Active energy ray-curable resin composition

Abstract

To provide an active energy ray-curable resin composition that has excellent adhesion to various base materials and is, therefore, useful as a coating-forming material and an adhesive.SOLUTION: An active energy ray-curable resin composition contains a partially ethylenically unsaturated group-containing epoxy resin (A) that is obtained by the reaction between an epoxy resin (a) having three or more epoxy groups in one molecule and a compound (b) having both of one or more ethylenically unsaturated groups and one carboxyl group in one molecule.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable resin composition, a film-forming material, an adhesive, and a cured product thereof. [Background technology]

[0002] Active energy ray-curable resin compositions that cure when irradiated with active energy rays such as ultraviolet rays or electron beams have been developed and are in practical use for a variety of applications, including printing, coatings, electrical insulation, etc. Their advantages include (1) being solvent-free and low-pollution, (2) being extremely fast in curing speed, resulting in high productivity, (3) being cured as a solid, resulting in extremely small volume change before and after curing, and (4) not causing heat loss or being affected by heat on the material, and various active energy ray-curable resin compositions have also been developed for use in coatings and adhesives for plastics, paper, inorganic materials, etc.

[0003] In active energy ray-curable resin compositions, (meth)acrylate oligomers or (meth)acrylate monomers are often used as polymerization components, as in Patent Document 1. Such (meth)acrylate compounds are highly reactive and readily homopolymerize or copolymerize with other ethylenically unsaturated group-containing compounds in the presence of heat, ultraviolet light, radiation, electron beams, or a polymerization initiator.

[0004] However, although the active energy ray-curable resin compositions that have been developed to date have excellent adhesive strength to specific substrates, there have been few adhesives that have excellent adhesive strength to multiple types of substrates, and therefore there has been a demand for the development of new active energy ray-curable resin compositions. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-36253 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have made this invention in view of the above circumstances, and it is an object of the present invention to provide an active energy ray-curable resin composition which contains a partially ethylenically unsaturated group-containing epoxy resin having a specific structure and which has excellent adhesion to a plurality of types of substrates. [Means for solving the problem]

[0007] As a result of intensive research to solve the above problems, the present inventors have found that an active energy ray-curable resin composition containing a partially ethylenically unsaturated group-containing epoxy resin having a specific structure has excellent adhesion to a plurality of types of substrates, and have arrived at the present invention.

[0008] That is, the present invention relates to the following [1] to

[11] . In this specification, "(meth)acrylate" means "acrylate" and / or "methacrylate".

[0009] [1] An active energy ray-curable resin composition containing a partially ethylenically unsaturated group-containing epoxy resin (A) obtained by reacting an epoxy resin (a) having three or more epoxy groups in one molecule with a compound (b) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule. [2] The active energy ray-curable resin composition according to the above item [1], wherein the epoxy equivalent of the component (a) is 200 to 500 g / eq. [3] The active energy ray-curable resin composition according to the above item [1] or [2], wherein the component (a) is an epoxy resin represented by the following formula (1):

[0010] [ka]

[0011] (In formula (1), R 1each independently represents a methyl group or a hydrogen atom; n1 and n2 are repeating numbers, and represent 1≦n1≦10 and 0≦n2≦10. [4] The active energy ray-curable resin composition according to any one of the above items [1] to [3], wherein the component (A) is obtained by reacting 20 to 80 equivalent percent of the component (b) with 1 equivalent of the epoxy group of the component (a). [5] The active energy ray-curable resin composition according to any one of the above items [1] to [4], further comprising a reactive compound (B), a photoradical polymerization initiator (C), and a photoacid generator (D). [6] The active energy ray-curable resin composition according to item [5], containing 1 to 300 parts by weight of component (B), 0.1 to 30 parts by weight of component (C), and 0.1 to 30 parts by weight of component (D) relative to 100 parts by weight of component (A). [7] The active energy ray-curable resin composition according to any one of the above items [1] to [6], which is a film-forming material. [8] The active energy ray-curable resin composition according to any one of the above items [1] to [6], which is an adhesive material. [9] A cured product of the active energy ray-curable resin composition according to any one of the preceding items [1] to [8].

[10] The method for producing an active energy ray-curable resin composition according to any one of items [1] to [8], wherein the component (a) uses a betaine-type quaternary ammonium salt (E) as a catalyst.

[11] The method according to the above item

[10] , wherein the component (E) is trimethylglycine. [Effects of the Invention]

[0012] The present invention can provide an active energy ray-curable resin composition that has excellent adhesion to a variety of substrates. DETAILED DESCRIPTION OF THE INVENTION

[0013] The active energy ray-curable resin composition of the present invention contains a partially ethylenically unsaturated group-containing epoxy resin (A) obtained by reacting an epoxy resin (a) having three or more epoxy groups in one molecule with a compound (b) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule. In the present invention, the active energy ray-curable resin composition refers to one that is cured by active energy rays such as ultraviolet rays or electron beams, and the partially ethylenically unsaturated group-containing epoxy resin (A) (hereinafter also simply referred to as "component (A)") refers to a compound having one or more epoxy groups and one or more ethylenically unsaturated groups in one molecule.

[0014] Epoxy resin (a) (hereinafter simply referred to as "component (a)") having three or more epoxy groups in one molecule has good curability, heat resistance, toughness, adhesiveness, etc., due to the presence of three or more epoxy groups in one molecule.

[0015] Specific examples of component (a) include phenol novolac epoxy resins, cresol novolac epoxy resins, trishydroxyphenylmethane epoxy resins, dicyclopentadienephenol epoxy resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, biphenol epoxy resins, bisphenol-A novolac epoxy resins, naphthalene skeleton-containing epoxy resins, glyoxal epoxy resins, and heterocyclic epoxy resins.

[0016] Examples of phenol novolac epoxy resins include Epiclon N-770 (manufactured by DIC Corporation) and EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.). Examples of cresol novolac epoxy resins include Epiclon N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide Corporation), and ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.).

[0017] Examples of trishydroxyphenylmethane type epoxy resins include EPPN-503, EPPN-502H, and EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX RTM -742 (Dow Chemical Company), jER RTM Examples of dicyclopentadiene phenol type epoxy resins include Epiclon EXA-7200 (manufactured by DIC Corporation) and TACTIX RTM -556 (manufactured by Huntsman Advanced Materials), etc.

[0018] Examples of bisphenol-type epoxy resins include bisphenol-A type epoxy resins such as NER-1202 and NER-1302 (manufactured by Nippon Kayaku Co., Ltd.), and bisphenol-F type epoxy resins such as NER-7403 and NER-7604 (manufactured by Nippon Kayaku Co., Ltd.).

[0019] Examples of biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000, NC-3000-H, and NC-3500 (manufactured by Nippon Kayaku Co., Ltd.), and bixylenol-type epoxy resins.

[0020] Examples of naphthalene skeleton-containing epoxy resins include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Corporation). Examples of glyoxal-type epoxy resins include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). Examples of alicyclic epoxy resins include EHPE-3150 (manufactured by Daicel Corporation). Examples of heterocyclic epoxy resins include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

[0021] Component (a) is more preferably a biphenyl type epoxy resin, a bisphenol A type epoxy resin, or a bisphenol F type epoxy resin, and is particularly preferably an epoxy resin represented by the following formula (1).

[0022] [ka]

[0023] In formula (1), R 1 each independently represents a methyl group or a hydrogen atom, and n1 and n2 represent the number of repetitions, and represent 1≦n1≦10 and 0≦n2≦10.

[0024] In formula (1), R 1 is usually a methyl group or a hydrogen atom, but is preferably a hydrogen atom. 1 When is a hydrogen atom, the epoxy resin has a suitable flexibility and the melting point or softening point falls within an appropriate range. The softening point of component (a) is preferably 40 to 100° C., more preferably 45 to 85° C., and particularly preferably 50 to 80° C. Within the above range, it is preferable because it is less sticky and has excellent high-temperature and solvent solubility.

[0025] From the viewpoint of flexibility, the epoxy equivalent of component (a) is preferably 150 to 1000 g / eq, more preferably 200 to 500 g / eq, and particularly preferably 220 to 350 g / eq.

[0026] A compound that has one or more ethylenically unsaturated groups and one carboxyl group in one molecule Examples of (b) (hereinafter, also simply referred to as "component (b)") include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or reaction products of saturated or unsaturated dibasic acids with unsaturated group-containing monoglycidyl compounds excluding monoglycidyl (meth)acrylate derivatives. Examples include (meth)acrylic acid, β-styryl (meth)acrylic acid, β-furfuryl (meth)acrylic acid, reaction products of (meth)acrylic acid and ε-caprolactone, (meth)acrylic acid dimer, half-esters which are equimolar reaction products of saturated or unsaturated dibasic acid anhydrides with (meth)acrylate derivatives having one hydroxyl group per molecule, and half-esters which are equimolar reaction products of saturated or unsaturated dibasic acids with monoglycidyl (meth)acrylate derivatives. Preferred are (meth)acrylic acid, reaction products of (meth)acrylic acid and ε-caprolactone, and cinnamic acid. The number of ethylenically unsaturated groups is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0027] In the reaction of component (a) and component (b), the amount of component (b) relative to 1 equivalent of component (a) is preferably 20 to 80 equivalent %, more preferably 30 to 70 equivalent %, and particularly preferably 40 to 60 equivalent %.

[0028] The reaction can be carried out without a solvent or diluted with a solvent. When a solvent is used, it is not particularly limited as long as it is an inert solvent for the reaction of component (a) and component (b). When a solvent is used, the amount of solvent used should be adjusted appropriately depending on the viscosity and use of the resulting resin, but it is preferable to use a solvent so that the solid content is 99 to 30 wt %, more preferably 99 to 45 wt %. When the compound used in the reaction has a high viscosity, the viscosity is suppressed and the reaction proceeds smoothly.

[0029] Examples of the solvent include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha, etc., ester solvents, ether solvents, ketone solvents, etc., as well as alcohols, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ether acetates, lactate esters, aliphatic carboxylic acid esters, amides, ketones, etc. These may be used alone or in combination of two or more.

[0030] Specific examples of the compounds include alcohols such as benzyl alcohol; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol. Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, and other dipropylene glycol monoalkyl ether acetates; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate; ethyl hydroxyacetate aliphatic carboxylic acid esters such as ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate;Examples of suitable solvents include amides such as N-methylformamide, N,N-dimethylformamide, N-methylacetamide, and N,N-dimethylacetamide; and ketones such as N-methylpyrrolidone and γ-butyrolactone. These may be used alone or in combination of two or more.

[0031] In the above reaction, it is preferable to use a catalyst to promote the reaction. As the catalyst, known general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and zirconium octanoate may be used. However, in the present invention, it is particularly preferable to use a betaine-type quaternary ammonium salt (E) (hereinafter simply referred to as "component (E)") as the catalyst. This is because component (E) also has excellent storage stability. When component (E) is used, its amount is about 0.1 to 10% by weight based on the total amount of components (a), (b), and the solvent, if used, The reaction temperature is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. As component (E), trimethylglycine is most preferred from the viewpoint of reactivity, and an example thereof is Aminocoat manufactured by Asahi Kasei Finechem Corporation.

[0032] In the above reaction, a thermal polymerization inhibitor may be used, such as hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, or 2,6-di-t-butyl-p-cresol.

[0033] The reaction is terminated when the acid value of the sample reaches 5 mg KOH / g or less, preferably 2 mg KOH / g or less, while sampling is carried out as needed.

[0034] Examples of the reactive compound (B) (hereinafter also referred to simply as "component (B)") that can be used in the present invention include so-called reactive oligomers such as radical-reactive acrylates, other cationic-reactive epoxy compounds, and vinyl compounds that react with both of these.

[0035] Examples of radical reaction type acrylates include monofunctional (meth)acrylates, difunctional (meth)acrylates, trifunctional or higher functional (meth)acrylates, polyester (meth)acrylates, urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and epoxy (meth)acrylate oligomers.

[0036] Examples of monofunctional (meth)acrylates include acryloylmorpholine; hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; cyclohexane-1,4-dimethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. and aromatic (meth)acrylates such as phenoxyethyl (meth)acrylate, phenyl(poly)ethoxy (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, phenylphenol(poly)ethoxy (meth)acrylate, and phenylphenol epoxy (meth)acrylate.

[0037] Examples of bifunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, bisphenol A (poly)ethoxy di(meth)acrylate, bisphenol A (poly)propoxy di(meth)acrylate, bisphenol F (poly)ethoxy di(meth)acrylate, ethylene glycol di(meth)acrylate, and di(meth)acrylates of ε-caprolactone adducts of (poly)ethylene glycol di(meth)acrylate hydroxypivalic acid neopentyl glycol (e.g., KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.).

[0038] Examples of trifunctional or higher (meth)acrylates include methylols such as ditrimethylolpropane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane (poly)propoxy tri(meth)acrylate, and trimethylolpropane (poly)ethoxy (poly)propoxy tri(meth)acrylate; pentaerythritol tri(meth)acrylate, pentaerythritol polyethoxytetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. Examples of the erythritol include erythritols such as pentaerythritol (poly)propoxy tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tris[(meth)acryloyloxyethyl]isocyanurate, caprolactone-modified tris[(meth)acryloyloxyethyl]isocyanurate; succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylates.

[0039] Examples of the (poly)ester (meth)acrylate oligomer include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, polyethylene glycol, and (poly)propylene glycol; 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,8-octanediol; and reaction products of (poly)ester diols, which are reaction products of diol compounds such as bisphenol A (poly)ethoxydiol or bisphenol A (poly)propoxydiol with the above-mentioned dibasic acids or anhydrides thereof, with (meth)acrylic acid.

[0040] Examples of the urethane (meth)acrylate oligomer include diol compounds (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1 ,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxydiol, etc.), or polyesters which are reaction products of these diol compounds with dibasic acids or their anhydrides (for example, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, or their anhydrides). and organic polyisocyanates (e.g., chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate), isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis(4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, Examples of such a reaction product include a reaction product obtained by reacting a cyclic saturated hydrocarbon isocyanate, such as hydrogenated xylene diisocyanate or hydrogenated toluene diisocyanate, or an aromatic polyisocyanate, such as 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate or 1,5-naphthalene diisocyanate, followed by addition of a hydroxyl group-containing (meth)acrylate.

[0041] The epoxy (meth)acrylate oligomer is a carboxylate compound of a compound having an epoxy group and (meth)acrylic acid. Examples include phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, trishydroxyphenylmethane epoxy (meth)acrylate, dicyclopentadienephenol epoxy (meth)acrylate, bisphenol A epoxy (meth)acrylate, bisphenol F epoxy (meth)acrylate, biphenol epoxy (meth)acrylate, bisphenol-A novolac epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal epoxy (meth)acrylate, and heterocyclic epoxy (meth)acrylate.

[0042] Examples of vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methylstyrene, and ethylstyrene. Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

[0043] The cationic reactive monomer is not particularly limited as long as it is a compound having an epoxy group. For example, glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Cylacure" manufactured by Union Carbide Corporation) can be used. RTMUVR-6110, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (Dow Chemical Company's ELR-4206, etc.), limonene dioxide (Daicel Corporation's Celloxide 3000, etc.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate (Dow Chemical Company's Cyracure RTM UVR-6128), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, and the like.

[0044] Of these, as component (B), monofunctional, bifunctional, trifunctional or higher functional (meth)acrylates and the like, which have good polymerizability, are most preferred.

[0045] Component (B) may be used alone or in combination of two or more. The proportion of component (B) used in the composition is preferably 1 to 300 parts by weight, more preferably 30 to 250 parts by weight, and particularly preferably 50 to 200 parts by weight, per 100 parts by weight of component (A). When the amount of component (B) used is 1 to 300 parts by weight, the sensitivity of the composition and the heat resistance and elastic properties of the resulting film-forming material, adhesive, etc. are improved.

[0046] Examples of the photoradical polymerization initiator (C) (hereinafter also referred to simply as "component (C)") include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, 2 Examples of known general photoradical polymerization initiators include anthraquinones such as t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0047] Examples of the photoacid generator (D) (hereinafter, also simply referred to as "component (D)") include onium complex salts. Typical examples of the onium complex salts include aromatic iodonium complex salts and aromatic sulfonium complex salts. Specific examples of aromatic iodonium complex salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, tolylcumyliodonium tetrakis(pentafluorophenyl)borate (manufactured by Rhodia, trade name: Rhodosil PI2074), and di(4-tert-butyl)iodonium tris(trifluoromethanesulfonyl)methanide (manufactured by BASF Japan, trade name: CGI BBI-C1).

[0048] Specific examples of aromatic sulfonium complex salts include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by San-Apro Co., Ltd., trade name CPI-101A), thiophenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate (manufactured by San-Apro Co., Ltd., trade name CPI-210S), 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate (manufactured by ADEKA Corporation, trade name SP-172), a mixture of aromatic sulfonium hexafluoroantimonates containing 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by ACETO Corporate USA, trade name CPI-6976), and triphenylsulfonium tris(trifluoromethanesulfonyl)methide (manufactured by BASF Japan Ltd., trade name CGI Examples include tris[4-(4-acetylphenyl)sulfonylphenyl]sulfonium tris(trifluoromethylsulfonyl)methide (manufactured by BASF Japan, trade name GSID 26-1), and tris[4-(4-acetylphenyl)sulfonylphenyl]sulfonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate (manufactured by BASF Japan, trade name Irgacure PAG290). Hexafluoroantimonate salt types are inexpensive but tend to generate hydrogen fluoride upon decomposition, making them suitable for applications that do not involve direct contact with metals. Methide salt and borate salt types do not generate hydrogen fluoride, making them suitable for all applications, including those that involve contact with metals.

[0049] Furthermore, the active energy ray-curable resin composition of the present invention may further contain, as appropriate, a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, an antifoaming agent, a leveling agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, a pigment, a dye, and the like. Furthermore, for the purpose of adjusting the viscosity depending on the intended use, a volatile solvent may be added in an amount of up to 50 parts by mass, more preferably up to 35 parts by mass, based on the total amount of the resin composition.

[0050] The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of active energy rays include ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, laser beams, and other electromagnetic waves, as well as alpha rays, beta rays, and electron beams. Among these, ultraviolet rays, laser beams, visible light, and electron beams are preferred in consideration of the preferred uses of the present invention.

[0051] In the present invention, the molding material refers to a material used in applications in which an uncured composition is placed in a mold or pressed against a mold to form an object, and then a curing reaction is caused by active energy rays to cause molding, or an uncured composition is irradiated with focused light such as a laser to cause a curing reaction to cause molding.

[0052] Specific examples of suitable applications include sheets formed into a flat shape, sealing materials for protecting elements, so-called nanoimprint materials in which a finely processed "mold" is pressed against an uncured composition to perform fine molding, and peripheral sealing materials for light-emitting diodes, photoelectric conversion elements, and the like, which have particularly strict thermal requirements.

[0053] In the present invention, a film-forming material is a material used for the purpose of coating the surface of a substrate. Specific applications include ink materials such as gravure ink, flexographic ink, silkscreen ink, and offset ink; coating materials such as hard coats, top coats, overprint varnishes, and clear coats; adhesive materials such as various adhesives and pressure-sensitive adhesives for lamination and optical disks; and resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, so-called dry films, which are produced by temporarily coating a film-forming material on a peelable substrate and then laminating it to the intended substrate to form a film, also fall under the category of film-forming material.

[0054] In the present invention, the adhesive material is used for the purpose of joining two objects, examples of which include metal, paper, fiber, silicon, plastic, and glass. [Example]

[0055] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, parts are by weight unless otherwise specified.

[0056] The epoxy equivalent weight and GPC were measured under the following conditions. Epoxy equivalent (WPE): Measured according to JIS K 7236:2001. Gel Permeation Chromatography (GPC) Model: TOSOH HLC-8220GPC Column: TSKGEL Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, temperature 40°C Detector: differential refractometer Molecular weight standard: polystyrene

[0057] [Synthesis Example 1] Partially ethylenically unsaturated group-containing epoxy resin solution (A-1) In a 300 mL flask equipped with a stirrer and a reflux condenser, 29.92 g of propylene glycol monomethyl ether, 51.17 g of bisphenol F type multifunctional epoxy resin (NER-7403, WPE=290 g / eq, softening point=58.2°C, Nippon Kayaku Co., Ltd.), and 51.17 g of bisphenol F type multifunctional epoxy resin (NER-7604, WPE=342 g / eq, softening point=69.1°C, Nippon Kayaku Co., Ltd.) were added. 11.04 g of acrylic acid (Mw=72.1), 7.60 g of acrylic acid (Mw=72.1), 0.21 g of 2,6-di-t-butyl-p-cresol, and 0.07 g of trimethylglycine (Aminocoat, Asahi Kasei Chemicals Corp.) were added and reacted at 120°C for 7 hours until the acid value of the reaction solution reached 3 mg KOH / g or less, yielding a solution (A-1) of partially ethylenically unsaturated epoxy resin (A). The epoxy equivalent of A-1 was 682.7 g / eq.

[0058] [Synthesis Example 2] Comparative ethylenically unsaturated group-containing epoxy resin (A'-1) In a 300 mL flask equipped with a stirrer and reflux condenser, 29.92 g of propylene glycol monomethyl ether, 46.15 g of a bisphenol F-type multifunctional epoxy resin (NER-7403, WPE=290 g / eq, softening point=58.2 °C, Nippon Kayaku Co., Ltd.), 9.97 g of a bisphenol F-type multifunctional epoxy resin (NER-7604, WPE=342 g / eq, softening point=69.1 °C, Nippon Kayaku Co., Ltd.), 13.70 g of acrylic acid (Mw=72.1) as component (b), 0.21 g of 2,6-di-t-butyl-p-cresol, and 0.21 g of triphenylphosphine were added and reacted at 120 °C for 12 hours until the acid value of the reaction solution reached 3 mg KOH / g or less, yielding an ethylenically unsaturated epoxy resin solution (A'-1). The epoxy equivalent of A'-1 was 1.1 kg / eq.

[0059] [Synthesis Example 3] Comparative partially ethylenically unsaturated group-containing epoxy resin solution (A'-2) A 300 mL flask equipped with a stirrer and reflux condenser was charged with 29.92 g of propylene glycol monomethyl ether, 57.42 g of a bifunctional bisphenol F epoxy resin (RE-304S, WPE=169 g / eq, liquid, Nippon Kayaku Co., Ltd.), 12.36 g of acrylic acid (Mw=72.1), 0.21 g of 2,6-di-t-butyl-p-cresol, and 0.10 g of triphenylphosphine. The mixture was reacted at 120°C for 8 hours until the acid value of the reaction solution reached 3 mg KOH / g or less, yielding a partially ethylenically unsaturated epoxy resin solution (A'-2). The epoxy equivalent of A'-2 was 411.0 g / eq.

[0060] [Example 1, Comparative Examples 1 and 2] 4.0 g of the partially ethylenically unsaturated group-containing epoxy resin obtained in Synthesis Examples 1 to 3 or the resin solution containing the ethylenically unsaturated group-containing epoxy resin was added to 2.8 g of PHE (phenoxyethyl acrylate, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as the reactive compound (B), 0.112 g of Omnirad907 (manufactured by IGM Resins BV) and 0.01 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) as the photoradical polymerization initiator (C), 0.112 g of Irgacure 290 (manufactured by BASF Japan Ltd.) as the photoacid generator (D), and propylene glycol monomethyl ether as a concentration-adjusting solvent, and the solid content concentration was adjusted to 60 wt %. The mixture was uniformly dispersed to obtain an active energy ray-curable resin composition.

[0061] Each evaluation item will be described in detail.

[0062] Storage stability evaluation (abbreviations in the table: storage stability) The resin solutions containing the partially ethylenically unsaturated group-containing epoxy resins obtained in Synthesis Examples 1 and 3 were stored at 40° C., and the molecular weights after 150 days were measured by GPC. Storage stability = molecular weight after 150 days / initial molecular weight

[0063] Copper adhesion evaluation (abbreviation in the table: copper adhesion) The active energy ray-curable resin composition was applied to a copper-clad laminate ELC-4762 (manufactured by Sumitomo Bakelite) using an applicator to a thickness of 20 μm, and the coating film was dried in a hot air dryer at 80°C for 30 minutes. After that, it was irradiated with 1000 mJ / cm using an ultraviolet irradiator (manufactured by GS YUASA: CS 30L-1). 2 The cured film was subjected to a substrate peel test (JIS K 5400-8.5) to evaluate the peeling degree. Evaluation criteria: The total number of squares on the board (100) was used as the denominator, and the number of remaining squares was used as the numerator.

[0064] Glass adhesion evaluation (abbreviation in the table: glass adhesion) A cured film was prepared in the same manner as in the copper adhesion evaluation, except that plain glass was used as the substrate, and then the degree of peeling was evaluated by a substrate peel test (JIS K 5400-8.5).

[0065] Polycarbonate adhesion evaluation (abbreviation in the table: Polycarbonate adhesion) A cured film was prepared in the same manner as in the copper adhesion evaluation, except that polycarbonate (PC-2151 (Teijin Limited)) was used as the substrate, and the degree of peeling was evaluated using a substrate peel test (JIS K 5400-8.5).

[0066] -Easy-to-adhere PET adhesion evaluation (abbreviation in the table: PET adhesion) A cured film was prepared using the same procedure as for the copper adhesion evaluation, except that an easily adhesive PET (Cosmoshine A4300 (manufactured by Toyobo Co., Ltd.)) was used as the substrate, and then the degree of peeling was evaluated using a substrate grain peel test (JIS K 5400-8.5).

[0067] [Table 1] "-" in the table indicates that the data was not measured.

[0068] The results in Table 1 confirm that the active energy ray-curable resin composition of the present invention has good adhesion to all substrates and excellent storage stability. On the other hand, both Comparative Examples 1 and 2 did not adhere to anything other than the highly adhesive PET film, and Comparative Example 2 also had poor storage stability. [Industrial Applicability]

[0069] The active energy ray-curable resin composition of the present invention has excellent adhesion to various substrates and is therefore useful as a film-forming material or adhesive.

Claims

1. An active energy ray-curable resin composition containing a partially ethylenically unsaturated group-containing epoxy resin (A) obtained by reacting an epoxy resin (a) having three or more epoxy groups in one molecule with a compound (b) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule, using a betaine-type quaternary ammonium salt (E) as a catalyst, The component (a) is an epoxy resin represented by the following formula (1): The component (A) is obtained by reacting 20 to 80 equivalent percent of the component (b) with 1 equivalent of the epoxy group of the component (a), The active energy ray-curable resin composition, wherein the component (E) is trimethylglycine. 【Chemical 1】 (In formula (1), R １ represents a hydrogen atom. n1 and n2 are the numbers of repetitions, and represent 1≦n1≦10 and 0≦n2≦10.)

2. 2. The active energy ray-curable resin composition according to claim 1, wherein the epoxy equivalent of the component (a) is 200 to 500 g / eq.

3. The active energy ray-curable resin composition according to claim 1 or 2, further comprising a reactive compound (B), a photoradical polymerization initiator (C), and a photoacid generator (D).

4. 4. The active energy ray-curable resin composition according to claim 3, comprising 1 to 300 parts by weight of the component (B), 0.1 to 30 parts by weight of the component (C), and 0.1 to 30 parts by weight of the component (D) relative to 100 parts by weight of the component (A).

5. The active energy ray-curable resin composition according to claim 1 , which is a film-forming material.

6. The active energy ray-curable resin composition according to claim 1 , which is an adhesive material.

7. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 6.

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