Fluorine-containing resin, active energy ray-curable composition, thermosetting composition, and cured product of the above composition

Abstract

Provided is a fluorine-containing resin capable of undergoing cation polymerization, which provides a cured product having excellent antifouling properties and sliding properties. A fluorine-containing resin is a copolymer comprising a compound (A) and a compound (B) as polymerization components, wherein the compound (A) has a functional group capable of undergoing cation polymerization and a free radical polymerizable unsaturated group, and the compound (B) has a poly(perfluoroalkylene ether) chain and a free radical polymerizable unsaturated group.

Description

Technical Field

[0001] The present invention relates to a fluorine-containing resin, an active energy ray-curable composition, a thermosetting composition, and a cured product of the above composition. Background Art

[0002] The screen surfaces of display devices such as liquid crystal displays, organic EL displays, and touch panels, and the housing surfaces of terminals such as smartphones and notebook computers are coated with antifouling coating for the purpose of stain resistance and / or scratch resistance.

[0003] The coating is usually formed by applying a coating liquid containing a fluorine-containing resin, and curing the coated surface by irradiating the coated surface with active energy rays, performing a heat treatment, or the like.

[0004] The antifouling coating is used not only on the screen surface of display devices, but also on outdoor installations, automobile components, etc., and the applications and application sites are expanding. In the curing using active energy rays, free radical polymerization curing using a resin having an unsaturated polymerizable functional group and a free radical generator is generally used (for example, Patent Document 1). As the applications and application sites expand, fluorine-containing resins that can be cured by methods other than free radical polymerization curing are required.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent document 1: International Publication No. 12 / 002361 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] An object of the present invention is to provide a cationically polymerizable fluorine-containing resin which provides a cured product having excellent antifouling properties and sliding properties.

[0010] Solutions for solving problems

[0011] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that a copolymer comprising a compound (A) having a cationically polymerizable functional group and a radically polymerizable unsaturated group and a compound (B) having a poly(perfluoroalkylene ether) chain and a radically polymerizable unsaturated group as polymerization components, i.e., a fluorine-containing resin, can be suitably used as a surface modifier, and that a cured product obtained by subjecting a resin composition containing the fluorine-containing resin to cationically polymerize has excellent antifouling properties and slip properties, thereby completing the present invention.

[0012] That is, the present invention relates to a fluorine-containing resin, which is a copolymer comprising a compound (A) having a functional group capable of cation polymerization and a free radical polymerizable unsaturated group, and a compound (B) having a poly(perfluoroalkylene ether) chain and a free radical polymerizable unsaturated group as polymerization components.

[0013] Effects of the Invention

[0014] According to the present invention, there can be provided a cationically polymerizable fluorine-containing resin which provides a cured product having excellent antifouling properties and sliding properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a diagram showing the IR spectrum of the fluorine-containing resin obtained in Synthesis Example 1.

[0016] Figure 2 To show the fluorine-containing resin obtained in Synthesis Example 1 13 Figure 1. C-NMR spectrum. DETAILED DESCRIPTION

[0017] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiment, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[0018] [Fluorine-containing resin]

[0019] The fluorine-containing resin of the present invention is a copolymer comprising, as polymer components, a compound (A) having a cationically polymerizable functional group and a radically polymerizable unsaturated group and a compound (B) having a poly(perfluoroalkylene ether) chain and a radically polymerizable unsaturated group.

[0020] Here, "as a polymerization component" means that the fluorine-containing resin of the present invention uses compound (A) and compound (B) as necessary reaction raw materials, wherein the compound (A) has a functional group capable of undergoing cation polymerization and a free radical polymerizable unsaturated group, and the compound (B) has a poly(perfluoroalkylene ether) chain and a free radical polymerizable unsaturated group.

[0021] The fluorine-containing resin of the present invention can exhibit high antifouling performance through the poly(perfluoroalkylene ether) chain, and can improve the sustainability of the antifouling performance through the functional group capable of undergoing cationic polymerization.

[0022] Next, the polymerizable components of the fluorine-containing resin will be described.

[0023] (Compound (A))

[0024] The compound (A) is a compound having a cationically polymerizable functional group and a radically polymerizable unsaturated group.

[0025] The fluorine-containing resin of the present invention can be cationically polymerized by the cationically polymerizable functional group possessed by the compound (A).

[0026] Examples of the cationically polymerizable functional group possessed by the compound (A) include a cyclic ether group and the like.

[0027] Examples of the cyclic ether group which is a functional group capable of cation polymerization include an epoxy group and an oxetanyl group, and an epoxy group is preferred.

[0028] As the radical polymerizable unsaturated group possessed by the compound (A), for example, any group containing a vinyl group may be used, and examples thereof include a (meth)acryloyl group, a (meth)acryloyloxy group, and a styryl group.

[0029] In addition, "(meth)acryloyl" means one or both of acryloyl and methacryloyl. In addition, "(meth)acrylate" mentioned later means one or both of methacrylate and acrylate.

[0030] The compound (A) is preferably a (meth)acrylate compound having a cationically polymerizable functional group and / or a styrene compound having a cationically polymerizable functional group, and more preferably a compound represented by the following formula (a1).

[0031]

[0032] (In the above formula (a1),

[0033] R a1 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0034] Y is a group containing a cyclic ether structure.)

[0035] The group containing a cyclic ether structure of Y in formula (a1) is, for example, a group containing an oxirane ring and / or an oxetane ring, and is preferably a group containing an oxirane ring and / or an oxetane ring at a terminal.

[0036] The compound represented by formula (a1) is preferably a compound represented by the following formula (a2).

[0037]

[0038] (In the above formula (a1),

[0039] R a1 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0040] R a2It is a divalent linking group formed by an alkylene group, an arylene group, or a combination of two or more selected from the group consisting of an alkylene group, an arylene group, and an ether bond (—O—).

[0041] Z is a glycidyl group, an oxetane group, an alkyloxetane group having 4 to 10 carbon atoms, or an epoxycycloalkyl group having 5 to 10 carbon atoms)

[0042] As R a2 Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms. The alkylene group may be linear, branched, or cyclic.

[0043] As R a2 The arylene group includes, for example, an arylene group having 6 to 18 carbon atoms, preferably an arylene group having 6 to 14 carbon atoms. The arylene group may be a monocyclic ring or a condensed ring. a2 Specific examples of the arylene group include phenylene and naphthylene.

[0044] R a2 The alkylene group and the arylene group may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, and the like.

[0045] Specific examples of compound (A) include epoxy group-containing (meth)acrylate compounds such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; oxetane group-containing (meth)acrylate compounds such as (3-ethyloxetane-3-yl)methyl acrylate; and mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether.

[0046] The compound (A) used as a polymerization component of the fluorine-containing resin of the present invention may be used alone or in combination of two or more.

[0047] The compound (A) can be produced by a known method, or a commercially available product can be used.

[0048] Examples of commercially available products of the compound (A) include SR-378 (manufactured by Sartmer) which is a commercial product of glycidyl acrylate; Lightester G (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer G (manufactured by NOF Corporation), SR-379 (manufactured by Sartmer), OXE-10, OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and Cyclomer M100 (manufactured by Daicel Corporation) which are commercially available products of glycidyl methacrylate.

[0049] (Compound (B))

[0050] The compound (B) is a compound having a poly(perfluoroalkylene ether) chain and a radical polymerizable unsaturated group. The poly(perfluoroalkylene ether) chain of the compound (B) enables the fluorine-containing resin of the present invention to exhibit antifouling properties.

[0051] Examples of the poly(perfluoroalkylene ether) chain of the compound (B) include a linking group having a structure in which divalent fluorinated hydrocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately linked.

[0052] Examples of the poly(perfluoroalkylene ether) chain include a linking group represented by the following formula (X-1).

[0053]

[0054] (In the above formula (X-1),

[0055] A plurality of Xs are each independently a perfluoroalkylene group.

[0056] Among the plurality of Xs, two or more perfluoroalkylene groups may be present randomly or in blocks.

[0057] n is the number of repeating units. n is, for example, 1 to 300, preferably 2 to 200, more preferably 3 to 100, further preferably 6 to 70, and most preferably 12 to 50.

[0058] Examples of the perfluoroalkylene group represented by X include the following perfluoroalkylene groups (Y-1) to (Y-6).

[0059]

[0060] X is preferably independently a perfluoromethylene group or a perfluoroethylene group, and more preferably a perfluoromethylene group and a perfluoroethylene group are present together from the viewpoint of industrial availability.

[0061] When the perfluoromethylene group (a) and the perfluoroethylene group (b) coexist, the abundance ratio (a / b) (ratio in number) thereof is preferably 1 / 10 to 10 / 1, more preferably 3 / 10 to 10 / 3.

[0062] The total number of fluorine atoms contained in one poly(perfluoroalkylene ether) chain is preferably in the range of 18 to 200, more preferably in the range of 25 to 150.

[0063] The radically polymerizable unsaturated group contained in the compound (B) is, for example, a group containing a vinyl group, and preferably a group represented by the following formulae (U-1) to (U-5).

[0064]

[0065] The compound (B) is preferably a compound having a radical polymerizable unsaturated group at both ends of the poly(perfluoroalkylene ether) chain.

[0066] Specific examples of the compound having a radically polymerizable unsaturated group at both ends of the poly(perfluoroalkylene ether) chain include compounds represented by the following formulae (b1) to (b13).

[0067] It should be noted that PFPE in formulas (b1) to (b13) is a linking group represented by the above formula (X-1).

[0068]

[0069]

[0070] The compound (B) used as a polymerization component of the fluorine-containing resin of the present invention may be used alone or in combination of two or more.

[0071] Examples of methods for producing the compound (B) include: a method of obtaining by subjecting a compound having one hydroxyl group at each end of a poly(perfluoroalkylene ether) chain to a dehydrochlorination reaction of (meth)acrylic acid; a method of obtaining by subjecting 2-(meth)acryloyloxyethyl isocyanate to an amine reaction; a method of obtaining by subjecting itaconic anhydride to an esterification reaction; a method of obtaining by reacting with styrene having a chloromethyl group in the presence of a base; a method of obtaining by subjecting a compound having one carboxyl group at each end of a poly(perfluoroalkylene ether) chain to an esterification reaction of 4-hydroxybutyl acrylate glycidyl ether; a method of obtaining by subjecting glycidyl (meth)acrylate to an esterification reaction; a method of introducing a compound having one isocyanate group at each end of a poly(perfluoroalkylene ether) chain by reacting 2-hydroxyethyl (meth)acrylate; and a method of reacting 2-hydroxyethyl (meth)acrylamide.

[0072] Among them, a method of obtaining a compound having one hydroxyl group at each end of a poly(perfluoroalkylene ether) chain by subjecting (meth)acryloyl chloride to a dehydrochlorination reaction and a method of obtaining the compound by subjecting 2-(meth)acryloyloxyethyl isocyanate to an amine reaction are particularly preferred in terms of ease of synthesis.

[0073] (Compound (C))

[0074] The fluorine-containing resin of the present invention may be a copolymer having as polymerization components a compound (A) having a functional group capable of undergoing cation polymerization and a free radical polymerizable unsaturated group, and a compound (B) having a poly(perfluoroalkylene ether) chain and a free radical polymerizable unsaturated group, and may contain compounds other than the compound (A) and the compound (B) as polymerization components.

[0075] As a polymerization component other than compound (A) and compound (B), a compound (C) having one or more functional groups selected from the group consisting of a hydroxyl group, an alkyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, and a group containing a silicone chain (hereinafter, the functional group is sometimes referred to as a "functional functional group") and a free radical polymerizable unsaturated group is preferred.

[0076] By using the compound (C) having a functional group as a polymerization component, the following functions can be imparted to the fluorine-containing resin of the present invention: higher antifouling performance and slip properties, and / or improved compatibility between the fluorine-containing resin and other resins to be mixed.

[0077] As the radical polymerizable unsaturated group possessed by the compound (C), for example, any group containing a vinyl group may be used, and examples thereof include a (meth)acryloyl group, a (meth)acryloyloxy group, and a styryl group.

[0078] The compound (C) is preferably a (meth)acrylate compound having a functional group and / or a styrene compound having a functional group.

[0079] Examples of the alkyl group as the functional group possessed by the compound (C) include alkyl groups having 1 to 18 carbon atoms.

[0080] Specific examples of the compound (C) having an alkyl group as a functional group include (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate.

[0081] Examples of the hydroxyl group as the functional group possessed by the compound (C) include hydroxyalkyl groups having 1 to 18 carbon atoms.

[0082] Specific examples of the compound (C) having a hydroxyalkyl group as a functional group include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 4-hydroxystyrene, and the like.

[0083] Examples of the alicyclic hydrocarbon group as the functional group possessed by the compound (C) include a dicyclopentyl group, an isobornyl group, and an adamantyl group.

[0084] Specific examples of the compound (C) having an alicyclic hydrocarbon group as a functional group include dicyclopentyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, hydroxyadamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and the like.

[0085] When the functional group is an adamantyl group, the compound (C) having an adamantyl group is preferably a compound represented by the following formula (C-ad).

[0086]

[0087] (In the above formula (C-ad),

[0088] R c1 A hydrogen atom or a methyl group.

[0089] R c2 It is a single bond or an alkylene group having 1 to 8 carbon atoms.

[0090] R c3 Each is independently a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group or a carboxylic anhydride group.

[0091] R c4 Each is independently a single bond or an alkylene group having 1 to 8 carbon atoms.

[0092] n is an integer from 0 to 15. )

[0093] Specific examples of the compound (C) having an adamantyl group include the following.

[0094]

[0095] Examples of the group containing an organic silicon chain as the functional group possessed by the compound (C) include a group containing a siloxane structure represented by the following formula (S1) and a group represented by the following formula (S2).

[0096]

[0097] (In the above formulas (S-1) and (S-2),

[0098] R c5Each is independently an alkyl group having 1 to 18 carbon atoms or a phenyl group.

[0099] n is the number of repeating units, which is an integer from 1 to 200. )

[0100] Specific examples of the compound (C) having a group containing an organic silicon chain as a functional group include compounds represented by the following formulae (c-si1) to (c-si8).

[0101]

[0102] (In the above formulas (c-si1) to (c-si8),

[0103] m is an integer of 1-6 for each independently.

[0104] n is an integer of 0-250 for each independently.

[0105] R c5 Each is independently an alkyl group having 1 to 18 carbon atoms or a phenyl group.

[0106] R c6 are each independently a hydrogen atom or a methyl group.)

[0107] As the compound (C) having a group including an organic silicon chain, commercially available products can be used, and examples thereof include Silaplane FM-0711, Silaplane FM-0721K, Silaplane FM-0725, and Silaplane TM-0701T (all manufactured by JNC Corporation).

[0108] When the functional group is a group containing a polyoxyalkylene chain, the compound (C) having a group containing a polyoxyalkylene chain is preferably a compound represented by the following formula (C-pae1) or (C-pae2).

[0109]

[0110] (In the above formulas (C-pae1) and (C-pae2),

[0111] R c7 Each is independently a hydrogen atom or a methyl group.

[0112] R c8 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0113] p is an integer greater than or equal to 0, q is an integer greater than or equal to 0, r is an integer greater than or equal to 0, and p+q+r is an integer greater than or equal to 1.

[0114] X, Y and Z are each independently an alkylene group having 1 to 6 carbon atoms.

[0115] As the compound (C) having a group containing a polyoxyalkylene chain, a commercially available product can be used. For example, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer AP-800, Blemmer 50PEP-300, Blemmer 70PEP-350B, Blemmer AEP series, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-800, Blemmer AET series, Blemmer 30PPT-800, Blemmer 50PPT-800, Blemmer 70PPT-800, Blemmer APT series, Blemmer 10PPB-500B, Blemmer 10APB-500B (all manufactured by NOF Corporation);As alkyl-terminated polyalkylene glycol mono(meth)acrylate, Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer 50POEP-800B, Blemmer 50AOEP-800B, Blemmer PLE-200, Blemmer ALE-200, Blemmer ALE-800, Blemmer PSE-400, Blemmer PSE-1300, Blemmer ASEP series, Blemmer PKEP series, Blemmer AKEP series, Blemmer ANE-300, Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANEP-500, Blemmer70ANEP-550 (above, manufactured by Nippon Oils and Fats Co., Ltd.), Lightester MC, Lightester 130MA, Lightester 041MA, LIGHTACRYLATE BO-A, LIGHT ACRYLATE EC-A, LIGHT ACRYLATE MTG-A, LIGHT ACRYLATE 130A, LIGHT ACRYLATE DPM-A, LIGHT ACRYLATE P-200A, LIGHT ACRYLATE NP-4EA, LIGHT ACRYLATE NP-8EA (above, manufactured by Kyeisha Chemical Co., Ltd.), etc. ;

[0116] The compound (C) used as a polymerization component of the fluorine-containing resin of the present invention may be used alone or in combination of two or more.

[0117] [Method for producing fluorine-containing resin]

[0118] The fluorine-containing resin of the present invention can be produced, for example, by polymerizing the compound (A), the compound (B), and any compound (C) in an organic solvent using a radical polymerization initiator.

[0119] As the organic solvent used in the manufacture of the fluorine-containing resin of the present invention, it is possible to appropriately select in consideration of boiling point, compatibility of polymerization components with each other, and polymerizability, and preferably ketones, esters, amides, sulfoxides, ethers, and hydrocarbons. In addition, halogen-based organic solvents in which a part or all of the hydrogen atoms contained in the structure of these organic solvents are substituted by halogens may also be used.

[0120] Specific examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene, chloroform, and 1,3-bis(trifluoromethyl)benzene.

[0121] Examples of the radical polymerization initiator used for the production of the fluorine-containing resin of the present invention include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile.

[0122] In addition to the above-mentioned radical polymerization initiators, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid, etc. may be used as necessary.

[0123] The compound (B) used for polymerization is, for example, 1 to 100 parts by mass, preferably 5 to 90 parts by mass, more preferably 10 to 75 parts by mass, further preferably 20 to 70 parts by mass, based on 100 parts by mass of the compound (A).

[0124] When the amount of the compound (B) is from 1 to 100 parts by mass based on 100 parts by mass of the compound (A), compatibility with the solvent of the obtained fluorine-containing resin and / or other resins can be ensured.

[0125] When the compound (C) is used, the amount of the compound (C) used in the polymerization can be appropriately set, and is, for example, 10 to 300 parts by mass, preferably 15 to 250 parts by mass, more preferably 30 to 200 parts by mass, and further preferably 30 to 150 parts by mass, based on 100 parts by mass of the compound (A).

[0126] The fluorine-containing resin of the present invention is preferably a copolymer comprising a structural unit represented by the following formula (A1) and a structural unit represented by the following formula (B1).

[0127] In the above copolymer, the structural unit represented by the formula (A1) is a structural unit derived from the compound (A), and the structural unit represented by the formula (B1) is a structural unit derived from the compound (B).

[0128]

[0129] (In the above formulas (A1) and (B1),

[0130] R a1 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0131] R a2 It is a divalent linking group.

[0132] Y is a group including a cyclic ether structure.

[0133] A plurality of Xs are each independently a perfluoroalkylene group.

[0134] a and b are each independently the number of repeating units. )

[0135] As R a2 A divalent linking group such as an alkylene group, an alkenylene group, an arylene group, a heterocyclic group, -O-, -S-, -NR N1 -, -CO-, -CS-, -SO2-, or a divalent linking group formed by a combination thereof. N1 is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

[0136] Examples of the alkylene group include a linear or branched alkylene group having 1 to 20 carbon atoms and a cyclic alkylene group having 3 to 20 carbon atoms.

[0137] Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms, and alkenylene groups having 2 to 8 carbon atoms are preferred.

[0138] The arylene group is preferably an arylene group having 6 to 18 carbon atoms, and more preferably an arylene group having 6 to 14 carbon atoms. The arylene group is a monocyclic or condensed ring, and is preferably a monocyclic or condensed ring having 2 to 8 condensed rings, and more preferably a monocyclic or condensed ring having 2 to 4 condensed rings. Specific examples include phenylene and naphthylene.

[0139] The heterocyclic group includes a heteroalicyclic group containing a heteroatom in an alicyclic group and an aromatic heterocyclic group containing a heteroatom in an aromatic ring group. In addition, the heterocyclic group may be a monocyclic ring or a condensed ring. Specific examples of the heterocyclic ring include, for example, an oxirane ring, an oxane ring, a sulfane ring, an oxazole ring, a thiophene ring, a thianthrene ring, a furan ring, a pyran ring, an isobenzofuran ring, a chromene ring, an xanthene ring, a phenoxazine ring, a pyrrole ring, a pyrazole ring, an isothiazole ring, an isoxazole ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an isoindolizine ring, an indole ring, an indazole ring, a purine ring, a quinolizine ring, an isoquinoline ring, a phthalazine ring, a naphthyridine ring, a quinazoline ring, a cinnoline ring, a pteridine ring, a carbazole ring, a carboline ring, a phenanthrene ring, an acridine ring, a pyrimidine ring, a phenanthroline ring, a phthalazine ring, a phenelzine ring, a phenoxazine ring, a furazan ring, and the like. Preferably, the heterocyclic group is a divalent group corresponding to these heterocyclic rings.

[0140] R N1The alkyl group may be linear, branched or cyclic. As a linear or branched alkyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is preferred, and a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms is more preferred. The cyclic alkyl group may be monocyclic or polycyclic. As a cyclic alkyl group, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms is preferred, and a substituted or unsubstituted cycloalkyl group having 4 to 14 carbon atoms is more preferred.

[0141] As R N1 The aryl group is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 14 carbon atoms. N1 Specific examples of the aryl group include phenyl and naphthyl.

[0142] As R N1 The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 15 carbon atoms.

[0143] Composition R a2 The divalent linking group of alkylene, alkenylene, arylene and heterocyclic groups, and R N1 The alkyl group, aryl group and aralkyl group may further have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a carboxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a methacryloyloxy group, an acryloxy group, an amide group, an acyl group, an aralkyl group and the like.

[0144] Examples of the group having a cyclic ether structure of Y include a cyclic ether group, and an epoxy group and an oxetanyl group are preferred, and an epoxy group is more preferred.

[0145] The structural unit represented by the formula (A1) is preferably a structural unit represented by the following formula (A1-1).

[0146]

[0147] (In the above formula (A1-1),

[0148] R a1 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0149] R a3 It is a divalent linking group formed by an alkylene group, an arylene group, or a combination of two or more selected from the group consisting of an alkylene group, an arylene group, and an ether bond (—O—).

[0150] Y 1 It is a cyclic ether group.

[0151] a is the number of repeating units. )

[0152] The structural unit represented by formula (B1) corresponds to the linking group represented by formula (X-1) of compound (B).

[0153] Preferred embodiments of the structural unit represented by formula (B1) are the same as preferred embodiments of the linking group represented by formula (X-1).

[0154] The abundance ratio of the structural unit represented by the formula (A1) and the structural unit represented by the formula (B1) in the fluorine-containing resin of the present invention is, for example, (A1):(B1)=100:0.1 to 100:100, preferably (A1):(B1)=100:1 to 100:75, more preferably 100:1 to 100:50, further preferably 100:1 to 100:30, and most preferably 100:1 to 100:15.

[0155] The ratio of formula (A1) and (B1) can be determined by 1 The copolymer may be a block copolymer or a random copolymer.

[0156] The fluorine-containing resin of the present invention preferably further contains a structural unit represented by the following formula (C1).

[0157] The structural unit represented by the formula (C1) is a structural unit derived from the compound (C).

[0158]

[0159] (In the above formula (C1),

[0160] R c1 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0161] R c2 It is a divalent linking group.

[0162] Z is a group containing one or more functional groups selected from the group consisting of a hydroxyl group, an alkyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, and a group containing a silicone chain.

[0163] c is the number of repeating units. )

[0164] As R c2 The divalent linking group may be R a2 The divalent linking groups are the same.

[0165] As the functional group of Z, a hydroxyalkyl group, a hydroxyphenyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, or a group containing a silicone chain is preferred; a hydroxyalkyl group, an isobornyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted dicyclopentyl group, a substituted or unsubstituted dicyclopentenyl group, or a group containing a polyoxyalkylene chain and a group containing a polyalkylsiloxane are more preferred; a hydroxyalkyl group, a substituted or unsubstituted adamantyl group, a polyalkylene ether group, or a polyalkylsiloxane group is most preferred.

[0166] The amount of the structural unit represented by the formula (C1) in the fluorine-containing resin of the present invention is not particularly limited and can be appropriately set.

[0167] The number average molecular weight (Mn) of the fluorine-containing resin of the present invention is preferably in the range of 500 to 20,000, more preferably in the range of 1,200 to 10,000.

[0168] The weight average molecular weight (Mw) of the fluorine-containing resin of the present invention is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 50,000.

[0169] The number average molecular weight and weight average molecular weight are values ​​obtained by measuring by gel permeation chromatography (hereinafter, sometimes referred to as "GPC") and converted to polystyrene. The conditions for the GPC measurement are the conditions described in the Examples.

[0170] [Resin composition]

[0171] The resin composition containing the fluorine-containing resin of the present invention has a functional group capable of undergoing cationic polymerization, and therefore, by further comprising a photoacid generator or a thermal acid generator, cationic polymerization can be performed. By comprising a photoacid generator, the composition of the present invention can be formed into an active energy ray-curable resin composition, and by comprising a thermal acid generator, the composition of the present invention can be formed into a thermally curable resin composition.

[0172] Cationic polymerization is different from radical polymerization in that curing is not inhibited by oxygen and, since it is polymerization that occurs simultaneously with ring opening, volume shrinkage during curing is small, and degradation of the performance of the obtained cured product can be suppressed.

[0173] The photoacid generator is a compound that generates an acid by irradiation with active energy rays such as visible light, ultraviolet light, X-rays, and electron beams, and examples thereof include onium salt-type acid generators formed by a combination of complex ions such as sulfonium salts, diazonium salts, ammonium salts, iodonium salts, thioxanthonium salts, selenium salts, selenonium salts, and iron complex salts as the cation part and onium ions such as chloride ion (Cl-), bromide ion (Br-), tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), hexafluoroantimonate (SbF6-), hexafluoroarsenate (AsF6-), and hexachloroantimonate (SbCl6-) as the anion part.

[0174] As the photoacid generator, commercially available products can be used, for example, CD1010 (Sartmer), WPAG-281, WPAG-336, WPAG-367, WPI-113 (all from Wako Pure Chemical Industries, Ltd.), IPTX, CI-5102, CI-2855 (all from Nippon Soda Co., Ltd.), UVI-6970, UVI-6974 (all from Union Carbide Corporation), RHODORSIL Photoinitiato R2074 (all from Rhone-Poulenc), IRGACURE 250 (BASF Japan Ltd.), SP-150, SP-151, SP-152, SP-170, SP-171, SP-172 (all from ADEKA Co., Ltd.), CPI-100P, CPI-101A, CPI-210S, CPI-300PG (all from San-Apro Ltd.).

[0175] The thermal acid generator is a compound that generates an acid by heat, and examples thereof include a compound having a cation part that is a sulfonium salt, a diazonium salt, an ammonium salt, a phosphonium salt, an iodonium salt, an oxidized sulfonium salt, and a complex ion such as a chloride ion (Cl - ), bromide ion (Br - ) and the like to form an onium salt type acid generator.

[0176] As the thermal acid generator, commercially available products can be used, for example, CI-2624, CI-2855 (all from Nippon Soda Co., Ltd.), SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-145, SI-150, SI-160, SI-180, SI-180L (all from Sanshin Chemical Co., Ltd.), TA-90, TA-100, TA-120, TA-160, IK-1, IK-2 (all from San-Apro Ltd.), Adeka Opton CP-66, Adeka Opton CP-77 (all from ADEKA Corporation), etc.

[0177] The content of the photoacid generator or the thermal acid generator is preferably in the range of, for example, 0.01 to 0.1 parts by mass based on 100 parts by mass of the fluorine-containing resin.

[0178] The composition comprising the fluorine-containing resin of the present invention may further comprise a base monomer.

[0179] Examples of the base monomer include:

[0180] Compounds having an epoxy group such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis-(3,4-epoxycyclohexyl) adipate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexanone-methyl-dioxane, bis-(2,3-epoxycyclopentyl) ether, 2-ethylhexyl diglycol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, and trimethylolpropane triglycidyl ether;

[0181] Compounds having an oxetane ring, such as 3,3-dimethyloxetane, 2-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, and 3-methyl-3-methoxymethyloxetane;

[0182] Lactone compounds such as β-propiolactone, γ-butyrolactone, ε-caprolactone, σ-valerolactone, etc.

[0183] Cyclic carbonate compounds such as ethylene carbonate, propylene carbonate, butylene carbonate, etc.;

[0184] Polyglycidyl ether compounds of aliphatic polyols having four or more hydroxyl groups in one molecule, such as sorbitol polyglycidyl ether (DENACOL EX-611, DENACOL EX-612, DENACOL EX-614, DENACOL EX-614B, DENACOL EX-622: all manufactured by Nagase ChemteX Corporation) and pentaerythritol polyglycidyl ether (DENACOL EX-411: manufactured by Nagase ChemteX Corporation);

[0185] A polyglycidyl ether compound of a polyether polyol obtained by adding one or two or more alkylene oxides to an aliphatic polyol having four or more hydroxyl groups in one molecule;

[0186] A polyglycidyl ether compound of a polyether alcohol obtained by adding an alkylene oxide to a phenol having four or more hydroxyl groups in one molecule;

[0187] Aliphatic polycarboxylic acid derivatives having 4 or more carboxyl groups in one molecule, such as butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (Epolide GT-401: manufactured by Daicel Corporation) and ethanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) ester, and compounds having one or more epoxy groups or oxetane groups;

[0188] A condensation reaction product of 3-ethyl-3-oxetanemethanol and a silane tetraol polycondensate or the like (ARONE OXETANEOXT-191 (average condensation degree of silane tetraol polycondensate 5): manufactured by Toagosei Co., Ltd.);

[0189] Silanetriol or silanetetraol or a condensation product derivative thereof, and a compound having one or two or more epoxy groups or oxetane groups, etc.

[0190] The composition comprising the fluorine-containing resin of the present invention preferably contains an organic solvent from the viewpoint of being able to adjust the viscosity of the composition and adjust the thickness of the obtained coated film.

[0191] Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tert-butyl alcohol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0192] These organic solvents may be used alone or in combination of two or more.

[0193] The composition containing the fluorine-containing resin of the present invention may contain various particles such as PTFE (polytetrafluoroethylene) particles, polyethylene particles, polypropylene particles, carbon particles, titanium oxide particles, aluminum oxide particles, copper particles, and silica particles within the range that does not impair the effects of the present invention; various additives such as polymerization initiators, inhibitors, antistatic agents, defoaming agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, antioxidants, rust inhibitors, slip agents, waxes, gloss modifiers, release agents, compatibilizers, conductivity modifiers, pigments, dyes, dispersants, dispersion stabilizers, and surfactants.

[0194] [cured material]

[0195] The cured product obtained by curing the active energy ray-curable resin composition of the present invention or the thermosetting resin composition of the present invention has excellent antifouling properties and slip properties. Therefore, by applying it to the surface of an article and curing it, antifouling properties and slip properties can be imparted to the surface of the article, and an article that is not easily contaminated or scratched can be formed.

[0196] The cured product obtained by curing the active energy ray-curable resin composition of the present invention or the thermosetting resin composition of the present invention has excellent antifouling properties and slip properties, and can therefore be suitably used as a protective film (hard coat) or resist material for displays such as liquid crystal displays and OLED displays.

[0197] As wireless communication systems become more sophisticated, the use of microwaves with extremely short wavelengths is promoted. In order to prevent the attenuation of microwaves, the need to replace the housing of smartphones from metal to plastic has also increased. However, the plastic hard coating formed by the cured product of the composition of the present invention can impart excellent antifouling and sliding properties (scratch resistance) to the surface of the plastic smartphone housing.

[0198] When the cured product obtained by curing the active energy ray-curable resin composition of the present invention or the thermosetting resin composition of the present invention is made into a protective film for a display, the thickness of the protective film can be set to, for example, 1 to 200 μm, preferably 1 to 100 μm, and more preferably 1 to 70 μm. Compared with free radical polymerization curing, cationic polymerization curing has no curing hindrance caused by oxygen and has less curing shrinkage, so the film thickness can be increased to improve the hardness of the film.

[0199] Example

[0200] Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples.

[0201] It should be noted that the IR spectrum of the obtained fluorine-containing polymerizable resin 13 The measurement conditions of C-NMR spectrum and GPC are as follows.

[0202] [IR spectrum measurement conditions]

[0203] The resin solutions obtained in Examples were measured by the KBr method using the following apparatus.

[0204] Device: "FT / IR-6100" manufactured by JASCO Corporation

[0205] [ 13 C-NMR spectroscopy conditions]

[0206] Device: JNM-ECA500 manufactured by JEOL Ltd.

[0207] Solvent: Acetone-d6

[0208] [GPC measurement conditions]

[0209] Measuring device: HLC-8220GPC manufactured by Tosoh Corporation

[0210] Column: Protective column "HHR-H" manufactured by Tosoh Corporation (6.0 mm I.D. × 4 cm)

[0211] + "TSK-GEL GMHHR-N" made by Tosoh Corporation (7.8mmI.D.×30cm)

[0212] + "TSK-GEL GMHHR-N" made by Tosoh Corporation (7.8mmI.D.×30cm)

[0213] + "TSK-GEL GMHHR-N" made by Tosoh Corporation (7.8mmI.D.×30cm)

[0214] + "TSK-GEL GMHHR-N" made by Tosoh Corporation (7.8mmI.D.×30cm)

[0215] Detector: Evaporative light scattering detector (ELSD2000 manufactured by Alltech Japan Co., Ltd.)

[0216] Data processing: Tosoh Corporation "GPC-8020model II data analysis version 4.30"

[0217] Determination conditions: column temperature 40°C

[0218] Developing solvent: tetrahydrofuran (THF)

[0219] Flow rate 1.0ml / min

[0220] Sample: A tetrahydrofuran solution having a solid content of 1.0% by mass was filtered through a microfilter (5 μl).

[0221] Standard sample: According to the measurement manual of the aforementioned "GPC-8020 model II data analysis version 4.30", the following monodisperse polystyrene with a known molecular weight was used.

[0222] (monodisperse polystyrene)

[0223] "A-500" manufactured by Tosoh Corporation

[0224] "A-1000" manufactured by Tosoh Corporation

[0225] "A-2500" manufactured by Tosoh Corporation

[0226] "A-5000" manufactured by Tosoh Corporation

[0227] "F-1" manufactured by Tosoh Corporation

[0228] "F-2" manufactured by Tosoh Corporation

[0229] "F-4" manufactured by Tosoh Corporation

[0230] "F-10" manufactured by Tosoh Corporation

[0231] "F-20" manufactured by Tosoh Corporation

[0232] "F-40" manufactured by Tosoh Corporation

[0233] "F-80" manufactured by Tosoh Corporation

[0234] "F-128" manufactured by Tosoh Corporation

[0235] "F-288" manufactured by Tosoh Corporation

[0236] "F-550" manufactured by Tosoh Corporation

[0237] Synthesis example 1

[0238] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (b-1), 20 parts by mass of diisopropyl ether as a solvent, 0.02 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 3.1 parts by mass of triethylamine as a neutralizing agent were placed, and stirring was started under an air flow. While the temperature in the flask was maintained at 10° C., 2.7 parts by mass of acryloyl chloride was added dropwise over 1 hour.

[0239] After completion of the dropwise addition, the mixture was stirred at 10°C for 1 hour, heated to 30°C for 1 hour, and then heated to 50°C and stirred for 10 hours to allow the reaction to proceed. The resulting reaction solution was measured by gas chromatography to confirm the disappearance of methacryloyl chloride.

[0240]

[0241] (Where,

[0242] A plurality of Xs are each independently a perfluoromethylene group or a perfluoroethylene group. An average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present in one molecule, and an average of 46 fluorine atoms are present.

[0243] The number average molecular weight based on GPC was 1500. )

[0244] Next, 40 parts by mass of diisopropyl ether and 80 parts by mass of ion exchange water were added to the reaction solution as a solvent, and the mixture was stirred and then allowed to stand, and the separated water layer was removed, and washing was repeated three times. 0.02 parts by mass of p-methoxyphenol was added to the reaction solution after washing as a polymerization inhibitor, and 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day to completely dehydrate, and the dehydrating agent was filtered out.

[0245] Next, the solvent was distilled off under reduced pressure to obtain a compound having a poly(perfluoroalkylene ether) chain represented by the following formula (B-1) (hereinafter, abbreviated as “compound (B-1)”).

[0246]

[0247] (Where,

[0248] Multiple Xs are each independently a perfluoromethylene group or a perfluoroethylene group, and there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups in each molecule, and the average number of fluorine atoms is 46.)

[0249] Synthesis example 2

[0250] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the above formula (b-1), 10 parts by mass of diisopropyl ether as a solvent, 0.006 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 3.3 parts by mass of triethylamine as a neutralizing agent were placed, and stirring was started under an air flow. While the temperature in the flask was maintained at 10° C., 3.1 parts by mass of methacryloyl chloride was added dropwise over 2 hours.

[0251] After completion of the dropwise addition, the mixture was stirred at 10°C for 1 hour, heated to 30°C for 1 hour, and then heated to 50°C and stirred for 10 hours to allow the reaction to proceed. The resulting reaction solution was measured by gas chromatography to confirm the disappearance of methacryloyl chloride.

[0252] Next, 70 parts by mass of diisopropyl ether and 80 parts by mass of ion exchange water were added to the reaction solution as a solvent, and the mixture was stirred and then allowed to stand, and the separated water layer was removed, and washing was repeated three times. 0.02 parts by mass of p-methoxyphenol was added to the reaction solution after washing as a polymerization inhibitor, and 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day to completely dehydrate, and the dehydrating agent was filtered out.

[0253] Next, the solvent was distilled off under reduced pressure to obtain a compound having a poly(perfluoroalkylene ether) chain represented by the following formula (B-2) (hereinafter, abbreviated as “compound (B-2)”).

[0254]

[0255] (Where,

[0256] Multiple Xs are each independently a perfluoromethylene group or a perfluoroethylene group, and there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups in each molecule, and the average number of fluorine atoms is 46.)

[0257] Synthesis example 3

[0258] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 200 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the above formula (b-1), 123.4 parts by mass of p-chloromethylstyrene, 0.06 parts by mass of p-methoxyphenol, 32.3 parts by mass of a 50% by mass aqueous solution of benzyltriethylammonium chloride, and 1.35 parts by mass of potassium iodide were placed, and stirring was started under an air flow. While the temperature in the flask was maintained at 45° C., 9.2 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 2 hours.

[0259] After completion of the dropwise addition, the mixture was stirred at 60° C. for 1 hour, 37.1 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 4 hours, and then the mixture was reacted for further 15 hours.

[0260] After the reaction is completed, the generated salt is filtered off, the filtrate is allowed to stand, and the supernatant is removed. Further 500 mL of water is added and washed with water three times. After washing with water, it is further washed with 500 mL of methanol three times. In the reaction solution after washing, 0.06 parts by mass of p-methoxyphenol and 0.2 parts by mass of 3,5-di-tert-butyl-4-hydroxytoluene (hereinafter referred to as "BHT") as inhibitors are added, and the methanol is distilled off while concentrating with a water bath set to 45°C and a rotary evaporator, thereby obtaining a compound having a poly(perfluoroalkylene ether) chain and styrene groups at both ends thereof as shown in the following formula (B-3) (hereinafter referred to as "compound (B-3)").

[0261]

[0262] (Where,

[0263] Multiple Xs are each independently a perfluoromethylene group or a perfluoroethylene group, and there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups in each molecule, and the average number of fluorine atoms is 46.)

[0264] Synthesis example 4

[0265] A compound represented by the following formula (B-4) was obtained by carrying out the reaction in the same manner as in Synthesis Example 3 except that the compound represented by the following formula (b-2) was used instead of the above formula (b-1).

[0266]

[0267] (Where,

[0268] A plurality of Xs are each independently a perfluoromethylene group or a perfluoroethylene group. An average of 19 perfluoromethylene groups and an average of 19 perfluoroethylene groups are present in one molecule, and an average of 114 fluorine atoms are present.

[0269] The number average molecular weight based on GPC was 4000. )

[0270]

[0271] (Where,

[0272] Multiple Xs are each independently a perfluoromethylene group or a perfluoroethylene group, and there are an average of 19 perfluoromethylene groups and an average of 19 perfluoroethylene groups in each molecule, and the average number of fluorine atoms is 114.

[0273] [Manufacture of fluorine-containing resin]

[0274] Synthesis Example 1

[0275] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 180 parts by mass of butyl acetate as a solvent was placed, and the temperature was raised to 105° C. under a nitrogen gas stream while stirring. Next, three dropping liquids, namely, 36 parts by mass of the liquid of the compound (B-1) having a poly(perfluoroalkylene ether) chain prepared in Synthesis Example 1, a monomer solution mixed with 144 parts by mass of glycidyl methacrylate and 327 parts by mass of butyl acetate as a solvent, and an initiator solution mixed with 27 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 33 parts by mass of butyl acetate as a solvent, were attached to the dropping devices, respectively, and the flask was kept at 105° C. while being dropped simultaneously over 2 hours.

[0276] After completion of the dropwise addition, the mixture was stirred at 105°C for 5 hours and cooled to room temperature. Butyl acetate was added to the reaction mixture for dilution and then filtered to obtain a butyl acetate solution containing 20 mass % of the fluorinated resin (P1) having a cationically polymerizable group.

[0277] The molecular weight of the obtained fluorine-containing resin (P1) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,700 and the weight average molecular weight was 6,500.

[0278] It should be noted that the structure of the obtained fluorine-containing resin (P1) can be determined from IR spectrum and 13 The results of IR spectrum are shown in Figure 1 ,about 13 The results of C-NMR spectroscopy are shown in Figure 2 .

[0279] Synthesis Example 2

[0280] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 180 parts by mass of butyl acetate as a solvent was placed, and the temperature was raised to 105° C. under a nitrogen gas stream while stirring. Next, three dropping liquids, namely, 36 parts by mass of a liquid of the compound (B-2) having a poly(perfluoroalkylene ether) chain prepared in Synthesis Example 1, a monomer solution mixed with 72 parts by mass of glycidyl methacrylate, 72 parts by mass of 2-hydroxypropyl methacrylate, and 327 parts by mass of butyl acetate as a solvent, and an initiator solution mixed with 27 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 33 parts by mass of butyl acetate as a solvent, were attached to the dropping devices, respectively, and the flask was kept at 105° C. while being dropped simultaneously over 2 hours.

[0281] After completion of the dropwise addition, the mixture was stirred at 105°C for 5 hours and cooled to room temperature. Butyl acetate was added to the reaction solution for dilution and then filtered to obtain a butyl acetate solution containing 20 mass % of the fluorinated resin (P2) having a cationically polymerizable group.

[0282] The molecular weight of the obtained fluorine-containing resin (P2) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 1,400 and the weight average molecular weight was 4,000.

[0283] Synthesis Example 3

[0284] Polymerization was carried out in the same manner as in Synthesis Example 2, except that a single terminal methacryloyl group-containing monomer having a polydimethylsiloxane chain represented by the following formula (C-1) was used instead of 2-hydroxypropyl methacrylate as the hydroxyl-containing monomer, and a monomer solution prepared by mixing 126 parts by mass of glycidyl methacrylate, 18 parts by mass of a single terminal methacryloyl group-containing monomer having a polydimethylsiloxane chain represented by the following formula (C-1), and 327 parts by mass of butyl acetate as a solvent was used as the monomer solution. A fluorine-containing resin (P3) having a cationically polymerizable group was obtained.

[0285] The molecular weight of the obtained fluorine-containing resin (P3) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,800 and the weight average molecular weight was 8,000.

[0286]

[0287] (In the formula, n is 65 on average.)

[0288] Synthesis Example 4

[0289] Polymerization was carried out in the same manner as in Synthesis Example 2, except that polypropylene glycol monomethacrylate ("Blemmer PP-1000" manufactured by NOF Corporation, hydroxyl value 382, ​​number of repeating units of propylene oxide unit: average 6) as a monomer having a hydroxyl group and a polyoxyalkylene chain was used instead of 2-hydroxypropyl methacrylate as a hydroxyl monomer, to obtain a fluorine-containing resin (P4) having a cationically polymerizable group.

[0290] The molecular weight of the obtained fluorine-containing resin (P4) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,200 and the weight average molecular weight was 5,300.

[0291] Synthesis Example 5

[0292] Polymerization was carried out in the same manner as in Synthesis Example 2, except that the compound (B-3) prepared in Synthesis Example 3 was used instead of the compound (B-1), and 2-methyl-2-adamantyl methacrylate was used as the adamantyl monomer instead of 2-hydroxypropyl methacrylate as the hydroxyl monomer, to obtain a fluorine-containing resin (P5) having a cationically polymerizable group.

[0293] The molecular weight of the obtained fluorine-containing resin (P5) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 1,500 and the weight average molecular weight was 4,400.

[0294] Synthesis Example 6

[0295] Polymerization was carried out in the same manner as in Synthesis Example 1 except that the compound (B-4) prepared in Synthesis Example 4 was used instead of the compound (B-1) and 1,3-bis(trifluoromethyl)benzene was used instead of butyl acetate as the solvent to obtain a fluorine-containing resin (P6) having a cationically polymerizable group.

[0296] The molecular weight of the obtained fluorine-containing resin (P6) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 1,600 and the weight average molecular weight was 10,000.

[0297] Synthesis Comparative Example 1

[0298] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 210.5 parts by mass of methyl isobutyl ketone as a solvent was placed, and the temperature was raised to 105° C. under a nitrogen gas stream while stirring. Next, three dropping liquids, 42.1 parts by mass of the liquid of the compound (B-1) having a poly(perfluoroalkylene ether) chain obtained in Synthesis Example 1, a monomer solution in which 168.4 parts by mass of polypropylene glycol monomethacrylate (“Blemmer PP-1000” manufactured by NOF Corporation, hydroxyl value 382, ​​number of repeating units of propylene oxide units: average 6) and 109.3 parts by mass of methyl isobutyl ketone as a solvent were mixed, and an initiator solution in which 31.6 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 71.2 parts by mass of methyl isobutyl ketone as a solvent were mixed were respectively installed in the dropping devices, and the flask was kept at 105° C. and dropped simultaneously over 2 hours.

[0299] After completion of the dropwise addition, the mixture was stirred at 105°C for 5 hours and cooled to room temperature. Methyl isobutyl ketone was added to the reaction solution to dilute it, and the mixture was filtered to obtain a methyl isobutyl ketone solution containing 20% ​​by mass of the fluorinated resin (Q1).

[0300] The molecular weight of the fluorine-containing resin (Q1) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,400 and the weight average molecular weight was 5,700.

[0301] Synthesis Comparative Example 2

[0302] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 128.3 parts by mass of methyl isobutyl ketone as a solvent was placed, and the temperature was raised to 90° C. while stirring under a nitrogen gas stream. Next, two dropping liquids, a monomer solution containing 30.4 parts by mass of 2-(perfluorohexyl)ethyl acrylate, 65.8 parts by mass of glycidyl methacrylate, and 76.9 parts by mass of methyl isobutyl ketone as a solvent, and an initiator solution containing 5.8 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a free radical polymerization initiator and 19.2 parts by mass of methyl isobutyl ketone as a solvent, were respectively installed in the dropping devices, and the flask was kept at 90° C. while being dropped simultaneously over 2 hours.

[0303] After completion of the dropwise addition, the mixture was stirred at 90°C for 10 hours and cooled to room temperature. Methyl isobutyl ketone was added to the reaction solution to dilute it, and the mixture was filtered to obtain a methyl isobutyl ketone solution containing 20% ​​by mass of the fluorinated resin (Q2).

[0304] The molecular weight of the fluorine-containing resin (Q2) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,300 and the weight average molecular weight was 5,000.

[0305] Comparative Synthesis Example 3

[0306] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 180 parts by mass of butyl acetate as a solvent was placed, and the temperature was raised to 105° C. under a nitrogen gas stream while stirring. Next, three kinds of dropping liquids, namely, 36 parts by mass of a single terminal methacryloyl group-containing monomer having a polydimethylsiloxane chain represented by the above formula (C-1), a monomer solution mixed with 144 parts by mass of glycidyl methacrylate and 327 parts by mass of butyl acetate as a solvent, and an initiator solution mixed with 27 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 33 parts by mass of butyl acetate as a solvent, were attached to the dropping devices respectively, and the flask was kept at 105° C. while being dropped simultaneously over 2 hours.

[0307] After completion of the dropwise addition, the mixture was stirred at 105°C for 5 hours and cooled to room temperature. Butyl acetate was added to the reaction solution for dilution and the mixture was filtered to obtain a butyl acetate solution containing 20% ​​by mass of the fluorine-containing resin (Q3).

[0308] The molecular weight of the fluorine-containing resin (Q3) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,300 and the weight average molecular weight was 6,000.

[0309] [Preparation and evaluation of resin composition]

[0310] Example 1

[0311] 40 parts by mass of pentaerythritol polyglycidyl ether ("DENACOL EX-411" manufactured by NAGASE CHEMTEX CORPORATION), 2 parts by mass of the butyl acetate solution containing 20% ​​by mass of the fluorine-containing resin (P1) prepared in Synthesis Example 1, 2 parts by mass of diphenyl[4-(phenylthio)phenyl]sulfonium trifluorotris(pentafluoroethyl)phosphate ("CPI-210S" manufactured by San-Apro Ltd.) as a photoacid generator, and 24 parts by mass of toluene, 12 parts by mass of 2-propanol, 12 parts by mass of ethyl acetate and 12 parts by mass of propylene glycol monomethyl ether as a solvent were mixed and dissolved to obtain a resin composition.

[0312] The obtained resin composition was applied onto a 188 μm thick PET film using a bar coater No. 13, and then dried at 60° C. for 5 minutes in a dryer to evaporate the solvent. The film was cured using an ultraviolet curing device (under a nitrogen atmosphere, using a high-pressure mercury lamp, ultraviolet irradiation of 25 kJ / m 2 ) to solidify the coating on the PET film and form a hard coating layer with a thickness of 10 μm on the PET film.

[0313] The following evaluations were performed on the obtained PET film having a hard coat layer. The results are shown in Table 1.

[0314] (Water repellency evaluation)

[0315] A 3 μL drop of ultrapure water was dropped onto the hard coat layer using a contact angle measuring device (DM-500 manufactured by Kyowa Interface Science Co., Ltd.) to measure the contact angle of the drop. The contact angle was measured five times, and the average value of the five times was taken as the contact angle of the hard coat surface.

[0316] (Oil repellency evaluation)

[0317] A 3 μL drop of n-decane was dropped onto the hard coat layer using a contact angle measuring device (DM-500 manufactured by Kyowa Interface Science Co., Ltd.) to measure the contact angle of the drop. The contact angle was measured five times, and the average of the five times was taken as the contact angle of the hard coat surface.

[0318] (Antifouling evaluation)

[0319] A line was drawn on the surface of the hard coat layer with a felt pen (Magic ink large blue manufactured by Teranishi Chemical Industry Co., Ltd.), and the ink adhesion state on the surface of the hard coat layer was visually observed. The antifouling property of the hard coat layer was evaluated according to the following criteria.

[0320] ◎: Ink is spherical and repelled

[0321] ○: The ink is not repelled in a spherical shape, but linearly repelled (the line width is less than 50% of the pen tip width)

[0322] △: The ink is not repelled in a spherical shape, but is repelled linearly (the line width is more than 50% and less than 100% of the pen tip width)

[0323] ×: The ink is not repelled at all and is applied cleanly on the surface

[0324] After the above anti-fouling test, wipe off all the attached ink with tissue paper, draw a line on the same part of the hard coating surface with a felt pen again, wipe off all the attached ink with tissue paper, and repeat this operation. The number of times the contaminant is wiped off until the ink is no longer repelled on the hard coating surface is evaluated.

[0325] This operation was performed 10 times at most, and when the hard coat layer repelled the ink even after wiping off the attached ink 10 times, the evaluation result was recorded as ">10".

[0326] (Sliding property evaluation)

[0327] The dynamic friction coefficient was measured using a dynamic friction coefficient measuring device (Tribogear TYPE: 38, manufactured by Shinto Scientific Co., Ltd.). The dynamic friction coefficient of the hard coating surface was measured using a ball indenter, a load of 100 g, and a travel speed of 300 mm / min. The measurement was performed three times, and the average value of the three times was taken as the dynamic friction coefficient of the hard coating surface.

[0328] Examples 2-6 and Comparative Examples 1-4

[0329] The resin compositions were prepared and evaluated in the same manner as in Example 1 except that the fluorine-containing resins shown in Table 1 were used in place of the fluorine resin (P1).

[0330] In addition, in Comparative Example 4, no fluorine-containing resin was used.

[0331] [Table 1]

[0332]

[0333] Example 7

[0334] 40 parts by mass of pentaerythritol polyglycidyl ether ("DENACOL EX-411" manufactured by NAGASE CHEMTEX CORPORATION), 2 parts by mass of the butyl acetate solution containing 20% ​​by mass of the fluorine-containing resin (P1) prepared in Synthesis Example 1, 2 parts by mass of an aromatic sulfonium antimony hexafluoride salt ("SAN-AID SI-60L" manufactured by Sanshin Chemical Co., Ltd.) as a thermal acid generator, and 24 parts by mass of toluene, 12 parts by mass of 2-propanol, 12 parts by mass of ethyl acetate, and 12 parts by mass of propylene glycol monomethyl ether as a solvent were mixed and dissolved to obtain a resin composition.

[0335] The obtained resin composition was applied on a glass plate having a thickness of 2 mm using a bar coater No. 13, and then dried at 60° C. for 5 minutes in a dryer to volatilize the solvent. The coating on the glass plate was heated at 90° C. for 90 minutes to cure, thereby forming a hard coating layer having a thickness of 7 μm on the glass plate.

[0336] The obtained glass plate with hard coating was evaluated in the same manner as in Example 1. As a result, the water contact angle was 109°, the dodecane contact angle was 59°, and the dynamic friction coefficient was 0.16. From these results, it can be seen that the same antifouling property and sliding property can be obtained even when a thermal acid generator is used instead of a photoacid generator.

Claims

1. A resin composition comprising a fluorine-containing resin, wherein the fluorine-containing resin is a copolymer of a compound A having a functional group capable of undergoing cation polymerization and a free radical polymerizable unsaturated group and a compound B having a poly(perfluoroalkylene ether) chain and a free radical polymerizable unsaturated group, or a copolymer of the compound A, the compound B and a compound C, wherein the compound C has one or more functional groups selected from the group consisting of a hydroxyl group, an alkyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, and a group containing a silicone chain, and a free radical polymerizable unsaturated group, The compound B is one or more of the compounds represented by the following formulas (b1) to (b13), The PFPE in the formulas (b1) to (b13) is a linking group represented by the following formula (X-1), In the formula (X-1), A plurality of X's are each independently a perfluoroalkylene group, Among the plurality of X, two or more perfluoroalkylene groups may exist randomly or in blocks. n is the number of repeating units, ranging from 1 to 300, The amount of the compound B is 1 to 100 parts by mass based on 100 parts by mass of the compound A, and the amount of the compound C is 10 to 300 parts by mass based on 100 parts by mass of the compound A.

2. The resin composition according to claim 1, wherein The free radical polymerizable unsaturated group is a vinyl group.

3. The resin composition according to claim 1 or 2, wherein The compound A is a (meth)acrylate compound having a functional group capable of undergoing cation polymerization and / or a styrene compound having a functional group capable of undergoing cation polymerization.

4. The resin composition according to claim 1 or 2, wherein The compound A is a (meth)acrylate compound having a functional group capable of undergoing cation polymerization.

5. The resin composition according to claim 1 or 2, wherein The functional group capable of undergoing cationic polymerization is a cyclic ether group.

6. The resin composition according to claim 1 or 2, wherein The functional group capable of undergoing cationic polymerization is an epoxy group or an oxetane group.

7. The resin composition according to claim 1, wherein The fluorine-containing resin comprises a structural unit represented by the following formula (A1) and a structural unit represented by the following formula (B1), In the formulas (A1) and (B1), R a1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R a2 is a divalent linking group, Y is a group containing a cyclic ether structure, A plurality of X's are each independently a perfluoroalkylene group, a and b are each independently the number of repeating units.

8. The resin composition according to claim 7, wherein The fluorine-containing resin has a structural unit represented by the following formula (C1): In the formula (C1), R c1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R c2 is a divalent linking group, Z is a group containing one or more functional groups selected from the group consisting of a hydroxyl group, an alkyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, and a group containing a silicone chain, c is the number of repeating units. 9 . The resin composition according to claim 1 , which is an active energy ray-curable resin composition further comprising a photoacid generator. 10 . The resin composition according to claim 1 , which is a thermosetting resin composition further comprising a thermal acid generator. 11 . A cured product, which is a cured product of the composition according to claim 9 or 10. 12 . The cured product according to claim 11 , which is a protective film for a display, a plastic hard coat, or a resist material.

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