polymer

Abstract

Provided is a polymer formed with a mixture of monomers, wherein the mixture comprises a monomer represented by formula (A1): CH2=C(R1)-COO-X-Si[OSi(R2)3]n[R3]3-n and a monomer represented by formula (B): CH2=C(R4)-COO-Y-RH, and further contains a monomer represented by formula (C): CH2=C(R5)-COO-R6 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 does not contain formula (C). The symbols are as described in the description.

Description

polymer

[0001] The present disclosure relates to polymers.

[0002] Conventionally, techniques have been studied for providing a surface treatment agent on a substrate to impart functions such as antifouling properties. For example, in applications requiring high transparency, such as screen protection for mobile terminals, it is desirable to treat the surface with a thin film having a thickness of about one molecule to several molecules, and silane coupling agents made of alkylsilanes, polymers containing alkyl acrylate or alkyl methacrylate as a main component, and the like have been used as surface treatment agents capable of forming thin films (e.g., Patent Document 1).

[0003] JP 2010 / 159338 A

[0004] However, although silane coupling agents made of alkylsilanes and polymers containing alkyl acrylates or alkyl methacrylates as their main components have excellent water repellency, they have the problem of being poor in oil repellency.

[0005] An object of the present disclosure is to provide a polymer that has water and oil repellency and also has good adhesion to a substrate.

[0006] According to the present disclosure, the following aspects are provided: [1] A polymer formed from a mixture of monomers, the mixture comprising: a monomer represented by 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 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 one or more carbon atoms; and n is an integer of 1 to 3.] and a monomer represented by formula (B): CH ２ = C(R ４ )-COO-Y-R Ｈ [In the formula: R ４is a hydrogen atom or a methyl group; R Ｈ is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto; and Y is a divalent organic group containing an alkylene group having one or more carbon atoms.], and further comprising a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ is a monovalent organic group not containing a Si atom. ] is 5 mol % or less of a monomer represented by formula (A1), a monomer represented by formula (B), and a monomer represented by formula (C), or does not contain a monomer represented by formula (C). [2] A polymer formed from a mixture of monomers, the mixture comprising a monomer represented by 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 are each independently a monovalent hydrocarbon group; R ３ is a monovalent hydrocarbon group; and X is a divalent organic group containing an alkylene group having one or more carbon atoms.] and a monomer represented by 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 is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto; and Y is a divalent organic group containing an alkylene group having one or more carbon atoms.], and further comprising a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６is a monovalent organic group not containing a Si atom. A polymer containing a monomer represented by the formula (A2), (B), and (C) 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 not containing a 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] The polymer according to any one of [1] to [4], wherein the number average molecular weight is in the range of 1,000 to 50,000. [6] The polymer according to any one of [1] to [5], wherein the dispersity is less than 2.0. [7] The polymer according to any one of [1] to [6], wherein the polymer has a terminal halogen atom. [8] A surface treatment agent containing the polymer according to any one of [1] to [7]. [9] The surface treatment agent according to [8], which contains a polymerization initiator or a residue of a polymerization initiator.

[10] The surface treatment agent according to [8] or [9], which is for vacuum deposition.

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

[12] A pellet containing the surface treatment agent according to any one of [8] to

[11] .

[13] A coating agent for waterproof and moisture-proof treatment, which contains the polymer according to any one of [1] to [7].

[14] The coating agent for waterproof and moisture-proof treatment according to

[13] , which contains a polymerization initiator or a residue of a polymerization initiator.

[15] The coating agent for waterproof and moisture-proof treatment according to

[13] or

[14] , which is for electronic devices.

[16] An article comprising a substrate and a layer formed on the substrate from the polymer according to any one of [1] to [7].

[17] The article according to

[16] , which contains an intermediate layer containing silicon oxide between the substrate and the layer.

[18] The article according to

[16] or

[17] , which is an optical member.

[19] The article according to any one of

[16] to

[18] , which is a display.

[20] Formula (D): HalCR ７ ２ -COO-Z-R ８ wherein: Hal is a halogen atom; ７are each independently a hydrogen atom or a methyl group; R ８ is a monovalent group; and Z is a divalent organic group containing an alkylene group having one or more carbon atoms.] and a mixture of monomers, wherein the mixture is a monomer represented by the 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 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 one or more carbon atoms; and n is an integer of 1 to 3.] and a monomer represented by 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 is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto; and Y is a divalent organic group containing an alkylene group having one or more carbon atoms.], and further comprising a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ is a monovalent organic group not containing a Si atom.] 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 does not contain a monomer represented by formula (C).

[21] A method for producing a polymerizable polymerizable compound having a structure represented by formula (D): HalCR ７ ２ -COO-Z-R ８ wherein: Hal is a halogen atom; ７are each independently a hydrogen atom or a methyl group; R ８ is a monovalent group; and Z is a divalent organic group containing an alkylene group having one or more carbon atoms.] and a mixture of monomers, wherein the mixture is a polymerization initiator represented by the 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 are each independently a monovalent hydrocarbon group; R ３ is a monovalent hydrocarbon group; and X is a divalent organic group containing an alkylene group having one or more carbon atoms.] and a monomer represented by 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 is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto; and Y is a divalent organic group containing an alkylene group having one or more carbon atoms.], and further comprising a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ is a monovalent organic group not containing a Si atom.] 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 does not contain a monomer represented by formula (C).

[0007] According to the present disclosure, there is provided a polymer that is water- and oil-repellent and further has good adhesion to a substrate.

[0008] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, resulting from the elimination of one hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include hydrocarbon groups having 1 to 20 carbon atoms, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups, which may be substituted with one or more substituents. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. The hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at its terminal or in the molecular chain.

[0009] As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but examples thereof include a halogen atom; a C １－６ Alkyl group, C ２－６ Alkenyl group, C ２－６ Alkynyl group, C ３－１０ Cycloalkyl group, C ３－１０ Unsaturated cycloalkyl groups, 5- to 10-membered heterocyclyl groups, 5- to 10-membered unsaturated heterocyclyl groups, C ６－１０ The alkyl group may include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0010] As used herein, the term "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. Note that when simply referring to an "organic group," it refers to a monovalent organic group. Furthermore, the term "divalent organic group" refers to a divalent group containing carbon. Examples of such divalent organic groups include divalent groups obtained by further eliminating one hydrogen atom from an organic group.

[0011] As used herein, the term "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, i.e., a group that can be removed from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR ｈ１ , -OCOR ｈ１ , —O—N═CR ｈ１ ２ , -NR ｈ１ ２ , -NHR ｈ１ , halogen (wherein R ｈ１ represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), and preferably —OR ｈ１ (i.e., an alkoxy group). ｈ１ Examples of the alkyl group include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl and ethyl groups being more preferred.

[0012] First Embodiment [Polymer] The polymer in the first embodiment is formed from a mixture of monomers, and the mixture is a monomer represented by the formula (A1): CH ２ = C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ｎ [R ３ ] ３－ｎ and a monomer represented by formula (B): CH ２ = C(R ４ )-COO-Y-R Ｈ and a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ The monomer represented by the formula (A1), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 5 mol % or less relative to the total amount of the monomer represented by the formula (A1), the monomer represented by the formula (B), and the monomer represented by the formula (C), or the monomer represented by the formula (C) is not contained.

[0013] The polymer has good adhesion to substrates because the monomer represented by formula (B) has a silane coupling moiety that has good adhesion to substrates such as glass, and can have high water and oil repellency because the monomer represented by formula (A1) has a siloxane moiety. Therefore, the polymer can have high water and oil repellency even after the surface of the formed surface treatment layer is wiped with an alcohol such as ethanol. In addition, the polymer may contain a small amount of the monomer represented by formula (C), or may not contain the monomer represented by formula (C).

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

[0015] [Formula (A1)] A monomer represented by the following formula: Component (A1) CH ２ = 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. 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 with one or more substituents. Preferably, R ２ is not substituted.

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

[0019] R ３ are each independently a monovalent hydrocarbon group. The hydrocarbon group may be substituted with one or more substituents. Preferably, R３ is not substituted.

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

[0021] n is an integer of 1 to 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 having one or more carbon atoms. The alkylene group may be linear or branched. The alkylene group may preferably 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 １１－３０ It may be an alkylene group. The number of carbon atoms in such an alkylene group may be preferably 12 or more, more preferably 16 or more, even more preferably 18 or more, and still more preferably 22 or more. The number of carbon atoms in the alkylene group may be preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and still more preferably 24 or less. The number of carbon atoms in the alkylene group may be preferably 11 to 60, more preferably 12 to 40, and still 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—, —NR Ｘ --, --CONR Ｘ -, -NR Ｘ CO-, -OCONR Ｘ -, -NR Ｘ COO-, -NR Ｘ -CO-NR Ｘ It may be a divalent organic group containing -, -O-, or -S-, and is preferably -CO- or -NRＸ --, --CONR Ｘ -, -NR Ｘ CO-, -OCONR Ｘ -or-NR Ｘ COO-, more 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.

[0026] X is preferably C １－３０ an alkylene group, or -(CH ２ ) ｎ２１ -X １ - (CH ２ ) ｎ３１ - is.

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

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

[0029] In one embodiment, X is —(CH ２ ) ｎ２１ -X １ - (CH ２ ) ｎ３１ -. In addition, -(CH ２ ) ｎ２１ - is bonded to the -COO- group, and -(CH ２ ) ｎ３１ - is -Si[OSi(R ２ ) ３ ] ｎ [R ３ ] ３－ｎ Combine with.

[0030] n21 is an integer from 0 to 30, n31 is an integer from 0 to 30, and the sum of n21 and n31 is 1 or more.

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

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

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

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

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

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

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

[0038] In one embodiment, n21 is an integer of 12 to 30, and n31 is an integer of 12 to 30, and preferably, n21 is an integer of 18 to 24, and n31 is an integer of 18 to 24.

[0039] In one embodiment, n21 is 2 and n31 is 3.

[0040] X １ is -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 C１－６ It is an alkyl group, preferably a hydrogen atom.

[0041] X is, for example, C １－３０ Alkylene, C １－３０ Alkylene -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.

[0042] In one embodiment, the monomer represented by formula (A1) is represented by formula (A1-1): CH ２ = C(R １ )-COO-X １１ -Si[OSi(R ２ ) ３ ] ｎ [R ３ ] ３－ｎ In the formula: １ , R ２ , R ３ and n is as defined above; X １１ is C １－８ Alkylene group (preferably C １－６ alkylene group) or -(CH ２ ) ｎ２１１ -X １ - (CH ２ ) ｎ３１１ - and X １ has the same meaning as above; n211 is an integer of 1 to 8, preferably an integer of 1 to 6; n311 is an integer of 1 to 8, preferably an integer of 1 to 6.

[0043] In one embodiment, the monomer represented by formula (A1) is represented by formula (A1-2): CH ２ = C(R １ )-COO-X １２ -Si[OSi(R ２ ) ３ ] ｎ [R ３ ] ３－ｎ In the formula:１ , R ２ , R ３ and n is as defined above; X １２ is C １２－３０ Alkylene group (preferably C １８－２４ alkylene group) or -(CH ２ ) ｎ２１２ -X １ - (CH ２ ) ｎ３１２ - and X １ has the same meaning as above; n212 is an integer of 12 to 30, preferably an integer of 18 to 24; n312 is an integer of 12 to 30, preferably an integer of 18 to 24.

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

[0045] Examples of the monomer represented by formula (A1) include: ２ =C(CH ３ )-COO-C ３ H ６ -Si[OSi(CH ３ ) ３ ] ３ , C.H. ２ =CH-COO-C ３ H ６ -Si[OSi(CH ３ ) ３ ] ３ , C.H. ２ =C(CH ３ )-COO-C ４ H ８ -Si[OSi(CH ３ ) ３ ] ３ , C.H. ２ =C(CH ３ )-COO-C ３ H ６ -Si[OSi(C ２ H５ ) ３ ] ３ CH ２ =CH-COO-C ３ H ６ -Si[OSi(C) ２ H ５ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C ４ H ８ -Si[OSi(C) ２ H ５ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C ３ H ６ -Si[OSi(C) ３ H ７ ) ３ ] ３ CH ２ =CH-COO-C ３ H ６ -Si[OSi(C) ３ H ７ ) ３ ] ３ CH ２ =CH-COO-C ４ H ８ -Si[OSi(C) ３ H ７ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C １０ H ２０ -Si[OSi(CH ３ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C １６ H ３２ -Si[OSi(CH ３ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C １８ H ３６ -Si[OSi(CH ３ ) ３] ３ CH ２ =C(CH ３ )-COO-C ２０ H ４０ -Si[OSi(CH ３ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C ２２ H ４４ -Si[OSi(CH ３ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C ２４ H ４８ -Si[OSi(CH ３ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C ２６ H ５２ -Si[OSi(CH ３ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C ２８ H ５６ -Si[OSi(CH ３ ) ３ ] ３ CH ２ =C(CH ３ )-COO-C ３０ H ６０ -Si[OSi(CH ３ ) ３ ] ３ CH ２ =CH-COO-C ３ H ６ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ４ H ８ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH２ =C(CH ３ )-COO-C ３ H ６ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =CH-COO-C ３ H ６ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ４ H ８ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ３ H ６ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =CH-COO-C ３ H ６ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =CH-COO-C ４ H ８ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C １０ H ２０ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C １６ H ３２ -Si[OSi(CH ３ )３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C １８ H ３６ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ２０ H ４０ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ２２ H ４４ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ２４ H ４８ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ２６ H ５２ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ２８ H ５６ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３ ]、 CH ２ =C(CH ３ )-COO-C ３０ H ６０ -Si[OSi(CH ３ ) ３ ] ２ [CH] ３] can be mentioned.

[0046] [Formula (B)] A monomer represented by the following formula: Component (B) CH ２ = C(R ４ )-COO-Y-R Ｈ

[0047] R ４ is a hydrogen atom or a methyl group. 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 —SiR Ｈ１ ｎ１ R Ｈ２ ３－ｎ１ It is expressed as: R Ｈ１ is a hydroxyl group or a hydrolyzable group. Ｈ２ is a hydrogen atom or a monovalent organic group. Ｈ２ is R Ｈ１ n1 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0050] Y is a divalent organic group containing an alkylene group having one or more carbon atoms. The alkylene group may be linear or branched. The alkylene group may preferably 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 １１－３０It may be an alkylene group. The number of carbon atoms in such an alkylene group may be preferably 12 or more, more preferably 16 or more, even more preferably 18 or more, and still more preferably 22 or more. The number of carbon atoms in the alkylene group may be preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and still more preferably 24 or less. The number of carbon atoms in the alkylene group may be preferably 11 to 60, more preferably 12 to 40, and still more preferably 18 to 30.

[0053] In one embodiment, Y is an alkylene group having one or more carbon atoms and further includes —CO—, —COO—, —OCO—, —NR Ｘ --, --CONR Ｘ -, -NR Ｘ CO-, -OCONR Ｘ -, -NR Ｘ COO-, -NR Ｘ -CO-NR Ｘ It may be a divalent organic group containing -, -O-, or -S-, and is preferably -CO- or -NR Ｘ --, --CONR Ｘ -, -NR Ｘ CO-, -OCONR Ｘ -or-NR Ｘ COO-, more 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.

[0054] Y is preferably C １－３０ an alkylene group, or -(CH ２ ) ｎ２２ -Y １ - (CH ２ ) ｎ３２ - is.

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

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

[0057] In one embodiment, Y is —(CH ２ ) ｎ２２ -Y １ - (CH ２ ) ｎ３２ -. In addition, -(CH ２ ) ｎ２２ - is bonded to the -COO- group, and -(CH ２ ) ｎ３２ - is -R Ｈ Attaches to the group.

[0058] n22 is an integer from 0 to 30, n32 is an integer from 0 to 30, and the sum of n22 and n32 is 1 or more.

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

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

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

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

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

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

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

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

[0067] Y １ is -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 Alkylene -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.

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

[0070] In one embodiment, the monomer represented by formula (B) is represented by formula (B-1): CH ２ = C(R ４ )-COO-Y １１ -R Ｈ In the formula: ４ , and R Ｈ is as defined above; Y １１ is C １－８ Alkylene group (preferably C １－６ alkylene group) or -(CH ２ )ｎ２２１ -Y １ - (CH ２ ) ｎ３２１ n221 is an integer of 1 to 8, preferably an integer of 1 to 6; n321 is an integer of 1 to 8, preferably an integer of 1 to 6.

[0071] In one embodiment, the monomer represented by formula (B) is represented by formula (B-2): CH ２ = C(R ４ )-COO-Y １２ -R Ｈ In the formula: ４ , and R Ｈ is as defined above; Y １２ is C １－８ Alkylene group (preferably C １－６ alkylene group) or -(CH ２ ) ｎ２２２ -Y １ - (CH ２ ) ｎ３２２ n222 is an integer of 12 to 30, preferably an integer of 18 to 24; n322 is an integer of 12 to 30, preferably an integer of 18 to 24.

[0072] In one embodiment, the composition 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 molar ratio of the monomer represented by formula (B-1) to the monomer represented by formula (B-2) is 1:9 to 9:1, specifically 3:7 to 7:3.

[0073] Examples of the monomer represented by formula (B) include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri(isopropoxy)silane, 3-acryloxypropyltri(isopropoxy)silane, methacryloxymethyltrimethoxysilane, methacryloxymethylmethyldimethoxysilane, O-(methacryloxyoxyethyl)-n-(triethoxysilylpropyl)carbamate, CH ２ =C(CH ３ )-COO-C １０ H ２０ -Si(OCH ３ ) ３ , C.H. ２ =C(CH ３ )-COO-C １６ H ３２ -Si(OCH ３ ) ３ , C.H. ２ =C(CH ３ )-COO-C １８ H ３６ -Si(OCH ３ ) ３ , C.H. ２ =C(CH ３ )-COO-C ２０ H ４０ -Si(OCH ３ ) ３ , C.H. ２ =C(CH ３ )-COO-C ２２ H ４４ -Si(OCH ３ ) ３ , C.H. ２ =C(CH ３ )-COO-C ２４ H ４８ -Si(OCH ３ ) ３ , C.H. ２ =C(CH ３ )-COO-C ２６ H ５２-Si(OCH ３ ) ３ , C.H. ２ =C(CH ３ )-COO-C ２８ H ５６ -Si(OCH ３ ) ３ , C.H. ２ =C(CH ３ )-COO-C ３０ H ６０ -Si(OCH ３ ) ３ Examples include:

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

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

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

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

[0078] In one embodiment, the polymer contains 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 contains 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 contains 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 contains 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 contains a monomer represented by formula (A1-1), a monomer represented by formula (A1-2), 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, more preferably 7 / 3 to 5 / 5. By having the above-mentioned structure, a layer (e.g., a surface treatment layer) formed from the polymer has high water repellency and oil repellency, and also has good adhesion to a substrate such as glass.

[0084] [Formula (C)] A monomer represented by the following formula: Component (C) CH ２ = C(R ５ )-COO-R ６

[0085] R ５ is a hydrogen atom or a methyl group. ５ is a hydrogen atom. ５ 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. ６ is not substituted.

[0087] R ６ The monovalent organic group is preferably C １－３０ The alkyl group may be a straight chain or a branched chain, and is preferably a straight chain.

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

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

[0090] In one embodiment, the monomer represented by formula (C) is represented by formula (C-1): CH ２ = C(R ５ )-COO-R ６１ In the formula: ５ has the same meaning as above; R ６１ is C １－８ is an alkyl group, preferably C １－６ It is an alkyl group.

[0091] In one embodiment, the monomer represented by formula (C) is represented by formula (C-2): CH ２ = C(R ５ )-COO-R ６２ In the formula: ５ has the same meaning as above; R ６２ is C １２－３０ is an alkyl group, preferably C １８－２４ It is an alkyl group.

[0092] In one embodiment, the composition 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 molar ratio of the monomer represented by formula (C-1) to the monomer represented by formula (C-2) is 1:9 to 9:1, specifically 3:7 to 7:3.

[0093] Examples of the monomer 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, CH ２ =C(CH ３ )-COO-C １０ H ２１ , C.H. ２ =C(CH ３ )-COO-C １６ H３３ , C.H. ２ =C(CH ３ )-COO-C １８ H ３７ , C.H. ２ =C(CH ３ )-COO-C ２０ H ４１ , C.H. ２ =C(CH ３ )-COO-C ２２ H ４５ , C.H. ２ =C(CH ３ )-COO-C ２４ H ４９ , C.H. ２ =C(CH ３ )-COO-C ２６ H ５３ , C.H. ２ =C(CH ３ )-COO-C ２８ H ５７ , C.H. ２ =C(CH ３ )-COO-C ３０ H ６１ Examples include:

[0094] The monomer represented by formula (C) preferably accounts for 3 mol % or less of 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, and more preferably 1 mol % or less of the total amount of the monomer represented by formula (C), or the monomer represented by formula (C) is not contained.

[0095] In one embodiment, the monomer represented by formula (C) is contained in an amount of preferably 3 mol % or less, more preferably 1 mol % or less, based on 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 is, for example, 0.1 mol % or more, based on 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 is CH ３ is.

[0098] The polymer may further contain other groups. The other groups are not particularly limited, but include groups derived from a polymerization initiator. The polymerization initiator will be described later.

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

[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, and specifically in the range of 1,000 to 6,000. The number average molecular weight can be measured using gel permeation chromatography (GPC). As the GPC, a 1260 Infinity II (manufactured by Agilent) can be used.

[0101] The dispersity 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 dispersity is, for example, 1.0 or more. Here, the dispersity refers to the value of Mw / Mn when the weight average molecular weight Mn and the number average molecular weight Mw are used. The dispersity can be measured using GPC.

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

[0103] [Production Method] The above polymer can be produced as follows: ７ ２ -COO-Z-R ８ and a mixture of a monomer and a polymerization initiator represented by formula (A1): CH２ = C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ｎ [R ３ ] ３－ｎ and a monomer represented by formula (B): CH ２ = C(R ４ )-COO-Y-R Ｈ and a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ The monomer represented by the formula (A1), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 5 mol % or less relative to the total amount of the monomer represented by the formula (A1), the monomer represented by the formula (B), and the monomer represented by the formula (C), or the monomer represented by the formula (C) is not contained.

[0104] R １ , X, R ２ , R ３ , n, R ４ , Y., R. Ｈ , R ５ and R ６ have the same meanings as 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 terminal of the polymer.

[0106] R ７ are each independently a hydrogen atom or a methyl group. ７ is a hydrogen atom. ７ is a methyl group.

[0107] R ８ is a monovalent group.

[0108] R ８ is, for example, -R ｈ３ or a hydrogen atom.

[0109] In one embodiment, R ８ is -R ｈ３and is, for example, a monovalent group containing a Si atom to which a hydrolyzable group is bonded.

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

[0111] R ８１ 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 alkyl group, more preferably C １－６ alkyl group, more preferably C １－３ It is an alkyl group.

[0113] m is an integer of 1 to 3. m may be, for example, 1, 2, or 3. Preferably, m is 3.

[0114] Z is a divalent organic group containing an alkylene group having one or more carbon atoms. The alkylene group may be linear or branched. The alkylene group may preferably 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 may be preferably 12 or more, more preferably 16 or more, even more preferably 18 or more, and still more preferably 22 or more. The number of carbon atoms in the alkylene group may be preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and still more preferably 24 or less. The number of carbon atoms in the alkylene group may be preferably 11 to 60, more preferably 12 to 40, and still 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—, —NR Ｘ --, --CONR Ｘ -, -NR Ｘ CO-, -OCONR Ｘ -, -NR Ｘ COO-, -NR Ｘ -CO-NR Ｘ It may be a divalent organic group containing -, -O-, or -S-, and is preferably -CO- or -NR Ｘ --, --CONR Ｘ -, -NR Ｘ CO-, -OCONR Ｘ -or-NR Ｘ COO-, more 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.

[0118] Z is preferably C １－３０ an alkylene group, or -(CH ２ ) ｎ２３ -Z １ - (CH ２ ) ｎ３３ - is.

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

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

[0121] In one embodiment, Z is —(CH ２ ) ｎ２３ -Z １ - (CH ２ ) ｎ３３ -. In addition, -(CH ２ ) ｎ２３ - is bonded to the -COO- group, and -(CH ２ ) ｎ３３ - is -R ８ Combine with.

[0122] n23 is an integer from 0 to 30, n33 is an integer from 0 to 30, and the sum of n23 and n33 is 1 or more.

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

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

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

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

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

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

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

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

[0131] Z １ is -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 Alkylene -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 may be a group having a structure different from X. Z is preferably a group having the same structure as X.

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

[0135] Examples of the polymerization initiator 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 production method may include, for example, the following steps: Step I: Reacting with HalCR (D): ７ ２ -COO-Z-R ８ to a mixture of monomers, wherein the mixture is a polymerization initiator represented by formula (A1): CH ２ = C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ｎ [R ３ ] ３－ｎ and a monomer represented by formula (B): CH ２ = C(R ４ )-COO-Y-R Ｈ and a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ The monomer represented by the formula (A1), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 5 mol % or less, or the monomer represented by the formula (C) is not contained. Radical polymerization is thereby carried out to produce a polymer.

[0137] Formula (D), Formula (A1), Formula (B) and Formula (C) have the same meanings as above. １ , X, R ２ , n, R ３ , R ４ , Y., R. Ｈ , R ５ , R ６ , Hal, R. ７, Z, and R ８ have the same meanings as above.

[0138] The order of mixing the polymerization initiator represented by formula (D), and the monomers represented by formula (A1), formula (B), and formula (C) is not particularly limited. For example, the compounds represented by formula (A1), formula (B), and formula (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 formula (A1), formula (B), and formula (C), or the compounds represented by formula (A1), formula (B), formula (C), and formula (D) may be added in no particular order.

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

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

[0141] The catalyst may contain a metal salt and a ligand. Examples of the metal salt 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. Examples of the ligand 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-pyridylmethanimine, N-octyl-2-pyridylmethanimine, N-dodecyl-N-(2-pyridylmethylene)amine, N-octadecyl-N-(2-pyridylmethylene)amine, N,N,N',N'',N'''-pentame 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, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, and the like.

[0142] The ligands may be added in an amount equal to at least the number of ligands that can be coordinated to the metal salt. The molar ratio of the metal salt to the ligand is not particularly limited, but may be in the range of 1:2 to 1:10.

[0143] The catalyst preferably used 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 can be carried out at, but not limited to, a temperature of 20 to 80°C.

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

[0146] The above step I may be carried out in a solvent.

[0147] The solvent is not particularly limited as long as it dissolves the monomer and the polymer, and examples thereof 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, 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, and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether. glycol ethers such as 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., C; ６ F １３ CH ２ CH ３ (For example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), C ６ F １３ H (for example, Asahiklin (registered trademark) AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Zeon Corporation); fluorine-containing 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; CF ３ CH ２ OH, CF ３ CF ２ CH ２ OH, (CF ３ ) ２ fluorine-containing alcohols such as CHOH; hydrofluoroethers (HFEs) (for example, perfluoropropyl methyl ether (C ３ F ７ OCH ３ ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C ４ F ９ OCH ３ ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ４ F ９ O.C. ２ H ５ ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C ２ F ５ CF (OCH ３ ) C ３ F ７) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF ３ CH ２ OCF ２ CHF ２ (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF ３ CH═CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.), CHF ２ Examples of suitable solvents include ethers such as CF═CHCl (for example, AMOLEA (registered trademark) 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 sulfoxide. Alternatively, a mixed solvent of two or more of these solvents may be used, and preferably, toluene, anisole, tetrahydrofuran, N,N-dimethylformamide, or the like may be used.

[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 weight or more. The polymer is contained in the solvent in an amount of preferably 30 to 70% by weight, more preferably 40 to 60% by weight.

[0149] The above step I may further include a reducing agent.

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

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

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

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

[0154] The residue of the polymerization initiator refers to a compound formed after the group involved in the polymerization is eliminated. The residue of the polymerization initiator is, for example, CH ２ =CR ７ -COO-Z-R ８ It is. ７ , Z, and R ８ has the same meaning as above.

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

[0156] The solvent is not particularly limited as long as it dissolves the polymer, and examples thereof 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-hydrocarbonyl acetate. esters such as 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, methyl amino ketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether ... 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; diethylene glycol monoethyl ether acetate;Polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C; ６ F １３ CH ２ CH ３ (For example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), C ６ F １３ H (for example, Asahiklin (registered trademark) AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Zeon Corporation); fluorine-containing 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; CF ３ CH ２ OH, CF ３ CF ２ CH ２ OH, (CF ３ ) ２ fluorine-containing alcohols such as CHOH; hydrofluoroethers (HFEs) (for example, perfluoropropyl methyl ether (C ３ F ７ OCH ３ ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C ４ F ９ OCH ３ ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ４ F ９ O.C. ２ H ５ ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C ２ F ５ CF (OCH ３ ) C ３ F ７) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF ３ CH ２ OCF ２ CHF ２ (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF ３ CH═CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.), CHF ２ Examples of suitable solvents include ethers such as CF═CHCl (for example, AMOLEA (registered trademark) 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 sulfoxide. Alternatively, examples include mixed solvents of two or more of these. Among these, aliphatic hydrocarbons, esters, glycol ethers, alcohols, ether alcohols, and siloxanes are preferred. Preferred examples of the solvent include 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, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, diethylene glycol monomethyl ether, hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octamethylcyclotetrasiloxane, and octamethylcyclopentasiloxane. The solvent may be the same as that used in producing 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 weight or more. The polymer is contained in the solvent in a range of preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, and even more preferably 10 to 20% by weight.

[0158] The surface treatment agent can impart water repellency, oil repellency, antifouling properties, surface slip properties, and friction durability to a substrate. That is, for example, a surface treatment layer can be formed on a substrate using the surface treatment agent. The surface treatment layer may also be a laminate of multiple surface treatment films. The substrate used here will be described later.

[0159] [Pellets] The surface treatment agent of the present disclosure can be impregnated into a porous substance, such as a porous ceramic material or a metal fiber, such as steel wool, to form pellets. The pellets can be used, for example, for vacuum deposition.

[0160] [Waterproof and / or Moisture-Proof Coating Agent] The polymer may be used as a waterproof and / or moisture-proof coating agent, specifically as a waterproof and / or moisture-proof coating agent.

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

[0162] The residue of the polymerization initiator has the same meaning as above.

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

[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 weight or more. The polymer is contained in the solvent in a range of preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, and even more preferably 10 to 20% by weight.

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

[0166] [Article] The article of the present disclosure includes a layer or film formed from a composition (e.g., a surface treatment agent, a coating agent for waterproofing and / or moisture-proofing treatment). That is, the article of the present disclosure includes a treated object and a layer or film formed on the surface of the treated object from the polymer of the present disclosure. The layer or film may cover the entire treated object or only a portion of the treated object.

[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 using the surface treatment agent containing the polymer of the present disclosure.

[0168] The substrate that can be used in this embodiment may be made of any appropriate material, such as glass, resin (which may be a natural or synthetic resin, for example, a general plastic material, and may be in the form of a plate, a film, or any other form), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., or building materials.

[0169] For example, when the article to be manufactured is an optical component, the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic. When the article to be manufactured is an optical component, some layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the substrate. Either a single-layer anti-reflection layer or a multi-layer anti-reflection layer may be used as the anti-reflection layer. Examples of inorganic materials that can be used for the anti-reflection layer include SiO ２ , SiO, ZrO ２ , TiO ２ , TiO, Ti ２ O ３ , Ti ２ O ５ , Al ２ O ３ , Ta ２ O ５ , CeO ２ , MgO, Y ２ O ３ , SnO ２ , MgF ２ , W.O. ３ These inorganic substances may be used alone or in combination of two or more (for example, as a mixture). In the case of a multi-layer antireflection layer, the outermost layer may contain SiO ２ and / or SiO is preferably used. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, or the like, depending on its specific specifications.

[0170] The shape of the substrate is not particularly limited. The surface region of the substrate on which the surface treatment layer is to be formed may be at least a part of the substrate surface, and may be appropriately determined depending on the application and specific specifications of the article to be manufactured.

[0171] Such substrates may be made of materials that inherently contain hydroxyl groups, at least at their surface. Examples of such materials include glass, metals (especially base metals), ceramics, semiconductors, and the like, on whose surfaces native oxide or thermal oxide films form. Alternatively, in cases where the presence of hydroxyl groups is insufficient, such as in resins, or in cases where hydroxyl groups are not inherently present, some pretreatment of the substrate can be used to introduce or increase the number of hydroxyl groups on the substrate 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 monomolecular film on the substrate surface by the Langmuir-Blodgett method (LB method) or chemical adsorption method, and then the unsaturated bonds are cleaved in an atmosphere containing oxygen, nitrogen, or the like.

[0172] Alternatively, at least the surface portion of such a substrate may be made of a material containing 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 of this embodiment can be carried out by applying the surface treatment agent to the surface of the substrate so as to coat the surface. The coating method is not particularly limited. For example, a wet coating method or a dry coating method can be used.

[0175] Examples of wet coating methods include dip 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 beam, high frequency heating using microwaves or the like, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

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

[0178] When using the wet coating method, the surface treatment agent of the present disclosure may be diluted with a solvent and then applied to the surface of a substrate. From the viewpoint of the stability of the surface treatment agent 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, mineral spirits, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha, etc.; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, calcium acetate, Esters such as sorbitol, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; ethyl cellosolve, methyl cellosolve, and the like. Glycol ethers such as cellulose acetate, 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., C; ６ F １３ CH ２ CH ３ (For example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), C ６ F １３ H (for example, Asahiklin (registered trademark) AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Zeon Corporation); fluorine-containing 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; CF ３ CH ２ OH, CF ３ CF ２ CH ２ OH, (CF ３ ) ２ fluorine-containing alcohols such as CHOH; hydrofluoroethers (HFEs) (for example, perfluoropropyl methyl ether (C ３ F ７ OCH ３ ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C ４ F ９ OCH ３ ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ４ F ９ O.C. ２ H ５ ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C ２ F ５ CF (OCH３ ) C ３ F ７ ) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF ３ CH ２ OCF ２ CHF ２ (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF ３ CH═CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.), CHF ２ethers such as CF═CHCl (for example, AMOLEA (registered trademark) 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 sulfoxide. These solvents can be used alone or as a mixture of two or more. Of these, aliphatic hydrocarbons, esters, glycol ethers, alcohols, ether alcohols, and siloxanes are preferred. Particularly preferred examples of the solvent include 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, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, diethylene glycol monomethyl ether, hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octamethylcyclotetrasiloxane, and octamethylcyclopentasiloxane. Preferably, the solvent used in the wet coating method is the same as the solvent used in the surface treatment agent of the present disclosure.

[0179] When the dry coating method is used, the surface treatment agent of the present disclosure may be subjected to the dry coating method as it is, or may be subjected to the dry coating method after being diluted with the above-mentioned solvent.

[0180] The surface treatment agent of this embodiment can be effectively used in wet coating methods, particularly spray coating, because it has good dispersibility.

[0181] The layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation.Conveniently, in the case of a wet coating method, the surface treatment agent of the present disclosure may be diluted with a solvent, and then a catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure just before application to the substrate surface.In the case of a dry coating method, the surface treatment agent of the present disclosure to which the catalyst has been added may be directly vapor-deposited (usually, vacuum vapor-deposited), or a metal porous body such as iron or copper may be impregnated with the surface treatment agent of the present disclosure to which the catalyst has been added, and then vapor-deposited (usually, vacuum vapor-deposited) using a pellet-shaped material.

[0182] Any suitable acid or base can be used as the catalyst. Examples of acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts that can be used 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 produced. The layer obtained thereby has both high surface slippage and high friction durability. Furthermore, in addition to high friction durability, depending on the composition of the surface treatment agent used, the layer may have water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (preventing water penetration into electronic components, etc.), surface slippage (or lubricity, for example, ease of wiping off stains such as fingerprints and excellent tactile feel to the fingers), etc., and can be suitably used as a functional thin film.

[0184] That is, this aspect also relates to an optical material having the above-mentioned surface treatment layer as the outermost layer.

[0185] Preferred examples of the optical material include optical materials relating to displays and the like, such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), and field emission displays (FEDs), or protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.

[0186] The article having the layer obtained by this embodiment may be, but is not particularly limited to, an optical member. Examples of optical members include lenses for eyeglasses and the like; front protective plates, anti-reflection 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 MO discs; optical fibers; and the display surfaces of watches and clocks.

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

[0188] Furthermore, the article having the layer obtained by this embodiment may be an interior or exterior component of an automobile. Examples of exterior components include windows, light covers, and exterior camera covers. Examples of interior components include instrument panel covers, navigation system touch panels, and decorative interior components.

[0189] The thickness of the layer is not particularly limited. In the case of optical members, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm, from the viewpoints of optical performance, surface slipperiness, friction 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, adhesion between the glass and the surface treatment layer is improved, and 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 making the thickness of the intermediate layer equal to or greater than the lower limit of the above range, the effect of the intermediate layer in improving adhesiveness becomes greater.

[0192] [Use as a coating agent for waterproofing and / or moisture-proofing treatment] In one aspect, the article of the present disclosure includes a film formed from the coating agent for waterproofing and / or moisture-proofing treatment. The article of this aspect includes a substrate and a film formed on the surface of the substrate from a coating agent containing the polymer of the present disclosure. Note that a layer may be used instead of the film formed from the coating agent.

[0193] The coating agent of this embodiment can impart excellent waterproof and / or moisture-proof properties, and the coating formed from the coating agent also has good durability, such as abrasion resistance. Therefore, when treating electronic components, it is possible to impart excellent waterproof and / or moisture-proof properties without impairing their performance. This can significantly reduce the possibility of failure in treated objects that may become wet (e.g., electronic devices).

[0194] The article of this aspect can be effectively used, for example, to apply a waterproof and / or moisture-proof coating treatment to components such as housings and printed circuit boards of electronic devices that may malfunction when exposed to liquids such as water. For example, applying the treatment to the housing can prevent water from entering the housing, and applying the treatment to components such as printed circuit boards can suppress water adhesion even if water does enter the housing. Furthermore, adhering water can be easily removed by drying, greatly reducing the possibility of malfunction due to water.

[0195] Examples of electronic devices that may become wet include portable electronic devices such as smartphones, tablet PCs, portable music players, portable radios, IC recorders, and wireless audio receivers, as well as measuring instruments used in wet or seawater environments, such as fish finders, depth sounders, radioactivity measuring instruments, residual chlorine meters, salinity meters, spectrodensitometers, and saccharometers. In particular, when treating electronic components including substrates and semiconductors, the use of a waterproof and / or moisture-proof coating agent makes it possible to form a durable waterproof and moisture-proof film using a solvent with low chemical corrosion, thereby imparting good waterproof and moisture-proof properties to the electronic components without impairing their performance.

[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 EL (electroluminescence) or LED (light-emitting diode) lighting; biochips, particularly substrates for medical microchannels; and the like.

[0197] The method of treatment with the coating agent of this embodiment is not particularly limited, and any method can be used as long as it allows sufficient contact between the polymer of the present disclosure and the object to be treated. 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 typically 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 treatment is typically carried out at room temperature. There are also no particular limitations on the treatment time, but typically the immersion time is approximately 1 second to 24 hours.

[0199] In order to form a coating having higher durability, it is preferable to wash the substrate with acetone, ethanol, isopropyl alcohol, hydrofluoroether, hydrofluoroolefin, etc., to remove oil from the substrate surface prior to treatment with the coating agent of this embodiment, and then dry the washed substrate. Furthermore, if the substrate is pretreated with UV ozone, atmospheric pressure plasma, oxygen plasma, etc., in addition to the above-mentioned washing, the durability of the coating can be further improved compared to an untreated substrate.

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

[0201] Second Embodiment [Polymer] The polymer in the second embodiment is formed from a mixture of monomers, and the mixture is a monomer represented by the formula (A2): CH ２ = C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ２ [R ３ and a monomer represented by formula (B): CH ２ = C(R ４ )-COO-Y-R Ｈ and a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ The monomer represented by the formula (A2), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 50 mol % or less relative to the total amount of the monomer represented by the formula (A2), the monomer represented by the formula (B), and the monomer represented by the formula (C), or the monomer represented by the formula (C) is not contained.

[0202] The polymer has a silane coupling moiety that has good adhesion to a substrate such as glass, and therefore has good adhesion to the substrate and can have high water and oil repellency. Furthermore, the surface of the formed surface treatment layer can have high water and oil repellency even after wiping the surface with an alcohol such as ethanol.

[0203] [Formula (A2)] Monomer represented by the following formula: Component (A2) CH ２ = 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) in which n is 2. １ , R ２ , R ３ and X are as defined above.

[0205] In one embodiment, the monomer represented by formula (A2) is represented by formula (A2-1): CH ２ = C(R １ )-COO-X １１ -Si[OSi(R ２ ) ３ ] ２ [R ３ In the formula: １ , R ２ , R ３ and n is as defined above; X １１ is C １－８ Alkylene group (preferably C １－６ alkylene group) or -(CH ２ ) ｎ２１１ -X １ - (CH ２ ) ｎ３１１ - and X １ has the same meaning as above; n211 is an integer of 1 to 8, preferably an integer of 1 to 6; n311 is an integer of 1 to 8, preferably an integer of 1 to 6.

[0206] In one embodiment, the monomer represented by formula (A2) is represented by formula (A2-2): CH ２ = C(R １ )-COO-X １１ -Si[OSi(R ２ ) ３ ] ２ [R ３ In the formula: １ , R ２ , R ３ and n is as defined above; X １２ is C １２－３０ Alkylene group (preferably C １８－２４ alkylene group) or -(CH ２ ) ｎ２１２ -X １ - (CH ２ ) ｎ３１２ - and X １has the same meaning as above; n212 is an integer of 12 to 30, preferably an integer of 18 to 24; n312 is an integer of 12 to 30, preferably an integer of 18 to 24.

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

[0208] [Formula (B)] The monomer represented by formula (B) has the same meaning 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 contains a monomer represented by formula (A2-1) and a monomer represented by formula (B-1).

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

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

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

[0214] In one embodiment, the polymer contains 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 contains 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 contains 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 contains 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 contains a monomer represented by formula (A2-1), a monomer represented by formula (A2-2), a monomer represented by formula (B-1), and a monomer represented by formula (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, more preferably 7 / 3 to 5 / 5. By having the above-mentioned structure, a layer (e.g., a surface treatment layer) formed from the polymer has high water repellency and oil repellency, and also has good adhesion to a substrate such as glass.

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

[0221] The monomer represented by formula (C) is contained preferably in an amount of 30 mol % or less, or no monomer represented by formula (C), 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), and more preferably in an amount of 10 mol % or less, or no monomer represented by formula (C).

[0222] In one embodiment, the monomer represented by formula (C) is contained in an amount of preferably 30 mol % or less, more preferably 10 mol % or less, based on 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 is, for example, 1 mol % or more, based on 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). As the GPC, a 1260 Infinity II (manufactured by Agilent) can be used.

[0225] The dispersity 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 dispersity is, for example, 1.0 or more. Here, the dispersity refers to the value of Mw / Mn when the weight average molecular weight Mn and the number average molecular weight Mw are used. The dispersity can be measured using GPC.

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

[0227] [Production Method] The above polymer can be produced as follows: ７ ２ -COO-Z-R ８ and a mixture of a monomer and a polymerization initiator represented by formula (A2): CH ２ = C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ２ [R ３ and a monomer represented by formula (B): CH ２ = C(R ４ )-COO-Y-R Ｈ and a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ The monomer represented by the formula (A2), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 50 mol % or less relative to the total amount of the monomer represented by the formula (A2), the monomer represented by the formula (B), and the monomer represented by the formula (C), or the monomer represented by the formula (C) is not contained.

[0228] Formula (D), Formula (A2), Formula (B) and Formula (C) have the same meanings as above. １ , X, R ２ , R ３ , R ４ , Y., R. Ｈ , R ５ , R ６ , Hal, R. ７ , Z, and R ８ have the same meanings as above.

[0229] The above production method may include, for example, the following steps: Step I': Reacting with HalCR of formula (D): ７ ２ -COO-Z-R ８ to a mixture of monomers, wherein the mixture is a polymerization initiator represented by formula (A2): CH ２ = C(R １ )-COO-X-Si[OSi(R ２ ) ３ ] ２ [R ３ and a monomer represented by formula (B): CH ２ = C(R ４ )-COO-Y-R Ｈ and a monomer represented by formula (C): CH ２ = C(R ５ )-COO-R ６ The monomer represented by the formula (A2), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 50 mol % or less relative to the total amount of the monomer represented by the formula (A2), the monomer represented by the formula (B), and the monomer represented by the formula (C), or the monomer represented by the formula (C) is not contained.

[0230] Step I' can be carried out in the same atmosphere, temperature range, and time as Step I. The catalyst and compound further contained in Step I' are the same as those in Step I.

[0231] The surface treatment agent (composition) containing the polymer, the pellets impregnated with the surface treatment agent, and the article using the surface treatment agent are each defined as above.

[0232] The polymer of the present disclosure, the surface treatment agent containing the polymer, the article having a substrate and a layer formed by the surface treatment agent, the method for producing the polymer, etc. The polymer of the present disclosure, the composition containing the polymer, the substrate and the composition are not limited to the examples given above, and various modifications in form and details are possible without departing from the spirit and scope of the claims.

[0233] The present 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 by the following methods.

[0235] [Film Thickness] The film thickness was optically measured using a spectroscopic ellipsometer M2000 (manufactured by J.A. Woollam Co.).

[0236] [Static Contact Angle] The static contact angle was measured using a fully automatic contact angle meter DropMaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) by the following method.

[0237] <Measurement of static contact angle> The static contact angle was determined by dropping 2 μL of water or n-hexadecane (HD) from a microsyringe onto a horizontally placed substrate and taking a still image 1 second after the drop using a video microscope. The static contact angles of water and n-hexadecane were measured at five different points on the surface treatment layer of the substrate, and the average values ​​were calculated and used.

[0238] [Measurement of Monomer Content] １ Measurement was performed using a H-NMR (manufactured by JEOL Ltd.).

[0239] [Measurement of number average molecular weight] Measurement was carried out using GPC under the following conditions: Solvent: tetrahydrofuran Flow rate: 0.5 mL / 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 placed in a screw bottle, purged with nitrogen, and then the lid was closed and sealed. The mixture was stirred at room temperature for 120 hours, and purified by separation with acetonitrile to obtain Polymer 1. Polymerization initiator: 3-(triethoxysilyl)propyl 2-bromo-2-methylpropanoate Component (A): 3-[tris(trimethylsilyloxy)silyl]propyl methacrylic acid Component (B): 3-(trimethoxysilyl)propyl methacrylic acid

[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 placed in a screw bottle, and after purging with nitrogen, the bottle was sealed with a lid. The mixture was stirred at room temperature for 120 hours, and then purified by liquid separation with acetonitrile to obtain Polymer 2.

[0242] Synthesis Example 3 A screw bottle was charged with 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, and the bottle was purged with nitrogen and then sealed with a lid. The mixture was stirred at room temperature for 120 hours, and then purified by liquid separation with acetonitrile to obtain Polymer 3.

[0243] Synthesis Example 4 A screw bottle was charged with 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, and the bottle was purged with nitrogen and then sealed with a lid. The mixture was stirred at room temperature for 120 hours, and then purified by separation with acetonitrile to obtain Polymer 4.

[0244] Synthesis Example 5 A screw bottle was charged with 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, and the bottle was purged with nitrogen and then sealed with a lid. The mixture was stirred at room temperature for 120 hours, and purified by liquid separation with acetonitrile to obtain Polymer 5.

[0245] (Surface Treatment Agents 1 to 5) The polymers 1 to 5 were diluted to give 20 wt % hexamethyldisiloxane solutions, thereby obtaining surface treatment agents 1 to 5.

[0246] <Formation of Surface Treatment Layer> (Examples 1 to 5) Chemically strengthened glass (manufactured by Corning Inc., Gorilla Glass, thickness 0.7 mm) was irradiated with UV / O for 10 minutes. ３ After the treatment and dry cleaning, surface treatment agents 1 to 5 diluted to 1 wt % with toluene were spin-coated at 3000 rpm for 30 seconds, followed by heat treatment in an oven at 150°C for 120 minutes to obtain a surface treatment layer.

[0247] Comparative Example 1: Chemically strengthened glass (Corning Gorilla Glass, thickness 0.7 mm) was subjected to UV / O3 treatment for 10 minutes and dry cleaning, and then octadecyltrimethoxysilane diluted to 1 wt % with toluene was spin-coated at 3000 rpm for 30 seconds. Subsequently, a heat treatment was performed in an oven at 150°C for 120 minutes to obtain a surface treatment layer.

[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 dispersity in polymers 1 to 5.

[0249]

[0250] Table 2 shows the film thickness, contact angle with water, and contact angle with hexadecane (HD) in the state in which the surface treatment layers of the Examples and Comparative Examples were wiped with Kimwipe (manufactured by Nippon Paper Industries Co., Ltd.) moistened with ethanol for 10 seconds to remove unreacted monomers and components that do not adhere to the substrate.

[0251]

[0252] Synthesis Example 6: 0.25 mL of O-(methacryloxyoxyethyl)-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 bottle, and after purging with nitrogen, the bottle was sealed with a lid. The mixture was stirred at room temperature for 120 hours, and then purified by separation with acetonitrile to obtain Polymer 6. Component (A): O-(methacryloxyoxyethyl)-n-(triethoxysilylpropyl)carbamate

[0253] Synthesis Example 7 A screw bottle was charged with 0.05 mL of O-(methacryloxyoxyethyl)-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, and the bottle was purged with nitrogen and then sealed with a lid. The mixture was stirred at room temperature for 120 hours, and then purified by liquid separation with acetonitrile to obtain Polymer 7.

[0254] (Surface Treatment Agents 6 to 7) Using polymers 6 and 7, surface treatment agents were obtained in the same manner as in Example 1.

[0255] <Formation of Surface Treatment Layer> (Examples 6 and 7) A surface treatment layer was obtained in the same manner as in Example 1 using the surface treatment agent.

[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 dispersity in polymers 6 and 7.

[0257]

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

[0259]

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

[0261] The polymer of the present disclosure has good water and oil repellency and good adhesion to substrates, and can be suitably used in a variety of fields.

Claims

A polymer formed from a mixture of monomers, The mixture comprises: 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 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 one or more carbon atoms; n is an integer of 1 to 3. and a monomer represented by 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 is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group having one or more carbon atoms. and a monomer represented by Further, formula (C): CH ２ =C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ is a monovalent organic group that does not contain a Si atom. The monomer represented by the formula (A1), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 5 mol % or less, or the monomer represented by the formula (C) is not contained. Polymer. A polymer formed from a mixture of monomers, The mixture comprises: 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 are each independently a monovalent hydrocarbon group; R ３ is a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group having one or more carbon atoms. and a monomer represented by 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 is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group having one or more carbon atoms. and a monomer represented by Further, formula (C): CH ２ =C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ is a monovalent organic group that does not contain a Si atom. A polymer containing a monomer represented by the formula (A2), a monomer represented by the formula (B), and a monomer represented by the formula (C) in an amount of 50 mol % or less relative to the total amount of the monomer represented by the formula (A2), the monomer represented by the formula (B), and the monomer represented by the formula (C), or not containing a monomer represented by the formula (C).

2. 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.

3. 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. The polymer according to any one of claims 1 to 4, having a number average molecular weight in the range of 1,000 to 50,000. 　 The polymer according to any one of claims 1 to 5, having a dispersity of less than 2.

0. The polymer according to any one of claims 1 to 6, which has a halogen atom at its terminal. 　 A surface treatment agent comprising the polymer according to any one of claims 1 to 7. The surface treatment agent according to claim 8 , which contains a polymerization initiator or a residue of a polymerization initiator. The surface treatment agent according to claim 8 or 9, which is for vacuum deposition. 　 The surface treatment agent according to claim 8 or 9, which is for wet coating. 　 A pellet containing the surface treatment agent according to any one of claims 8 to 11. 　 A coating agent for waterproof and moisture-proof treatment, comprising the polymer according to any one of claims 1 to 7. 　 The coating agent for waterproof and moisture-proof treatment according to claim 13, which contains a polymerization initiator or a residue of a polymerization initiator. 　 The coating agent for waterproof and moisture-proof treatment according to claim 13 or 14, which is for use in electronic devices. 　 An article comprising a substrate and a layer formed on the substrate from the polymer according to any one of claims 1 to 7.

17. The article of claim 16, comprising an intermediate layer between the substrate and the layer comprising silicon oxide.

18. The article according to claim 16 or 17, which is an optical element. 　 The article according to any one of claims 16 to 18, which is a display. 　 Formula (D): HalCR ７ ２ -COO-Z-R ８ [In the formula: Hal is a halogen atom; R ７ are each independently a hydrogen atom or a methyl group; R ８ is a monovalent group; Z is a divalent organic group containing an alkylene group having one or more carbon atoms. A polymerization initiator represented by a mixture of monomers and 1. A method for producing a polymer formed from The mixture comprises: 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 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 one or more carbon atoms; n is an integer of 1 to 3. and a monomer represented by 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 is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group having one or more carbon atoms. and a monomer represented by Further, formula (C): CH ２ =C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ is a monovalent organic group that does not contain a Si atom. The monomer represented by the formula (A1), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 5 mol % or less, or the monomer represented by the formula (C) is not contained. Manufacturing method. 　 Formula (D): HalCR ７ ２ -COO-Z-R ８ [In the formula: Hal is a halogen atom; R ７ are each independently a hydrogen atom or a methyl group; R ８ is a monovalent group; Z is a divalent organic group containing an alkylene group having one or more carbon atoms. A polymerization initiator represented by a mixture of monomers and 1. A method for producing a polymer formed from The mixture comprises: 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 are each independently a monovalent hydrocarbon group; R ３ is a monovalent hydrocarbon group; X is a divalent organic group containing an alkylene group having one or more carbon atoms. and a monomer represented by 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 is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; Y is a divalent organic group containing an alkylene group having one or more carbon atoms. and a monomer represented by Further, formula (C): CH ２ =C(R ５ )-COO-R ６ [In the formula: R ５ is a hydrogen atom or a methyl group; R ６ is a monovalent organic group that does not contain a Si atom. the monomer represented by the formula (A2), the monomer represented by the formula (B), and the monomer represented by the formula (C) is contained in an amount of 50 mol% or less, or the monomer represented by the formula (C) is not contained; Manufacturing method.

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