polymer

Abstract

撥油性を有する重合体であって、さらに、基材との密着性の良好な重合体が提供される。【解決手段】モノマーの混合物から形成される重合体であって、前記混合物は、式(A1):CH2=C(R1)-COO-X-Si[OSi(R2)3]n[R3]3-nで表されるモノマーと式(B):CH2=C(R4)-COO-Y-RHで表されるモノマーとを含み、さらに式(C):CH2=C(R5)-COO-R6で表されるモノマーを、式(A1)で表されるモノマーと式(B)で表されるモノマーと式(C)で表されるモノマーとの合計量に対し、5mol%以下含むか、又は、式(C)を含まない、重合体。各符号は、明細書に記載のとおりである。

Description

[Technical Field]

[0001] This disclosure relates to polymers. [Background technology]

[0002] Conventionally, technologies have been studied that impart functions such as stain resistance by applying a surface treatment agent to a substrate. For example, in applications requiring high transparency, such as screen protection for mobile devices, it is desirable to treat the surface with a thin film having a thickness of one to several molecules. As surface treatment agents that can form thin films, silane coupling agents consisting of alkylsilanes, or polymers mainly composed of alkyl acrylates or alkyl methacrylates have been used (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2010 / 159338 Public Relations [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, silane coupling agents consisting of alkylsilanes, and polymers mainly composed of alkyl acrylates or alkyl methacrylates, had the drawback of having excellent water repellency but poor oil repellency.

[0005] The object of this disclosure is to provide a polymer having water-repellent and oil-repellent properties, and furthermore, a polymer with good adhesion to a substrate. [Means for solving the problem]

[0006] The following aspects are provided according to this disclosure. [1] A polymer formed from a mixture of monomers, The aforementioned mixture is Formula (A1): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3] n [R 3 3-n [where: R 1 is a hydrogen atom or a methyl group; R 2 are each independently a monovalent hydrocarbon group; R 3 are each independently a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group having 1 or more carbon atoms; n is an integer of 1 to 3.] The monomer represented by Formula (B): CH2=C(R 4 )-COO-Y-R H [where: R 4 is a hydrogen atom or a methyl group; R H is a monovalent group containing a Si atom bonded with a hydroxyl group or a hydrolyzable group; Y is a divalent organic group containing an alkylene group having 1 or more carbon atoms.] including the monomer represented by and further Formula (C): CH2=C(R 5 )-COO-R 6 [where: R 5 is a hydrogen atom or a methyl group; R 6 is a monovalent organic group not containing a Si atom.] The polymer contains the monomer represented by less than or equal to 5 mol% with respect to the total amount of the monomers represented by Formula (A1), Formula (B), and Formula (C), or does not contain the monomer represented by Formula (C). Polymer. [2] A polymer formed from a mixture of monomers, where the mixture Formula (A2): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3]2[R 3 ] [In formula: R 1 is a hydrogen atom or a methyl group; R 2 Each of these is independently a monovalent hydrocarbon group; R 3 It is a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group with one or more carbon atoms. Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H [In formula: R 4 is a hydrogen atom or a methyl group; R H This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group with one or more carbon atoms. It includes monomers represented by, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 [In formula: R 5 is a hydrogen atom or a methyl group; R 6 It is a monovalent organic group that does not contain a Si atom. A polymer that contains the monomer represented by formula (A2) in an amount of 50 mol or less relative to the total amount of the monomer represented by formula (B) and the monomer represented by formula (C), or does not contain the monomer represented by formula (C). [3] The polymer according to [1], wherein the molar ratio of the monomer represented by formula (A1) to the monomer represented by formula (B) is in the range of 9 / 1 to 4 / 6. [4] The polymer according to [2], wherein the molar ratio of the monomer represented by formula (A2) to the monomer represented by formula (B) is in the range of 9 / 1 to 4 / 6. [5] A polymer according to any one of [1] to [4], having a number-average molecular weight in the range of 1,000 to 50,000. [6] A polymer according to any one of [1] to [5], wherein the degree of dispersion is less than 2.0. [7] A polymer according to any one of [1] to [6], having a halogen atom at its terminal. [8] A surface treatment agent containing the polymer described in any one of [1] to [7]. [9] The surface treatment agent according to [8], comprising a polymerization initiator or a polymerization initiator residue.

[10] A surface treatment agent for vacuum deposition as described in [8] or [9].

[11] A surface treatment agent according to [8] or [9], for wet coating.

[12] A pellet containing one of the surface treatment agents described in [8] to

[11] .

[13] A waterproof and moisture-proof coating agent containing a polymer described in any one of [1] to [7].

[14] A waterproof and moisture-proof coating agent according to

[13] , comprising a polymerization initiator or a polymerization initiator residue.

[15] A waterproof and moisture-proof coating agent for electronic equipment, as described in

[13] or

[14] .

[16] An article comprising a base material and a layer formed on the base material from any one of the polymers described in [1] to [7].

[17] The article according to

[16] , comprising an intermediate layer containing silicon dioxide between the substrate and the layer.

[18] An article described in

[16] or

[17] , which is an optical component.

[19] The article described in

[16] or

[17] is a display.

[20] Formula (D): HalCR 7 2-COO-ZR 8 [In formula: Hal is a halogen atom; R 7 Each of these is independently either a hydrogen atom or a methyl group; R 8 It is a monovalent base; Z is a divalent organic group containing an alkylene group with one or more carbon atoms. A polymerization initiator represented by and A mixture of monomers and A method for producing a polymer formed from, The aforementioned mixture is Formula (A1): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3] n [R 3 ] 3-n [In formula: R 1 is a hydrogen atom or a methyl group; R 2 Each of these is independently a monovalent hydrocarbon group; R 3 Each of these is independently a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group with one or more carbon atoms; n is an integer between 1 and 3. Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H [In formula: R 4 is a hydrogen atom or a methyl group; R H This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group with one or more carbon atoms. It includes monomers represented by, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 [In formula: R 5 is a hydrogen atom or a methyl group; R 6 It is a monovalent organic group that does not contain a Si atom. The monomer represented by is contained in an amount of 5 mol% or less relative to the total amount of the monomer represented by formula (A1), the monomer represented by formula (B), and the monomer represented by formula (C), or the monomer represented by formula (C) is not contained. Manufacturing method. [twenty one] Formula (D): HalCR 7 2-COO-ZR 8 [In formula: Hal is a halogen atom; R 7 Each of these is independently either a hydrogen atom or a methyl group; R 8 It is a monovalent base; Z is a divalent organic group containing an alkylene group with one or more carbon atoms. A polymerization initiator represented by and A mixture of monomers and A method for producing a polymer formed from, The aforementioned mixture is Formula (A2): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3]2[R 3 ] [In formula: R 1 is a hydrogen atom or a methyl group; R 2 Each of these is independently a monovalent hydrocarbon group; R 3 It is a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group with one or more carbon atoms. Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H [In formula: R 4 is a hydrogen atom or a methyl group; R H This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group with one or more carbon atoms. It includes monomers represented by, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 [In formula: R 5 is a hydrogen atom or a methyl group; R 6 It is a monovalent organic group that does not contain a Si atom. The monomer represented by is contained in an amount of 50 mol% or less relative to the total amount of the monomer represented by formula (A2), the monomer represented by formula (B), and the monomer represented by formula (C), or the monomer represented by formula (C) is not contained. Manufacturing method. [Effects of the Invention]

[0007] According to this disclosure, a polymer having water-repellent and oil-repellent properties is provided, and furthermore, a polymer having good adhesion to a substrate is provided. [Modes for carrying out the invention]

[0008] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing one hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures. In addition, such hydrocarbon groups may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at their terminals or in their molecular chains.

[0009] In the use herein, the substituents of the "hydrocarbon group" are not particularly limited, but include, for example, halogen atoms; C, which may be substituted with one or more halogen atoms. 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0010] As used herein, "monovalent organic group" means a monovalent group containing carbon. This means that the monovalent organic group is not particularly limited, but can be a hydrocarbon group or a derivative thereof. It is possible. A hydrocarbon derivative is a hydrocarbon group with one or more hydrocarbon groups at the end or in the molecular chain. N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyl oxy This refers to a group that possesses such properties. Note that when simply referred to as "organic group," it means a monovalent organic group. Furthermore, "divalent organic group" refers to a divalent group containing carbon. Examples of the underlying mechanism include a divalent group obtained by removing one more hydrogen atom from an organic group. It can be done.

[0011] In this specification, "hydrolyzable group" means a group that can undergo hydrolysis, that is, a group that can be removed from the main skeleton of a compound by hydrolysis. Examples of hydrolyzable groups include -OR h1 , -OCOR h1 , -ON=CR h1 2. -NR h1 2, -NHR h1 , halogen (in these formulas, R h1 Examples include -OR (where - represents a substituted or unsubstituted C1-C4 alkyl group), and preferably -OR h1 (That is, an alkoxy group). h1 Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred.

[0012] <First Embodiment> [polymer] The polymer in the first embodiment is formed from a mixture of monomers, The aforementioned mixture is Formula (A1): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3] n [R 3 ] 3-n Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H Monomers represented by and Includes, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 The monomer represented by is contained in an amount of 5 mol% or less, or does not contain the monomer represented by formula (C), relative to the total amount of the monomer represented by formula (A1), the monomer represented by formula (B), and the monomer represented by formula (C).

[0013] Since the polymer has a silane coupling site where the monomer represented by formula (B) has good adhesion to a substrate such as glass, it has good adhesion to the substrate. Since the monomer represented by formula (A1) has a siloxane site, it can have high water repellency and oil repellency. Therefore, even after wiping the surface of the formed surface treatment layer with an alcohol such as ethanol, it can have high water repellency and oil repellency. In addition, the monomer represented by formula (C) may be contained in a small amount, or the monomer represented by formula (C) may not be contained.

[0014] The content of the monomer represented by formula (C) can be measured using an NMR (nuclear magnetic resonance analysis) apparatus. As the NMR apparatus, JNM-ECZ400S (manufactured by JEOL Ltd.) can be used.

[0015] [Formula (A1)] The monomer represented by the following formula: Component (A1) CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3] n [R 3 3-n

[0016] R 1 is a hydrogen atom or a methyl group. In one embodiment, R 1 is H. In one embodiment, R 1 is a methyl group.

[0017] R 2 are each independently a monovalent hydrocarbon group. The hydrocarbon group may be substituted by one or more substituents. Preferably, R 2 is unsubstituted.​

[0018] R 2 Preferably, C 1-6 It is an alkyl group, more preferably C 1-3 It is an alkyl group, and more preferably a methyl group.

[0019] R 3 Each of these is independently a monovalent hydrocarbon group. The hydrocarbon group may be substituted with one or more substituents. Preferably, R 3 It has not been replaced.

[0020] R 3 Preferably, C 1-6 It is an alkyl group, more preferably C 1-3 It is an alkyl group, and more preferably a methyl group.

[0021] n is an integer between 1 and 3. For example, n may be 1, 2, or 3. Preferably, n is 2 or 3.

[0022] X is a divalent organic group containing an alkylene group with one or more carbon atoms. The alkylene group described above may be a straight chain or a branched chain. Preferably, it may be an alkylene group having 1 to 30 carbon atoms.

[0023] In one embodiment, the alkylene group is, for example, C 1-10 Alkylene group, C 1-8 Alkylene group, C 1-6 It may be an alkylene group.

[0024] In one embodiment, the alkylene group is, for example, C 11-30It may be an alkylene group. The number of carbon atoms in such an alkylene group is preferably 12 or more, more preferably 16 or more, even more preferably 18 or more, and even more preferably 22 or more. The number of carbon atoms in the alkylene group is preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and even more preferably 24 or less. The number of carbon atoms in the alkylene group is preferably 11 to 60, more preferably 12 to 40, and even more preferably 18 to 30.

[0025] In one embodiment, X is an alkylene group having one or more carbon atoms, and further includes -CO-, -COO-, -OCO-, and -NR groups. X -, -CONR X -, -NR X CO-, -OCONR X -, -NR X COO-, -NR X -CO-NR X The group may be a divalent organic group containing -, -O-, or -S-, preferably -CO- or -NR X -, -CONR X -, -NR X CO-, -OCONR X - or -NR X COO-, futur-CONR X -, -NR X CO-, -OCONR X - or -NR X COO- R X is a hydrogen atom or C 1-6 It is an alkyl group, preferably a hydrogen atom.

[0026] X is preferably C 1-30 Alkylene group, or -(CH2) n21 -X 1 -(CH2) n31 - is

[0027] In one embodiment, X is C 1-8 It is an alkylene group, preferably C 1-6 It is an alkylene group.

[0028] In one embodiment, X is C 12-30 It is an alkylene group, preferably C 18-24 It is an alkylene group.

[0029] In one embodiment, X is -(CH2) n21 -X 1 -(CH2) n31 -. Note that -(CH2) n21 - is bonded to the -COO- group, and -(CH2) n31 -ga-Si[OSi(R 2 )3] n [R 3 ] 3-n Combine.

[0030] n21 is an integer between 0 and 30, n31 is an integer between 0 and 30, and the sum of n21 and n31 is 1 or greater.

[0031] In one embodiment, n21 is an integer between 1 and 8, preferably between 1 and 6.

[0032] In one embodiment, n21 is an integer between 12 and 30, preferably between 18 and 24.

[0033] In one embodiment, n31 is an integer between 1 and 8, preferably between 1 and 6.

[0034] In one embodiment, n31 is an integer between 12 and 30, preferably between 18 and 24.

[0035] In one embodiment, n21 is an integer between 1 and 8, and n31 is an integer between 1 and 8, preferably n21 is an integer between 1 and 6, and n31 is an integer between 1 and 6.

[0036] In one embodiment, n21 is an integer between 1 and 8, and n31 is an integer between 12 and 30, preferably n21 is an integer between 1 and 6, and n31 is an integer between 18 and 24.

[0037] In one embodiment, n21 is an integer from 12 to 30, n31 is an integer from 1 to 8. Preferably, n21 is an integer from 18 to 24, and n31 is an integer from 1 to 6.

[0038] In one embodiment, n21 is an integer from 12 to 30, n31 is an integer from 12 to 30. Preferably, n21 is an integer from 18 to 24, and n31 is an integer from​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​3 ] 3-n It is represented as follows. During the ceremony: R 1 , R 2 , R 3 And n are equivalent to the above; X 11 C 1-8 Alkylene group (preferably C 1-6 (Alkylene group) or -(CH2) n211 -X 1 -(CH2) n311 -and; X 1 This is synonymous with the above; n211 is an integer between 1 and 8, preferably between 1 and 6; n311 is an integer between 1 and 8, preferably between 1 and 6.

[0043] In one embodiment, the monomer represented by formula (A1) is formula (A1-2): CH2=C(R 1 )-COO-X 12 -Si[OSi(R 2 )3] n [R 3 ] 3-n It is represented as follows. During the ceremony: R 1 , R 2 , R 3 And n are equivalent to the above; X 12 C 12-30 Alkylene group (preferably C 18-24 (Alkylene group) or -(CH2) n212 -X 1 -(CH2) n312 -and; X 1 This is synonymous with the above; n212 is an integer between 12 and 30, preferably between 18 and 24; n312 is an integer between 12 and 30, preferably between 18 and 24.

[0044] In one embodiment, the mixture contains a monomer represented by formula (A1-1) and a monomer represented by formula (A1-2). The mixing ratio of the monomer represented by formula (A1-1) and the monomer represented by formula (A1-2) is not particularly limited, but for example, the ratio of the monomer represented by formula (A1-1) to the monomer represented by formula (A1-2) is 1:9 to 9:1 in molar ratio, specifically 3:7 to 7:3.

[0045] Examples of monomers represented by formula (A1) include: CH2=C(CH3)-COO-C3H6-Si[OSi(CH3)3]3, CH2=CH-COO-C3H6-Si[OSi(CH3)3]3, CH2=C(CH3)-COO-C4H8-Si[OSi(CH3)3]3, CH2=C(CH3)-COO-C3H6-Si[OSi(C2H5)3]3, CH2=CH-COO-C3H6-Si[OSi(C2H5)3]3, CH2=C(CH3)-COO-C4H8-Si[OSi(C2H5)3]3, CH2=C(CH3)-COO-C3H6-Si[OSi(C3H7)3]3, CH2=CH-COO-C3H6-Si[OSi(C3H7)3]3, CH2=CH-COO-C4H8-Si[OSi(C3H7)3]3, CH2=C(CH3)-COO-C 10 H 20 -Si[OSi(CH3)3]3, CH2=C(CH3)-COO-C 16 H 32 -Si[OSi(CH3)3]3, CH2=C(CH3)-COO-C 18 H 36 -Si[OSi(CH3)3]3, CH2=C(CH3)-COO-C 20 H 40 -Si[OSi(CH3)3]3, CH2=C(CH3)-COO-C 22 H 44-Si[OSi(CH3)3]3、 CH2=C(CH3)-COO-C 24 H 48 -Si[OSi(CH3)3]3、 CH2=C(CH3)-COO-C 26 H 52 -Si[OSi(CH3)3]3、 CH2=C(CH3)-COO-C 28 H 56 -Si[OSi(CH3)3]3、 CH2=C(CH3)-COO-C 30 H 60 -Si[OSi(CH3)3]3、 CH2=CH-COO-C3H6-Si[OSi(CH3)3]2[CH3]、 CH2=C(CH3)-COO-C4H8-Si[OSi(CH3)3]2[CH3]、 CH2=C(CH3)-COO-C3H6-Si[OSi(CH3)3]2[CH3]、 CH2=CH-COO-C3H6-Si[OSi(CH3)3]2[CH3]、 CH2=C(CH3)-COO-C4H8-Si[OSi(CH3)3]2[CH3]、 CH2=C(CH3)-COO-C3H6-Si[OSi(CH3)3]2[CH3]、 CH2=CH-COO-C3H6-Si[OSi(CH3)3]2[CH3]、 CH2=CH-COO-C4H8-Si[OSi(CH3)3]2[CH3]、 CH2=C(CH3)-COO-C 10 H 20 -Si[OSi(CH3)3]2[CH3]、 CH2=C(CH3)-COO-C 16 H 32 -Si[OSi(CH3)3]2[CH3]、 CH2=C(CH3)-COO-C 18 H 36 -Si[OSi(CH3)3]2[CH3]、 CH2=C(CH3)-COO-C 20 H 40-Si[OSi(CH3)3]2[CH3], CH2=C(CH3)-COO-C 22 H 44 -Si[OSi(CH3)3]2[CH3], CH2=C(CH3)-COO-C 24 H 48 -Si[OSi(CH3)3]2[CH3], CH2=C(CH3)-COO-C 26 H 52 -Si[OSi(CH3)3]2[CH3], CH2=C(CH3)-COO-C 28 H 56 -Si[OSi(CH3)3]2[CH3], CH2=C(CH3)-COO-C 30 H 60 -Si[OSi(CH3)3]2[CH3] can be mentioned.

[0046] 〔Formula (B)〕 The monomer represented by the following formula: Component (B) CH2=C(R 4 )-COO-Y-R H

[0047] R 4 is a hydrogen atom or a methyl group. In one embodiment, R 4 is H. In one embodiment, R 4 is a methyl group.

[0048] R H is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0049] R H is preferably represented by -SiR H1 n1 R H2 3-n1 . R H1 is a hydroxyl group or a hydrolyzable group. R H2 is a hydrogen atom or a monovalent organic group. RH2 R H1 It does not contain the group represented by [the specified group]. n1 is an integer between 1 and 3, preferably 2 or 3, and more preferably 3.

[0050] Y is a divalent organic group containing an alkylene group with one or more carbon atoms. The alkylene group described above may be a straight chain or a branched chain. Preferably, it may be an alkylene group having 1 to 30 carbon atoms.

[0051] In one embodiment, the alkylene group is, for example, C 1-10 Alkylene group, C 1-8 Alkylene group, or C 1-6 It may be an alkylene group.

[0052] In one embodiment, the alkylene group is, for example, C 11-30 It may be an alkylene group. The number of carbon atoms in such an alkylene group is preferably 12 or more, more preferably 16 or more, even more preferably 18 or more, and even more preferably 22 or more. The number of carbon atoms in the alkylene group is preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and even more preferably 24 or less. The number of carbon atoms in the alkylene group is preferably 11 to 60, more preferably 12 to 40, and even more preferably 18 to 30.

[0053] In one embodiment, Y is an alkylene group having 1 or more carbon atoms, and further includes -CO-, -COO-, -OCO-, and -NR X -, -CONR X -, -NR X CO-, -OCONR X -, -NR X COO-, -NR X -CO-NR X The group may be a divalent organic group containing -, -O-, or -S-, preferably -CO- or -NR X -, -CONR X -, -NR X CO-, -OCONR X- or -NR X COO-, futur-CONR X -, -NR X CO-, -OCONR X - or -NR X COO- R X is a hydrogen atom or C 1-6 It is an alkyl group, preferably a hydrogen atom.

[0054] Y is preferably C 1-30 Alkylene group, or -(CH2) n22 -Y 1 -(CH2) n32 - is

[0055] Y is, in one way, C 1-8 It is an alkylene group, preferably C 1-6 It is an alkylene group.

[0056] Y is, in one way, C 12-30 It is an alkylene group, preferably C 18-24 It is an alkylene group.

[0057] Y is, in one embodiment, -(CH2) n22 -Y 1 -(CH2) n32 -. Note that -(CH2) n22 - is bonded to the -COO- group, and -(CH2) n32 -ga-R H To bond to a base.

[0058] n22 is an integer between 0 and 30, n32 is an integer between 0 and 30, and the sum of n22 and n32 is 1 or greater.

[0059] In one embodiment, n22 is an integer between 1 and 8, preferably between 1 and 6.

[0060] In one embodiment, n22 is an integer between 12 and 30, preferably between 18 and 24.

[0061] In one embodiment, n32 is an integer between 1 and 8, preferably between 1 and 6.

[0062] In one embodiment, n32 is an integer between 12 and 30, preferably between 18 and 24.

[0063] In one embodiment, n22 is an integer between 1 and 8, and n32 is an integer between 1 and 8, preferably n22 is an integer between 1 and 6, and n32 is an integer between 1 and 6.

[0064] In one embodiment, n22 is an integer between 1 and 8, and n32 is an integer between 12 and 30, preferably n22 is an integer between 1 and 6, and n32 is an integer between 18 and 24.

[0065] In one embodiment, n22 is an integer between 12 and 30, and n32 is an integer between 1 and 8, preferably n22 is an integer between 18 and 24, and n32 is an integer between 1 and 6.

[0066] In one embodiment, n22 is an integer between 12 and 30, n32 is an integer between 12 and 30, preferably n22 is an integer between 18 and 24, and n32 is an integer between 18 and 24.

[0067] Y 1 -CO-, -NR X -, -CONR X -, -NR X CO-, -OCONR X - or -NR X COO-, preferably -CONR X -, -NR X CO-, -OCONR X -, or -NR X COO- R X is a hydrogen atom or C 1-6 It is an alkyl group, preferably a hydrogen atom.

[0068] Y is, for example, C 1-30 Alkylene, C 1-30 Alkilen-CONH-C1-30 Alkylene, C 1-30 Alkylene-NHCO-C 1-30 Alkylene, C 1-30 Alkylene-OCO-C 1-30 Alkylene, or C 1-30 Alkylene-OCONH-C 1-30 It is alkylene.

[0069] Y may be a group having the same structure as X, or a group having a different structure from X. Preferably, Y is a group having the same structure as X.

[0070] In one embodiment, the monomer represented by formula (B) is formula (B-1): CH2=C(R 4 )-COO-Y 11 -R H It is represented as follows. During the ceremony: R 4 , and R H This is synonymous with the above; Y 11 C 1-8 Alkylene group (preferably C 1-6 (Alkylene group) or -(CH2) n221 -Y 1 -(CH2) n321 -and; n221 is an integer between 1 and 8, preferably between 1 and 6; n321 is an integer between 1 and 8, preferably between 1 and 6.

[0071] In one embodiment, the monomer represented by formula (B) is formula (B-2): CH2=C(R 4 )-COO-Y 12 -R H It is represented as follows. During the ceremony: R 4 , and R H This is synonymous with the above; Y 12 C 1-8 Alkylene group (preferably C1-6 (Alkylene group) or -(CH2) n222 -Y 1 -(CH2) n322 -and; n222 is an integer between 12 and 30, preferably between 18 and 24; n322 is an integer between 12 and 30, preferably between 18 and 24.

[0072] In one embodiment, the mixture contains a monomer represented by formula (B-1) and a monomer represented by formula (B-2). The mixing ratio of the monomer represented by formula (B-1) and the monomer represented by formula (B-2) is not particularly limited, but for example, the ratio of the monomer represented by formula (B-1) to the monomer represented by formula (B-2) is 1:9 to 9:1 in molar ratio, specifically 3:7 to 7:3.

[0073] Examples of monomers represented by formula (B) include: 3-Methacryloxypropyltrimethoxysilane, 3-Acryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-Acryloxypropyltriethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane, 3-Methacryloxypropyltri(isopropexy)silane, 3-Acryloxypropyltri(isopropexy)silane, Methacryloxymethyltrimethoxysilane, Methacryloxymethylmethyldimethoxysilane, O-(methacryloxyethyl)-n-(triethoxysilylpropyl)carbamate, CH2=C(CH3)-COO-C 10 H 20 -Si(OCH3)3, CH2=C(CH3)-COO-C 16 H 32 -Si(OCH3)3, CH2=C(CH3)-COO-C 18 H 36 -Si(OCH3)3, CH2=C(CH3)-COO-C 20 H 40 -Si(OCH3)3, CH2=C(CH3)-COO-C 22 H 44 -Si(OCH3)3, CH2=C(CH3)-COO-C 24 H 48 -Si(OCH3)3, CH2=C(CH3)-COO-C 26 H 52 -Si(OCH3)3, CH2=C(CH3)-COO-C 28 H 56 -Si(OCH3)3, CH2=C(CH3)-COO-C 30 H 60 -Si(OCH3)3 One could list these:

[0074] In one embodiment, the polymer comprises a monomer represented by formula (A1-1) and a monomer represented by formula (B-1).

[0075] In one embodiment, the polymer comprises a monomer represented by formula (A1-1) and a monomer represented by formula (B-2).

[0076] In one embodiment, the polymer comprises a monomer represented by formula (A1-2) and a monomer represented by formula (B-1).

[0077] In one embodiment, the polymer comprises a monomer represented by formula (A1-2) and a monomer represented by formula (B-2).

[0078] In one embodiment, the polymer comprises a monomer represented by formula (A1-1), a monomer represented by formula (A1-2), and a monomer represented by formula (B-1).

[0079] In one embodiment, the polymer comprises a monomer represented by formula (A1-1), a monomer represented by formula (A1-2), and a monomer represented by formula (B-2).

[0080] In one embodiment, the polymer comprises a monomer represented by formula (A1-1), a monomer represented by formula (B-1), and a monomer represented by formula (B-2).

[0081] In one embodiment, the polymer comprises a monomer represented by formula (A1-2), a monomer represented by formula (B-1), and a monomer represented by formula (B-2).

[0082] In one embodiment, the polymer comprises a monomer represented by formula (A1-1) and a monomer represented by formula (A1-2), and a monomer represented by formula (B-1) and a monomer represented by formula (B-2).

[0083] The molar ratio of the monomer represented by formula (A1) to the monomer represented by formula (B) is preferably in the range of 9 / 1 to 4 / 6, and more preferably in the range of 7 / 3 to 5 / 5. With the above configuration, the layer formed from the polymer (e.g., a surface treatment layer) has high water and oil repellency while also having good adhesion to a substrate such as glass.

[0084] [Formula (C)] Monomer represented by the following formula: Component (C) CH2=C(R 5 )-COO-R 6

[0085] R 5 is a hydrogen atom or a methyl group. In one embodiment, R 5 is a hydrogen atom. In one embodiment, R 5 This is a methyl group.

[0086] R 6 is a monovalent organic group that does not contain a Si atom and may be substituted with one or more substituents. Preferably, R 6 It has not been replaced.

[0087] R 6 The monovalent organic group is preferably C 1-30 It is an alkyl group. The alkyl group may be linear or branched, and is preferably linear.

[0088] In one embodiment, R 6 is C 1-8 It is an alkyl group, preferably C 1-6 It is an alkyl group.

[0089] In one embodiment, R 6 is C 12-30 It is an alkyl group, preferably C 18-24 It is an alkyl group.

[0090] In one embodiment, the monomer represented by formula (C) is formula (C-1): CH2=C(R 5 )-COO-R 61 It is represented as follows. During the ceremony: R 5 This is synonymous with the above; R 61 C 1-8 It is an alkyl group, preferably C 1-6 It is an alkyl group.

[0091] In one embodiment, the monomer represented by formula (C) is formula (C-2): CH2=C(R 5 )-COO-R 62 It is represented as follows. During the ceremony: R 5 This is synonymous with the above; R 62 C 12-30 It is an alkyl group, preferably C 18-24 It is an alkyl group.

[0092] In one embodiment, the mixture contains a monomer represented by formula (C-1) and a monomer represented by formula (C-2). The mixing ratio of the monomer represented by formula (C-1) and the monomer represented by formula (C-2) is not particularly limited, but for example, the ratio of the monomer represented by formula (C-1) to the monomer represented by formula (C-2) is 1:9 to 9:1 in molar ratio, specifically 3:7 to 7:3.

[0093] Examples of monomers represented by formula (C) include: Methyl methacrylate, Methyl acrylate, Ethyl methacrylate, Ethyl acrylate, Butyl methacrylate, Butyl acrylate, 2-(dimethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl methacrylate, 3-(dimethylamino)propyl acrylate, 2-(diethylamino)ethyl methacrylate, 2-(diethylamino)ethyl acrylate, CH2=C(CH3)-COO-C 10 H 21 , CH2=C(CH3)-COO-C 16 H 33 , CH2=C(CH3)-COO-C 18 H 37 , CH2=C(CH3)-COO-C 20 H 41 , CH2=C(CH3)-COO-C 22 H 45 , CH2=C(CH3)-COO-C 24 H 49 , CH2=C(CH3)-COO-C 26 H 53 , CH2=C(CH3)-COO-C 28 H 57 , CH2=C(CH3)-COO-C 30 H 61 One could list these:

[0094] The monomer represented by formula (C) is preferably present in an amount of 3 mol% or less, or the monomer represented by formula (C) is not present, more preferably 1 mol% or less, or the monomer represented by formula (C) is not present, relative to the total amount of the monomer represented by formula (A1), the monomer represented by formula (B), and the monomer represented by formula (C).

[0095] In one embodiment, the monomer represented by formula (C) is preferably present in an amount of 3 mol% or less, more preferably 1 mol% or less, relative to the total amount of the monomer represented by formula (A1), the monomer represented by formula (B), and the monomer represented by formula (C). The lower limit of the content of the monomer represented by formula (C) is not particularly limited, but for example, it is 0.1 mol% or more, relative to the total amount of the monomer represented by formula (A1), the monomer represented by formula (B), and the monomer represented by formula (C).

[0096] In one embodiment, the monomer represented by formula (C) is not included.

[0097] In one embodiment, R 1 , R 4 and R 5 This is CH3.

[0098] The polymer may also contain other groups. These other groups are not particularly limited, but include groups derived from polymerization initiators. Polymerization initiators will be discussed later.

[0099] The monomer mixture may further contain other compounds. These other compounds are not particularly limited, but may include, for example, polymerization initiators or polymerization initiator residues.

[0100] The number-average molecular weight of the polymer is preferably in the range of 1,000 to 50,000, more preferably in the range of 1,000 to 20,000, and even more preferably in the range of 1,000 to 10,000, for example, in the range of 1,000 to 8,000, specifically in the range of 1,000 to 6,000. The number-average molecular weight can be measured using gel permeation chromatography (GPC). A 1260 Infinity II (manufactured by Agilent) can be used as the GPC.

[0101] The degree of dispersion of the polymer is preferably less than 2.0, more preferably 1.8 or less, and even more preferably 1.65 or less. The lower limit of the degree of dispersion is, for example, 1.0 or more. Here, the degree of dispersion refers to the Mw / Mn value when the polymer has a weight-average molecular weight Mn and a number-average molecular weight Mw. The degree of dispersion can be measured using GPC.

[0102] Preferably, the molecule has a halogen atom at its terminal end. The halogen atom is preferably F, Cl, Br, or I, more preferably Cl, Br, and even more preferably Br.

[0103] [Manufacturing method] The above polymer can be produced as follows. Formula (D): HalCR 7 2-COO-ZR 8 A polymerization initiator represented by and A mixture of monomers and A method for producing a polymer formed from, The aforementioned mixture is Formula (A1): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3] n [R 3 ] 3-n Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H It includes monomers represented by, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 The monomer represented by formula (A1), is present in an amount of 5 mol% or less relative to the total amount of monomers represented by formula (A1), formula (B), and formula (C), or the monomer represented by formula (C) is not present.

[0104] R 1 X, R 2 , R 3 , n, R 4 , Y, R H , R 5 and R 6 These terms are equivalent to the above.

[0105] [Formula (D)] Hal is a halogen atom. The halogen atom is preferably F, Cl, Br, or I, more preferably Cl or Br, and even more preferably Br. Hal may be the same atom as the halogen atom present at the ends of the polymer.

[0106] R 7 Each is independently a hydrogen atom or a methyl group. In one embodiment, R 7 is a hydrogen atom. In one embodiment, R 7 This is a methyl group.

[0107] R 8 It is a monovalent group.

[0108] R 8 For example, -R h3 Or it is a hydrogen atom.

[0109] In one embodiment, R 8 is, -R h3 It is a monovalent group containing, for example, a monovalent group containing a Si atom to which a hydrolyzable group is bonded.

[0110] In one embodiment, R 8 This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded, for example, -SiR 81 m R 82 3-m It is represented as follows.

[0111] R 81 This is a hydroxyl group or a hydrolyzable group.

[0112] R 82 is a hydrogen atom or a monovalent organic group, preferably a monovalent organic group. The monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 It is an alkyl group, and more preferably C 1-3 It is an alkyl group.

[0113] m is an integer between 1 and 3. For example, m may be 1, 2, or 3. Preferably, m is 3.

[0114] Z is a divalent organic group containing an alkylene group with one or more carbon atoms. The alkylene group described above may be a straight chain or a branched chain. Preferably, it may be an alkylene group having 1 to 30 carbon atoms.

[0115] In one embodiment, the alkylene group is, for example, C 1-10 Alkylene group, C 1-8 Alkylene group, C 1-6 It may be an alkylene group.

[0116] In one embodiment, the alkylene group is, for example, C 11-30It may be an alkylene group. The number of carbon atoms in such an alkylene group is preferably 12 or more, more preferably 16 or more, even more preferably 18 or more, and even more preferably 22 or more. The number of carbon atoms in the alkylene group is preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and even more preferably 24 or less. The number of carbon atoms in the alkylene group is preferably 11 to 60, more preferably 12 to 40, and even more preferably 18 to 30.

[0117] In one embodiment, Z is an alkylene group having one or more carbon atoms, and further includes -CO-, -COO-, -OCO-, and -NR. X -, -CONR X -, -NR X CO-, -OCONR X -, -NR X COO-, -NR X -CO-NR X The group may be a divalent organic group containing -, -O-, or -S-, preferably -CO- or -NR X -, -CONR X -, -NR X CO-, -OCONR X - or -NR X COO-, futur-CONR X -, -NR X CO-, -OCONR X - or -NR X COO- R X is a hydrogen atom or C 1-6 It is an alkyl group, preferably a hydrogen atom.

[0118] Z is preferably C 1-30 Alkylene group, or -(CH2) n23 -Z 1 -(CH2) n33 - is

[0119] In one embodiment, Z is C 1-8 It is an alkylene group, preferably C 1-6 It is an alkylene group.

[0120] In one embodiment, Z is C 12-30 It is an alkylene group, preferably C 18-24 It is an alkylene group.

[0121] In one embodiment, Z is -(CH2) n23 -Z 1 -(CH2) n33 -. Note that -(CH2) n23 - is bonded to the -COO- group, and -(CH2) n33 -ga-R 8 Combine.

[0122] n23 is an integer between 0 and 30, n33 is an integer between 0 and 30, and the sum of n23 and n33 is 1 or greater.

[0123] In one embodiment, n23 is an integer between 1 and 8, preferably an integer between 1 and 6.

[0124] In one embodiment, n23 is an integer between 12 and 30, preferably between 18 and 24.

[0125] In one embodiment, n33 is an integer between 1 and 8, preferably an integer between 1 and 6.

[0126] In one embodiment, n33 is an integer between 12 and 30, preferably between 18 and 24.

[0127] In one embodiment, n23 is an integer between 1 and 8, and n33 is an integer between 1 and 8, preferably n23 is an integer between 1 and 6, and n33 is an integer between 1 and 6.

[0128] In one embodiment, n23 is an integer between 1 and 8, and n33 is an integer between 12 and 30, preferably n23 is an integer between 1 and 6, and n33 is an integer between 18 and 24.

[0129] In one embodiment, n23 is an integer between 12 and 30, n33 is an integer between 1 and 8, preferably n23 is an integer between 18 and 24, and n33 is an integer between 1 and 6.

[0130] In one embodiment, n23 is an integer between 12 and 30, n33 is an integer between 12 and 30, preferably n23 is an integer between 18 and 24, and n33 is an integer between 18 and 24.

[0131] Z 1 -CO-, -NR X -, -CONR X -, -NR X CO-, -OCONR X - or -NR X COO-, preferably -CONR X -, -NR X CO-, -OCONR X -, or -NR X COO- R X is a hydrogen atom or C 1-6 It is an alkyl group, preferably a hydrogen atom.

[0132] Z is, for example, C 1-30 Alkylene, C 1-30 Alkilen-CONH-C 1-30 Alkylene, C 1-30 Alkylene-NHCO-C 1-30 Alkylene, C 1-30 Alkylene-OCO-C 1-30 Alkylene, or C 1-30 Alkylene-OCONH-C 1-30 It is alkylene.

[0133] Z may be a group having the same structure as X, or a group having a different structure from X. Preferably, Z is a group having the same structure as X.

[0134] Z may be a group having the same structure as Y, or a group having a different structure from Y. Preferably, Z is a group having the same structure as Y.

[0135] Examples of the polymerization initiators mentioned above include 3-(trimethoxysilyl)propyl 2-bromo-2-methylpropanoate, 3-(triethoxysilyl)propyl 2-bromo-2-methylpropanoate, ethyl 2-bromoisobutyrate, dodecyl 2-bromoisobutyrate, octadecyl 2-bromoisobutyrate, 10-undecenyl 2-bromoisobutyrate, 2-hydroxyethyl 2-bromo-2-methylpropanoate, 11-mercaptoundecyl 2-bromo-2-methylpropanoate, and [11-(2-bromo-2-methylpropanoyl)oxyundecyl]phosphonic acid.

[0136] The above manufacturing method may involve the following steps, for example. ·Process I Formula (D): HalCR 7 2-COO-ZR 8 A step of adding a polymerization initiator represented by to a mixture of monomers, The aforementioned mixture is Formula (A1): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3] n [R 3 ] 3-n Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H Monomers represented by and Includes, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 The monomer represented by formula (A1), formula (B), and formula (C) is present in an amount of 5 mol% or less relative to the total amount of monomers represented by formula (A1), formula (B), and formula (C), or the monomer represented by formula (C) is not present. Radical polymerization is carried out to produce a polymer.

[0137] Equations (D), (A1), (B), and (C) are equivalent to those above. 1 X, R 2 , n, R 3 , R 4 , Y, R H , R 5 , R 6 Hal, R 7 , Z, and R 8 These terms are equivalent to the above.

[0138] The mixing order of the polymerization initiator represented by formula (D), and the monomers represented by formulas (A1), (B), and (C) is not particularly limited. For example, the compounds represented by formulas (A1), (B), and (C) may be added to the compound represented by formula (D), the compound represented by formula (D) may be added to the compounds represented by formulas (A1), (B), and (C), or the compounds represented by formulas (A1), (B), (C), and (D) may be added without any particular order being specified.

[0139] Preferably, polymerization is carried out under an inert gas atmosphere.

[0140] Preferably, a catalyst is added to the mixture.

[0141] As a catalyst, a metal salt and a ligand can be added. Examples of metal salts include copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, titanium(II) chloride, titanium(III) chloride, titanium(IV) chloride, titanium(IV) bromide, iron(II) chloride, iron(III) chloride, iron(II) bromide, iron(III) bromide, cobalt(II) chloride, cobalt(II) bromide, nickel(II) chloride, nickel(II) bromide, molybdenum(III) chloride, molybdenum(V) chloride, and ruthenium(III) chloride. Ligands include 2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-di-t-butyl-2,2'-bipyridyl, 4,4'-dinonyl-2,2'-bipyridyl, N-butyl-2-pyridylmethanymine, N-octyl-2-pyridylmethanymine, N-dodecyl-N-(2-pyridylmethylene)amine, N-octadecyl-N-(2-pyridylmethylene)amine, and N,N,N',N'',N'''-pentame Examples include trildiethylenetriamine, tris(2-pyridylmethyl)amine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, tris(2-dimethylaminoethyl)amine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, and N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine.

[0142] The ligands can be added in an amount sufficient to coordinate with the metal salt. The ratio of the metal salt to the ligands is not particularly limited, but can be in the range of 1:2 to 1:10 in molar ratio.

[0143] Preferably, the catalyst is copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-di-t-butyl-2,2'-bipyridyl, 4,4'-dinonyl-2,2'-bipyridyl, N,N,N',N'',N'''-pentamethyldiethylenetriamine, tris(2-pyridylmethyl)amine, and / or tris(2-dimethylaminoethyl)amine.

[0144] Step I is not particularly limited, but can be carried out at, for example, 20 to 80°C.

[0145] Process I can be carried out, for example, in 6 to 120 hours.

[0146] Step I described above may be carried out in a solvent.

[0147] The solvent is not particularly limited as long as the monomers and polymers are dissolved, but examples include: aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha, and anisole; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, and ethyl pyruvate. Esters such as ethyl-2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ethyl Glycol ethers such as methyl glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; and diethylene glycol monoethyl ether acetate.Polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F); 13 CH2CH3 (for example, Asahi Clean® AC-6000 manufactured by Asahi Glass Co., Ltd.), C6F 13H (for example, AsahiClean® AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeolora® H manufactured by Nippon Zeon Co., Ltd.); fluorinated hydrocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), and 1,3-bis(trifluoromethyl)benzene; CF3CH2OH, CF3 Fluorine-containing alcohols such as CF2CH2OH and (CF3)2CHOH; hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Co., Ltd.), perfluoro Alkyl perfluoroalkyl ethers such as o-lohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF3CH=CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.) Examples include ethers such as CHF2CF=CHCl (for example, AMOLEA® AS-300 manufactured by Asahi Glass Co., Ltd.), cyclopentyl methyl ether; siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane; and dimethyl sulfoxides.Alternatively, a mixture of two or more of these solvents may be used, preferably toluene, anisole, tetrahydrofuran, N,N-dimethylformamide, etc.

[0148] The upper limit of the polymer content is not particularly limited, but is, for example, 90% by weight or less. The lower limit of the polymer content is not particularly limited, but is, for example, 10% by mass or more. The polymer is preferably contained in the solvent in the range of 30 to 70% by mass, and more preferably in the range of 40 to 60% by mass.

[0149] Step I described above may further include a reducing agent.

[0150] Examples of reducing agents include tin(II) 2-ethylhexanoate, ascorbic acid, glucose, and hydrazine.

[0151] Preferably, at least one of tin(II) 2-ethylhexanoate and ascorbic acid is used as the reducing agent, and more preferably, tin(II) 2-ethylhexanoate or ascorbic acid is used.

[0152] [Surface treatment agent] The above polymer may also be used as a surface treatment agent.

[0153] The surface treatment agent may further contain a polymerization initiator or a polymerization initiator residue. As the polymerization initiator, a compound represented by the above formula (D) may be used.

[0154] Polymerization initiator residues are compounds formed after the polymerization-initiating groups are eliminated. For example, polymerization initiator residues include CH2=CR 7 -COO-ZR 8 That is. R 7 , Z, and R 8 This is synonymous with the above.

[0155] The surface treatment agent may further contain a solvent, catalyst, reducing agent, surfactant, polymerization inhibitor, sensitizer, etc.

[0156] The solvent is not particularly limited as long as the polymer is dissolved, but examples include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl-2-hydro Esters such as xybutyrate, ethyl acetacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, prop Glycol ethers such as ethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; and diethylene glycol monoethyl ether acetate.Polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F); 13 CH2CH3 (for example, Asahi Clean® AC-6000 manufactured by Asahi Glass Co., Ltd.), C6F 13H (for example, AsahiClean® AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeolora® H manufactured by Nippon Zeon Co., Ltd.); fluorinated hydrocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), and 1,3-bis(trifluoromethyl)benzene; CF3CH2OH, CF3 Fluorine-containing alcohols such as CF2CH2OH and (CF3)2CHOH; hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Co., Ltd.), perfluoro Alkyl perfluoroalkyl ethers such as o-lohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF3CH=CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.) Examples include ethers such as ), CHF2CF=CHCl (for example, AMOLEA® AS-300 manufactured by Asahi Glass Co., Ltd.), and cyclopentyl methyl ether; siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane; and dimethyl sulfoxides. Alternatively, mixed solvents of two or more of these are also possible.Among these, aliphatic hydrocarbons, esters, glycol ethers, alcohols, ether alcohols, and siloxanes are preferred. For example, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, diethylene glycol monomethyl ether, hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octamethylcyclotetrasiloxane, and octamethylcyclopentasiloxane are preferred. The solvent may be the same type as the solvent used in the production of the polymer.

[0157] The upper limit of the polymer content is not particularly limited, but is, for example, 50% by weight or less. The lower limit of the polymer content is not particularly limited, but is, for example, 0.1% by mass or more. The polymer is preferably contained in the solvent in the range of 0.1 to 50% by mass, more preferably in the range of 1 to 30% by mass, and even more preferably in the range of 10 to 20% by mass.

[0158] The above-mentioned surface treatment agent can impart water repellency, oil repellency, stain resistance, surface slipperiness, and friction resistance to the substrate. That is, a surface treatment layer can be formed on the substrate using the surface treatment agent. Furthermore, the surface treatment layer may be a laminate of multiple surface treatment films. The substrate used here will be described later.

[0159] [pellet] The surface treatment agent disclosed herein can be formed into pellets by impregnating porous materials, such as porous ceramic materials, or metal fibers, such as steel wool compressed into a cotton-like form. These pellets can be used, for example, in vacuum deposition.

[0160] [Waterproofing and / or moisture-proofing coating agent] The above polymer may be used as a coating agent for waterproofing and / or moisture-proofing, specifically as a coating agent for waterproofing and moisture-proofing.

[0161] The above coating agent may further contain a polymerization initiator or a polymerization initiator residue. As the polymerization initiator, a compound represented by formula (D) above may be used.

[0162] The polymerization initiator residue is equivalent to the above.

[0163] The above coating agent may further contain a solvent, catalyst, reducing agent, surfactant, polymerization inhibitor, sensitizer, etc. The solvent is the same as that used in surface treatment agents.

[0164] The upper limit of the polymer content is not particularly limited, but is, for example, 50% by weight or less. The lower limit of the polymer content is not particularly limited, but is, for example, 0.1% by mass or more. The polymer is preferably contained in the solvent in the range of 0.1 to 50% by mass, more preferably in the range of 1 to 30% by mass, and even more preferably in the range of 10 to 20% by mass.

[0165] The above-mentioned coating agent is, for example, a coating agent for electronic equipment. That is, the above-mentioned coating agent is used to waterproof and / or moisture-proof the surface of electronic equipment. Furthermore, the above-mentioned coating agent can also be used as an antifouling coating agent.

[0166] [Goods] The articles of this disclosure include a layer or film formed from a composition (e.g., a surface treatment agent, a waterproofing and / or moisture-proofing coating agent). That is, the articles of this disclosure include an object to be treated and a layer or film formed from the polymer of this disclosure on the surface of the object to be treated. The layer or film may cover the entire object to be treated or only a part of it.

[0167] [Use as a surface treatment agent] In one embodiment, the article of the present disclosure includes a layer formed from the surface treatment agent. That is, the article of this embodiment includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from a surface treatment agent containing the polymer of the present disclosure.

[0168] The substrates usable in this embodiment may consist of any suitable material, such as glass, resin (natural or synthetic resin, such as a common plastic material, which may be in the form of a sheet, film, or other), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (textile, nonwoven fabric, etc.), fur, leather, wood, ceramics, stone, building materials, etc.

[0169] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate may be an optical component material, such as glass or transparent plastic. Also, if the article to be manufactured is an optical component, some layer (or film), such as a hard coat layer or an anti-reflective layer, may be formed on the surface (outermost layer) of the substrate. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. Examples of inorganic materials that can be used for the anti-reflective layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials may be used individually or in combination of two or more (for example, as a mixture). When a multi-layer anti-reflective layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. If the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on a portion of the surface of the substrate (glass). Furthermore, depending on its specific specifications, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module.

[0170] The shape of the substrate is not particularly limited. Furthermore, the surface area of ​​the substrate on which the surface treatment layer is to be formed only needs to be at least a part of the substrate surface and can be appropriately determined according to the intended use and specific specifications of the article to be manufactured.

[0171] Such a substrate may consist of a material that originally contains hydroxyl groups, at least on its surface. Examples of such materials include glass, as well as metals (especially base metals) on which a native oxide film or thermal oxide film is formed on the surface, ceramics, semiconductors, etc. Alternatively, if the material does not have enough hydroxyl groups, such as resins, or if it does not originally contain hydroxyl groups, the substrate can be pretreated to introduce or increase hydroxyl groups on its surface. Examples of such pretreatment include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface and can also be suitably used to clean the substrate surface (remove foreign matter, etc.). Another example of such pretreatment is a method in which an interfacial adsorbent having carbon-carbon unsaturated bond groups is formed in the form of a monolayer on the substrate surface by the LB method (Langmuir-Bludget method) or chemical adsorption method, and then the unsaturated bonds are cleaved in an atmosphere containing oxygen or nitrogen.

[0172] Alternatively, such a substrate may consist of a material in which at least its surface portion is made of another reactive group, such as a silicone compound having one or more Si-H groups, or an alkoxysilane.

[0173] Next, a layer formed from the surface treatment agent of the present disclosure is provided on the surface of the substrate, and this layer is post-treated as necessary, thereby forming a layer from the surface treatment agent of the present disclosure.

[0174] The layer formation of the surface treatment agent in this embodiment can be carried out by applying the above-mentioned surface treatment agent to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

[0175] Examples of wet coating methods include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and similar methods.

[0176] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum deposition) include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0177] Furthermore, coating using the atmospheric pressure plasma method is also possible.

[0178] When using a wet coating method, the surface treatment agents of the present disclosure may be diluted with a solvent before being applied to the substrate surface. From the viewpoint of the stability of the surface treatment agents of the present disclosure and the volatility of the solvent, the following solvents are preferably used: aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, and methyl acetate. Esters such as rubitol, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cello Glycol ethers such as solv, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone;Ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F); 13 CH2CH3 (for example, Asahi Clean® AC-6000 manufactured by Asahi Glass Co., Ltd.), C6F 13H (for example, AsahiClean® AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeolora® H manufactured by Nippon Zeon Co., Ltd.); fluorinated hydrocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), and 1,3-bis(trifluoromethyl)benzene; CF3CH2OH, C Fluorine-containing alcohols such as F3CF2CH2OH and (CF3)2CHOH; hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Co., Ltd.), Alkyl perfluoroalkyl ethers such as perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., AsahiClean® AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF3CH=CHCl (e.g., CELEFIN® manufactured by Central Glass Co., Ltd.) Ethers such as 1233Z), CHF2CF=CHCl (e.g., AMOLEA® AS-300 manufactured by Asahi Glass Co., Ltd.), and cyclopentyl methyl ether; siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane; and dimethyl sulfoxides. These solvents can be used individually or as mixtures of two or more.Among these, aliphatic hydrocarbons, esters, glycol ethers, alcohols, ether alcohols, and siloxanes are preferred. For example, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, diethylene glycol monomethyl ether, hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octamethylcyclotetrasiloxane, and octamethylcyclopentasiloxane are particularly preferred. Preferably, the same solvent as the solvent of the surface treatment agent of this disclosure is used as the solvent used in the wet coating method.

[0179] When using the dry coating method, the surface treatment agent of this disclosure may be subjected to the dry coating method as is, or it may be diluted with the solvent described above before being subjected to the dry coating method.

[0180] From the viewpoint of good dispersibility, the surface treatment agent of this embodiment can be effectively used in wet coating methods, particularly in spray coating.

[0181] The layer formation of the surface treatment agent is preferably carried out such that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. For convenience, in the case of a wet coating method, the surface treatment agent of the present disclosure may be diluted with a solvent, and the catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before application to the substrate surface. In the case of a dry coating method, the surface treatment agent of the present disclosure with the catalyst added may be directly vapor-deposited (usually by vacuum deposition), or a pelletized material in which the surface treatment agent of the present disclosure with the catalyst added may be impregnated, such as iron or copper, may be vapor-deposited (usually by vacuum deposition).

[0182] Any suitable acid or base can be used as a catalyst. Examples of acid catalysts include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts include ammonia and organic amines.

[0183] As described above, a layer derived from the surface treatment agent of the present disclosure is formed on the surface of the substrate, and an article of the present disclosure is manufactured. The resulting layer has both high surface slipperiness and high friction resistance. In addition to high friction resistance, the layer may also have water repellency, oil repellency, stain resistance (e.g., preventing the adhesion of dirt such as fingerprints), waterproofness (preventing water from entering electronic components, etc.), and surface slipperiness (or lubricity, e.g., ease of wiping away dirt such as fingerprints and excellent tactile feel to the fingers), depending on the composition of the surface treatment agent used, and can be suitably used as a functional thin film.

[0184] In other words, this embodiment further relates to an optical material having the above-mentioned surface treatment layer as its outermost layer.

[0185] As optical materials, a wide variety of optical materials are preferred, in addition to optical materials related to displays, as exemplified below: for example, displays such as cathode ray tubes (CRTs; e.g., PC monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs), or protective plates for such displays, or materials on which an anti-reflective coating has been applied to their surface.

[0186] Articles having the layer obtained by this embodiment are not particularly limited, but may be optical components. Examples of optical components include: lenses such as those in eyeglasses; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and display surfaces of watches.

[0187] Furthermore, the article having the layer obtained by this embodiment may be a medical device or a medical material.

[0188] Furthermore, articles having layers obtained by this embodiment may also be automotive interior and exterior components. Examples of exterior components include: windows, light covers, and aftermarket camera covers. Examples of interior components include: instrument panel covers, navigation system touch panels, and decorative interior components.

[0189] The thickness of the above layer is not particularly limited. In the case of optical components, the thickness of the above layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and more preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, frictional durability, and antifouling properties.

[0190] In one embodiment, the article of the present disclosure may include an intermediate layer containing silicon oxide between the glass and the surface treatment layer. By providing such an intermediate layer, the adhesion between the glass and the surface treatment layer is improved, and the durability is improved.

[0191] The thickness of the intermediate layer is not particularly limited, but is preferably 1 to 200 nm, and particularly preferably 1 to 20 nm. By setting the thickness of the intermediate layer to be above the lower limit of the above range, the effect of improving adhesion by the intermediate layer becomes greater.

[0192] [Use as a coating agent for waterproofing and / or moisture-proofing] In one embodiment, the article of the present disclosure includes a film formed from the waterproof and / or moisture-proof coating agent. The article of this embodiment includes an object to be treated and a film formed on the surface of the object to be treated from a coating agent containing the polymer of the present disclosure. A layer may be used instead of a film formed from the coating agent.

[0193] The coating agent of this embodiment provides excellent waterproofing and / or moisture-proofing performance, and the film formed from the coating agent also exhibits good durability, such as abrasion resistance. Therefore, when electronic components are the target of the treatment, it is possible to provide good waterproofing and / or moisture-proofing performance without impairing their performance. This significantly reduces the possibility of failure in treated objects that may get wet (e.g., electronic equipment).

[0194] The articles in this embodiment can be effectively used to apply a waterproof and / or moisture-proof coating to components such as the casings and printed circuit boards of electronic devices that may malfunction when exposed to liquids such as water. For example, by applying the coating to the casing, it is possible to prevent water from entering the inside of the casing, and by applying the coating to components such as printed circuit boards, it is possible to suppress the adhesion of water even if water does enter the inside of the casing, and furthermore, the adhered water can be easily removed by drying, thereby greatly reducing the possibility of malfunctions caused by water.

[0195] Examples of electronic devices that may get wet include portable electronic devices such as smartphones, tablet PCs, portable music players, portable radios, IC recorders, and wireless audio receivers; and measuring instruments used in water-related or seawater environments, such as fish finders, depth sounders, radiation detectors, residual chlorine meters, salinity meters, spectrometers, and refractometers. In particular, when processing electronic components including substrates and semiconductors, using a waterproofing and / or moisture-proofing coating agent makes it possible to form a highly durable waterproof and moisture-proof film using a solvent with low chemical erosion properties, thereby providing good waterproofing and moisture-proofing performance without impairing the performance of the electronic components.

[0196] The coating agent of this embodiment can be applied not only to the electronic components described above, but also to fuel cells, particularly membrane electrode assemblies (MEAs); elements such as organic electroluminescent (EL) or light-emitting diode (LED) lighting; biochips, particularly substrates for medical microfluidic channels, etc.

[0197] The treatment method using the coating agent of this embodiment is not particularly limited, and any method that allows sufficient contact between the polymer of this disclosure and the object to be treated is acceptable. For example, various methods such as vapor deposition, immersion, spray coating, brush coating, and spin coating can be applied.

[0198] For example, in the case of immersion, the object to be treated is usually immersed in the coating agent of this embodiment and then dried in the air. There are no particular limitations on the temperature during immersion, and the treatment is usually carried out at room temperature. There are also no particular limitations on the treatment time, but the immersion time is usually between 1 second and 24 hours.

[0199] To form a coating with higher durability, it is preferable to wash the substrate surface with acetone, ethanol, isopropyl alcohol, hydrofluoroether, hydrofluoroolefin, etc., to remove oil from the substrate surface before treatment with the coating agent of this embodiment, and then dry it. Furthermore, in addition to the above washing, pretreatment with UV ozone, atmospheric pressure plasma, oxygen plasma, etc., can further improve the durability of the coating compared to when it is untreated.

[0200] Unless otherwise specified, the materials (e.g., solvents, etc.) and physical properties (e.g., film thickness, etc.) that can be used in this embodiment may be those described above as surface treatment agents.

[0201] <Second Embodiment> [polymer] The polymer in the second embodiment is formed from a mixture of monomers, The aforementioned mixture is Formula (A2): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3]2[R 3 ] Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H Monomers represented by and Includes, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 The monomer represented by formula (A2) is present in an amount of 50 mol% or less relative to the total amount of monomers represented by formula (B) and monomers represented by formula (C), or the monomer represented by formula (C) is not present.

[0202] The polymer has silane coupling sites that provide good adhesion to substrates such as glass, and therefore exhibits good adhesion to the substrate and high water and oil repellency. Furthermore, the surface of the formed surface treatment layer may retain high water and oil repellency even after being wiped with an alcohol such as ethanol.

[0203] [Formula (A2)] The monomer represented by the following formula: component (A2) CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3]2[R 3 ]

[0204] The monomer represented by formula (A2) is the monomer represented by formula (A1) when n is 2. 1 , R 2 , R 3 And X have the same meaning as above.

[0205] In one embodiment, the monomer represented by formula (A2) is formula (A2-1): CH2=C(R 1 )-COO-X 11 -Si[OSi(R 2 )3]2[R 3 ] It is represented as follows. During the ceremony: R 1 , R 2 , R 3 And n are equivalent to the above; X 11 C 1-8 Alkylene group (preferably C 1-6 (Alkylene group) or -(CH2) n211 -X 1 -(CH2) n311 -and; X 1 This is synonymous with the above; n211 is an integer between 1 and 8, preferably between 1 and 6; n311 is an integer between 1 and 8, preferably between 1 and 6.

[0206] In one embodiment, the monomer represented by formula (A2) is formula (A2-2): CH2=C(R 1 )-COO-X 11 -Si[OSi(R 2 )3]2[R 3 ] It is represented as follows. During the ceremony: R 1 , R 2 , R 3 And n are equivalent to the above; X 12 C 12-30 Alkylene group (preferably C 18-24 (Alkylene group) or -(CH2) n212 -X 1 -(CH2) n312 -and; X 1 This is synonymous with the above; n212 is an integer between 12 and 30, preferably between 18 and 24; n312 is an integer between 12 and 30, preferably between 18 and 24.

[0207] In one embodiment, the mixture contains a monomer represented by formula (A2-1) and a monomer represented by formula (A2-2). The mixing ratio of the monomer represented by formula (A2-1) and the monomer represented by formula (A2-2) is not particularly limited, but for example, the ratio of the monomer represented by formula (A2-1) to the monomer represented by formula (A2-2) is 1:9 to 9:1 in molar ratio, specifically 3:7 to 7:3.

[0208] [Formula (B)] The monomer represented by formula (B) is the same as in the first embodiment.

[0209] Preferably, the molar ratio of the monomer represented by formula (A2) to the monomer represented by formula (B) is in the range of 9 / 1 to 4 / 6.

[0210] In one embodiment, the polymer comprises a monomer represented by formula (A2-1) and a monomer represented by formula (B-1).

[0211] In one embodiment, the polymer comprises a monomer represented by formula (A2-1) and a monomer represented by formula (B-2).

[0212] In one embodiment, the polymer comprises a monomer represented by formula (A2-2) and a monomer represented by formula (B-1).

[0213] In one embodiment, the polymer comprises a monomer represented by formula (A2-2) and a monomer represented by formula (B-2).

[0214] In one embodiment, the polymer comprises a monomer represented by formula (A2-1), a monomer represented by formula (A2-2), and a monomer represented by formula (B-1).

[0215] In one embodiment, the polymer comprises a monomer represented by formula (A2-1), a monomer represented by formula (A2-2), and a monomer represented by formula (B-2).

[0216] In one embodiment, the polymer comprises a monomer represented by formula (A2-1), a monomer represented by formula (B-1), and a monomer represented by formula (B-2).

[0217] In one embodiment, the polymer comprises a monomer represented by formula (A2-2), a monomer represented by formula (B-1), and a monomer represented by formula (B-2).

[0218] In one embodiment, the polymer comprises monomers represented by formula (A2-1) and (A2-2), and monomers represented by formula (B-1) and (B-2).

[0219] The molar ratio of the monomer represented by formula (A2) to the monomer represented by formula (B) is preferably in the range of 9 / 1 to 4 / 6, and more preferably in the range of 7 / 3 to 5 / 5. With the above configuration, the layer formed from the polymer (e.g., a surface treatment layer) has high water and oil repellency while also having good adhesion to a substrate such as glass.

[0220] [Formula (C)] The monomer represented by formula (C) is the same as in the first embodiment.

[0221] The monomer represented by formula (C) is preferably present in an amount of 30 mol% or less, or not present at all, relative to the total amount of the monomer represented by formula (A2), the monomer represented by formula (B), and the monomer represented by formula (C), more preferably present in an amount of 10 mol% or less, or not present at all.

[0222] In one embodiment, the monomer represented by formula (C) is preferably present in an amount of 30 mol% or less, more preferably 10 mol% or less, relative to the total amount of the monomer represented by formula (A2), the monomer represented by formula (B), and the monomer represented by formula (C). The lower limit of the content of the monomer represented by formula (C) is not particularly limited, but for example, it is 1 mol% or more relative to the total amount of the monomer represented by formula (A2), the monomer represented by formula (B), and the monomer represented by formula (C).

[0223] In one embodiment, the monomer represented by formula (C) is not included.

[0224] The number-average molecular weight of the polymer is preferably in the range of 1,000 to 50,000, more preferably in the range of 1,000 to 20,000, and even more preferably in the range of 1,000 to 10,000. The number-average molecular weight can be measured using gel permeation chromatography (GPC). A 1260 Infinity II (manufactured by Agilent) can be used as the GPC.

[0225] The degree of dispersion of the polymer is preferably less than 2.0, more preferably 1.8 or less, and even more preferably 1.65 or less. The lower limit of the degree of dispersion is, for example, 1.0 or more. Here, the degree of dispersion refers to the Mw / Mn value when the polymer has a weight-average molecular weight Mn and a number-average molecular weight Mw. The degree of dispersion can be measured using GPC.

[0226] Preferably, the molecule has a halogen atom at its terminal end. The halogen atom is preferably F, Cl, Br, or I, more preferably Cl, Br, and even more preferably Br.

[0227] [Manufacturing method] The above polymer can be produced as follows. Formula (D): HalCR 7 2-COO-ZR 8 A polymerization initiator represented by and A mixture of monomers and A method for producing a polymer formed from, The aforementioned mixture is Formula (A2): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3]2[R 3 ] Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H It includes monomers represented by, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 The monomer represented by formula (A2) is present in an amount of 50 mol% or less relative to the total amount of monomers represented by formula (B) and monomers represented by formula (C), or formula (C) is not present.

[0228] Equations (D), (A2), (B), and (C) are equivalent to those above. 1 X, R 2 , R 3 , R 4 , Y, R H , R 5 , R 6 Hal, R 7 , Z, and R 8 These terms are equivalent to the above.

[0229] The above manufacturing method may involve the following steps, for example. ·Process I' Formula (D): HalCR 7 2-COO-ZR 8 A step of adding a polymerization initiator represented by to a mixture of monomers, The aforementioned mixture is Formula (A2): CH2=C(R 1 )-COO-X-Si[OSi(R 2 )3]2[R 3 ] Monomers represented by and Formula (B): CH2=C(R 4 )-COO-YR H Monomers represented by and Includes, Furthermore, equation (C): CH2=C(R 5 )-COO-R 6 The monomer represented by formula (A2) is present in an amount of 50 mol% or less relative to the total amount of monomers represented by formula (B) and monomers represented by formula (C), or formula (C) is not present.

[0230] Step I' can be carried out under the same atmosphere, temperature range, and time as Step I. The catalysts and compounds further included in Step I' are the same as those in Step I.

[0231] The above-mentioned surface treatment agent (composition) containing the polymer, pellets impregnated with the surface treatment agent, and articles using the surface treatment agent are all defined as described above.

[0232] The polymer of the present disclosure, a surface treatment agent containing the polymer, an article having a substrate and a layer formed by the surface treatment agent, and a method for producing the polymer have been described in detail above. However, the polymer of the present disclosure, the composition containing the polymer, the substrate and the composition are not limited to those exemplified above, and various modifications in form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0233] This disclosure will be explained in more detail through the following examples, but is not limited to these examples.

[0234] Each surface treatment film was evaluated using the following method.

[0235] [Film thickness] The measurement was performed optically using a spectroscopic ellipsometer M2000 (manufactured by JAWoollam).

[0236] [Static contact angle] The static contact angle was measured using a fully automatic contact angle meter, DropMaster700 (manufactured by Kyowa Interface Science Co., Ltd.), in the following manner.

[0237] <Measurement of static contact angle> The static contact angle was determined by dropping 2 μL each of water and n-hexadecane (HD) onto a horizontally placed substrate using a microsyringe, and capturing a still image 1 second after dropping with a video microscope. For the static contact angle measurements of water and n-hexadecane, five points with different surface treatment layers on the substrate were measured, and the average value was calculated and used.

[0238] [Measurement of monomer content] 1 Measurements were taken using 1H-NMR (manufactured by JEOL Ltd.).

[0239] [Measurement of number-average molecular weight] Measurements were taken using GPC under the following conditions. • Solvent: tetrahydrofuran ·Flow rate: 0.5mL / min • Column: KF-803L • GPC: 1260 Infinity II (manufactured by Agilent) • Reference material: Polystyrene

[0240] (Synthesis Example 1) 0.20 mL of 3-(triethoxysilyl)propyl 2-bromo-2-methylpropanoate, 1.58 mL of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylic acid, 0.09 mL of 3-(trimethoxysilyl)propyl methacrylic acid, 0.21 mg of copper(II) chloride, 4.2 μL of tris[2-(dimethylamino)ethyl]amine, 4.9 μL of tin(II) 2-ethylhexanoate, and 1.67 mL of anisole were added to a screw-top bottle, and the bottle was sealed by purging with nitrogen. Polymer 1 was obtained by stirring at room temperature for 120 hours and then separating and purifying with acetonitrile. Polymerization initiator: 3-(triethoxysilyl)propyl bromo-2-methylpropanoate [ka] Ingredient (A): 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate [ka] Ingredient (B): 3-(trimethoxysilyl)propyl methacrylate [ka]

[0241] (Synthesis Example 2) 0.20 mL of 3-(triethoxysilyl)propyl 2-bromo-2-methylpropanoate, 1.23 mL of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylic acid, 0.27 mL of 3-(trimethoxysilyl)propyl methacrylic acid, 0.21 mg of copper(II) chloride, 4.2 μL of tris[2-(dimethylamino)ethyl]amine, 4.9 μL of tin(II) 2-ethylhexanoate, and 1.50 mL of anisole were added to a screw-top bottle, and the bottle was sealed by purging with nitrogen. Polymer 2 was obtained by stirring at room temperature for 120 hours and then separating and purifying with acetonitrile.

[0242] (Synthesis Example 3) 25.6 μL of 3-(triethoxysilyl)propyl 2-bromo-2-methylpropanoate, 1.23 mL of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylic acid, 0.27 mL of 3-(trimethoxysilyl)propyl methacrylic acid, 0.21 mg of copper(II) chloride, 4.2 μL of tris[2-(dimethylamino)ethyl]amine, 4.9 μL of tin(II) 2-ethylhexanoate, and 1.50 mL of anisole were added to a screw-top bottle, and the bottle was sealed by purging with nitrogen. Polymer 3 was obtained by stirring at room temperature for 120 hours and then separating and purifying with acetonitrile.

[0243] (Synthesis Example 4) 0.20 mL of 3-(triethoxysilyl)propyl 2-bromo-2-methylpropanoate, 0.88 mL of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylic acid, 0.46 mL of 3-(trimethoxysilyl)propyl methacrylic acid, 0.21 mg of copper(II) chloride, 4.2 μL of tris[2-(dimethylamino)ethyl]amine, 4.9 μL of tin(II) 2-ethylhexanoate, and 1.50 mL of anisole were added to a screw-top bottle, and the bottle was purged with nitrogen and then sealed. Polymer 4 was obtained by stirring at room temperature for 120 hours and then separating and purifying with acetonitrile.

[0244] (Synthesis Example 5) 65.7 μL of 3-(triethoxysilyl)propyl 2-bromo-2-methylpropanoate, 1.80 mL of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylic acid, 1.40 mL of 3-(trimethoxysilyl)propyl methacrylic acid, 1.33 mg of copper(II) chloride, 26.8 μL of tris[2-(dimethylamino)ethyl]amine, 31.6 μL of tin(II) 2-ethylhexanoate, and 3.20 mL of anisole were added to a screw-top bottle, and the bottle was sealed by purging with nitrogen. Polymer 5 was obtained by stirring at room temperature for 120 hours and then separating and purifying with acetonitrile.

[0245] (Surface treatment agents 1-5) The polymers 1 to 5 were diluted to obtain a 20 wt% hexamethyldisiloxane solution to obtain surface treatment agents 1 to 5.

[0246] <Formation of surface treatment layer> (Examples 1-5) Chemically strengthened glass (Corning Gorilla Glass, 0.7 mm thick) was treated with UV / O3 for 10 minutes and then dry-cleaned. Surface treatment agents 1 to 5, diluted to 1 wt% with toluene, were then spin-coated at 3000 rpm for 30 seconds each. Subsequently, a surface treatment layer was obtained by heating the material in an oven at 150°C for 120 minutes.

[0247] (Comparative Example 1) Chemically strengthened glass (Corning Gorilla Glass, 0.7 mm thick) was treated with UV / O3 for 10 minutes and then dry-cleaned. After that, octadecyltrimethoxysilane diluted to 1 wt% with toluene was spin-coated at 3000 rpm for 30 seconds. Subsequently, a surface treatment layer was obtained by heating the material in an oven at 150°C for 120 minutes.

[0248] Table 1 shows the molar ratio of the monomer represented by formula (A1) to the monomer represented by formula (B), the number-average molecular weight, and the degree of dispersion for polymers 1 to 5.

[0249] [Table 1]

[0250] Table 2 shows the film thickness, contact angles with water, and contact angles with hexadecane (HD) after wiping the surface treatment layers of the examples and comparative examples with a Kimwipe (manufactured by Nippon Paper Industries) moistened with ethanol for 10 seconds to remove unreacted monomers and components that do not adhere to the substrate.

[0251] [Table 2]

[0252] (Synthesis Example 6) 0.25 mL of O-(methacrylateoxyoxyethyl)-n-(triethoxysilylpropyl)carbamate, 1.50 mL of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylic acid, 0.51 mL of 3-(trimethoxysilyl)propyl methacrylic acid, 0.63 mg of copper(II) chloride, 12.8 μL of tris[2-(dimethylamino)ethyl]amine, 15.0 μL of tin(II) 2-ethylhexanoate, and 2.01 mL of anisole were added to a screw-top bottle, and the bottle was sealed by purging with nitrogen. Polymer 6 was obtained by stirring at room temperature for 120 hours and then separating and purifying with acetonitrile. Ingredient (A): O-(methacrylateoxyoxyethyl)-n-(triethoxysilylpropyl)carbamate [ka]

[0253] (Synthesis Example 7) 0.05 mL of O-(methacrylateoxyoxyethyl)-n-(triethoxysilylpropyl)carbamate, 2.50 mL of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylic acid, 0.85 mL of 3-(trimethoxysilyl)propyl methacrylic acid, 1.06 mg of copper(II) chloride, 21.3 μL of tris[2-(dimethylamino)ethyl]amine, 25.1 μL of tin(II) 2-ethylhexanoate, and 3.35 mL of anisole were added to a screw-top bottle, and the bottle was sealed by purging with nitrogen. Polymer 7 was obtained by stirring at room temperature for 120 hours and then separating and purifying with acetonitrile.

[0254] (Surface treatment agents 6-7) Using polymers 6 and 7, surface treatment agents were obtained based on the same method as in Example 1.

[0255] <Formation of surface treatment layer> (Examples 6-7) Using the aforementioned surface treatment agent, a surface treatment layer was obtained in the same manner as in Example 1.

[0256] Table 3 shows the molar ratio of the monomer represented by formula (A1) to the monomer represented by formula (B), the number-average molecular weight, and the degree of dispersion for polymers 6 and 7.

[0257] [Table 3]

[0258] Table 4 shows the film thickness, contact angles with water, and contact angles with hexadecane (HD) after wiping the surface treatment layer of the examples with a Kimwipe (manufactured by Nippon Paper Industries) moistened with ethanol for 10 seconds to remove unreacted monomers and components that do not adhere to the substrate.

[0259] [Table 4]

[0260] As shown in Tables 2 and 4, in Examples 1 to 7, surface treatment layers with high water-repellent and oil-repellent properties were obtained. [Industrial applicability]

[0261] This disclosure describes a polymer that exhibits good water and oil repellency and good adhesion to a substrate, and can be suitably used in a wide range of fields.

Claims

1. A polymer formed from a mixture of monomers, The aforementioned mixture is Formula (A1): CH ２ =C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ｎ [R ３ ] ３－ｎ [In the formula: R １ is a hydrogen atom or a methyl group; R ２ is, independently of one another, a monovalent hydrocarbon group; R ３ Each of these is independently a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group with one or more carbon atoms; n is an integer between 1 and 3. Monomers represented by and Formula (B): CH ２ =C(R ４ )-COO-Y-R Ｈ [In the formula: R ４ is a hydrogen atom or a methyl group; R Ｈ This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group with one or more carbon atoms. It includes monomers represented by, Furthermore, equation (C): CH ２ =C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ It is a monovalent organic group that does not contain a Si atom. The monomer represented by is contained in an amount of 5 mol% or less relative to the total amount of the monomer represented by formula (A1), the monomer represented by formula (B), and the monomer represented by formula (C), or the monomer represented by formula (C) is not contained. Polymer.

2. A polymer formed from a mixture of monomers, The aforementioned mixture is Formula (A2): CH ２ =C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ２ [R ３ ] [In the formula: R １ is a hydrogen atom or a methyl group; R ２ Each of these is independently a monovalent hydrocarbon group; R ３ It is a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group with one or more carbon atoms. Monomers represented by and Formula (B): CH ２ =C(R ４ )-COO-Y-R Ｈ [In the formula: R ４ is a hydrogen atom or a methyl group; R Ｈ This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group with one or more carbon atoms. It includes monomers represented by, Furthermore, equation (C): CH ２ =C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ It is a monovalent organic group that does not contain a Si atom. A polymer that contains 50 mol% or less of the monomer represented by formula (A2), the monomer represented by formula (B), and the monomer represented by formula (C), or does not contain the monomer represented by formula (C).

3. The polymer according to claim 1, wherein the molar ratio of the monomer represented by formula (A1) to the monomer represented by formula (B) is in the range of 9 / 1 to 4 / 6.

4. The polymer according to claim 2, wherein the molar ratio of the monomer represented by formula (A2) to the monomer represented by formula (B) is in the range of 9 / 1 to 4 / 6.

5. The polymer according to claim 1 or 2, wherein the number average molecular weight is in the range of 1,000 to 50,000.

6. The polymer according to claim 1 or 2, wherein the degree of dispersion is less than 2.

0.

7. The polymer according to claim 1 or 2, having a halogen atom at its terminal.

8. A surface treatment agent comprising the polymer according to claim 1 or 2.

9. The surface treatment agent according to claim 8, comprising a polymerization initiator or a polymerization initiator residue.

10. A surface treatment agent according to claim 8, for use in vacuum deposition.

11. The surface treatment agent according to claim 8, which is for wet coating.

12. A pellet containing the surface treatment agent described in claim 8.

13. A coating agent for waterproofing and moisture-proofing treatment comprising the polymer according to claim 1 or 2.

14. A waterproof and moisture-proof coating agent according to claim 13, comprising a polymerization initiator or a polymerization initiator residue.

15. A waterproof and moisture-proof coating agent according to claim 13, for use in electronic devices.

16. An article comprising a base material and a layer formed on the base material from the polymer described in claim 1 or 2.

17. The article according to claim 16, further comprising an intermediate layer containing silicon oxide between the substrate and the layer.

18. The article according to claim 16, which is an optical component.

19. The article according to claim 16, which is a display.

20. Formula (D): HalCR ７ ２ -COO-Z-R ８ [In the formula: Ha is a halogen atom; R ７ Each of these is independently either a hydrogen atom or a methyl group; R ８ is a monovalent group; Z is a divalent organic group containing an alkylene group with one or more carbon atoms. A polymerization initiator represented by and A mixture of monomers and A method for producing a polymer formed from, The aforementioned mixture is Formula (A1): CH ２ =C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ｎ [R ３ ] ３－ｎ [In the formula: R １ is a hydrogen atom or a methyl group; R ２ Each of these is independently a monovalent hydrocarbon group; R ３ Each of these is independently a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group with one or more carbon atoms; n is an integer between 1 and 3. Monomers represented by and Formula (B): CH ２ =C(R ４ )-COO-Y-R Ｈ [In the formula: R ４ is a hydrogen atom or a methyl group; R Ｈ This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group with one or more carbon atoms. It includes monomers represented by, Furthermore, equation (C): CH ２ =C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ It is a monovalent organic group that does not contain a Si atom. The monomer represented by is contained in an amount of 5 mol% or less relative to the total amount of the monomer represented by formula (A1), the monomer represented by formula (B), and the monomer represented by formula (C), or the monomer represented by formula (C) is not contained. Manufacturing method.

21. Formula (D): HalCR ７ ２ -COO-Z-R ８ [In the formula: Ha is a halogen atom; R ７ Each of these is independently either a hydrogen atom or a methyl group; R ８ is a monovalent group; Z is a divalent organic group containing an alkylene group with one or more carbon atoms. A polymerization initiator represented by and A mixture of monomers and A method for producing a polymer formed from, The aforementioned mixture is Formula (A2): CH ２ =C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ２ [R ３ ] [In the formula: R １ is a hydrogen atom or a methyl group; R ２ Each of these is independently a monovalent hydrocarbon group; R ３ It is a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group with one or more carbon atoms. Monomers represented by and Formula (B): CH ２ =C(R ４ )-COO-Y-R Ｈ [In the formula: R ４ is a hydrogen atom or a methyl group; R Ｈ This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group with one or more carbon atoms. It includes monomers represented by, Furthermore, equation (C): CH ２ =C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ It is a monovalent organic group that does not contain a Si atom. The monomer represented by is contained in an amount of 50 mol% or less relative to the total amount of the monomer represented by formula (A2), the monomer represented by formula (B), and the monomer represented by formula (C), or the monomer represented by formula (C) is not contained. Manufacturing method.

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