L 2 -,

[0039] R 26 and R 27 Each is independently an alkyl group.

[0040] R 28 and R 29 Each is independently an alkyl or R f1 -L 2 -,

[0041] R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1,

[0042] z21 is an integer greater than or equal to 1.

[0043] z22 is an integer greater than or equal to 0.

[0044] There are multiple R 24 R 25 R 26 R 27 R2 or T 1 In the case of the multiple Rs that exist 24 R 25 R 26 R 27 R 2 or T 1 Choose whether they are the same or different from each other.

[0045] [4] According to the compound described above [1], wherein the compound represented by the above formula (1) is the compound represented by the following formula (1-3).

[0046]

[0047] in,

[0048] R 31 For R f1 -L 2 -,

[0049] R 32 alkyl or R f1 -L 2 -,

[0050] R 33 and R 34 Each is independently an alkyl group.

[0051] R 35 -R 1 -L 1 -(R 2 -T 1 ) x1 ,

[0052] R 36 It is an alkyl group.

[0053] R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1,

[0054] z31 is an integer greater than or equal to 1.

[0055] z32 is an integer greater than or equal to 0.

[0056] The sum of z31 and z32 is an integer greater than or equal to 2.

[0057] There are multiple R 31 R 32 R 33 R 34 R 2 or T 1 In the case of the multiple Rs that exist 31 R 32 R 33 R 34 R 2 or T 1 Choose whether they are the same or different from each other.

[0058] [5] The compound according to any one of [1] to [4] above, wherein the above T 1 It can be any of the following groups: -Ar, -SR 10 -NOR 10 -C(=O)R 10 -N(R) 10 )2、-N + (R 10 )3X 3 -C≡N, -C(=NR) 10 )-R 10 -N + ≡N、-N=NR 10 -C(=O)OR 10 -C(=O)OX 2 -C(=O)X 4 -C(=O)OC(=O)R 10 -SO2R 10 -SO3H, -SO3X 2 -OP(=O)(-OR) 10 2. -OP (=O)(-OR) 10 (-OX) 2 -N=C=O, -SiR a1 z1 R a11 3-z1 -C(R) 10 )=C(R 10 )2、-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

[0059]

[0060] in,

[0061] R 10 The atom is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms optionally having a substituent, a fluoroalkyl group having 1 to 6 carbon atoms optionally having a substituent, or an aryl group having a substituent.

[0062] Ar is an aryl group that is optionally substituent.

[0063] X 2 They are alkali metal ions or ammonium ions.

[0064] X 3 It is a halide ion.

[0065] X 4 Halogen atoms,

[0066] R a1 It is a hydrolyzable group or hydroxyl group.

[0067] R a11 It is a hydrocarbon group.

[0068] z1 is an integer from 1 to 3.

[0069] There are multiple R 10 R a1 、or R a11 In the case of the multiple Rs that exist 10 R a1 、or R a11 Choose whether they are the same or different from each other.

[0070] [6] According to the compound described above [5], wherein the above T 1 -SiR a1 z1 R a11 3-z1 .

[0071] [7] The compound according to any one of [1] to [6] above, wherein the monovalent cyclic hydrocarbon group containing fluorine atoms is a group represented by the following formula (g-1), the following formula (g-2), the following formula (g-3) or the following formula (g-4).

[0072]

[0073] in,

[0074] p1 is an integer greater than or equal to 1.

[0075] p2 is an integer greater than or equal to 1.

[0076] R y1 For a monovalent substituent, in R y1 In the case of fluorine atoms, p3 and p4 are both integers greater than 0 and p3 + p4 is an integer greater than 1, in R y1 In the absence of fluorine atoms, p3 is an integer greater than or equal to 1 and p4 is an integer greater than or equal to 0.

[0077] R y2 For a monovalent substituent, in R y2 In the case of fluorine atoms, p5 and p6 are both integers greater than 0 and p5 + p6 is an integer greater than 1, in R y2 In the absence of fluorine atoms, p5 is an integer greater than or equal to 1 and p6 is an integer greater than or equal to 0.

[0078] *For L 2 The bonding positions.

[0079] [8] According to the compound described above [7], wherein the above R y1 And the above R y2 The monovalent substituents mentioned above are each independently a halogen atom other than a fluorine atom, an alkyl group, an alkenyl group, an alkoxy group, a perfluoroalkyl group, or a -C(X) group having an ether-like oxygen atom between carbon atoms. 20 )F2、-C(X 20 -2F, -SF5, -OCF3, -SCF3, fluorovinyl, fluoroacetylene, or -NX 21 X 22 ,

[0080] X 20 The elements are H, Cl, Br, or I, and there are multiple X. 20 In the case of the existence of multiple X 20 Choose either the same or different from each other, X 21 It is a fluoroalkyl group, X 22 It is an alkyl or fluoroalkyl group.

[0081] [9] A surface treatment agent comprising any one of the compounds described in any one of [1] to [8].

[0082]

[10] The surface treatment agent described above [9] further comprises a liquid medium.

[0083]

[11] The surface treatment agent described in [9] or

[10] above is a stain-resistant coating agent or a waterproof coating agent.

[0084]

[12] An article having a surface layer formed on the surface of a substrate using any one of the compounds described in any one of [1] to [8].

[0085]

[13] The article described above

[12] has the aforementioned surface layer on the surface of the component constituting the finger touch surface of the touch panel.

[0086]

[14] The article described in

[12] or

[13] above is an optical component.

[0087]

[15] A method for manufacturing an article, wherein a surface layer is formed by dry coating using any of the surface treatment agents described in any of the preceding [9] to

[11] .

[0088]

[16] A method for manufacturing an article, wherein a surface layer is formed by wet coating using any of the surface treatment agents described in any of the preceding [9] to

[11] .

[0089] The effects of the invention

[0090] According to the present invention, a compound capable of forming a surface layer with excellent oil repellency, a surface treatment agent, an article having a surface layer formed by the compound, and a method for manufacturing the article can be provided. Attached Figure Description

[0091] Figure 1 This is a schematic cross-sectional view illustrating an example of the article of the present invention. Detailed Implementation

[0092] The terms used in this invention have the following meanings.

[0093] In this specification, the compound represented by formula (1) is designated as compound 1. Compounds represented by other formulas are also based on this designation.

[0094] "Fluoroalkyl" is a general term encompassing both perfluoroalkyl and partially fluoroalkyl groups. A "perfluoroalkyl" group refers to an alkyl group in which all hydrogen atoms are replaced by fluorine atoms. Conversely, a "partially fluoroalkyl" group refers to an alkyl group having one or more hydrogen atoms replaced by fluorine atoms. In other words, a fluoroalkyl group is an alkyl group having one or more fluorine atoms. It should be noted that fluoroalkylene groups are also based on this standard.

[0095] "Reactive silyl group" is a general term for hydrolyzable silyl group and silanol group (Si-OH). "Hydrolyzable silyl group" refers to a group that can undergo hydrolysis to form a silanol group.

[0096] "Organic group" refers to a hydrocarbon group that may have substituents and may have heteroatoms or other bonds in its carbon chain. "Hydrocarbon group" refers to a group composed of aliphatic hydrocarbon groups (straight-chain alkylene groups, branched alkylene groups, cycloalkylene groups, etc.), aromatic hydrocarbon groups (phenylene groups, etc.), and combinations thereof.

[0097] "Surface layer" refers to a layer formed on the surface of a substrate.

[0098] "Number-average molecular weight" (Mn) is a value determined by size exclusion chromatography (gel permeation chromatography) using polystyrene as a standard.

[0099] The "~" sign, which indicates a range of values, refers to the values ​​recorded before and after it as the lower and upper limits.

[0100] The bonding order of the divalent groups is not limited unless otherwise specified. For example, in the L group described later... 1 -C(O)N(R) 26 In the case of the group shown in )-, the left-hand linker can be bonded to R in formula (1). 1 The side, or the right side, can be connected to the R in equation (1). 1 side.

[0101] In this specification, when a compound or group is represented by a specific formula (X), the compound or group represented by the formula (X) is sometimes referred to as compound (X) or compound X, and group (X) or group X, respectively.

[0102] It should be noted that when the same symbol exists in a chemical formula, the same symbol can be the same structure as each other, or it can be a structure that is different from each other within a specified range.

[0103] In this specification, "Me" sometimes means methyl.

[0104] [Compound 1]

[0105] The compounds of the present invention are represented by the following formula (1).

[0106] (R f1 -L 2 ) y1 -L 3 -R 1 -L 1 -(R 2 -T 1 ) x1 …(1)

[0107] In equation (1),

[0108] R f1 The selection is based on perfluoroalkyl groups, -C(X) 10 )F2、-C(X 10 -2F, -SF5, -OCF3, -SCF3, fluorovinyl, fluoroacetylene, -NX 11 X 12 Fluorine-containing groups in the group consisting of monovalent cyclic hydrocarbon groups containing fluorine atoms and monovalent heterocyclic groups containing fluorine atoms.

[0109] X 10 H, Cl, Br, or I, X 11 It is a fluoroalkyl group, X 12 It is an alkyl or fluoroalkyl group.

[0110] In equation (1),

[0111] L 2 It is a single bond or a divalent linker.

[0112] L 3 It consists of organopolysiloxane residues with a valence of 1+y1.

[0113] R 1 It is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms and an ether-like oxygen atom.

[0114] L 1 It is a single bond or a 1+x1 valence group.

[0115] R 2 It is an alkylene group, or an alkylene group having an ether-like oxygen atom.

[0116] T 1 It is a reactive group.

[0117] y1 is an integer greater than or equal to 1.

[0118] x1 is an integer from 1 to 10.

[0119] There are multiple R f1 L 2 R 2 T 1 or X 10 In the case of the multiple Rs that exist f1 L 2 R 2 T 1 or X 10 Choose whether they are the same or different from each other.

[0120] In compound 1, an R group containing a fluorine atom is disposed at one end as a fluorine-containing group. f1 At the other end, a T group is configured as a reactive group. 1 .

[0121] When compound 1 is used to form a surface layer, the reactive groups of compound 1 are easily disposed on the substrate side, and the reactive groups are firmly chemically bonded to the substrate, thus the resulting surface layer has excellent abrasion resistance.

[0122] Furthermore, although the detailed reasons are not yet clear, by giving compound 1 an R at one end as a fluorine-containing group... f1Surprisingly, a surface layer with excellent oil repellency was obtained.

[0123] In addition, since compound 1 contains polysiloxane residues, it is able to form a surface layer with excellent water repellency.

[0124] R f1 The selection is based on perfluoroalkyl groups, -C(X) 10 )F2、-C(X 10 -2F, -SF5, -OCF3, -SCF3, fluorovinyl, fluoroacetylene, -NX 11 X 12 Fluorine-containing groups are those consisting of monovalent cyclic hydrocarbon groups containing fluorine atoms and monovalent heterocyclic groups containing fluorine atoms.

[0125] R f1 The perfluoroalkyl group in the perfluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4, and even more preferably 1 to 4. When the perfluoroalkyl group has 3 or more carbon atoms, the perfluoroalkyl group with 3 or more carbon atoms can be straight-chain, or it can have a branched chain or a cyclic structure.

[0126] R f1 In the middle, -C(X) 10 )F2 and -C(X 10 )2F of X 10 It can be H, Cl, Br, or I. It should be noted that -C(X) 10 In 2F, there are 2 X's. 10 They can be the same or different.

[0127] As R f1 Specific examples of fluorovinyl groups include CF2=CF-, CF2=CH-, CFH=CF-, CFH=CH-, and CH2=CF-.

[0128] R f1 -NX 11 X 12 In the middle, X 11 It is a fluoroalkyl group, X 12 It is an alkyl or fluoroalkyl group. X 11 and X 12 The fluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4, and even more preferably 1 to 3. When the fluoroalkyl group has 3 or more carbon atoms, it can be a straight chain, or it can have a branched chain or a cyclic structure. 12 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4, and even more preferably 1 to 3. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms can be straight-chain, or it can have a branched or cyclic structure.

[0129] A monovalent cyclic hydrocarbon group containing a fluorine atom refers to a group in which at least one hydrogen atom in the cyclic hydrocarbon group is replaced by a fluorine atom or a substituent containing a fluorine atom. It should be noted that all hydrogen atoms in the cyclic hydrocarbon group can be replaced by a fluorine atom or a substituent containing a fluorine atom.

[0130] In a monovalent cyclic hydrocarbon group containing a fluorine atom, the cyclic hydrocarbon group can be an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

[0131] The cyclic hydrocarbons that make up the monovalent cyclic hydrocarbon group containing fluorine atoms can be monocyclic or fused rings. Alternatively, they can be bridged rings.

[0132] Cyclic hydrocarbons that constitute a monovalent cyclic hydrocarbon group containing a fluorine atom can also be tetrahedral alkanes, cubic alkanes, dodecahedral alkanes, fullerenes, and other rings with polyhedral structures.

[0133] Preferred examples of monovalent cyclic hydrocarbon groups containing fluorine atoms include groups g-1 to g-4.

[0134]

[0135] In group g-1, p1 is an integer greater than or equal to 1.

[0136] In the group g-2, p2 is an integer greater than or equal to 1.

[0137] In group g-3, R y1 For a monovalent substituent, in R y1 In the case of fluorine atoms, p3 and p4 are both integers greater than 0 and p3 + p4 is an integer greater than 1, in R y1 In the absence of fluorine atoms, p3 is an integer greater than or equal to 1 and p4 is an integer greater than or equal to 0.

[0138] In group g-4, R y2 For a monovalent substituent, in R y2 In the case of fluorine atoms, p5 and p6 are both integers greater than 0 and p5 + p6 is an integer greater than 1, in R y2 In the absence of fluorine atoms, p5 is an integer greater than or equal to 1 and p6 is an integer greater than or equal to 0.

[0139] In groups g-1 to g-4, * indicates a relationship with L. 2 The bonding positions.

[0140] Group g-1 is a fullerene C with hydrogen atoms replaced by p1 fluorine atoms. 60 The monovalent group of the derivative.

[0141] p1 is an integer greater than or equal to 1, preferably an integer from 1 to 59, and more preferably an integer from 8 to 59.

[0142] Group g-2 is a monovalent group with a cuboethane ring in which hydrogen atoms are replaced by p2 fluorine atoms.

[0143] p2 is an integer greater than or equal to 1, preferably an integer from 1 to 7, and more preferably an integer from 4 to 7.

[0144] Group g-3 is a group with a hydrogen atom surrounded by p3 fluorine atoms and p4 R atoms. y1 A monovalent group substituted on a benzene ring.

[0145] As R y1 Specific examples of monovalent substituents include halogen atoms other than fluorine atoms (e.g., Cl, Br, I), alkyl, alkenyl, alkoxy, perfluoroalkyl, and -C(X) groups optionally having ether-like oxygen atoms between carbon atoms. 20 )F2、-C(X 20 -2F, -SF5, -OCF3, -SCF3, fluorovinyl, fluoroacetylene, or -NX 21 X 22 .

[0146] The alkyl, alkenyl, alkoxy, and perfluoroalkyl groups in the monovalent substituents preferably have 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 to 3. When these groups have 3 or more carbon atoms, they can be straight chains, branched chains, or ring structures.

[0147] Specific examples of fluorovinyl groups in monovalent substituents and R f1 The specific examples of fluorovinyl groups are the same.

[0148] In -C(X) 20 )F2 and -C(X 20 In 2F, X 20 It can be H, Cl, Br, or I. It should be noted that -C(X) 20 In 2F, there are 2 X's. 20 They can be the same or different.

[0149] -NX 21 X 22 In the middle, X 21 It is a fluoroalkyl group, X 22 It is an alkyl or fluoroalkyl group. X 21 and X 22 The fluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4, and even more preferably 1 to 3. When the fluoroalkyl group has 3 or more carbon atoms, it can be a straight chain, or it can have a branched chain or a cyclic structure. 22 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4, and even more preferably 1 to 3. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms can be straight-chain, or it can have a branched or cyclic structure.

[0150] In R y1 When fluorine atoms are included, p3 and p4 are both integers greater than or equal to 0, and p3 + p4 is an integer greater than or equal to 1. In this case, p3 is preferably an integer from 0 to 5, more preferably an integer from 2 to 5. Furthermore, p4 is preferably an integer from 0 to 5, more preferably an integer from 0 to 3. Additionally, p3 + p4 is preferably 1 to 5, more preferably 1 to 5.

[0151] In R y1 In the absence of fluorine atoms, p3 is an integer of 1 or more, and p4 is an integer of 0 or more. In this case, p3 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and p4 is preferably an integer of 0 to 5, more preferably an integer of 0 to 2. Wherein, p3 + p4 is 5 or less.

[0152] Group g-4 is a group with a hydrogen atom surrounded by p5 fluorine atoms and p6 R atoms. y2 The monovalent group of the substituted adamantane ring.

[0153] R y2 Specific examples and preferred methods of monovalent substituents in R y1 The monovalent substituents are the same.

[0154] In R y2 When fluorine atoms are included, p5 and p6 are both integers greater than or equal to 0, and p5 + p6 is an integer greater than or equal to 1. In this case, p5 is preferably an integer from 0 to 15, more preferably an integer from 1 to 3. Furthermore, p6 is preferably an integer from 0 to 14, more preferably an integer from 3 to 12. Additionally, p5 + p6 is preferably from 1 to 15, more preferably from 1 to 10.

[0155] In R y2 In the absence of fluorine atoms, p5 is an integer of 1 or more, and p6 is an integer of 0 or more. In this case, p5 is preferably an integer of 1 to 15, more preferably an integer of 1 to 3, and p6 is preferably an integer of 0 to 14, more preferably an integer of 3 to 12. Wherein, p5 + p6 is 15 or less.

[0156] A monovalent heterocyclic group containing a fluorine atom is a group in which at least one hydrogen atom in the heterocyclic group is replaced by a fluorine atom or a substituent containing a fluorine atom.

[0157] In monovalent heterocyclic groups containing fluorine atoms, the heterocyclic group can be either aromatic or non-aromatic.

[0158] Specific examples of heteroatoms contained in a monovalent heterocyclic group containing a fluorine atom include N, O, and S.

[0159] Specific examples of heterocycles constituting a monovalent heterocyclic group containing a fluorine atom include non-aromatic heterocycles such as pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, dioxane, and quinine ring, as well as aromatic heterocycles such as furan, pyrrole, thiophene, pyridine, triazine, triazole, pyrazole, thiazole, and benzothiazole.

[0160] L 2 It is a single bond or a divalent linker.

[0161] As L 2 Specific examples of divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO2-, and -N(R) groups. d -, -C(O)-, -Si(R) e )2-, and groups formed by combining two or more of them.

[0162] As a divalent hydrocarbon group, it can be a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenyl group, or an alkyne group.

[0163] The divalent saturated hydrocarbon group can be straight-chain, branched, or cyclic, such as alkylene groups. The preferred number of carbon atoms is 1 to 20.

[0164] As a divalent aromatic hydrocarbon group, a group having 5 to 20 carbon atoms is preferred, such as phenylene.

[0165] The number of carbon atoms in the alkenyl group is preferably 2 to 20. The number of carbon atoms in the ynyl group is preferably 2 to 20.

[0166] Specific examples of heteroatoms contained in divalent heterocyclic groups include N, O, and S.

[0167] The divalent heterocyclic group can be either aromatic or non-aromatic.

[0168] Specific examples of heterocycles constituting a divalent heterocyclic group include non-aromatic heterocycles such as pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, dioxane, and quinine ring, as well as aromatic heterocycles such as furan, pyrrole, thiophene, pyridine, triazine, triazole, pyrazole, thiazole, and benzothiazole.

[0169] R e It is an alkyl group (preferably with 1 to 10 carbon atoms) or a phenyl group. d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0170] Furthermore, specific examples of groups formed by combining two or more of these can be listed as: -C(O)O-, -C(O)S-, -C(O)N(R) d )-、-N(R d )C(O)N(R d )-、-N(R d)C(O)O-、-SO2N(R d -、Having -C(O)N(R) d )-alkylene groups, having -N(R d alkylene groups of C(O)O-, alkylene groups having ether-like oxygen atoms, alkylene groups having -S-, alkylene groups having -C(O)O-, alkylene groups having -C(O)S-, alkylene groups having -N(R) d )-alkylene groups, having -N(R d )C(O)N(R d )-alkylene groups, having -SO2N(R d )-alkylene, alkylene-Si(R) e )2-Phenylidene-Si(R e )2-.

[0171] Among them, L 2 Preferably, it is a divalent hydrocarbon group, a divalent heterocyclic group, -O-, -S-, -SO2-, or -N(R) d -, -C(O)-, -Si(R) e )2-, -C(O)O-, -C(O)S-, -C(O)N(R d )-、-N(R d )C(O)N(R d )-、-N(R d )C(O)O-、-SO2N(R d )-、-N(R d SO2-, possessing -C(O)N(R) d )-alkylene groups, having -N(R d )C(O)- alkylene groups, having -N(R d alkylene groups of C(O)O-, alkylene groups having ether-like oxygen atoms, alkylene groups having -S-, alkylene groups having -C(O)O-, alkylene groups having -C(O)S-, alkylene groups having -N(R) d )-alkylene groups, having -N(R d )C(O)N(R d )-alkylene groups, or those having -SO2N(R d )- alkylene groups, more preferably -C(O)O- or -C(O)N(R) d -(especially -C(O)NH-).

[0172] y1 is an integer greater than or equal to 1, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0173] L 3 These are organopolysiloxane residues with a valence of 1+y1. These organopolysiloxane residues can be chain-like or cyclic.

[0174] R 1 It is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms with an ether-like oxygen atom. R 1 When it is a single bond, L 3 With L 1 Direct bonding.

[0175] R 1 When the fluoroalkyl group has 3 to 20 carbon atoms, it can be a straight chain, or it can have a branched chain or a cyclic structure.

[0176] R 1 When the alkylene group has 3 to 20 carbon atoms, it can be a straight chain, or it can have a branched chain or a cyclic structure.

[0177] R 1 When the alkylene group has 3 to 20 carbon atoms and contains an ether-containing oxygen atom, the alkylene group can be straight-chain, branched, or cyclic. Furthermore, the ether-containing oxygen atom can be located at the end of the alkylene group or between carbon atoms.

[0178] R 1 When R is a fluorinated alkylene, an alkylene group, or an alkylene group having an ether-like oxygen atom, 1 The carbon number is 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

[0179] L 1 It can be a single bond or a 1+x1 valence group. The 1+x1 valence group can have heteroatoms such as N, O, S, and Si, and can also have branch points. L 1 In R 1 and R 2 The bonding atoms are each preferably N, O, S, Si, carbon atoms forming the branch points, or carbon atoms with hydroxyl or oxo groups (=O).

[0180] L 1 When it is a single bond, R in equation (1) 1 With R 2 Direct bonding. Additionally, in L... 1 It is a single bond and R 1 In the case of a single bond, the L in compound 1 3 With R 2 Direct bonding.

[0181] L 1 When the group is trivalent or higher, L 1 Having at least one branch point (hereinafter referred to as "branch point P") from the group consisting of organopolysiloxane residues selected from C, N, Si, ring structures and (1+x1) valences. 1 ”).

[0182] At branch point P, N is the branch point. 1 In the case of branch point P 1 For example, it can be represented by *-N(-**)2, where * is R. 1 The connection key on the side is **R. 2 The connection key on the side.

[0183] C is the branch point P 1 In the case of branch point P 1 For example, *-C(-**)3 or *-CR 29 (-**)2 represents the expression. Here, * and ** are branch points P and N are the branch points. 1 The situation is the same, R 29 It is a monovalent group, and examples include hydrogen atoms, hydroxyl groups, alkyl groups, alkoxy groups, etc.

[0184] With Si as the branch point P 1 In the case of branch point P 1 For example, *-Si(-**)3 or *-SiR 29 (-**)2 represents the expression. Here, * and ** are branch points P and N are the branch points. 1 The situation is the same, R 29 P is a branch point with C. 1 The situation is the same.

[0185] As a branch point P 1 The ring structure, from the perspective of ease of synthesis and superior surface layer abrasion resistance, light resistance and chemical resistance, is preferably selected from the group consisting of aliphatic rings of 3 to 8 members, aromatic rings of 3 to 8 members, heterocyclic rings of 3 to 8 members, and fused rings composed of two or more of these rings, and more preferably the ring structure listed in the following formula.

[0186] The ring structure can have substituents such as halogen atoms, alkyl groups (optionally including ether oxygen atoms between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, and oxo groups (=O).

[0187]

[0188] As a branch point P 1 The organopolysiloxane residues, for example, include the following groups. Wherein, R in the following formula... 25 It can be a hydrogen atom, alkyl group, alkoxy group, or phenyl group. R 25 The alkyl and alkoxy groups preferably have 1 to 10 carbon atoms, more preferably 1.

[0189]

[0190] L with a valence of 2 or higher 1 It can have the option of -C(O)N(R) 26 )-, -C(O)O-, -C(O)-, -C(OH)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)N(R 26 )-、-SO2N(R 26 )-、-N(R 26 SO2-, -Si(R) 26 )2-、-OSi(R 26 At least one bond (hereinafter referred to as "bond B") in the group consisting of -Si(CH3)2-, -Si(CH3)2-, Ph-Si(CH3)2-, and divalent organopolysiloxane residues. 1 ”).

[0191] Among them, R 26 It is a hydrogen atom, an alkyl or phenyl group having 1 to 6 carbon atoms, and Ph is a phenylene group. From the perspective of easily producing compound 1, R... 26 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0192] Examples of divalent organopolysiloxane residues include groups of the following formula.

[0193] Wherein, R in the following formula 27 It can be a hydrogen atom, alkyl group, alkoxy group, or phenyl group. R 27 The alkyl and alkoxy groups preferably have 1 to 10 carbon atoms, more preferably 1.

[0194]

[0195] As key B 1 From the perspective of ease of synthesis, it is preferable to select -C(O)NR. 26 -、-C(O)- and -NR 26 -At least one bond in the group consisting of -C(O)NR is more preferably -C(O)NR from the perspective of superior lightfastness and chemical resistance of the surface layer. 26 -or -C(O)-.

[0196] L as divalent 1 Preferred with R 1 and R 2 Each bonded atom is independently an N, O, S, or Si atom, or a carbon atom with a hydroxyl or oxo group (=O). That is, it is preferred to bond with R. 1 and R 2 The adjacent atoms are bonds B. 1 The constituent elements. As L with a valence of 2 or higher.1 For specific examples, more than one key B can be listed. 1 (For example, *-B) 1 -**、*-B 1 -R 28 -B 1 -**). Among them, R 28 Organic groups that are single bonds or divalent, * indicates R 1 The connection key on the side is **R. 2 The connection key on the side.

[0197] L with trivalent or higher 1 Preferred and R 1 and R 2 The bonded atoms are each independently N, O, S, Si, the carbon atom forming the branch point, or a carbon atom with a hydroxyl or oxo group (=O). That is, preferably bonded to R. 1 and R 2 The adjacent atoms are bonds B. 1 Or branch point P 1 The constituent elements. As L with a valence of 3 or higher. 1 For specific examples, more than one branch point P can be listed. 1 (e.g., {*-P) 1 (-**) x1}), more than one branch point P 1 With more than one B 1 Combinations (e.g., {*-B) 1 -R 28 -P 1 (-**) x1}、{*-B 1 -R 28 -P 1 (-R 28 -B 1 -**) x1}). Among them, R 28 Organic groups that are single bonds or divalent, * indicates R 1 The connection key on the side is **R. 2 The connection key on the side.

[0198] As mentioned above, R 28 The divalent organic groups in the group can include, for example, divalent aliphatic hydrocarbon groups (alkylene, cycloalkylene, etc.) and divalent aromatic hydrocarbon groups (phenylene, etc.). In hydrocarbon groups with two or more carbon atoms, carbon atoms can have B bonds between them. 1 The number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0199] As mentioned above L 1From the perspective of facilitating the manufacture of compound 1, the preferred group is any of the groups shown in formulas (E1) to (E7).

[0200]

[0201] -E 1 -C(R E2 ) 3-e3 (-E 22 -) e3 …Formula (E2)

[0202] -E 2 -N(-E 23 -)2…Formula (E3)

[0203] -E 3 -Z 1 (-E 24 -) e4 ...Formula (E4)

[0204] -E 2 -Si(R E3 ) 3-e3 (-E 25 -) e3 …Formula (E5)

[0205] -E 1 -E 26 …Formula (E6)

[0206] -E 1 -CH(-E 22 -)-Si(R E3 ) 3-e5 (-E 25 -) e5 …Formula (E7)

[0207] In equations (E1) to (E7), E 1 E 2 or E 3 The side of R in equation (1) 1 Connection, E 22 E 23 E 24 E 25 or E 26 Side and R 2 connect.

[0208] Here, E 1 For single key, -B 5 -、-B 6 -R 40 -or-B 6 -R 40 -B 5-, where R 40 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms in the carbon-carbon bond. E6 -、-C(O)-、-NR E6 - or -O- groups, B 5 -C(O)NR E6 -、-C(O)-、-NR E6 -or-O-, B 6 -C(O)NR E6 -、-C(O)- or -NR E6 -,

[0209] E 2 For single key or -B 6 -R 40 -,

[0210] In E 3 The bonded Z 1 When the atom in E is a carbon atom, 3 For E 1 In E 3 The bonded Z 1 When the atom in E is a nitrogen atom, 3 For E 2 ,

[0211] E 11 It is a single bond, -O-, alkylene, or an alkylene group having -C(O)NR between carbon atoms. E6 -、-C(O)-、-NR E6 - or -O- groups,

[0212] E 22 For single key, -B 5 -、-R 40 -B 6 -or-B 5 -R 40 -B 6 - Having more than 2 E 22 At that time, more than 2 E 22 They can be the same or different.

[0213] E 23 For single key or -R 40 -B 6 -, 2 E 23 They can be the same or different.

[0214] In E 24 The bonded Z 1 When the atom in E is a carbon atom, 24 For E 22 In E24 The bonded Z 1 When the atom in E is a nitrogen atom, 24 For E 23 In the case of having more than 2 E 24 In the case of more than 2 E 24 They can be the same or different.

[0215] E 25 For single key or -R 40 -B 6 - Having more than 2 E 25 At that time, more than 2 E 25 They can be the same or different.

[0216] E 26 For single key or -R 40 -B 6 -,

[0217] Z 1 It is a (e4+1) valence group with a cyclic structure, which has a relationship with E 3 Directly bonded carbon or nitrogen atoms, and having an affinity for E 24 Directly bonded carbon or nitrogen atoms,

[0218] R E1 It is a hydrogen atom or an alkyl group, having two or more R atoms. E1 At that time, more than 2 R E1 They can be the same or different.

[0219] R E2 It can be a hydrogen atom, hydroxyl group, alkyl group or acyloxy group.

[0220] R E3 It is an alkyl group.

[0221] R E6 It consists of hydrogen atoms and alkyl or phenyl groups having 1 to 6 carbon atoms.

[0222] e1 is an integer from 0 to 2, e2 is an integer from 0 to 3, and e1+e2 is an integer from 1 to 5.

[0223] e3 is an integer from 1 to 3.

[0224] e4 is an integer greater than or equal to 1.

[0225] e5 is an integer from 1 to 3.

[0226] It should be noted that e1+e2=x1, e3=x1, e4=x1, and e5+1=x1.

[0227] From the perspectives of ease of manufacturing Compound 1, and superior surface layer properties such as abrasion resistance, light resistance, and chemical resistance, R 40 The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 4. The lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0228] As Z 1 The ring structures mentioned above can be listed, and the preferred methods are also the same. It should be noted that Z... 1 The ring structure in E 24 Direct bonding, therefore it is not a ring structure connected to, for example, an alkylene group, which in turn is bonded to E. 24 connect.

[0229] From the perspective of ease of manufacturing compound 1, R E1 R E2 or R E3 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0230] From the perspective of ease of manufacturing compound 1, R E2 The alkyl moiety of the acyloxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0231] From the perspectives of ease of manufacturing compound 1, superior abrasion resistance of the surface layer, and better fingerprint stain removal, e4 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0232] As L 1 Other ways may be listed as groups represented by any of the following formulas (E11) to (E17).

[0233]

[0234] -E 1 -C(R E2 ) 3-e3 (-E 22 -E G ) e3 …Formula (E12)

[0235] -E 2 -N(-E 23 -E G Equation 2… (E13)

[0236] -E 3 -Z 1 (-E 24 -E G ) e4 …Formula (E14)

[0237] -E 2 -Si(R E3 ) 3-e3 (-E 25 -E G ) e3 …Formula (E15)

[0238] -E 1 -E 26 -E G …Formula (E16)

[0239] -E 1 -CH(-E 22 -)-Si(R E3 ) 3-e5 (-E 25 -E G ) e5 …Formula (E17)

[0240] In equations (E11) to (E17), E 1 E 2 or E 3 The side of R in equation (1) 1 Connection, E 22 E 23 E 24 E 25 or E 26 Side and R 2 Connection. E G For the following formula (E) G ), L 1 Having more than 2 E G They can be the same or different. The symbols other than G are the same as those in equations (E1) to (E7).

[0241] -Si(R 23 ) 3-k (-E 3 -) k …formula (E) G )

[0242] Wherein, formula (E) G In the context of Si and E 22 E 23 E 24 E 25 or E 26 Connection, E 3 Side and R 2 Connection. R 23 It is an alkyl group. E 3 For single key, or -R 45 -B 6-, where R 45 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms in the carbon-carbon bond. 46 -、-C(O)-、-NR 46 - or -O- groups, or -(OSi(R 24 )2) p -O-, more than 2 E 3 They can be the same or different. k is 2 or 3. R 46 It consists of a hydrogen atom and an alkyl or phenyl group having 1 to 6 carbon atoms. R 24 It is an alkyl, phenyl, or alkoxy group, with two Rs. 24 They can be the same or different. p is an integer from 0 to 5. When p is 2 or higher, there are two or more (OSi(R)) 24 )2) They can be the same or different.

[0243] From the perspective of ease of manufacturing Compound 1, and superior surface layer properties such as abrasion resistance, light resistance, and chemical resistance, E 3 The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 4. The lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0244] From the perspective of ease of manufacturing compound 1, R 23 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0245] From the perspective of ease of manufacturing compound 1, R 24 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0246] Based on the excellent storage stability of compound 1, R 24 The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0247] p is preferably 0 or 1.

[0248] R 2 It is an alkylene group or an alkylene group having an ether-like oxygen atom.

[0249] There are multiple R 2 At that time, there are multiple R 2 Choose whether they are the same or different from each other.

[0250] R 2The alkylene group and the alkylene group having an ether-like oxygen atom preferably have 1 to 20 carbon atoms, more preferably 1 to 15, and even more preferably 1 to 11. When the alkylene group or the alkylene group having an ether-like oxygen atom has 3 or more carbon atoms, the alkylene group with 3 or more carbon atoms or the alkylene group having an ether-like oxygen atom can be straight-chain, or it can have a branched chain or a cyclic structure.

[0251] In alkylene groups having ether-like oxygen atoms, it can be with L 1 The bonded atom is an ether-type oxygen atom, or it can be an ether-type oxygen atom between carbon atoms.

[0252] R 2 Preferably, it contains the group represented by the following formula (H1).

[0253] *-(O) a4 -(R g11 O) a5 -R g12 -**…(H1)

[0254] in,

[0255] R g11 It is an alkylene group having 1 to 12 carbon atoms, and contains multiple R groups. g11 At that time, multiple existing R g11 Choose either the same or different from each other.

[0256] R g12 It is an alkylene group having 1 to 12 carbon atoms.

[0257] a4 is either 0 or 1.

[0258] a5 is an integer greater than or equal to 0.

[0259] *For L 1 The bonded connection key,

[0260] **For T 1 The bonding connection key.

[0261] When a4 is 0, the atom with the connecting bond* is a carbon atom; when a4 is 1, the atom with the connecting bond* is an oxygen atom. In compound 1, a4 can be either 0 or 1, and can be chosen appropriately based on factors such as ease of synthesis.

[0262] a5 is R g11 The number of repetitions of O is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1, from the perspective of durability as a surface layer.

[0263] R g11The alkylene group can be a straight-chain or branched alkylene group having 1 to 12 carbon atoms, preferably a alkylene group having 1 to 6 carbon atoms, and more preferably a alkylene group having 1 to 3 carbon atoms. In addition, the alkylene group is preferably a straight-chain alkylene group.

[0264] R g12 The alkylene group can be a straight-chain or branched alkylene group having 1 to 12 carbon atoms, preferably a alkylene group having 2 to 6 carbon atoms, and more preferably a alkylene group having 2 to 3 carbon atoms. In addition, the alkylene group is preferably a straight-chain alkylene group.

[0265] L 1 When it is a single key, -R 1 -L 1 -(R 2 -T 1 ) x1 It can be represented by the following formula (RL-1).

[0266] *-R 43 -(OR 44 ) y4 -T 1 …Formula (RL-1)

[0267] in,

[0268] R 43 It is a single bond or an alkylene group having 1 to 6 carbon atoms.

[0269] R 44 It is an alkylene group having 1 to 6 carbon atoms, and contains multiple R groups. 44 At that time, multiple existing R 44 Choose either the same or different from each other.

[0270] y4 is an integer greater than or equal to 0.

[0271] * is L in equation (1) 3 The bonding connection key.

[0272] Among them, in R 43 When it is a single key, y4 is an integer greater than or equal to 1.

[0273] It should be noted that R 43 When it is a single bond, compound 1 has (OR 44 ) y4 The end of O and the L in equation (1) 3 Direct bonding structure.

[0274] Furthermore, when y4 is 0, compound 1 has R 43 With T 1 Direct bonding structure.

[0275] T 1 It is a reactive group, because T1 Due to its reactivity, compound 1 exhibits various functions. These functions include, for example, improving adhesion to the substrate surface, imparting photocurability and / or thermocurability to compound 1, imparting acidity or alkalinity to compound 1, adjusting the solubility of compound 1 in specific solvents, and serving as a precursor in the synthesis of other compounds.

[0276] As T 1 Specific examples include -Ar and -SR. 10 -NOR 10 -C(=O)R 10 -N(R) 10 )2、-N + (R 10 )3X 3 -C≡N, -C(=NR) 10 )-R 10 -N + ≡N、-N=NR 10 -C(=O)OR 10 -C(=O)OX 2 -C(=O)X 4 -C(=O)OC(=O)R 10 -SO2R 10 -SO3H, -SO3X 2 -OP(=O)(-OR) 10 2. -OP (=O)(-OR) 10 (-OX) 2 -N=C=O, -SiR a1 z1 R a11 3-z1 -C(R) 10 )=C(R 10 )2、-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, and the groups shown below.

[0277]

[0278] in,

[0279] R 10The atom is hydrogen, optionally an alkyl group having 1 to 6 carbon atoms with substituents, or optionally a fluoroalkyl group having 1 to 6 carbon atoms with substituents, or optionally an aryl group having substituents.

[0280] Ar is an aryl group that is optionally substituent.

[0281] X 2 They are alkali metal ions or ammonium ions.

[0282] X 3 It is a halide ion.

[0283] X 4 Halogen atoms,

[0284] R a1 It is a hydrolyzable group or hydroxyl group.

[0285] R a11 It is a hydrocarbon group.

[0286] z1 is an integer from 1 to 3.

[0287] There are multiple R 10 R a1 or R a11 In the case of the multiple Rs that exist 10 R a1 or R a11 Choose whether they are the same or different from each other.

[0288] R 10 The fluoroalkyl group has 1 to 6 carbon atoms, preferably 1 to 4. This fluoroalkyl group may have other substituents. Having a fluoroalkyl group as T... 1 Compound 1 is a compound with a high fluorine content, exhibiting excellent properties such as low refractive index, low dielectric constant, water / oil repellency, heat resistance, chemical resistance, chemical stability, and transparency. As optional substituents in the fluoroalkyl group, examples include halogen atoms such as chlorine atoms, and groups identical to those exemplified as functional donor groups T.

[0289] Ar and R 10 Examples of aryl groups include phenyl and naphthyl groups, which may optionally have further substituents. Examples of substituents that may be optionally present on an aryl group include halogen atoms such as fluorine and chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and groups that are the same as those exemplified as functional donor groups T.

[0290] R 10 The alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The alkyl group may optionally have other substituents. Examples of optional substituents for the alkyl group include halogen atoms such as chlorine atoms, and groups identical to those exemplified later as functional donor groups T.

[0291] The reactive group T has hydroxyl, N-hydroxyl, aldehyde, ketone, amino, quaternary ammonium, nitrile, imino, diazo, carboxyl, carboxylate, acid anhydride, sulfonyl, sulfonate, phosphate, and phosphate groups (hereinafter, these groups will also be referred to as "functional donor groups T"). 1 Compound 1 is endowed with various properties such as acidity, basicity, and hydrophilicity through the functionalizing group T. For example, it can impart improved solubility in specific solvents or improved adhesion to specific substrates. 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.

[0292] The reactive group T contains a group with a carbon-carbon double bond. 1 Compound 1 can be combined with photoinitiators to prepare photocurable compositions, and the cured coating obtained from this composition has both water and oil repellency and hard coating properties. Examples of groups having carbon-carbon double bonds include acryloyl, methacryl, vinyl, allyl, acryloyloxy, methacryloxy, and olefins.

[0293] In addition, T has isocyanate group, epoxy group, glycidyl group, oxetyl group, and mercapto group as reactive groups. 1 Compound 1 can be combined with an epoxy curing agent to prepare thermosetting or photocurable compositions, and the cured coating obtained from the composition has both water and oil repellency and hard coating properties.

[0294] reactive group T 1 The amide bond, ester bond, ether bond, thioether bond, siloxane bond, and urea bond in the T are... 1 The bonds formed by alkyl, fluoroalkyl, aryl, and heteroaryl groups can also be used to further endow the product with other functional groups.

[0295] T is the reactive group of compound 1. 1 From the perspectives of synthesis, chemical stability, and adhesion to the substrate, hydroxyl, amino, or carbon-carbon double bond groups are preferred. Furthermore, among groups with carbon-carbon double bonds, acryloyl, methacryl, vinyl, allyl, or olefin groups are preferred.

[0296] Furthermore, when compound 1 is used as a surface treatment agent for forming a surface layer with excellent durability, such as abrasion resistance, T 1 Preferably, it is a group having a reactive silyl group. As a group having a reactive silyl group, the group shown in the following formula (2) is preferred.

[0297] -SiR a1 z1 R a113-z1 …Formula (2)

[0298] In equation (2),

[0299] R a1 It is a hydrolyzable group or hydroxyl group.

[0300] R a11 It is a hydrocarbon group.

[0301] z1 is an integer from 1 to 3.

[0302] There are multiple R a1 or R a11 At that time, the multiple R that exist a1 or R a11 Choose either the same or different.

[0303] R a1 When the hydroxyl group is present, it forms a silanol (Si-OH) group together with the Si atom. Additionally, the hydrolyzable group becomes a hydroxyl group through a hydrolysis reaction. The silanol group further reacts intermolecularly to form a Si-O-Si bond. Furthermore, the silanol group undergoes a dehydration condensation reaction with the hydroxyl group (substrate-OH) on the substrate surface to form a chemical bond (substrate-O-Si). This is achieved by giving compound 1 one or more T atoms. 1 The surface layer exhibits excellent abrasion resistance after formation.

[0304] As R a1 Hydrolyzable groups include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, and isocyanate groups (-NCO). As an alkoxy group, an alkoxy group with 1 to 4 carbon atoms is preferred. As an acyl group, an acyl group with 1 to 6 carbon atoms is preferred. As an acyloxy group, an acyloxy group with 1 to 6 carbon atoms is preferred.

[0305] From the perspective of ease of synthesis, R a1 Preferably, it is an alkoxy or halogen atom with 1 to 4 carbon atoms. Considering the excellent storage stability of compound 1 and the suppression of gas venting during the reaction, R... a1 The alkoxy group is preferably an alkoxy group with 1 to 4 carbon atoms. From the perspective of long-term storage stability, an ethoxy group is more preferred, and from the perspective of shortening the hydrolysis reaction time, a methoxy group is more preferred. In addition, as a halogen atom, a chlorine atom is particularly preferred.

[0306] R a11 The hydrocarbon group is a hydrocarbon group. Examples of hydrocarbon groups include alkyl, cycloalkyl, alkenyl, and allyl groups, with alkyl being preferred from the perspective of ease of synthesis. Furthermore, from the perspective 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.

[0307] R in the group shown in formula (2)a1 The quantity z1 can be 1 to 3, but from the perspective of adhesion to the substrate, it is preferred to be 2 or 3, and more preferably 3.

[0308] Specific examples of the group represented by formula (2) include -Si(OCH3)3, -SiCH3(OCH3)2, -Si(OCH2CH3)3, -SiCl3, -Si(OCOCH3)3, and -Si(NCO)3. From the perspective of ease of handling in manufacturing, -Si(OCH3)3 is preferred.

[0309] T in one molecule of compound 1 1 The quantity x1 can be 1 to 10. Considering the ease of synthesis and the ease of processing compound 1, x1 is preferably 1 to 6, and more preferably 1 to 3. One molecule of compound 1 contains two or more T atoms. 1 In this case, the T 1 They can have the same structure or different structures.

[0310] As T 1 Specific examples of structures that do not possess reactive silane groups include the following structures. Wherein, R in the formula... a R represents an alkyl, fluoroalkyl, or aryl group optionally having a substituent, R represents an alkyl group having 1 to 6 carbon atoms optionally having a substituent or a fluoroalkyl group having 1 to 6 carbon atoms optionally having a substituent, L represents an aryl group having 1 to 6 carbon atoms optionally having a substituent or a fluoroaryl group having 1 to 3 carbon atoms optionally having a substituent, and c represents an integer from 0 to 3. b * indicates a fluoroalkyl or aryl group with optional substituents, and * indicates a linking bond.

[0311]

[0312] Additionally, as L 1 -(R 2 -T 1 ) x1 Specific examples can be listed as the groups listed in the following formulas.

[0313]

[0314] <Preferred method for compound 1>

[0315] From the perspective of further improving the effects of the present invention, compound 1 is preferably the compound shown in formula (1-1) (hereinafter also referred to as "compound 1-1"), the compound shown in formula (1-2) (hereinafter also referred to as "compound 1-2"), or the compound shown in formula (1-3) (hereinafter also referred to as "compound 1-3").

[0316] (Compound 1-1)

[0317] Compound 1-1 is the compound represented by the following formula (1-1).

[0318] R f1 -L 2 -SiR 11 R 12 -O-(SiR 13 R 14 -O) z11 -SiR 15 R 16 -R 1 -L 1 -(R 2 -T 1 ) x1 …(1-1)

[0319] In equation (1-1),

[0320] R 11 and R 12 Each is independently an alkyl or R f1 -L 2 -,

[0321] R 13 R 14 R 15 and R 16 Each is independently an alkyl group.

[0322] R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1,

[0323] z11 is an integer greater than or equal to 1.

[0324] There are multiple R 13 R 14 R 2 or T 1 In the case of the multiple Rs that exist 13 R 14 R 2 or T 1 Choose whether they are the same or different from each other.

[0325] R 11 R 12 R13 R 14 R 15 and R 16 The alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms can be straight-chain, branched, or have a cyclic structure.

[0326] z11 is an integer greater than or equal to 1, preferably 1 to 100, more preferably 1 to 30, and even more preferably 5 to 20.

[0327] As a specific example of compound 1-1, compounds represented by the following formula can be listed. It should be noted that in the table below, for example, the compound "No. 1" refers to R of the above formula (1-1). f1 For CF3, L 2 For (CH2)a, (CH2) a a is 0~20, R 11 For Me, R 12 For Me, R 13 For Me, R 14 For Me, z11 is 5~100, R 15 For Me, R 16 For Me, R 1 (CH2) b (CH2) b b is 0-20, L 1 For C(=O)NH, R 2 (CH2) C (CH2) C C is 1-20, T 1 It is a compound of Si(OMe)3 and x1 is 1.

[0328] [Table 1]

[0329]

[0330] [Table 2]

[0331]

[0332] [Table 3]

[0333]

[0334] [Table 4]

[0335]

[0336] [Table 5]

[0337]

[0338] [Table 6]

[0339]

[0340] [Table 7]

[0341]

[0342] [Table 8]

[0343]

[0344] [Table 9]

[0345]

[0346] [Table 10]

[0347]

[0348] [Table 11]

[0349]

[0350] [Table 12]

[0351]

[0352] [Table 13]

[0353]

[0354] [Table 14]

[0355]

[0356] [Table 15]

[0357]

[0358] [Table 16]

[0359]

[0360] [Table 17]

[0361]

[0362] [Table 18]

[0363]

[0364] [Table 19]

[0365]

[0366] [Table 20]

[0367]

[0368] [Table 21]

[0369]

[0370] [Table 22]

[0371]

[0372] [Table 23]

[0373]

[0374] [Table 24]

[0375]

[0376] [Table 25]

[0377]

[0378] [Table 26]

[0379]

[0380] [Table 27]

[0381]

[0382] [Table 28]

[0383]

[0384] [Table 29]

[0385]

[0386] [Table 30]

[0387]

[0388] [Table 31]

[0389]

[0390] [Table 32]

[0391]

[0392] [Table 33]

[0393]

[0394] [Table 34]

[0395]

[0396] [Table 35]

[0397]

[0398] [Table 36]

[0399]

[0400] [Table 37]

[0401]

[0402] [Table 38]

[0403]

[0404] [Table 39]

[0405]

[0406] [Table 40]

[0407]

[0408] [Table 41]

[0409]

[0410] [Table 42]

[0411]

[0412] [Table 43]

[0413]

[0414] [Table 44]

[0415]

[0416] [Table 45]

[0417]

[0418] [Table 46]

[0419]

[0420] [Table 47]

[0421]

[0422] [Table 48]

[0423]

[0424] [Table 49]

[0425]

[0426] [Table 50]

[0427]

[0428] [Table 51]

[0429]

[0430] [Table 52]

[0431]

[0432] [Table 53]

[0433]

[0434] [Table 54]

[0435]

[0436] [Table 55]

[0437]

[0438] [Table 56]

[0439]

[0440] [Table 57]

[0441]

[0442] [Table 58]

[0443]

[0444] [Table 59]

[0445]

[0446] [Table 60]

[0447]

[0448] [Table 61]

[0449]

[0450] [Table 62]

[0451]

[0452] [Table 63]

[0453]

[0454] [Table 64]

[0455]

[0456] [Table 65]

[0457]

[0458] [Table 66]

[0459]

[0460] [Table 67]

[0461]

[0462] [Table 68]

[0463]

[0464] [Table 69]

[0465]

[0466] [Table 70]

[0467]

[0468] [Table 71]

[0469]

[0470] [Table 72]

[0471]

[0472] [Table 73]

[0473]

[0474] [Table 74]

[0475]

[0476] [Table 75]

[0477]

[0478] [Table 76]

[0479]

[0480] [Table 77]

[0481]

[0482] [Table 78]

[0483]

[0484] [Table 79]

[0485]

[0486] [Table 80]

[0487]

[0488] [Table 81]

[0489]

[0490] [Table 82]

[0491]

[0492] [Table 83]

[0493]

[0494] [Table 84]

[0495]

[0496] (Compounds 1-2)

[0497] Compounds 1-2 are compounds represented by the following formula (1-2).

[0498] SiR 21 R 22 R 23 -O-(SiR 24 R 25 -O) z21 -(SiR 26 R 27 -O) z22 -SiR 28 R 29 -R 1 -L 1 -(R 2 -T 1 )x1…(1-2)

[0499] In formula (1-2),

[0500] R 21 R 22 and R 23Each is independently an alkyl or R f1 -L 2 -,

[0501] R 24 For R f1 -L 2 -,

[0502] R 25 alkyl or R f1 -L 2 -,

[0503] R 26 and R 27 Each is an alkyl group independently.

[0504] R 28 and R 29 Each is independently an alkyl group or R f1 -L 2 -,

[0505] R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1,

[0506] z21 is an integer greater than or equal to 1.

[0507] z22 is an integer greater than or equal to 0.

[0508] There are multiple R 24 R 25 R 26 R 27 R 2 or T 1 In the case of the multiple Rs that exist 24 R 25 R 26 R 27 R 2 or T 1 Choose whether they are the same or different from each other.

[0509] R 21 R 22 R 23 R 25 R 26 R 27 R 28and R 29 The alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms can be straight-chain, branched, or have a cyclic structure.

[0510] z21 is an integer greater than or equal to 1, preferably 1 to 100, more preferably 1 to 30, and even more preferably 5 to 20.

[0511] z22 is an integer greater than or equal to 0, preferably 0 to 100, more preferably 1 to 30, and even more preferably 5 to 20.

[0512] In equation (1-2) (SiR) 24 R 25 -O) and (SiR 26 R 27 The bonding order of (-O) is arbitrary. In equation (1-2), z21 and z22 represent (SiR)... 24 R 25 -O) and (SiR 26 R 27 The number of -O) does not indicate the configuration. For example, (SiR) 24 R 25 -O) z21 Indicates (SiR) 24 R 25 The number of -O is z21, which does not mean (SiR) 24 R 25 -O) z21 The block configuration structure. Similarly, (SiR) 24 R 25 -O) and (SiR 26 R 27 The order in which -O is recorded does not represent the bonding order of the individual units.

[0513] For example, (SiR) 24 R 25 -O) and (SiR 26 R 27 -O) can be configured alternately, or it can be (SiR) 24 R 25 -O) and (SiR 26 R 27 -O) can be configured in a block format, or it can be undefined.

[0514] As specific examples of compounds 1-2, compounds represented by the following formulas can be listed. It should be noted that in the table below, for example, "No. 1" refers to R of the above formula (1-2). 21 For Me-(CH2)a and Me-(CH2)a In this context, a ranges from 0 to 20, and R... 22 For Me, R 23 For Me, R 24 For CF3-(CH2) a CF3-(CH2) a In this context, a ranges from 0 to 20, and R... 25 For Me, z21 is 5-100, z22 is 0, and R is... 28 For Me, R 29 For Me, R 1 (CH2) b (CH2) b b in the range is 0-20, L 1 For C(=O)NH, R 2 (CH2) C (CH2) C C is 1-20, T 1 It is a compound of Si(OMe)3 and x1 is 1.

[0515] [Table 85]

[0516]

[0517] [Table 86]

[0518]

[0519] [Table 87]

[0520]

[0521] [Table 88]

[0522]

[0523] [Table 89]

[0524]

[0525] [Table 90]

[0526]

[0527] [Table 91]

[0528]

[0529] [Table 92]

[0530]

[0531] [Table 93]

[0532]

[0533] [Table 94]

[0534]

[0535] [Table 95]

[0536]

[0537] [Table 96]

[0538]

[0539] [Table 97]

[0540]

[0541] [Table 98]

[0542]

[0543] [Table 99]

[0544]

[0545] [Table 100]

[0546]

[0547] [Table 101]

[0548]

[0549] [Table 102]

[0550]

[0551] [Table 103]

[0552]

[0553] [Table 104]

[0554]

[0555] [Table 105]

[0556]

[0557] [Table 106]

[0558]

[0559] [Table 107]

[0560]

[0561] [Table 108]

[0562]

[0563] [Table 109]

[0564]

[0565] [Table 110]

[0566]

[0567] [Table 111]

[0568]

[0569] [Table 112]

[0570]

[0571] [Table 113]

[0572]

[0573] [Table 114]

[0574]

[0575] [Table 115]

[0576]

[0577] [Table 116]

[0578]

[0579] [Table 117]

[0580]

[0581] [Table 118]

[0582]

[0583] [Table 119]

[0584]

[0585] [Table 120]

[0586]

[0587] [Table 121]

[0588]

[0589] [Table 122]

[0590]

[0591] [Table 123]

[0592]

[0593] [Table 124]

[0594]

[0595] [Table 125]

[0596]

[0597] [Table 126]

[0598]

[0599] [Table 127]

[0600]

[0601] [Table 128]

[0602]

[0603] [Table 129]

[0604]

[0605] [Table 130]

[0606]

[0607] [Table 131]

[0608]

[0609] [Table 132]

[0610]

[0611] [Table 133]

[0612]

[0613] [Table 134]

[0614]

[0615] [Table 135]

[0616]

[0617] [Table 136]

[0618]

[0619] [Table 137]

[0620]

[0621] [Table 138]

[0622]

[0623] [Table 139]

[0624]

[0625] [Table 140]

[0626]

[0627] [Table 141]

[0628]

[0629] [Table 142]

[0630]

[0631] [Table 143]

[0632]

[0633] [Table 144]

[0634]

[0635] [Table 145]

[0636]

[0637] [Table 146]

[0638]

[0639] [Table 147]

[0640]

[0641] [Table 148]

[0642]

[0643] [Table 149]

[0644]

[0645] [Table 150]

[0646]

[0647] [Table 151]

[0648]

[0649] [Table 152]

[0650]

[0651] [Table 153]

[0652]

[0653] [Table 154]

[0654]

[0655] [Table 155]

[0656]

[0657] [Table 156]

[0658]

[0659] [Table 157]

[0660]

[0661] [Table 158]

[0662]

[0663] [Table 159]

[0664]

[0665] [Table 160]

[0666]

[0667] [Table 161]

[0668]

[0669] [Table 162]

[0670]

[0671] [Table 163]

[0672]

[0673] [Table 164]

[0674]

[0675] [Table 165]

[0676]

[0677] [Table 166]

[0678]

[0679] [Table 167]

[0680]

[0681] [Table 168]

[0682]

[0683] [Table 169]

[0684]

[0685] [Table 170]

[0686]

[0687] [Table 171]

[0688]

[0689] [Table 172]

[0690]

[0691] [Table 173]

[0692]

[0693] [Table 174]

[0694]

[0695] [Table 175]

[0696]

[0697] [Table 176]

[0698]

[0699] [Table 177]

[0700]

[0701] [Table 178]

[0702]

[0703] [Table 179]

[0704]

[0705] [Table 180]

[0706]

[0707] [Table 181]

[0708]

[0709] [Table 182]

[0710]

[0711] [Table 183]

[0712]

[0713] [Table 184]

[0714]

[0715] [Table 185]

[0716]

[0717] [Table 186]

[0718]

[0719] [Table 187]

[0720]

[0721] [Table 188]

[0722]

[0723] [Table 189]

[0724]

[0725] [Table 190]

[0726]

[0727] [Table 191]

[0728]

[0729] [Table 192]

[0730]

[0731] [Table 193]

[0732]

[0733] [Table 194]

[0734]

[0735] [Table 195]

[0736]

[0737] [Table 196]

[0738]

[0739] [Table 197]

[0740]

[0741] [Table 198]

[0742]

[0743] [Table 199]

[0744]

[0745] [Table 200]

[0746]

[0747] [Table 201]

[0748]

[0749] [Table 202]

[0750]

[0751] [Table 203]

[0752]

[0753] [Table 204]

[0754]

[0755] [Table 205]

[0756]

[0757] [Table 206]

[0758]

[0759] [Table 207]

[0760]

[0761] [Table 208]

[0762]

[0763] [Table 209]

[0764]

[0765] [Table 210]

[0766]

[0767] [Table 211]

[0768]

[0769] [Table 212]

[0770]

[0771] [Table 213]

[0772]

[0773] [Table 214]

[0774]

[0775] [Table 215]

[0776]

[0777] [Table 216]

[0778]

[0779] [Table 217]

[0780]

[0781] [Table 218]

[0782]

[0783] [Table 219]

[0784]

[0785] [Table 220]

[0786]

[0787] [Table 221]

[0788]

[0789] [Table 222]

[0790]

[0791] [Table 223]

[0792]

[0793] [Table 224]

[0794]

[0795] [Table 225]

[0796]

[0797] [Table 226]

[0798]

[0799] [Table 227]

[0800]

[0801] [Table 228]

[0802]

[0803] [Table 229]

[0804]

[0805] [Table 230]

[0806]

[0807] [Table 231]

[0808]

[0809] [Table 232]

[0810]

[0811] [Table 233]

[0812]

[0813] [Table 234]

[0814]

[0815] [Table 235]

[0816]

[0817] [Table 236]

[0818]

[0819] [Table 237]

[0820]

[0821] [Table 238]

[0822]

[0823] [Table 239]

[0824]

[0825] [Table 240]

[0826]

[0827] [Table 241]

[0828]

[0829] [Table 242]

[0830]

[0831] [Table 243]

[0832]

[0833] [Table 244]

[0834]

[0835] [Table 245]

[0836]

[0837] [Table 246]

[0838]

[0839] [Table 247]

[0840]

[0841] [Table 248]

[0842]

[0843] [Table 249]

[0844]

[0845] [Table 250]

[0846]

[0847] [Table 251]

[0848]

[0849] [Table 252]

[0850]

[0851] [Table 253]

[0852]

[0853] [Table 254]

[0854]

[0855] [Table 255]

[0856]

[0857] [Table 256]

[0858]

[0859] [Table 257]

[0860]

[0861] [Table 258]

[0862]

[0863] [Table 259]

[0864]

[0865] [Table 260]

[0866]

[0867] [Table 261]

[0868]

[0869] [Table 262]

[0870]

[0871] [Table 263]

[0872]

[0873] [Table 264]

[0874]

[0875] [Table 265]

[0876]

[0877] [Table 266]

[0878]

[0879] [Table 267]

[0880]

[0881] [Table 268]

[0882]

[0883] [Table 269]

[0884]

[0885] [Table 270]

[0886]

[0887] [Table 271]

[0888]

[0889] [Table 272]

[0890]

[0891] [Table 273]

[0892]

[0893] [Table 274]

[0894]

[0895] [Table 275]

[0896]

[0897] [Table 276]

[0898]

[0899] [Table 277]

[0900]

[0901] [Table 278]

[0902]

[0903] [Table 279]

[0904]

[0905] [Table 280]

[0906]

[0907] [Table 281]

[0908]

[0909] [Table 282]

[0910]

[0911] [Table 283]

[0912]

[0913] [Table 284]

[0914]

[0915] [Table 285]

[0916]

[0917] [Table 286]

[0918]

[0919] [Table 287]

[0920]

[0921] [Table 288]

[0922]

[0923] [Table 289]

[0924]

[0925] [Table 290]

[0926]

[0927] [Table 291]

[0928]

[0929] [Table 292]

[0930]

[0931] [Table 293]

[0932]

[0933] [Table 294]

[0934]

[0935] [Table 295]

[0936]

[0937] [Table 296]

[0938]

[0939] [Table 297]

[0940]

[0941] [Table 298]

[0942]

[0943] [Table 299]

[0944]

[0945] [Table 300]

[0946]

[0947] [Table 301]

[0948]

[0949] [Table 302]

[0950]

[0951] [Table 303]

[0952]

[0953] [Table 304]

[0954]

[0955] [Table 305]

[0956]

[0957] [Table 306]

[0958]

[0959] [Table 307]

[0960]

[0961] [Table 308]

[0962]

[0963] [Table 309]

[0964]

[0965] [Table 310]

[0966]

[0967] [Table 311]

[0968]

[0969] [Table 312]

[0970]

[0971] [Table 313]

[0972]

[0973] [Table 314]

[0974]

[0975] [Table 315]

[0976]

[0977] [Table 316]

[0978]

[0979] [Table 317]

[0980]

[0981] [Table 318]

[0982]

[0983] [Table 319]

[0984]

[0985] [Table 320]

[0986]

[0987] [Table 321]

[0988]

[0989] [Table 322]

[0990]

[0991] [Table 323]

[0992]

[0993] [Table 324]

[0994]

[0995] [Table 325]

[0996]

[0997] [Table 326]

[0998]

[0999] [Table 327]

[1000]

[1001] [Table 328]

[1002]

[1003] [Table 329]

[1004]

[1005] [Table 330]

[1006]

[1007] [Table 331]

[1008]

[1009] [Table 332]

[1010]

[1011] [Table 333]

[1012]

[1013] [Table 334]

[1014]

[1015] [Table 335]

[1016]

[1017] [Table 336]

[1018]

[1019] [Table 337]

[1020]

[1021] [Table 338]

[1022]

[1023] [Table 339]

[1024]

[1025] [Table 340]

[1026]

[1027] [Table 341]

[1028]

[1029] [Table 342]

[1030]

[1031] [Table 343]

[1032]

[1033] [Table 344]

[1034]

[1035] [Table 345]

[1036]

[1037] [Table 346]

[1038]

[1039] [Table 347]

[1040]

[1041] [Table 348]

[1042]

[1043] [Table 349]

[1044]

[1045] [Table 350]

[1046]

[1047] [Table 351]

[1048]

[1049] [Table 352]

[1050]

[1051] [Table 353]

[1052]

[1053] [Table 354]

[1054]

[1055] [Table 355]

[1056]

[1057] [Table 356]

[1058]

[1059] [Table 357]

[1060]

[1061] [Table 358]

[1062]

[1063] [Table 359]

[1064]

[1065] [Table 360]

[1066]

[1067] [Table 361]

[1068]

[1069] [Table 362]

[1070]

[1071] [Table 363]

[1072]

[1073] [Table 364]

[1074]

[1075] [Table 365]

[1076]

[1077] [Table 366]

[1078]

[1079] [Table 367]

[1080]

[1081] [Table 368]

[1082]

[1083] [Table 369]

[1084]

[1085] [Table 370]

[1086]

[1087] [Table 371]

[1088]

[1089] [Table 372]

[1090]

[1091] [Table 373]

[1092]

[1093] [Table 374]

[1094]

[1095] [Table 375]

[1096]

[1097] [Table 376]

[1098]

[1099] [Table 377]

[1100]

[1101] [Table 378]

[1102]

[1103] [Table 379]

[1104]

[1105] [Table 380]

[1106]

[1107] [Table 381]

[1108]

[1109] [Table 382]

[1110]

[1111] [Table 383]

[1112]

[1113] (Compounds 1-3)

[1114] Compounds 1-3 are compounds represented by the following formula (1-3).

[1115]

[1116] In equation (1-3),

[1117] R 31 For R f1 -L 2 -,

[1118] R 32 alkyl or R f1 -L 2 -,

[1119] R 33 and R 34 Each is independently an alkyl group.

[1120] R 35 -R 1 -L 1 -(R 2 -T 1 ) x1 ,

[1121] R 36 It is an alkyl group.

[1122] R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1,

[1123] z31 is an integer greater than or equal to 1.

[1124] z32 is an integer greater than or equal to 0.

[1125] The sum of z31 and z32 is an integer greater than or equal to 2.

[1126] There are multiple R 31 R 32 R 33 R 34 R 2 or T 1 In the case of the multiple Rs that exist 31 R 32 R 33 R 34 R 2 or T 1 Choose whether they are the same or different from each other.

[1127] R 32 R 33 R 34 and R 36 The alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms can be straight-chain, branched, or have a cyclic structure.

[1128] z31 is an integer greater than or equal to 1, preferably 1 to 100, more preferably 1 to 30, and even more preferably 5 to 20.

[1129] z32 is an integer greater than or equal to 0, preferably 0 to 100, more preferably 1 to 30, and even more preferably 5 to 20.

[1130] z31+z32 is an integer greater than or equal to 1, preferably 1 to 200, more preferably 1 to 60, and even more preferably 10 to 40.

[1131] In equation (1-3) (SiR) 31 R 32 -O) z31 With (SiR) 33 R 34 -O) z32 The bonding order is arbitrary. In equation (1-3), z31 and z32 represent (SiR... 31 R 32 -O) and (SiR 33 R 34 The number of -O) does not indicate the configuration. For example, (SiR) 31 R 32 -O) z31 Indicates (SiR) 31 R 32 The number of -O is z31, which does not mean (SiR) 31 R 32 -O) z31 The block configuration structure. Similarly, (SiR) 31 R 32 -O) and (SiR 33 R 34 The order in which -O is recorded does not represent the bonding order of the individual units.

[1132] For example, (SiR) 31 R 32 -O) and (SiR 33 R 34 -O) can be configured alternately, or it can be (SiR) 31 R 32 -O) and (SiR 33 R 34 -O) can be configured in a block format, or it can be undefined.

[1133] As specific examples of compounds 1-3, compounds represented by the following formulas can be listed. It should be noted that in the table below, for example, "No. 1" refers to R of formula (1-3) above. 31 R in f1 For CF3, R 31 L in2 (CH2) a (CH2) a In this context, a ranges from 0 to 20, and R... 32 Me, z31 is 3, z32 is 0, R 35 R in 1 (CH2) b (CH2) b b is 0~20, R 35 L in 1 For C(=O)NH, R 35 R in 2 (CH2) C (CH2) C C is 1-20, R 35 T in 1 For Si(OMe)3, R 35 (R) 2 -T 1 ) x1 x1 is 1, R 36 It is a compound of Me.

[1134] [Table 384]

[1135]

[1136] [Table 385]

[1137]

[1138] [Table 386]

[1139]

[1140] [Table 387]

[1141]

[1142] [Table 388]

[1143]

[1144] [Table 389]

[1145]

[1146] [Table 390]

[1147]

[1148] [Table 391]

[1149]

[1150] [Table 392]

[1151]

[1152] [Table 393]

[1153]

[1154] [Table 394]

[1155]

[1156] [Table 395]

[1157]

[1158] [Table 396]

[1159]

[1160] [Table 397]

[1161]

[1162] [Table 398]

[1163]

[1164] [Table 399]

[1165]

[1166] [Table 400]

[1167]

[1168] [Table 401]

[1169]

[1170] [Table 402]

[1171]

[1172] [Table 403]

[1173]

[1174] [Table 404]

[1175]

[1176] [Table 405]

[1177]

[1178] [Table 406]

[1179]

[1180] [Table 407]

[1181]

[1182] [Table 408]

[1183]

[1184] [Table 409]

[1185]

[1186] [Table 410]

[1187]

[1188] [Table 411]

[1189]

[1190] [Table 412]

[1191]

[1192] [Table 413]

[1193]

[1194] [Table 414]

[1195]

[1196] [Table 415]

[1197]

[1198] [Table 416]

[1199]

[1200] [Table 417]

[1201]

[1202] [Table 418]

[1203]

[1204] [Table 419]

[1205]

[1206] [Table 420]

[1207]

[1208] [Table 421]

[1209]

[1210] [Table 422]

[1211]

[1212] [Table 423]

[1213]

[1214] [Table 424]

[1215]

[1216] [Table 425]

[1217]

[1218] [Table 426]

[1219]

[1220] <Physical properties of compound 1, etc.>

[1221] The number-average molecular weight (Mn) of compound 1 is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000.

[1222] If the Mn content is above 500, the surface layer exhibits superior wear resistance. If the Mn content is below 20,000, the viscosity can be easily adjusted to an appropriate range, and the solubility is improved, resulting in excellent operability during film formation.

[1223] [Surface treatment agent]

[1224] The surface treatment agent of the present invention (hereinafter also referred to as "the surface treatment agent") contains compound 1.

[1225] This surface treatment agent is suitable for applications requiring long-term performance that does not easily decrease in water and oil repellency even after repeated rubbing of the surface layer by fingers (abrasion resistance) and the ability to easily remove fingerprints adhering to the surface layer by wiping (fingerprint stain removal), such as components constituting the finger-touch surface of touch panels, eyeglass lenses, and surface treatment agents for displays of wearable terminals.

[1226] In addition, this surface treatment agent has excellent anti-slip properties, so it is also suitable for use in glass-coated housings of portable devices such as smartphones and tablets.

[1227] This surface treatment agent is also suitable for use in antifouling or waterproof coatings.

[1228] This surface treatment agent may further contain a liquid medium. In the following description, this surface treatment agent containing a liquid medium is sometimes referred to as a coating liquid.

[1229] The coating liquid can be any liquid, including solutions and dispersions. The coating liquid only needs to contain compound 1, but may also contain byproducts or impurities generated during the manufacturing process of compound 1.

[1230] The concentration of compound 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.

[1231] As a liquid medium, an organic solvent is preferred. The organic solvent can be a fluorinated organic solvent, a non-fluorinated organic solvent, or a mixture of both.

[1232] Specific examples of fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, fluorinated alkylamines, fluorinated alcohols, and hydrofluoroolefins (HFO).

[1233] As fluoroalkanes, compounds with 4 to 8 carbon atoms are preferred. A specific example of a commercially available product is C6F... 13 H (AGC Company, ASAHIKLIN (registered trademark) AC-2000), C6F 13 C2H5 (AGC Company, ASAHIKLIN (registered trademark) AC-6000), C2F5CHFCHFCF3 (Chemours Company, Vertrel (registered trademark) XF).

[1234] Specific examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.

[1235] As fluoroalkyl ethers, compounds with 4 to 12 carbon atoms are preferred. Specific examples of commercially available products include CF3CH2OCF2CF2H (manufactured by AGC, ASAHIKLIN (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, NOVEC (registered trademark (7100)), C4F9OC2H5 (manufactured by 3M, NOVEC (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, NOVEC (registered trademark) 7300).

[1236] Specific examples of fluoroalkylamines include perfluorotripropylamine and perfluorotributylamine.

[1237] Specific examples of fluorinated alcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[1238] As a specific example of HFO, 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) (manufactured by AGC Corporation, AMORARE (registered trademark) AS-300) can be cited.

[1239] As a non-fluorinated organic solvent, compounds containing only hydrogen and carbon atoms and compounds containing only hydrogen, carbon and oxygen atoms are preferred. Examples include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and glycol organic solvents.

[1240] Specific examples of hydrocarbon-based organic solvents include pentane, hexane, heptane, octane, hexadecane, isohexane, isooctane, isononane, cycloheptane, cyclohexane, dicyclohexane, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.

[1241] Specific examples of alcohol-based organic solvents include methanol, ethanol, 1-propanol, isopropanol, n-butanol, diacetone alcohol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene diol, 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, isothiazol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, and methylcyclohexanol.

[1242] Specific examples of ketone-based 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, 3,3,5-trimethylcyclohexanone, and isophorone.

[1243] Specific examples of ether-based organic solvents include diethyl ether, cyclopentylmethyl ether, tetrahydrofuran, and 1,4-dioxane.

[1244] 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, ethylene glycol monoethyl ether acetate, and ethylene glycol monoethyl ether acetate. Diethyl ether acetate, diethylene glycol monoethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol diacetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, γ-butyrolactone, triacetin, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

[1245] Specific examples of diol-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 ... Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,3-butanediol, 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, polyethylene glycol dimethyl ether.

[1246] In addition, other organic solvents include chlorinated organic solvents, nitrogen-containing compounds, sulfur-containing compounds, and siloxane compounds.

[1247] Specific examples of chlorinated organic solvents include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, and 1,2,3-trichloropropane.

[1248] Specific examples of nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolinone.

[1249] Specific examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.

[1250] Specific examples of siloxane compounds include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.

[1251] The coating liquid preferably contains 75 to 99.999% by mass of a liquid medium, more preferably 85 to 99.99% by mass, and even more preferably 90 to 99.9% by mass.

[1252] This surface treatment agent may contain other components besides compound 1 and the liquid medium, without impairing the effects of the present invention. Examples of other components include, for instance, known additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reactions of hydrolyzable silanes.

[1253] The content of other components in this surface treatment agent is preferably 10% by mass or less, more preferably 1% by mass or less.

[1254] Other components may include compounds represented by formula (3).

[1255] [Y 1 3Y 2 -(O) s1 -Y 3 ] s2 Y 4 (Si(Y 5 ) s3 (Y 6 ) 3-s3 ) s4 …(3)

[1256] In equation (3), Y 2 It is Si, Sn or Ge,

[1257] Y 1 It is a hydrocarbon group or a trialkylsilyloxy group.

[1258] s1 is 0 or 1.

[1259] Y 3 It is an alkylene chain or a polyepoxide chain, or a combination of an alkylene chain and divalent polysiloxane residues.

[1260] Y 4 It is a linking group with a single bond or a (s2+s4) valence.

[1261] Y 5 It is a hydrocarbon group.

[1262] Y 6 It is a hydrolyzable group or hydroxyl group.

[1263] Each s3 is an independent integer from 0 to 2.

[1264] s2 and s4 are each an integer greater than or equal to 1.

[1265] Y 1 Y 2 Y 3 Y 5 and Y 6 When multiple instances exist, each independently possesses the above definition.

[1266] As compound (3), Y is preferred. 3 Compounds with alkylene chains or polyepoxide chains.

[1267] Specific examples of compound (3) include compounds (3-1) to (3-3). In formula (3-3), α is preferably 9 to 50, more preferably 11 to 30, and particularly preferably 11 to 25.

[1268]

[1269] When the other component in this surface treatment agent is compound (3), the content of compound (3) is preferably 50% by mass or less, more preferably 40% by mass or less.

[1270] The total concentration of compound 1 in the coating liquid and other components (hereinafter also referred to as "solid component 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.

[1271] The concentration of solid components in 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.

[1272] [thing]

[1273] The article of the present invention (hereinafter also referred to as "the article") has a surface layer formed by compound 1 or the surface treatment agent on the surface of the substrate.

[1274] An example of this item is illustrated with reference to the accompanying drawings. Figure 1 This is a schematic cross-sectional view showing a first article as an example of the present article. The first article is an article 20 having a substrate 12, a base layer 14 and a surface layer 22 in sequence, wherein the base layer 14 contains an oxide containing silicon and the surface layer 22 contains a condensate of compound 1.

[1275] The material and shape of the substrate 12 may be appropriately selected according to the intended use of the article 20. Examples of materials that can be used for the substrate 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may also be chemically strengthened.

[1276] In particular, as a substrate 12 requiring water and oil repellency, examples include substrates for touch panels, substrates for displays, and substrates constituting the housing of electronic devices.

[1277] The substrates for touch panels and displays are light-transmitting. "Light-transmitting" means that the visible light transmittance under vertical incidence is 25% or more according to JIS R3106:1998 (ISO 9050:1990).

[1278] Glass or transparent resin are preferred materials for the substrate of touch panels.

[1279] The substrate 12 may be a substrate on which the surface of the base layer 14 is disposed has undergone surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment. For surfaces that have undergone surface treatment, the adhesion between the substrate 12 and the base layer 14 is better, and as a result, the abrasion resistance of the surface layer 22 is further improved.

[1280] As a surface treatment, corona discharge treatment or plasma treatment is preferred from the perspective of improving the abrasion resistance of the surface layer 22.

[1281] The substrate 14 is a layer containing at least an oxide comprising silicon, and may further contain other elements. By making the substrate 14 contain silicon oxide, the T of compound 1 1 Dehydration and condensation occur, forming Si-O-Si bonds between the substrate layer 14 and the substrate layer 14, which can form a surface layer 22 with better abrasion resistance.

[1282] The silicon oxide content in the substrate 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 oxide content is at or above the lower limit of the above range, Si-O-Si bonds are sufficiently formed in the substrate layer 14, and the mechanical properties of the substrate layer 14 can be adequately ensured.

[1283] The silicon dioxide content is the remainder after subtracting the total content of other elements (in the case of oxides) from the mass of the substrate 14.

[1284] From the perspective of the durability of the surface layer 22, the oxide in the base layer 14 preferably further contains one or more elements selected from alkali metals, alkaline earth metals, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. By containing these elements, the bonding between the base layer 14 and compound 1 is strengthened, and the abrasion resistance is improved.

[1285] When the base layer 14 contains one or more selected from iron, nickel and chromium, their total content relative to silicon oxide is preferably 10 to 1,100 ppm by mass, more preferably 50 to 1,100 ppm by mass, further preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass.

[1286] When the base layer 14 contains one or more selected from aluminum and zirconium, their combined content 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.

[1287] When the base layer 14 contains alkali metal elements, their total content 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. It should be noted that lithium, sodium, potassium, rubidium, and cesium can be listed as alkali metal elements.

[1288] When the base layer 14 contains platinum group elements, their total content 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. It should be noted that platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium.

[1289] When the base layer 14 contains one or more selected from boron and phosphorus, from the perspective of the abrasion resistance of the surface layer 22, their total content, in terms of the ratio of the total molar concentration of boron and phosphorus to the molar concentration of silicon, is preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5.

[1290] When the base layer 14 contains alkaline earth metal elements, from the perspective of the abrasion resistance of the surface layer 22, the total content of these elements, measured as the ratio of the total molar concentration of alkaline earth metal elements to the molar concentration of silicon, is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2. It should be noted that examples of alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

[1291] From the perspective of improving the adhesion of this surface treatment agent and improving the water and oil repellency and abrasion resistance of the article 20, the substrate layer 14 is preferably a silicon oxide layer containing alkali metal atoms. In this 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 particularly preferably 2.0 × 10⁻⁶. 19 atoms / cm 3 That's all. On the other hand, from the perspective of fully ensuring the mechanical properties of the silicon oxide layer, the average concentration of alkali metal atoms is preferably 4.0 × 10⁻⁶. 22 atoms / cm 3 the following.

[1292] The thickness of the substrate 14 is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm. If the thickness of the substrate 14 is above the lower limit of the above range, the improved adhesion effect brought by the substrate 14 can be easily and fully obtained. If the thickness of the substrate 14 is below the upper limit of the above range, the abrasion resistance of the substrate 14 itself becomes higher.

[1293] Methods for determining the thickness of the substrate 14 include cross-sectional observation of the substrate 14 using electron microscopy (SEM, TEM, etc.), and methods using optical interferometers, spectral ellipsometers, height difference meters, etc.

[1294] As a specific example of the method for forming the base layer 14, a method for depositing a vapor-deposited material having the desired composition of the base layer 14 on the surface of the substrate 12 can be listed.

[1295] As an example of vapor deposition, vacuum vapor deposition can be cited. Vacuum vapor deposition is a method in which the vapor deposition material is evaporated in a vacuum tank and adhered to the surface of the substrate 12.

[1296] The temperature during vapor deposition (for example, the temperature of the vessel for vapor deposition when using a vacuum vapor deposition apparatus) is preferably 100 to 3,000 °C, and particularly preferably 500 to 3,000 °C.

[1297] The pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the absolute pressure inside the tank where the vapor deposition material is placed is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less).

[1298] When using vapor deposition materials to form the base layer 14, one vapor deposition material can be used, or two or more vapor deposition materials containing different elements can be used.

[1299] Examples of evaporation methods for vapor deposition materials include the resistance heating method, which melts and evaporates the material on a resistance-heated boat made of a high-melting-point metal; and the electron gun method, which directly heats the vapor deposition material by irradiating it with an electron beam, causing the surface to melt and evaporate. Among the evaporation methods for vapor deposition materials, the electron gun method is preferred because it allows for localized heating, enabling the evaporation of high-melting-point substances; the areas not irradiated by the electron beam are at low temperatures, eliminating concerns about reactions with the container; and it minimizes the introduction of impurities. As for the vapor deposition material used in the electron gun method, molten granules or sintered bodies are preferred because they are less prone to dispersion even when airflow is generated.

[1300] The surface layer 22 on the substrate layer 14 contains a condensate of compound 1. The condensate of compound 1 comprises: a condensate of silanol groups (Si-OH) formed by hydrolysis of hydrolyzable silane groups in compound 1, which then undergo intermolecular condensation to form Si-O-Si bonds; and a condensate of silanol groups in compound 1 with silanol groups or Si-OM groups (where M is an alkali metal element) on the surface of the substrate layer 14 to form Si-O-Si bonds. Alternatively, the surface layer 22 may also contain condensates of compounds other than compound 1 contained in this surface treatment agent. The surface layer 22 may contain compounds having reactive silane groups in a state where some or all of the reactive silane groups of the compound have undergone condensation.

[1301] The thickness of the surface layer 22 is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. If the thickness of the surface layer 22 is above or below the lower limit of the above range, the effect based on the surface layer 22 can be fully obtained. If the thickness of the surface layer 22 is below or below the upper limit of the above range, the utilization efficiency is high.

[1302] The thickness of surface layer 22 is obtained using an X-ray diffractometer for thin film analysis. The thickness of surface layer 22 can be calculated from the vibration period of the interference pattern of reflected X-rays obtained by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis.

[1303] As another example of the articles of the present invention, a second article may be cited.

[1304] The second article is an article 20 having a substrate 10 with a base layer and a surface layer 22 in sequence, wherein the substrate 10 with the base layer contains an oxide containing silicon and the surface layer 22 contains a condensate of compound 1.

[1305] Since the substrate 10 of the second article has the same composition as the substrate 14 in the first article, the surface layer 22 exhibits excellent abrasion resistance even when it is formed directly on the substrate 10. The material of the substrate 10 in the second article only needs to have the same composition as the substrate 14; for example, it can be a glass substrate. The details of the material of the substrate 10 are the same as those of the substrate 12 and the substrate 14, so a description is omitted here. Furthermore, the composition of the surface layer 22 is also the same as that of the first article, so a description is omitted here.

[1306] Specific examples of articles of the present invention include optical components, touch panels, anti-reflective films, anti-reflective glass, SiO2-treated glass, tempered glass, sapphire glass, quartz substrates, and mold metals used as part of the following articles.

[1307] Products: Car navigation systems, mobile phones, digital cameras, digital camcorders, portable information terminals (PDAs), portable audio players, car stereos, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical instruments (gastroscopes, etc.), photocopiers, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprinted templates, molds, etc.

[1308] [How to make the item]

[1309] The method of manufacturing the article of the present invention is a method of forming a surface layer by using compound 1 or the surface treatment agent by a dry coating method or a wet coating method.

[1310] Compound 1 and this surface treatment agent can be directly used in dry coating methods, making them suitable for forming surface layers with excellent adhesion through dry coating. Examples of dry coating methods include vacuum evaporation, CVD, and sputtering. From the perspectives of suppressing the decomposition of this surface treatment agent and the simplicity of the apparatus, vacuum evaporation is a suitable method to utilize.

[1311] In vacuum evaporation, granular materials such as compound 1 can be supported on a porous metal body made of metal materials such as iron and steel. The granular materials supported on compound 1 can be manufactured by impregnating a solution containing compound 1 in a porous metal body and then drying to remove the liquid medium.

[1312] This surface treatment agent (coating liquid) containing a liquid medium is suitable for use in wet coating methods. Examples of wet coating methods include spin coating, wipe coating, spray coating, blade coating, dip coating, mold coating, inkjet coating, flow coating, roller coating, tape casting, Langmuir-Blodgett coating, and gravure coating.

[1313] To improve the abrasion resistance of the surface layer, operations can be performed to promote the reaction between compound 1 and the substrate, as needed. Examples of such operations include heating, humidification, and light irradiation. For instance, heating the substrate on which the surface layer is formed in a humid atmosphere can promote reactions such as the hydrolysis of hydrolyzable groups, the reaction of hydroxyl groups on the substrate surface with silanol groups, and the formation of siloxane bonds based on the condensation reaction of silanol groups.

[1314] After surface treatment, compounds that are part of the surface layer and are not chemically bonded to other compounds or the substrate can be removed as needed. Specific methods include, for example, pouring solvent onto the surface layer or wiping with a cloth soaked in solvent.

[1315] Example

[1316] The present invention will be described in detail below with examples. Examples 1 to 15 are embodiments, and Example 16 is a comparative example. However, the present invention is not limited to these examples.

[1317] [Example 1]

[1318] <Synthesis of Compound X1>

[1319] Compound X1 was obtained according to the method described in International Publication No. 2021 / 054413.

[1320]

[1321] <Synthesis of Compound X2>

[1322] In a glove box, a 20 mL THF (tetrahydrofuran) solution of 1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5-trimethylcyclotrisiloxane was added to a 300 mL round-bottom flask and cooled to 0 °C. Next, a 5.0 mL hexane solution of 1.6 M lithium was added dropwise, and the mixture was stirred for 1 hour. Then, a 100 mL THF solution of 1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5-trimethylcyclotrisiloxane was added dropwise, and the mixture was stirred for 2 hours. Further, 1.7 mL of dichlorosilane was added, and the mixture was stirred for 2 hours. The solvent and low-boiling components were removed by distillation, followed by washing with 100 mL of methanol. Then, the solvent and low-boiling components were removed by distillation again, yielding 14 g of a mixture of compound X2 and compound X2'.

[1323] according to 1 H-NMR measurements confirmed that the repeating unit n=19.

[1324]

[1325] (NMR spectrum of a mixture of compounds X2 and X2')

[1326] 1 H-NMR (400MHz, CDCl3) δ: 4.72 (p, J=2.8Hz, 1H), 3.49 (d, J=5.0Hz, 1H), 2.04 (ddt, J=14.9, 10.0, 5.2Hz, 38 H), 1.41-1.23 (m, 4H), 0.89 (t, J=6.9Hz, 3H), 0.83-0.70 (m, 37H), 0.65-0.52 (m, 2H), 0.23-0.10 (m, 57H).

[1327] 19 F-NMR (376MHz, CDCl3) δ: -68.35--68.66(m), -68.77.

[1328] <Synthesis of Compound X3>

[1329] Toluene (5.0 g) and methyl undecanoate (0.90 g) were added to a mixture (5.0 g) of compounds X2 and X2'. After stirring, a toluene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 31 mg) was added, and the mixture was stirred at 25 °C for 15 minutes. Then, the mixture was washed with methanol (20 mL), and the solvent and low-boiling components were removed by distillation, thereby obtaining a mixture of compounds X3, X3', and X2' of 1.8 g.

[1330]

[1331] (NMR spectra of a mixture of compounds X3, X3', and X2')

[1332] 1 H-NMR (400MHz, CDCl3) δ: 7.35 (s, 3H), 5.11 (s, 2H), 3.47 (s, 1H), 2.40-2.30 (m, 3H), 2.03 (dq, J=15.0, 10.1Hz, 133H), 1 .64 (s, 2H), 1.37-1.24 (m, 29H), 0.89 (t, J=7.0Hz, 10H), 0.82-0.66 (m, 118H), 0.65-0.48 (m, 9H), 0.19-0.06 (m, 173H).

[1333] 19 F-NMR (376MHz, CDCl3) δ: -68.87.

[1334] <Synthesis of Compound X4>

[1335] THF (2.0 mL) and palladium-activated carbon (Pd: 5% by mass, 0.20 g) were added to a mixture (2.2 g) of compounds X3, X3', and X2', and the mixture was stirred at 25 °C for 2 hours under a hydrogen atmosphere. The mixture was then filtered through diatomaceous earth (Celite) and distilled to remove the solvent and low-boiling components, thus yielding a mixture (2.2 g) of compounds X4, X3', and X2'.

[1336]

[1337] (NMR spectrum of a mixture of compounds X4, X3' and X2')

[1338] 1 H-NMR (400MHz, CDCl3) δ: 3.48 (s, 1H), 2.35 (t, J=7.5Hz, 2H), 2.12-1.94 (m, 128H), 1.39-1.22 (m, 42H), 0.89 (t, J=7.0Hz, 8H), 0.83-0.70 (m, 98H), 0.65-0.55 (m, 5H), 0.28-0.06 (m, 157H).

[1339] 19 F-NMR (376MHz, CDCl3) δ: -68.77.

[1340] <Synthesis of Compound X5>

[1341] A mixture (2.2 g) of compounds X4, X3', and X2' was mixed with THF (2.0 mL), compound X1 (0.20 g), triethylamine (0.10 g), and propylphosphonic anhydride (cyclic trimer) (50% ethyl acetate solution, approximately 1.7 M, 0.37 g). The mixture was stirred at 25 °C for 15 hours. The mixture was then filtered through diatomaceous earth, and the solvent and low-boiling components were removed by distillation to obtain a mixture (2.2 g) of compounds X5, X3', and X2'. This mixture was subjected to rapid column chromatography using silica gel (developing solvent: ethyl acetate / hexane) to yield 0.56 g of compound X5.

[1342] according to 1 H-NMR measurements confirmed that the repeating unit n = 31 in equation (X5).

[1343]

[1344] (NMR spectrum of compound X5)

[1345] 1 H-NMR (400MHz, CDCl3) δ: 5.81 (ddt, J=16.9, 10.1, 6.6Hz, 2H), 5.31 (s, 1H), 5.05-4.83 (m, 4H), 3.18 (t, J=6.0Hz, 2H), 2.16 (t, J=7.6Hz, 2H), 2.03 (qt, J =10.2, 4.9Hz, 66H), 1.61 (t, J = 7.4Hz, 2H), 1.50-1.18 (m, 51H), 0.88 (t, J = 6 .9Hz, 3H), 0.83-0.70 (m, 62H), 0.63-0.51 (m, 4H), 0.12 (d, J=30.5Hz, 99H).

[1346] 19 F-NMR (376MHz, CDCl3) δ: -68.76.

[1347] <Synthesis of Compounds 1-2A>

[1348] Compound X5 (0.53 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 1.4 mg), and trimethoxysilane (0.12 g) were added. After stirring at 25 °C for 15 minutes, the solvent was removed by vacuum distillation to obtain 0.54 g of compound 1-2A.

[1349] according to 1 H-NMR measurements confirmed that the repeating unit n = 21 in equation (1-2A).

[1350]

[1351] (NMR spectra of compounds 1-2A)

[1352] 1 H-NMR (400MHz, CDCl3) δ: 5.31 (s, 1H), 3.57 (s, 18H), 3.18 (t, J = 6.0Hz, 2H), 2.15 (t, J = 7.6Hz, 2H), 2.02 (dq, J = 20.1, 10.0Hz, 42H), 1.62 (t, J=11.2Hz, 2H), 1.27 (m, 59H), 0.89 (t, J=6.9Hz, 3H), 0.83-0.47 (m, 50H), 0.40--0.18 (m, 69H).

[1353] 19 F-NMR (376MHz, CDCl3) δ: -68.87.

[1354] [Example 2]

[1355] <Synthesis of Compound X6>

[1356] 10-Undecenoyl chloride (5.0 g), pentafluorophenol (6.8 g), triethylamine (5.0 g), and THF (50 mL) were added, and the mixture was stirred at 25 °C for 2 hours. The solvent was removed by distillation, and rapid column chromatography using silica gel (developing solvent: dichloromethane) was performed to give 5.2 g of compound X6.

[1357]

[1358] (NMR spectrum of compound X6)

[1359] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.81 (ddt, J=16.9, 10.2, 6.7Hz, 1H), 5.11-4.84 (m, 2H), 2.66 (t, J=7.4Hz, 2H), 2.12-1.95 (m, 2H), 1.50-1.14 (m, 12H).

[1360] <Synthesis of Compound X7>

[1361] Dichloromethane (20 g) and 2,4,6,8-tetramethylcyclotetrasiloxane (1.9 g) were added to compound X6 (0.40 g). After stirring, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg) was added, and the mixture was stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by distillation, allyl pentafluorobenzene (1.2 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 9.2 mg), and dichloromethane (20 g) were added, and the mixture was stirred at 25 °C for 2 hours.

[1362] After removing the solvent and low-boiling components by distillation, compound X1 (2.3 g) and dichloromethane (20 g) were added, and the mixture was stirred at 25 °C for 4 hours. After removing the solvent by distillation, rapid column chromatography using silica gel (developing solvent: dichloromethane / ethyl acetate) was performed to obtain 0.75 g of compound X7.

[1363]

[1364] (NMR spectrum of compound X7)

[1365] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.76 (ddt, J=17.0, 10.2, 6.7Hz, 2H), 5.29 (t, J=4.7Hz, 1H), 5.12-4.78 (m, 4H), 3.13 (t, J=5.9Hz, 2H), 2.75 -2.46 (m, 6H), 2.11 (t, J=7.6Hz, 2H), 2.04-1.91 (m, 4H), 1.67-1.47 (m, 11H), 1.39-1.07 (m, 44H), 0.58-0.27 (m, 8H), 0.11--0.11 (m, 12H).

[1366] <Synthesis of Compounds 1-3A>

[1367] Dichloromethane (10 g), compound X7 (0.50 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (0.50 g) were added. After stirring at 40 °C for 2 hours, the solvent was removed by vacuum distillation to obtain 0.55 g of compound 1-3A.

[1368]

[1369] (NMR spectra of compounds 1-3A)

[1370] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.29 (t, J=4.7Hz, 1H), 3.51 (s, 18H), 3.12 (t, J=6.0Hz, 2H), 2.73-2.52 (m , 6H), 2.10 (t, J=7.6Hz, 2H), 1.66-1.46 (m, 11H), 1.19 (s, 52H), 0.68-0.31 (m, 12H), 0.11--0.11 (m, 12H).

[1371] [Example 3]

[1372] Synthesis of Compound X8

[1373] 1.0 g of 4-hydroxyphenylthiopentafluoride was dissolved in dimethyl sulfoxide (5.0 g), and potassium carbonate (1.9 g) and 4-bromo-1-butene (1.8 g) were added. After stirring at 80 °C for 16 hours, water was added, and the mixture was extracted with hexane. After removing the solvent by distillation, rapid column chromatography using silica gel (developing solvent: ethyl acetate / hexane) was performed to give 0.83 g of compound X8.

[1374]

[1375] (NMR spectrum of compound X8)

[1376] 1 H-NMR (400MHz, CDCl3) δ (ppm): 7.72-7.50 (m, 2H), 6.96-6.69 (m, 2H), 5.82 (ddt, J=17.0, 10.3, 6.7Hz, 1H), 5.20-4.94 (m, 2H), 3.98 (t, J=6.7Hz, 2H), 2.49 (qt, J=6.7, 1.4Hz, 2H).

[1377] <Synthesis of Compound X9>

[1378] Dichloromethane (20 g) and 2,4,6,8-tetramethylcyclotetrasiloxane (1.9 g) were added to compound X6 (0.25 g). After stirring, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg) was added, and the mixture was stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by distillation, compound X8 (0.80 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 9.2 mg), and dichloromethane (20 g) were added, and the mixture was stirred at 25 °C for 2 hours.

[1379] After removing the solvent and low-boiling components by distillation, compound X1 (2.3 g) and dichloromethane (20 g) were added, and the mixture was stirred at 25 °C for 4 hours. After removing the solvent by distillation, rapid column chromatography using silica gel (developing solvent: dichloromethane / ethyl acetate) was performed to obtain 0.45 g of compound X9.

[1380]

[1381] (NMR spectrum of compound X9)

[1382] 1 H-NMR (400MHz, CDCl3) δ (ppm): 7.64-7.46 (m, 6H), 6.77 (qd, J=6.5, 5.7, 2.0Hz, 6H), 5 .72 (ddt, J=16.9, 10.3, 6.7Hz, 2H), 5.29 (t, J=4.7Hz, 1H), 5.03-4.68 (m, 4H), 4.04-3. 72 (m, 6H), 3.09 (t, J=6.0Hz, 2H), 2.05 (td, J=7.9, 3.0Hz, 2H), 2.02-1.87 (m, 4H), 1.83 -1.58(m, 5H), 1.58-0.94(m, 56H), 0.46(dt, J=28.2, 8.2Hz, 8H), 0.11--0.11(m, 12H).

[1383] <Synthesis of Compounds 1-3B>

[1384] Dichloromethane (10 g), compound X9 (0.40 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (0.50 g) were added. After stirring at 40 °C for 2 hours, the solvent was removed by vacuum distillation to obtain 0.45 g of compound 1-3B.

[1385]

[1386] (NMR spectra of compounds 1-3B)

[1387] 1H-NMR (400MHz, CDCl3) δ (ppm): 7.64-7.37 (m, 6H), 6.77 (qd, J=6.3, 5.9, 2.1Hz, 6H), 5.29 (t, J=4.7Hz, 1H), 3.88 (dq, J=8.2, 6.5 Hz, 6H), 3.48 (s, 18H), 3.09 (t, J=6.0Hz, 2H), 2.13-1.91 (m, 2H), 1.75-0.87 (m, 69H), 0.67-0.31 (m, 12H), 0.11--0.11 (m, 12H).

[1388] [Example 4]

[1389] <Synthesis of Compound X10>

[1390] In a 300 mL three-necked flask equipped with a stir bar and a serpentine condenser, magnesium (2.9 g), THF (3.0 mL), and iodine (1 tablet) were added under a dry nitrogen atmosphere, and stirring was continued until the THF became colorless and transparent.

[1391] Next, 15 g of 11-bromo-1-undecene was dissolved in 100 mL of THF and added slowly, and the mixture was refluxed for 1 hour. The mixture was then allowed to return to room temperature (23 °C, and so on) to prepare the Grignard reagent.

[1392] Next, in a 300 mL three-necked flask equipped with a stir bar and a serpentine condenser, under a dry nitrogen atmosphere, 16 g of 1-iodo-4,4,4-trifluorobutane, 0.51 g of copper bromide (I), and 100 mL of THF were added, and the flask was cooled to -15 °C. The prepared Grignard reagent was slowly added dropwise while stirring. After the addition was complete, the flask was allowed to return to room temperature, and stirring continued for 24 hours.

[1393] Then add 200 mL of 2N hydrochloric acid aqueous solution and separate the layers. Extract the aqueous layer with 200 mL of ethyl acetate. Separately, combine the organic layers and add anhydrous sodium sulfate.

[1394] The organic layer was filtered and concentrated using an evaporator to obtain a crude liquid. The crude liquid was purified by silica gel column chromatography to obtain 17g of compound X10.

[1395]

[1396] (NMR spectrum of compound X10)

[1397] 1H-NMR (400MHz, CDCl3) δ: 5.84 (ddt, J=16.9, 10.2, 6.7Hz, 1H), 5.15-4.84 (m, 2H), 2.20-1.95 (m, 4H), 1.50-1.19 (m, 20H).

[1398] <Synthesis of Compound X11>

[1399] In a 10 mL pear-shaped flask equipped with a stir bar, under a dry nitrogen atmosphere, compound X10 (0.52 g) and a toluene solution of the 1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 2.65 mg) were added, and stirring was started. Then, dimethylchlorosilane (0.44 mL) was added, and stirring continued for 24 hours at room temperature to obtain a crude reaction solution.

[1400] In a 10 mL round-bottom flask equipped with a stir bar, add THF (1.0 mL), triethylamine (1.0 mL), and water (70 μL). After stirring in an ice bath, slowly add the crude reaction solution dropwise and continue stirring for 1 hour. Then, add anhydrous sodium sulfate to the crude reaction solution, filter, and concentrate the filtrate.

[1401] The crude solution was purified by column chromatography to obtain 0.55 g of compound X11.

[1402]

[1403] (NMR spectrum of compound X11)

[1404] 1H-NMR (400MHz, CDCl3) δ: 2.06-1.82 (m, 2H), 1.55-1.07 (m, 24H), 0.47 (dd, J=9.4, 6.0Hz, 2H), 0.15--0.16 (m, 6H).

[1405] <Synthesis of Compound X12>

[1406] Compound X11 (0.27 g) and THF (0.80 mL) were added to a 10 mL round-bottom flask equipped with a stirrer under a dry nitrogen atmosphere, and stirring was started in an ice bath. Next, a 1.6 mol / L n-butyllithium hexane solution (0.50 mL) was slowly added. Then, a 1.1 M THF solution of hexamethylcyclotrisiloxane (5.0 mL) was slowly added, and stirring continued for 24 hours. Finally, dichlorosilane (0.18 mL) was added, and stirring continued for 2 hours.

[1407] After stirring, the mixture was concentrated using an evaporator to obtain a concentrate. Hexane (5.0 mL) was added to the concentrate, and the mixture was washed with water (5.0 mL).

[1408] Then, anhydrous sodium sulfate was added to the organic layer, followed by filtration and concentration using an evaporator to obtain a crude liquid. The crude liquid was washed with methanol to obtain 1.1 g of compound X12. According to... 1 H-NMR measurements confirmed that the repeating unit n = 28 of formula (X12).

[1409]

[1410] (NMR spectrum of compound X12)

[1411] 1H-NMR (400MHz, CDCl3) δ: 4.63 (p, J=2.8Hz, 1H), 2.09-1.85 (m, 2H), 1.20 (d, J=12.5Hz, 22H), 0.45 (t, J=7.7Hz, 2H), 0.11 (d, J=2.8Hz, 174H).

[1412] <Synthesis of Compound X13>

[1413] In a 30 mL flask equipped with a stir bar, under a dry nitrogen atmosphere, add compound X12 (1.0 g), dichloromethane (1.4 g), compound X6 (0.19 g), and a toluene solution of 1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 5.4 mg), and stir at room temperature for 3 hours.

[1414] After stirring, the solution was concentrated using an evaporator. Then, compound X1 (0.52 g) and THF (1.0 mL) were added, and the mixture was stirred at room temperature for 4 hours. The solution was further concentrated using an evaporator to obtain a crude liquid. The crude liquid was purified by silica gel column chromatography to obtain 0.22 g of compound X13. 1 H-NMR measurements confirmed that the repeating unit n = 21 of equation (X13).

[1415]

[1416] (NMR spectrum of compound X13)

[1417] 1 H-NMR (400MHz, CDCl3) δ: 5.81 (ddt, J=16.9, 10.1, 6.6Hz, 2H), 5.36 (s, 1H), 5.07-4.82 (m, 4H), 3.18 (t, J=5.9Hz, 2H), 2.17 (t, J=7.6Hz, 2H), 2.12-1.97 (m, 6H), 1.75-1.05 (m, 71H), 0.52 (t, J=7.4Hz, 4H), 0.20--0.14 (m, 131H).

[1418] <Synthesis of Compound 1-1A>

[1419] Compound X13 (0.20 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 0.0010 mg), trimethoxysilane (0.024 g), aniline (0.78 mg), and dichloromethane (0.27 g) were added, and the mixture was stirred at room temperature under a dry nitrogen atmosphere for 2 hours. Then, the solvent was removed by vacuum distillation to give 0.21 g of compound 1-1A. According to... 1 H-NMR measurements confirmed that the repeating unit n = 22 of equation (X13).

[1420]

[1421] (NMR spectrum of compound 1-1A)

[1422] 1 H-NMR (400MHz, CDCl3) δ: 5.36 (d, J=6.0Hz, 1H), 3.56 (d, J=1.1Hz, 18H), 3.18 (t, J=5.9Hz, 2H), 2.16 (t, J=7.6H z, 2H), 2.13-1.96 (m, 2H), 1.70-1.03 (m, 77H), 0.72-0.55 (m, 4H), 0.52 (t, J=7.4Hz, 4H), 0.20--0.17 (m, 138H).

[1423] [Example 5]

[1424] <Synthesis of Compound X14>

[1425] To compound X6 (0.40 g), dichloromethane (20 g) and 2,4,6,8-tetramethylcyclotetrasiloxane (1.9 g) were added and stirred. Then, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg) was added, and the mixture was stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by distillation, a dichloromethane solution of 3,3,3-trifluoropropylene (1 M, 79 mL) and a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 9.2 mg) were added, and the mixture was stirred at 25 °C for 2 hours.

[1426] After removing the solvent and low-boiling components by distillation, compound X1 (2.3 g) and dichloromethane (20 g) were added, and the mixture was stirred at 25 °C for 4 hours. After removing the solvent by distillation, rapid column chromatography using silica gel (developing solvent: dichloromethane / ethyl acetate) was performed to obtain 0.75 g of compound X14.

[1427]

[1428] (NMR spectrum of compound X14)

[1429] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.76 (ddt, J=17.0, 10.2, 6.7Hz, 2H), 5.29 (t, J=4.7Hz, 1H), 5.12-4.78 (m, 4H), 3.13 (t, J =5.9Hz, 2H), 2.12-1.91(m, 8H), 1.67-1.47(m, 5H), 1.39-1.07(m, 48H), 0.80(m, 6H), 0.40(m, 2H), 0.11--0.11(m, 12H).

[1430] <Synthesis of Compounds 1-3C>

[1431] Dichloromethane (10 g), compound X14 (0.50 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (0.50 g) were added. After stirring at 40 °C for 2 hours, the solvent was removed by vacuum distillation to obtain 0.55 g of compound 1-3C.

[1432]

[1433] (NMR spectra of compounds 1-3C)

[1434] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.29 (t, J=4.7Hz, 1H), 3.51 (s, 18H), 3.12 (t, J=6.0Hz, 2H), 2.12-1 .91(m, 8H), 1.66-1.46(m, 5H), 1.19(s, 52H), 0.80(m, 6H), 0.68-0.31(m, 6H), 0.11--0.11(m, 12H).

[1435] [Example 6]

[1436] <Synthesis of Compound X15>

[1437] Using 1.4 g of 3-(trifluoromethoxy)prop-1-ene instead of the dichloromethane solution of 3,3,3-trifluoropropene, 0.93 g of compound X15 was obtained in the same manner as the synthesis of compound X14.

[1438]

[1439] (NMR spectrum of compound X15)

[1440] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.87-5.69 (m, 2H), 5.29 (t, J=4.7Hz, 1H), 5.15-4.88 (m, 4H), 3.63-3.59 (m, 6H), 3.07 (dd , J=6.0, 5.3Hz, 2H), 2.23-1.99(m, 6H), 1.78-1.06(m, 55H), 0.88-0.80(m, 6H), 0.80-0.73(m, 2H), 0.11--0.11(m, 12H).

[1441] <Synthesis of Compounds 1-3D>

[1442] Using compound X15 (0.93 g) instead of compound X7, 1.10 g of compound 1-3D was obtained in the same manner as the synthesis of compound 1-3A.

[1443]

[1444] (NMR spectra of compounds 1-3D)

[1445] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.29 (t, J=4.7Hz, 1H), 3.62-3.55 (m, 24H), 3.07 (dd, J=6.0, 5.3Hz, 2H), 2.20(t, J=8.4Hz, 2H), 1.80-1.06(m, 63H), 0.88-0.80(m, 6H), 0.80-0.73(m, 2H), 0.11--0.11(m, 12H).

[1446] [Example 7]

[1447] <Synthesis of Compound X16>

[1448] Using allyl (trifluoromethyl)thion (1.6 g) instead of the dichloromethane solution of 3,3,3-trifluoropropylene, the same procedure as for the synthesis of compound X14 was followed to obtain 0.84 g of compound X16.

[1449]

[1450] (NMR spectrum of compound X16)

[1451] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.88-5.61 (m, 2H), 5.39 (t, J=4.7Hz, 1H), 5.18-4.71 (m, 4H), 3.07 (t, J=5.3Hz, 2H), 2 .84-2.64(m, 6H), 2.28-1.91(m, 6H), 1.73-1.03(m, 55H), 0.96-0.80(m, 6H), 0.82-0.64(m, 2H), 0.15--0.32(m, 12H).

[1452] <Synthesis of Compounds 1-3E>

[1453] Using compound X16 (0.84 g) instead of compound X7, 0.99 g of compound 1-3E was obtained in the same manner as the synthesis of compound 1-3A.

[1454]

[1455] (NMR spectra of compounds 1-3E)

[1456] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.39 (t, J=4.7Hz, 1H), 3.58 (s, 18H), 3.07 (t, J=5.3Hz, 2H), 2.80-2.66 (m, 6 H), 2.20 (t, J=8.4Hz, 2H), 1.76-1.05 (m, 63H), 0.93-0.82 (m, 6H), 0.80-0.61 (m, 6H), 0.14--0.07 (m, 12H).

[1457] [Example 8]

[1458] <Synthesis of Compound X17>

[1459] Using N,N-bis(trifluoromethyl)prop-2-en-1-amine (2.2 g) instead of the dichloromethane solution of 3,3,3-trifluoropropene, the same procedure as for the synthesis of compound X14 was followed to obtain 1.1 g of compound X17.

[1460]

[1461] (NMR spectrum of compound X17)

[1462] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.88-5.69 (m, 2H), 5.39 (t, J=4.7Hz, 1H), 5.16-4.88 (m, 4H), 3.07 (d d, J=6.0, 5.3Hz, 2H), 2.91-2.74(m, 6H), 2.27-1.92(m, 6H), 1.87-1.06(m, 55H), 0.85-0.69(m, 8H).

[1463] <Synthesis of Compounds 1-3F>

[1464] Using compound X17 (1.1 g) instead of compound X7, 1.2 g of compound 1-3F was obtained in the same manner as the synthesis of compound 1-3A.

[1465]

[1466] (NMR spectra of compounds 1-3F)

[1467] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.39 (t, J=4.7Hz, 1H), 3.58 (s, 18H), 3.07 (dd, J=6.0, 5.3Hz, 2H), 2.88-2.75 ( m, 6H), 2.20 (t, J=8.4Hz, 2H), 1.83-1.04 (m, 63H), 0.86-0.71 (m, 8H), 0.70-0.58 (m, 4H), 0.13--0.02 (m, 12H).

[1468] [Example 9]

[1469] <2-(pentafluorine-λ) 6 Synthesis of thioalkyl)acetaldehyde

[1470] Add 2-(pentafluoro-λ) to a solution of NaClO (1.6M, 300mL) and sodium bicarbonate (10g) at room temperature. 6 2-(pentafluoro-λ)ethane-1-ol (50 g), 2,2,6,6-tetramethylpiperidine-1-oxo radical (0.46 g), potassium bromide (4.2 g), water (20 mL), and dichloromethane (338 g) were stirred for 20 minutes. Then, sodium hypochlorite (100 mL) was added, and the mixture was stirred for another 15 minutes. 2-(pentafluoro-λ) was obtained by hexane extraction and distillation purification. 6 49g of thioalkyl acetaldehyde (refer to the following formula).

[1471]

[1472] (2-(pentafluorine-λ) 6 (NMR spectrum of thioalkyl)acetaldehyde)

[1473] 1 H-NMR (400MHz, CDCl3) δ (ppm): 9.60 (ddp, J=11.0, 7.1, 1.8Hz, 1H), 4.01 (hd, J=20.1, 9.2Hz, 2H).

[1474] <allylpentafluoro-λ 6 -Synthesis of thioalkylene>

[1475] Methyltriphenylphosphonium bromide (78 g) was suspended in THF (100 mL), cooled to -78 °C, and a 1.6 M, 330 mL solution of n-butyllithium hexane was added. The mixture was heated to 0 °C, stirred for 1 hour, and then cooled again to -78 °C. 2-(pentafluoro-λ) 6 A solution of 34 g of thioalkyl acetaldehyde was dissolved in 900 mL of THF. The solution was then stirred at 0 °C for 12 hours. An aqueous solution of ammonium chloride was added, and the mixture was extracted with diethyl ether. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and then purified by distillation to obtain allyl pentafluoro-λ. 6 - Thiane (refer to the following formula) 30g.

[1476]

[1477] (allylpentafluoro-λ) 6 -NMR spectrum of thioalkyl groups

[1478] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.75-5.60 (m, 1H), 5.43-5.29 (m, 2H), 3.66 (qdt, J=20.0, 10.4, 1.5Hz, 2H).

[1479] <Synthesis of Compound X18>

[1480] Dichloromethane (20 g) and 2,4,6,8-tetramethylcyclotetrasiloxane (1.9 g) were added to compound X6 (0.40 g). After stirring, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg) was added, and the mixture was stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by distillation, allyl pentafluoro-λ was added. 6 A toluene solution of thionine (13g) and platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 9.2mg) was stirred at 25°C for 2 hours.

[1481] After removing the solvent and low-boiling components by distillation, compound X1 (2.3 g) and dichloromethane (20 g) were added, and the mixture was stirred at 25 °C for 4 hours. After removing the solvent by distillation, rapid column chromatography using silica gel (developing solvent: hexane / ethyl acetate) was performed to obtain 0.85 g of compound X18.

[1482]

[1483] (NMR spectrum of compound X18)

[1484] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.76 (ddt, J=17.0, 10.2, 6.7Hz, 2H), 5.29 (t, J=4.7Hz, 1H), 5.12-4.78 (m, 4H), 3.13 (t, J=5. 9Hz, 2H), 2.95(m, 6H), 2.12(t, 2H), 1.67-1.47(m, 7H), 1.39-1.07(m, 48H), 0.80(m, 6H), 0.40(m, 2H), 0.11--0.11(m, 12H).

[1485] <Synthesis of Compounds 1-3G>

[1486] Dichloromethane (10 g), compound X18 (0.50 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (0.50 g) were added. After stirring at 40 °C for 2 hours, the solvent was removed by vacuum distillation to obtain 0.52 g of compound 1-3G.

[1487]

[1488] (NMR spectra of compounds 1-3G)

[1489] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.29 (t, J=4.7Hz, 1H), 3.51 (s, 18H), 3.12 (t, J=6.0Hz, 2H), 2.95 (m, 6H ), 2.12(t, 2H), 1.66-1.46(m, 7H), 1.19(s, 56H), 0.80(m, 6H), 0.68-0.31(m, 6H), 0.11--0.11(m, 12H).

[1490] [Example 10]

[1491] Synthesis of (2s,3R,4s,5S)-2,3,4,5,6,7,8-heptafluorocubic-1-carboxylic acid

[1492] 14 g of (2s,3R,4s,5S)-2,3,4,5,6,7,8-heptafluorocubocarboxylic acid benzyl ester (synthesized in reference (Science, 2022, 377, 756-759.) was mixed with ethyl acetate (30 g) and palladium-activated carbon (Pd 5%, 1.0 g), and stirred at 25 °C for 2 hours under a hydrogen atmosphere. Subsequently, the mixture was filtered through diatomaceous earth, and the solvent and low-boiling components were removed by distillation, yielding 10 g of (2s,3R,4s,5S)-2,3,4,5,6,7,8-heptafluorocubocarboxylic acid.

[1493] Synthesis of <((2s,3R,4s,5S)-perfluorocubic-1-yl)methanol>

[1494] Under a nitrogen atmosphere, a THF (100 mL) solution of (2s,3R,4s,5S)-2,3,4,5,6,7,8-heptafluorocubic-1-carboxylic acid (10 g) was cooled to -15 °C, and a borane-THF solution (1 M, 40 mL) was added dropwise. The reaction mixture was then brought to room temperature and stirred for 16 hours. After the reaction, the mixture was quenched with methanol (50 mL), stirred for 30 minutes, and the solvent and low-boiling components were removed by distillation. The mixture was then subjected to rapid column chromatography using silica gel (developing solvent: dichloromethane / methanol) to obtain 9.5 g of ((2s,3R,4s,5S)-perfluorocubic-1-yl)methanol (refer to the following formula).

[1495]

[1496] (NMR spectrum of (2s,3R,4s,5S)-perfluorocubic-1-yl)methanol)

[1497] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.48 (qd, J=3.1, 1.6Hz, 2H), 3.36 (t, J=1.6Hz, 1H).

[1498] Synthesis of (2R,3s,4S,5s)-1,2,3,4,5,6,7-heptafluoro-8-vinylcubane

[1499] Replace 2-(pentafluoro-λ)methanol with ((2s,3R,4s,5S)-perfluorocubic-1-yl)methanol. 6 -thioalkyl)ethane-1-ol, except for the above-mentioned "2-(pentafluoro-λ" 6 Synthesis of thioalkyl)acetaldehyde and allyl pentafluoro-λ6 The synthesis of thioanes yielded 7.5 g of (2R,3s,4S,5s)-1,2,3,4,5,6,7-heptafluoro-8-vinyl cubane (see formula below).

[1500]

[1501] NMR spectrum of (2R,3s,4S,5s)-1,2,3,4,5,6,7-heptafluoro-8-vinylcubane)

[1502] 1 H-NMR (400MHz, CDCl3) δ (ppm): 6.37 (ddq, J=12.2, 7.1, 3.1Hz, 1H), 5.41 (dd, J=12.3, 2.2Hz, 1H), 5.31 (dd, J=7.0, 2.2Hz, 1H).

[1503] <Synthesis of Compounds 1-3H>

[1504] By replacing compound X7 with (2R,3s,4S,5s)-1,2,3,4,5,6,7-heptafluoro-8-vinyl cubane, 0.3 g of compound 1-3H was obtained in the same manner as the synthesis of compound 1-3A.

[1505]

[1506] (NMR spectra of compounds 1-3H)

[1507] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.29 (t, J=4.7Hz, 1H), 3.51 (s, 18H), 3.12 (t, J=6.0Hz, 2H), 2.54 (m, 6H ), 2.12(t, 2H), 1.66-1.46(m, 5H), 1.19(s, 56H), 0.80(m, 6H), 0.68-0.31(m, 6H), 0.11--0.11(m, 12H).

[1508] [Example 11]

[1509] <Synthesis of Compound X19>

[1510] Dichloromethane (20 g) and 2,4,6-trimethylcyclotrisiloxane (2.0 g) were added to 7.0 g of 3-(trifluoromethoxy)prop-1-ene. After stirring, a toluene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg) was added, and the mixture was stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by distillation, rapid column chromatography using silica gel (developing solvent: dichloromethane / ethyl acetate) was performed to give 5.9 g of compound X19.

[1511]

[1512] (NMR spectrum of compound X19)

[1513] 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.65-3.53 (m, 6H), 1.71 (tt, J=9.8, 8.3Hz, 6H), 0.81 (t, J=8.2Hz, 6H), 0.03 (s, 9H).

[1514] <Synthesis of Compound X20>

[1515] Under a nitrogen atmosphere, tetrahydrofuran (10 mL) was added to a three-necked flask, and n-BuLi hexane solution (1.6 M, 0.7 mL) was added dropwise at 0 °C. A THF solution of compound X19 (1.0 M, 1.1 mL) was added dropwise, and the mixture was stirred for 5 minutes. Then, a THF solution of compound X19 (1.1 M, 6.7 mL) was added dropwise over 10 minutes, and the mixture was stirred for 6 hours. Next, 11-(chloro(dimethyl)silyl)undecanoic acid (2,3,4,5,6-pentafluorophenyl) ester (0.75 g) was added, and the mixture was stirred for 1 hour. Then, compound X1 (1.7 g) was added, and the mixture was stirred for 1 hour. Hexane and deionized water were added sequentially to the reaction mixture, and the mixture was separated, with the organic layer collected. After removing the solvent and low-boiling components by vacuum distillation, the mixture was purified by rapid column chromatography on silica gel (developing solvent: hexane / ethyl acetate) to obtain 1.8 g of compound X20. The average number of repetitions of the units enclosed in parentheses in the formula was calculated based on the NMR spectra, and the result was 21.

[1516]

[1517] (NMR spectrum of compound X20)

[1518] 1H-NMR (400MHz, CDCl3) δ (ppm): 5.87-5.60 (m, 2H), 5.39 (t, J=4.7Hz, 1H), 5.18-4.88 (m, 4H), 3.63-3.49 (m, 42H), 3.07 (dd, J=6.0, 5.3H z, 2H), 2.25-1.92 (m, 6H), 1.74-1.06 (m, 99H), 0.95 (t, J=7.1Hz, 3H), 0.75 (t, J=8.4Hz, 42H), 0.72-0.61 (m, 4H), 0.08--0.16 (m, 69H).

[1519] <Synthesis of Compounds 1-2B>

[1520] Using compound X20 (1.8 g) instead of compound X7, 1.9 g of compound 1-2B was obtained in the same manner as the synthesis of compounds 1-3A. The average number of repeats of the units enclosed in parentheses in the formula was calculated from the NMR spectra, and the result was 21.

[1521]

[1522] (NMR spectra of compounds 1-2B)

[1523] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.39 (t, J=4.7Hz, 1H), 3.61-3.55 (m, 60H), 3.07 (dd, J=6.0, 5.3Hz, 2H), 2.20 (t, J=8.4Hz , 2H), 1.77-1.06 (m, 103H), 0.95 (t, J=7.1Hz, 3H), 0.75 (t, J=8.4Hz, 42H), 0.73-0.62 (m, 8H), -0.06 (d, J=72.7Hz, 69H).

[1524] [Example 12]

[1525] <Synthesis of Compound X21>

[1526] Using allyl(trifluoromethyl)thion (7.9 g) instead of 3-(trifluoromethoxy)prop-1-ene, 6.5 g of compound X21 was obtained in the same manner as the synthesis of compound X19.

[1527]

[1528] (NMR spectrum of compound X21)

[1529] 1H-NMR (400MHz, CDCl3) δ (ppm): 2.83-2.68 (m, 6H), 1.75-1.59 (m, 6H), 0.85 (t, J=7.5Hz, 6H), 0.03 (s, 9H).

[1530] <Synthesis of Compound X22>

[1531] Using a THF solution (1.0 M, 7.8 mL) of compound X21 instead of compound X19, the synthesis of compound X22 was performed in the same manner as that of compound X19, yielding 1.8 g of compound X22. The average number of repeats of the units enclosed in parentheses in the formula was calculated from the NMR spectra, and the result was 24.

[1532]

[1533] (NMR spectrum of compound X22)

[1534] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.92-5.69 (m, 2H), 5.39 (t, J=4.7Hz, 1H), 5.17-4.85 (m, 4H), 3.07 (dd, J=6.0, 5.3Hz, 2H), 2.78-2.64 (m , 48H), 2.29-1.91 (m, 6H), 1.76-1.06 (m, 101H), 0.95 (t, J=7.1Hz, 3H), 0.75 (t, J=7.7Hz, 48H), 0.71-0.59 (m, 4H), 0.08--0.26 (m, 78H).

[1535] <Synthesis of Compounds 1-2C>

[1536] Using compound X22 (2.1 g) instead of compound X7, 2.1 g of compounds 1-2C were otherwise synthesized in the same manner as compounds 1-3A. The average number of repeats of the units enclosed in parentheses in the formulas was calculated from NMR spectra and the result was 24.

[1537]

[1538] (NMR spectra of compounds 1-2C)

[1539] 1H-NMR (400MHz, CDCl3) δ (ppm): 5.39 (t, J=4.7Hz, 1H), 3.58 (s, 18H), 3.07 (dd, J=6.0, 5.3Hz, 2H), 2.78-2.65 (m, 48H), 2.20 (t , J=8.4Hz, 2H), 1.71-1.05 (m, 109H), 0.95 (t, J=7.1Hz, 3H), 0.75 (t, J=7.7Hz, 48H), 0.72-0.59 (m, 8H), 0.11--0.22 (m, 78H).

[1540] [Example 13]

[1541] <Synthesis of Compound X23>

[1542] Using N,N-bis(trifluoromethyl)prop-2-en-1-amine (11 g) instead of 3-(trifluoromethoxy)prop-1-ene, 8.0 g of compound X23 was obtained in the same manner as the synthesis of compound X19.

[1543]

[1544] (NMR spectrum of compound X23)

[1545] 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.90-2.75 (m, 6H), 1.76 (tt, J=12.7, 7.7Hz, 6H), 0.78 (t, J=7.7Hz, 6H), 0.03 (s, 9H).

[1546] <Synthesis of Compound X24>

[1547] Using a THF solution (1.0 M, 7.8 mL) of compound X23 instead of compound X19, 2.6 g of compound X24 was obtained in the same manner as the synthesis of compound X20. The average number of repeats of the units enclosed in parentheses in the formula was calculated from the NMR spectra, and the result was 22.

[1548]

[1549] (NMR spectrum of compound X24)

[1550] 1H-NMR (400MHz, CDCl3) δ (ppm): 5.89-5.67 (m, 2H), 5.39 (t, J=4.7Hz, 1H), 5.17-4.85 (m, 4H), 3.07 (dd, J=6.0, 5.3Hz, 2H), 2. 91-2.72 (m, 44H), 2.30-1.96 (m, 6H), 1.83-1.02 (m, 101H), 0.95 (t, J=7.1Hz, 3H), 0.82-0.59 (m, 48H), 0.16--0.27 (m, 72H).

[1551] <Synthesis of Compounds 1-2D>

[1552] Using compound X24 (2.6 g) instead of compound X7, 2.7 g of compound 1-2D was obtained in the same manner as the synthesis of compounds 1-3A. The average number of repeats of the units enclosed in parentheses in the formula was calculated from the NMR spectra, and the result was 22.

[1553]

[1554] (NMR spectra of compounds 1-2D)

[1555] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.39 (t, J=4.7Hz, 1H), 3.58 (s, 18H), 3.07 (dd, J=6.0, 5.3Hz, 2H), 2.89-2.74 (m, 44H), 2.20 ( t, J=8.4Hz, 2H), 1.77-1.05 (m, 105H), 0.95 (t, J=7.1Hz, 3H), 0.74 (t, J=7.9Hz, 2H), 0.70-0.61 (m, 8H), 0.07--0.23 (m, 72H).

[1556] [Example 14]

[1557] <Synthesis of Compound X25>

[1558] Dichloromethane (20 g) and 2,4,6-trimethylcyclotrisiloxane (2.0 g) were added to allyl pentafluoro-λ 6 In a thione (9.3 g), after stirring, a toluene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg) was added, and the mixture was stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by distillation, rapid column chromatography using silica gel (developing solvent: dichloromethane / ethyl acetate) was performed to give 7.7 g of compound X25.

[1559]

[1560] (NMR spectrum of compound X25)

[1561] 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.96 (ht, J=20.3, 12.0Hz, 6H), 1.70-1.57 (m, 12H), 0.99 (t, J=9.2Hz, 9H).

[1562] <Synthesis of Compound X26>

[1563] Under a nitrogen atmosphere, 10 mL of THF was added to a three-necked flask, and n-BuLi hexane solution (1.6 M, 0.7 mL) was added dropwise at 0 °C. A THF solution of compound X25 (1.0 M, 1.1 mL) was added dropwise, and the mixture was stirred for 5 minutes. Then, a THF solution of compound X25 (1.1 M, 6.7 mL) was added dropwise over 10 minutes, and the mixture was stirred for 6 hours. Next, 0.75 g of 11-(chloro(dimethyl)silyl)undecanoic acid (2,3,4,5,6-pentafluorophenyl) ester was added, and the mixture was stirred for 1 hour. Then, compound X1 (1.7 g) was added, and the mixture was stirred for 1 hour. Hexane and deionized water were added sequentially to the reaction mixture, and the organic layer was separated. After removing the solvent and low-boiling components by vacuum distillation, the mixture was purified by rapid column chromatography on silica gel (developing solvent: hexane / ethyl acetate) to obtain 2.2 g of compound X26. The average number of repetitions of the units enclosed in parentheses in the formula was calculated based on the NMR spectra, and the result was 21.

[1564]

[1565] (NMR spectrum of compound X26)

[1566] 1 H-NMR (400MHz, CDCl3) 1 H NMR (400MHz, CDCl3) δ5.81 (ddt, J=16.9, 10.1, 6.6Hz, 2H), 5.31 (s, 1H), 5.05-4.83 (m, 4H), 3.18 (t, J=6.0Hz, 2H), 2.96 (m, 42H), 2. 16 (t, J=7.6Hz, 2H), 2.03 (m, 57H), 1.50-1.18 (m, 42H), 0.88 (t, J=6.9Hz, 3H), 0.83-0.70 (m, 42H), 0.63-0.51 (m, 4H), 0.12 (m, 69H).

[1567] <Synthesis of Compounds 1-2E>

[1568] The same procedure was followed as with compounds 1-3A, and 2.1 g of compounds 1-2E were obtained from compound X26 (2.0 g).

[1569] The average number of repetitions of the units enclosed in parentheses in the formula was calculated based on the NMR spectra, and the result was 21.

[1570]

[1571] (NMR spectra of compounds 1-2E)

[1572] 1 H-NMR (400MHz, CDCl3) 1 H NMR (400MHz, CDCl3) δ5.31 (s, 1H), 3.57 (s, 18H), 3.18 (t, J=6.0Hz, 2H), 2.96 (m, 42H), 2.15 (t, J=7.6Hz, 2H), 2.0 2 (m, 55H), 1.62 (d, J=11.2Hz, 2H), 1.27 (m, 42H), 0.89 (t, J=6.9Hz, 3H), 0.83-0.47 (m, 50H), 0.40--0.18 (m, 69H).

[1573] [Example 15]

[1574] <Synthesis of Compound X27>

[1575] Dichloromethane (20 g) and 2,4,6-trimethylcyclotrisiloxane (2.0 g) were added to (2R,3s,4S,5s)-1,2,3,4,5,6,7-heptafluoro-8-vinylcubane (14 g). After stirring, a toluene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 8.3 mg) was added, and the mixture was stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by distillation, rapid column chromatography using silica gel (developing solvent: dichloromethane / ethyl acetate) was performed to give 12 g of compound X27.

[1576]

[1577] (NMR spectrum of compound X27)

[1578] 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.44 (tq, J=8.4, 3.1Hz, 6H), 1.20 (t, J=8.4Hz, 6H), 0.06 (s, 9H).

[1579] <Synthesis of Compound X28>

[1580] Under a nitrogen atmosphere, 10 mL of THF was added to a three-necked flask, and n-BuLi hexane solution (1.6 M, 0.7 mL) was added dropwise at 0 °C. A THF solution of compound X27 (1.0 M, 1.1 mL) was added dropwise, and the mixture was stirred for 5 minutes. Then, a THF solution of compound X27 (1.1 M, 6.7 mL) was added dropwise over 10 minutes, and the mixture was stirred for 6 hours. Next, 0.75 g of 11-(chloro(dimethyl)silyl)undecanoic acid (2,3,4,5,6-pentafluorophenyl) ester was added, and the mixture was stirred for 1 hour. Then, compound X1 (1.7 g) was added, and the mixture was stirred for 1 hour. Hexane and deionized water were added sequentially to the reaction mixture, and the mixture was separated, with the organic layer collected. After removing the solvent and low-boiling components by vacuum distillation, the mixture was purified by rapid column chromatography on silica gel (developing solvent: hexane / ethyl acetate) to obtain 2.5 g of compound X28. The average number of repetitions of the units enclosed in parentheses in the formula was calculated based on the NMR spectra, and the result was 21.

[1581]

[1582] (NMR spectrum of compound X28)

[1583] 1 H NMR (400MHz, CDCl3) δ5.81(ddt,J=16.9,10.1,6.6Hz,2H),5.31(s,1H),5.05-4.83(m,4H),3.18(t,J=6.0Hz,2H),2.16(t,J=7.6Hz,2H),2.03(q t,J=10.2,4.9Hz,42H),1.61(d,J=7.4Hz,2H),1.50-1.18(m,55H),0.88 (t,J=6.9Hz,3H),0.83-0.70(m,42H),0.63-0.51(m,4H),0.12(m,69H).

[1584] <Synthesis of Compounds 1-2F>

[1585] Using compound X28 (2.0 g) instead of compound X7, 1.9 g of compound 1-2F was obtained in the same manner as the synthesis of compounds 1-3A. The average number of repeats of the units enclosed in parentheses in the formula was calculated from the NMR spectra, and the result was 21.

[1586]

[1587] (NMR spectra of compounds 1-2F)

[1588] 1H NMR (400MHz, CDCl3) δ5.31(s,1H),3.57(s,18H),3.18(t,J=6.0Hz,2H),2.15(t,J=7.6Hz,2H),2.02(dq,J=20.1,10.0Hz ,42H),1.62(d,J=11.2Hz,2H),1.27(d,J=13.0Hz,59H),0.89(t,J=6.9Hz,3H),0.83-0.47(m,50H),0.40--0.18(m,69H).

[1589] [Example 16]

[1590] The octadecyltrimethoxysilane described in International Publication No. 2008 / 016029 is designated as compound C1-1.

[1591] [Item crafting]

[1592] 30g of silicon dioxide was placed as the deposition source in a copper furnace cylinder within a vacuum evaporation apparatus (Ulvac Machine Works VTR-350M). A glass substrate was placed inside the vacuum evaporation apparatus, and the air inside the apparatus was vented to 5×10⁻⁶. -3 Pressure below Pa. The furnace cylinder is heated to about 2,000°C, and silicon oxide is vacuum-deposited on the surface of the substrate to prepare a substrate with a silicon oxide layer having a thickness of about 20 nm.

[1593] A substrate with a silicon oxide layer was placed on the sample stage of a spray coating machine (API-90RS, Apeiros Co., Ltd.) with the silicon oxide layer as the surface. Next, 13g of a heptane solution containing 0.2% by mass of the compound obtained in each example was added to the syringe inside the spray coating machine, and spraying was performed at an atomization pressure of 130 kPa, a nozzle-sample surface distance of 50 mm, and a scanning speed of 300 mm / s (wet coating method). Then, the substrate with the silicon oxide layer coated with the compound was heat-treated at 140°C for 30 minutes to obtain an evaluation sample (article) with a substrate, silicon oxide layer, and surface layer sequentially stacked.

[1594] [evaluate]

[1595] The following evaluation was conducted using the obtained items. The results of the evaluation tests are shown in Table 427.

[1596] Water repellency

[1597] Approximately 2 μL of distilled water was dropped onto the surface layer of the article, and the initial water 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 5 points on the surface layer, and the average value was calculated. The water repellency of the surface layer was evaluated based on the following criteria. It should be noted that the water contact angle was calculated using the 2θ method.

[1598] A: The average water contact angle exceeds 100 degrees.

[1599] B: The average water contact angle is 80–100 degrees.

[1600] C: The average water contact angle is less than 80 degrees.

[1601] Oil-repellent properties

[1602] Approximately 2 μL of oleic acid was dropped onto the surface layer of the article, 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 5 points on the surface layer, and the average value was calculated. The oil repellency of the surface layer was evaluated based on the following evaluation criteria. It should be noted that the oil contact angle was calculated using the 2θ method.

[1603] A: The average oil contact angle exceeds 55 degrees.

[1604] B: The average oil contact angle is 40–55 degrees.

[1605] C: The average oil contact angle is less than 40 degrees.

[1606] [Table 427]

[1607]

[1608] As shown in Table 427, it was confirmed that the compounds obtained in Examples 1 to 15 can form a surface layer with excellent oil repellency.

[1609] It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2023-050546, filed on March 27, 2023, are incorporated herein as a disclosure of the specification of this invention.

[1610] Industrial availability

[1611] As an example, articles having a surface layer containing compound 1 are useful as part of components used in the following products: optical articles, touch panels, anti-reflective films, anti-reflective glass, SiO2-treated glass, tempered glass, sapphire glass, quartz substrates, mold metals, etc.

[1612] Products: Car navigation systems, mobile phones, digital cameras, digital camcorders, portable information terminals (PDAs), portable audio players, car stereos, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical instruments (gastroscopes, etc.), photocopiers, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprinted templates, molds, etc.

[1613] Explanation of reference numerals in the attached figures

[1614] 10. Substrate with a base layer

[1615] 12 Substrate

[1616] 14 Basal layer

[1617] 20 items

[1618] 22 Surface layer

Claims

1. The compound represented by the following formula (1), (R f1 -L 2 ) y1 -L 3 -R 1 -L 1 -(R 2 -T 1 ) x1 …(1) in, R f1 The selection is based on perfluoroalkyl groups, -C(X) 10 )F2、-C(X 10 -2F, -SF5, -OCF3, -SCF3, fluorovinyl, fluoroacetylene, -NX 11 X 12 Fluorine-containing groups in the group consisting of monovalent cyclic hydrocarbon groups containing fluorine atoms and monovalent heterocyclic groups containing fluorine atoms, X 10 H, Cl, Br, or I, X 11 It is a fluoroalkyl group, X 12 It is an alkyl or fluoroalkyl group. L 2 It is a single bond or a divalent linker. L 3 It consists of organopolysiloxane residues with a valence of 1+y1. R 1 It is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms and an ether-like oxygen atom. L 1 It is a single bond or a 1+x1 valence group. R 2 It is an alkylene group, or an alkylene group having an ether-like oxygen atom. T 1 It is a reactive group. y1 is an integer greater than or equal to 1. x1 is an integer from 1 to 10. There are multiple R f1 L 2 R 2 T 1 or X 10 In the case of the multiple Rs that exist f1 L 2 R 2 T 1 or X 10 Choose whether they are the same or different from each other.

2. The compound according to claim 1, wherein, The compound represented by formula (1) is the compound represented by formula (1-1) below. R f1 -L 2 -SiR 11 R 12 -O-(SiR 13 R 14 -O) z11 -SiR 15 R 16 -R 1 -L 1 -(R 2 -T 1 ) x1 …(1-1) wherein, R 11 and R 12 Each is independently an alkyl or R f1 -L 2 -, R 13 R 14 R 15 and R 16 Each is independently an alkyl group. R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1, z11 is an integer greater than or equal to 1. There are multiple R 13 R 14 R 2 、 or T 1 In the case of the multiple Rs that exist 13 R 14 R 2 、 or T 1 Choose whether they are the same or different from each other.

3. The compound according to claim 1, wherein, The compound represented by formula (1) is the same as the compound represented by formula (1-2) below. SiR 21 R 22 R 23 -O-(SiR 24 R 25 -O) z21 -(SiR 26 R 27 -O) z22 -SiR 28 R 29 -R 1 -L 1 -(R 2 -T 1 ) x1 …(1-2) in, R 21 R 22 and R 23 Each is independently an alkyl or R f1 -L 2 -, R 24 For R f1 -L 2 -, R 25 alkyl or R f1 -L 2 -, R 26 and R 27 Each is independently an alkyl group. R 28 and R 29 Each is independently an alkyl or R f1 -L 2 -, R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1, z21 is an integer greater than or equal to 1. z22 is an integer greater than or equal to 0. There are multiple R 24 R 25 R 26 R 27 R 2 、 or T 1 In the case of the multiple Rs that exist 24 R 25 R 26 R 27 R 2 、 or T 1 Choose whether they are the same or different from each other.

4. The compound according to claim 1, wherein, The compound represented by formula (1) is the same as the compound represented by formulas (1-3) below. in, R 31 For R f1 -L 2 -, R 32 alkyl or R f1 -L 2 -, R 33 and R 34 Each is independently an alkyl group. R 35 -R 1 -L 1 -(R 2 -T 1 ) x1 , R 36 It is an alkyl group. R f1 L 2 R 1 L 1 R 2 T 1 x1 and x1 are respectively related to R in equation (1) f1 L 2 R 1 L 1 R 2 T 1 The same meaning as x1, z31 is an integer greater than or equal to 1. z32 is an integer greater than or equal to 0. The sum of z31 and z32 is an integer greater than or equal to 2. There are multiple R 31 R 32 R 33 R 34 R 2 、 or T 1 In the case of the multiple Rs that exist 31 R 32 R 33 R 34 R 2 、 or T 1 Choose whether they are the same or different from each other.

5. The compound according to claim 1, wherein, The T 1 It can be any of the following groups: -Ar, -SR 10 -NOR 10 -C(=O)R 10 -N(R) 10 )2、-N + (R 10 )3X 3 -C≡N, -C(=NR) 10 )-R 10 -N + ≡N、-N=NR 10 -C(=O)OR 10 -C(=O)OX 2 -C(=O)X 4 -C(=O)OC(=O)R 10 -SO2R 10 -SO3H, -SO3X 2 -OP(=O)(-OR) 10 2. -OP (=O)(-OR) 10 (-OX) 2 -N=C=O, -SiR a1 z1 R a11 3-z1 -C(R) 10 )=C(R 10 )2、-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 in, R 10 The atom is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms optionally having a substituent, a fluoroalkyl group having 1 to 6 carbon atoms optionally having a substituent, or an aryl group having a substituent. Ar is an aryl group that is optionally substituent. X 2 They are alkali metal ions or ammonium ions. X 3 It is a halide ion. X 4 Halogen atoms, R a1 It is a hydrolyzable group or hydroxyl group. R a11 It is a hydrocarbon group. z1 is an integer from 1 to 3. There are multiple R 10 R a1 、or R a11 In the case of the multiple Rs that exist 10 R a1 、or R a11 Choose whether they are the same or different from each other.

6. The compound according to claim 5, wherein, The T 1 -SiR a1 z1 R a11 3-z1 .

7. The compound according to claim 1, wherein, The monovalent cyclic hydrocarbon group containing a fluorine atom is a group represented by the following formula (g-1), the following formula (g-2), the following formula (g-3), or the following formula (g-4). in, p1 is an integer greater than or equal to 1. p2 is an integer greater than or equal to 1. R y1 For a monovalent substituent, in R y1 In the case of fluorine atoms, p3 and p4 are both integers greater than 0 and p3 + p4 is an integer greater than 1, in R y1 In the absence of fluorine atoms, p3 is an integer greater than or equal to 1 and p4 is an integer greater than or equal to 0. R y2 For a monovalent substituent, in R y2 In the case of fluorine atoms, p5 and p6 are both integers greater than 0 and p5 + p6 is an integer greater than 1, in R y2 In the absence of fluorine atoms, p5 is an integer greater than or equal to 1 and p6 is an integer greater than or equal to 0. *For L 2 The bonding positions.

8. The compound according to claim 7, wherein, The R y1 and the R y2 The monovalent substituents mentioned herein are each independently a halogen atom other than a fluorine atom, an alkyl group, an alkenyl group, an alkoxy group, a perfluoroalkyl group, or a -C(X) group having an ether-like oxygen atom between carbon atoms. 20 )F2、-C(X 20 -2F, -SF5, -OCF3, -SCF3, fluorovinyl, fluoroacetylene, or -NX 21 X 22 , X 20 The elements are H, Cl, Br, or I, and there are multiple X. 20 In the case of the multiple X's existence 20 Choose either the same or different from each other, X 21 It is a fluoroalkyl group, X 22 It is an alkyl or fluoroalkyl group.

9. A surface treatment agent comprising the compound according to any one of claims 1 to 8.

10. The surface treatment agent according to claim 9, further comprising a liquid medium.

11. The surface treatment agent according to claim 9, wherein it is an antifouling coating agent or a waterproof coating agent.

12. An article having a surface layer formed using any one of claims 1 to 8 on the surface of a substrate.

13. The article of claim 12, wherein the surface layer is present on the surface of a component constituting a finger-touch surface of a touch panel.

14. The article according to claim 12, wherein it is an optical component.

15. A method for manufacturing an article, wherein, A surface layer is formed by dry coating using the surface treatment agent as described in claim 9.

16. A method for manufacturing an article, wherein, A surface layer is formed by wet coating using the surface treatment agent as described in claim 10.

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