Resin components with cationic curing properties.

Abstract

An objective of the present invention is to provide a cation-curable resin composition having storage stability while maintaining photocurablity and low-temperature curability. Specifically, provided is a cation curable resin composition containing the following components (A)-(C). Component (A): a cation-polymerizable compound, Component (B): a photocationic polymerization initiator and, Component (C): a heat-cationic polymerization initiator containing an amine salt.

Description

Cation-curable resin composition The present invention relates to a cation-curable resin composition having storage stability while maintaining photocurability and low-temperature (for example, less than 100 ° C.) curability. Conventionally, cation-polymerizable resin compositions containing epoxy resins and the like have been used in various applications such as adhesives, sealants, potting agents, coating agents, and conductive pastes because of their excellent adhesive strength, sealing properties, high strength, heat resistance, electrical properties, and chemical resistance. Further, the targets are diverse, and in particular, in electronic devices, they are used in flat panel displays such as semiconductors, liquid crystal displays, organic electroluminescence, touch panels, hard disk devices, mobile terminal devices, camera modules, and the like. Patent Document 1 discloses a photocationic polymerizable resin composition containing an epoxy resin and a photocationic initiator that generates a Lewis acid upon irradiation with active energy rays such as ultraviolet rays. Patent Document 2 discloses a cation-curable epoxy resin composition containing an epoxy resin component, a photocationic initiator, a thermal cationic initiator, and a filler. Japanese Patent Application Laid-Open No. 59-204676 Pamphlet of International Publication No. 2005 / 059002 However, the cation-polymerizable resin composition disclosed in Patent Document 1 has a problem that it cannot cure a portion not irradiated with light. In order to solve this problem, it is conceivable to generate an acid from a cationic initiator by heating up to about 200 ° C. and cure it. However, since the curing conditions are too high, there is a problem that it is difficult to apply to applications such as liquid crystals and organic EL elements that are easily deteriorated by heat. Further, the cation-curable epoxy resin composition disclosed in Patent Document 2 has poor storage stability such as gelling within a few days at room temperature due to the combined use of a photocationic initiator and a thermal cationic initiator. An object of the present invention is to solve the above-mentioned problems, that is, to provide a cation-curable resin composition having storage stability while maintaining photocurability and low-temperature curability. The present invention overcomes the above-mentioned conventional problems. That is, the present invention has the following gist. A cation-curable resin composition containing the following components (A) to (C). Component (A): A cationically polymerizable compound Component (B): A photo cationic polymerization initiator Component (C): A thermal cationic polymerization initiator containing an amine salt Specifically, the present invention can be in the following aspects. [1] A cation-curable resin composition containing the following components (A) to (C). Component (A): A cationically polymerizable compound Component (B): A photo cationic polymerization initiator Component (C): A thermal cationic polymerization initiator containing an amine salt [2] The cation-curable resin composition according to [1] above, wherein the component (C) is a thermal cationic polymerization initiator containing a salt having a quaternary ammonium cation. [3] The cation-curable resin composition according to [1] or [2] above, wherein the component (C) is selected from the group consisting of a salt composed of a quaternary ammonium cation and a borate anion, a salt composed of a quaternary ammonium cation and an antimonate anion, and a salt composed of a quaternary ammonium cation and a phosphate anion. [4] The cation-curable resin composition according to any one of [1] to [3] above, wherein the component (C) is selected from the group consisting of a salt composed of a quaternary ammonium cation and a borate anion and a salt composed of a quaternary ammonium cation and an antimonate anion. [5] The cation-curable resin composition according to any one of [1] to [4] above, wherein the component (A) is selected from the group consisting of an epoxy resin, an oxetane compound, and a vinyl ether compound. [6] The cation-curable resin composition according to any one of [1] to [5] above, which contains 0.1 to 30 parts by mass of component (B) and 0.1 to 30 parts by mass of component (C) with respect to 100 parts by mass of component (A). [7] The cationic curable resin composition according to any one of [1] to [6] above, wherein the component (B) contains at least one of an aromatic iodonium salt and an aromatic sulfonium salt. [8] The cationic curable resin composition according to any one of [1] to [7] above, further containing a colorant as the component (D). [9] A method for adhering adherends, comprising: step 1 of disposing the cationic curable resin composition according to any one of [1] to [8] above between a pair of adherends; step 2 of irradiating the cationic curable resin composition with active energy rays; and step 3 of heating at a temperature of 45°C or higher and lower than 100°C after the irradiation.

[10] A cured product obtained by curing the cationic curable resin composition according to any one of [1] to [8] above. The present invention provides a cationic curable resin composition having storage stability while maintaining photocurability and low-temperature (for example, lower than 100°C) curability. The present invention will be described in detail below. <Cationic Curable Resin Composition> The present invention relates to a cationic curable resin composition containing the following components (A) to (C), and optionally component (D) and additives. Component (A): Cationically polymerizable compound Component (B): Photo cationic polymerization initiator Component (C): Thermal cationic polymerization initiator containing an amine salt Component (D): Colorant As each of the components (A) to (D) and additives of the cationic curable resin composition of the present invention, those satisfying any of the following conditions can be arbitrarily combined and used. <Component (A)> The cationic polymerizable compound as component (A) of the present invention is a compound that undergoes a crosslinking reaction by cationic species generated from a cationic polymerization initiator upon irradiation with active energy rays or heating. Component (A) is not particularly limited, and for example, epoxy resins, oxetane compounds, vinyl ether compounds, etc. can be used. Among them, epoxy resins are preferred from the viewpoint of excellent properties of the cured product. These can be used alone or in combination of two or more. When using two types of the cationic polymerizable compound as component (A), the two types of component (A) are, for example, in a mass ratio of 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3, still more preferably 2:1 to 1:2, and even more preferably 1:1. Here, examples of the active energy rays include ultraviolet rays, electron beams, visible light rays, etc. The integrated light amount of the active energy rays is, for example, 300 to 100000 mJ / cm 2 , preferably 500 to 50000 mJ / cm 2 , more preferably 1000 to 10000 mJ / cm 2 , still more preferably 2000 to 5000 mJ / cm 2 , even more preferably about 3000 mJ / cm 2 is appropriate. The wavelength of the active energy rays is preferably 150 to 830 nm, more preferably 200 to 600 nm, and still more preferably 250 to 380 nm. Also, the heating temperature of the cationic polymerizable compound is, for example, 45°C or higher and lower than 100°C, more preferably 50°C or higher and lower than 95°C, still more preferably 55°C or higher and lower than 90°C, and even more preferably 80°C ± 5°C. The component (A) is preferably in a liquid state at 25°C because of excellent workability and low-temperature curability. Also, the viscosity at 25°C is preferably 0.1 to 30000 mPa·s, more preferably 1 to 15000 mPa·s, still more preferably 5 to 10000 mPa·s, and particularly preferably 10 to 1000 mPa·s. Examples of the epoxy resin as the component (A) include hydrogenated (hydroxylated) epoxy resins, alicyclic epoxy resins, and aromatic epoxy resins. Among them, hydrogenated epoxy resins and alicyclic epoxy resins are preferred from the viewpoint of excellent low-temperature curability. The hydrogenated epoxy resin means a compound obtained by nuclear hydrogenation of the aromatic ring of the epoxy resin. The hydrogenated epoxy resin is not particularly limited. For example, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin, diglycidyl ether of an alkylene oxide adduct of hydrogenated bisphenol A type, diglycidyl ether of an alkylene oxide adduct of hydrogenated bisphenol F, hydrogenated phenol novolac epoxy resin, hydrogenated cresol novolac epoxy resin, etc. may be mentioned. Among them, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol E type epoxy resin are preferred because of their particularly excellent low-temperature curability. Examples of commercially available products of the above hydrogenated bisphenol A type epoxy resin include YX-8000, YX-8034 (manufactured by Mitsubishi Chemical Corporation), EXA-7015 (manufactured by DIC Corporation), ST-3000 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Rikarezin HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.), EX-252 (manufactured by Nagase ChemteX Corporation), etc. Examples of commercially available products of the hydrogenated bisphenol F type epoxy resin include YL-6753 (manufactured by Mitsubishi Chemical Corporation), etc. The alicyclic epoxy resin is not particularly limited. For example, 3,4-epoxycyclohexylmethyl (3',4'-epoxy) cyclohexanecarboxylate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexyl) adipate, 1,2-epoxy-4-vinylcyclohexane, 1,4-cyclohexanedimethanol diglycidyl ether, epoxyethyl divinylcyclohexane, diepoxyvinylcyclohexane, 1,2,4-triepoxyethylcyclohexane, limonene dioxide, alicyclic epoxy group-containing silicone oligomer, etc. may be mentioned. Commercially available products of the alicyclic epoxy resin are not particularly limited. For example, Celoxide 2081 (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate), Celoxide 2021P (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate), Celoxide 2000 (1,2-epoxy-4-vinylcyclohexane), Celoxide 3000 (1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane), EHPE3150 (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol) (manufactured by Daicel Corporation), TTA21 (manufactured by Jiangsu TetraChem), X-40-2670, X-22-169AS, X-22-169B (Shin-Etsu Chemical), etc. can be mentioned, but it is not limited to these. Examples of the aromatic epoxy resin include aromatic bisphenol A type epoxy resin, aromatic bisphenol F type epoxy resin, aromatic bisphenol E type epoxy resin, diglycidyl ether of an alkylene oxide adduct of aromatic bisphenol A type, diglycidyl ether of an alkylene oxide adduct of aromatic bisphenol F type, diglycidyl ether of an alkylene oxide adduct of aromatic bisphenol E type, aromatic novolak type epoxy resin, urethane-modified aromatic epoxy resin, nitrogen-containing aromatic epoxy resin, rubber-modified aromatic epoxy resin containing polybutadiene or nitrile butadiene rubber (NBR), etc. Examples of commercially available aromatic epoxy resins include jER825, 827, 828, 828EL, 828US, 828XA, 834, 806, 806H, 807, 604, 630 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EXA-830LVP, EXA-850CRP, 835LV, HP4032D, 703, 720, 726, HP820, N-660, N-680, N-695, N-655-EXP-S, N-665-EXP-S, N-685-EXP-S, N-740, N-775, N-865 (manufactured by DIC Corporation), EP4100, EP4000, EP4080, EP4085, EP4088, EP4100HF, EP4901HF, EP4000S, EP4000L, EP4003S, EP4010S, EP4010L (manufactured by ADEKA Corporation), Denacol EX614B, EX411, EX314, EX201, EX212, EX252 (manufactured by Nagase ChemteX Corporation), etc., but are not limited thereto. These may be used alone or in combination of two or more kinds. Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, ethyldiethylene glycol(3-ethyl-3-oxetanylmethyl)ether, tetrahydrofurfuryl(3-ethyl-3-oxetanylmethyl)ether, tetrabromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tetrabromophenoxyethyl(3-ethyl-3-oxetanylmethyl)ether, pentachlorophenyl(3-ethyl-3-oxetanylmethyl)ether, pentabromophenyl(3-ethyl-3-oxetanylmethyl)ether, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl)ether, etc. Examples of commercially available products of the oxetane compound include OXT-212, OXT-221, OXT-213, OXT-101 (manufactured by Toagosei Co., Ltd.), etc. Examples of the vinyl ether compound include 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, etc. Examples also include NPVE, IPVE, NBVE, IBVE, EHVE (manufactured by Nippon Carbide Industries Co., Ltd.), CHVE, HEVE, DEGV, HBVE (Maruzen Petrochemical Co., Ltd.), VEEA, VEEM (manufactured by Nippon Shokubai Co., Ltd.), etc. <(B) component> The (B) component of the present invention is a photo cationic polymerization initiator, which is a compound that generates cationic species upon irradiation with active energy rays. The (B) component is not particularly limited, and examples thereof include onium salts such as aromatic iodonium salts and aromatic sulfonium salts. These may be used alone or in combination of two or more. The aromatic sulfonium-based photo cationic polymerization initiator includes a photo cationic polymerization initiator containing a sulfonium ion in which all three groups bonded to the sulfur atom are aryl groups. The aromatic iodonium-based photo cationic polymerization initiator includes a photo cationic polymerization initiator containing an iodonium ion in which two groups bonded to the iodine atom are aryl groups. When using two types of (B) components, which are photo cationic polymerization initiators, it is appropriate to use the two types of (B) components at a mass ratio of, for example, 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3, still more preferably 2:1 to 1:2, and even more preferably 1:1. Here, the type of the preferred active energy rays, the integrated light quantity of the preferred active energy rays, and the wavelength of the preferred active energy rays are as described in the explanation of the above-mentioned (A) component. Examples of the aromatic iodonium salt include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium tetrakis(pentafluorophenyl)borate, and the like. Examples of commercially available products of the aromatic iodonium salt include Irgacure 250 (manufactured by BASF), PI-2074 (manufactured by Rhodia, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium - tetrakis(pentafluorophenyl)borate), B2380 (bis(4-tert-butylphenyl)iodonium hexafluorophosphate), B2381, D2238, D2248, D2253, I0591 (manufactured by Tokyo Chemical Industry Co., Ltd.), WPI-113 (bis[4-n-alkyl (C10-13)phenyl]iodonium hexafluorophosphate), WPI-116 (bis[n-alkyl (C10-13)phenyl]iodonium hexafluoroantimonate), WPI-169, WPI-170 (bis(4-tert-butylphenyl)iodonium hexafluorophosphate), WPI-124 (bis[4-n-alkyl (C10-13)phenyl]iodonium tetrakisfluorophenylborate) (manufactured by Wako Pure Chemical Industries, Ltd.), and the like. Examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'-bis[diphenylsulfonio]diphenyl sulfide-bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenyl sulfide-bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenyl sulfide-bishexafluorophosphate, 7-[di(p-tolyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-tolyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide-hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonio-diphenyl sulfide-hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-tolyl)sulfonio-diphenyl sulfide-tetrakis(pentafluorophenyl)borate, etc. The invention is not limited thereto. These photo cationic polymerization initiators may be used alone or in combination. Examples of commercially available products of aromatic sulfonium salts include SP-150, SP-170, SP-172 (manufactured by ADEKA Corporation), CPI-100P, CPI-101A, CPI-110B, CPI-200K, CPI-210S (manufactured by San-Apro Ltd.), T1608, T1609, T2041 (tris(4-methylphenyl)sulfonium hexafluorophosphate), T2042 (tri-p-tolylsulfonium trifluoromethanesulfonate) (manufactured by Tokyo Chemical Industry Co., Ltd.), UVI-6990, UVI-6974 (manufactured by Union Carbide Corporation), DTS-200 (manufactured by Midori Chemical Co., Ltd.), etc. The blending amount of component (B) in the cation-curable resin composition of the present invention is not particularly limited, but is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of component (A). If it is 0.1 part by mass or more, sufficient photocurability can be obtained, and if it is 30 parts by mass or less, it is preferably sufficiently soluble in component (A). A cationic polymerization initiator that is active to both active energy rays and heat (excluding component (C)) shall be treated as component (B) in the present invention. <(C) component> The component (C) of the present invention is a thermal cationic polymerization initiator containing an amine salt, and is a compound that generates a cationic species by heating. Examples of component (C) include thermal cationic polymerization initiators containing salts having a quaternary ammonium cation. More specific examples of component (C) include salts composed of a quaternary ammonium cation and a borate anion, salts composed of a quaternary ammonium cation and an antimony anion, salts composed of a quaternary ammonium cation and a phosphate anion, etc. Among them, salts composed of a quaternary ammonium cation and a borate anion, and salts composed of a quaternary ammonium cation and an antimony anion are preferred because of their excellent low-temperature curability. Examples of the borate anion include tetrafluoroborate anion, tetrakis(perfluorophenyl)borate anion, etc. Examples of the antimony anion include tetrafluoroantimony anion, tetrakis(perfluorophenyl)antimony anion, etc. Examples of the phosphate anion include hexafluorophosphate anion, trifluoro[tris(perfluoroethyl)], etc. Examples of commercially available products of component (C) include CXC-1612 (manufactured by King Industries, a thermal cationic polymerization initiator containing a salt composed of a quaternary ammonium cation and a borate anion), CXC-1821 (manufactured by King Industries, a thermal cationic polymerization initiator containing a salt composed of a quaternary ammonium cation and an antimony anion), etc. The blending amount of component (C) in the cation-curable resin composition of the present invention is not particularly limited, but it is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of component (A). If it is 0.1 part by mass or more, sufficient low-temperature curability can be obtained, and if it is 30 parts by mass or less, the storage stability will not deteriorate, which is preferable. Here, the blending ratio of component (B) and component (C) is the mass ratio of component (B): component (C), and for example, it is appropriately in the range of 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3, and still more preferably 3:1 to 3:2. <(D) component> Furthermore, for the cation-curable resin composition of the present invention, in the range that does not impair the characteristics of the present invention, as component (D), colorants such as pigments and dyes can be contained. Among them, pigments are preferable from the viewpoint of durability. Among the pigments, black pigments are preferable from the viewpoint of excellent hiding power. Examples of black pigments include carbon black, black titanium oxide, copper chromium black, cyanine black, aniline black, etc. Among them, carbon black is preferable from the viewpoints of hiding power and dispersibility with respect to component (A) of the present invention. The blending amount of component (D) in the cation-curable resin composition of the present invention is not particularly limited, but it is preferably in the range of 0.01 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of component (A). <Additives> Furthermore, the cation-curable resin composition of the present invention may be blended with an appropriate amount of additives such as a sensitizer, a silane coupling agent, a polyol compound, a peroxide, a thiol compound, and a storage stabilizer, as long as the properties of the present invention are not impaired. In addition, the cation-curable resin composition of the present invention may be blended with an appropriate amount of various additives such as inorganic fillers having an average particle size of 0.001 to 100 μm, such as calcium carbonate, magnesium carbonate, titanium oxide, magnesium hydroxide, talc, silica, alumina, glass, aluminum hydroxide, boron nitride, aluminum nitride, and magnesium oxide; conductive particles such as silver; flame retardants; rubbers such as acrylic rubber and silicone rubber; plasticizers; solvents such as organic solvents; antioxidants such as phenolic antioxidants and phosphorus-based antioxidants; light stabilizers; ultraviolet absorbers; defoamers; foaming agents; release agents; leveling agents; rheology control agents; tackifiers; curing retardants; polymers such as polyimide resins, polyamide resins, phenoxy resins, cyanate esters, poly(meth)acrylate resins, polyurethane resins, polyurea resins, polyester resins, polyvinyl butyral resins, SBS, SEBS, and thermoplastic elastomers, as long as the properties of the present invention are not impaired. By these additions, a cation-curable resin composition and its cured product having excellent resin strength, adhesion strength, flame retardancy, heat conductivity, workability, etc. can be obtained. Examples of the sensitizer include 9-fluorenone, anthrone, dibenzosuberone, fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2-iodofluorene, 2-fluorenamine, 9-fluorenol, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7-diaminofluorene, 9,9'-spirobi[9H-fluorene], 2-fluorene carboxaldehyde, 9-fluorenylmethanol, 2-acetylfluorene, benzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, nitro compounds, dyes, etc. The addition amount is not particularly limited, but it is necessary to refer to the absorption wavelength and the molar extinction coefficient. Examples of the silane coupling agent include glycidyl group-containing silane coupling agents such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; vinyl group-containing silane coupling agents such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; (meth)acrylic group-containing silane coupling agents such as γ-methacryloxypropyltrimethoxysilane; amino group-containing silane coupling agents such as N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; and others such as γ-mercaptopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane. Among these, glycidyl group-containing silane coupling agents are preferably used, and among the glycidyl group-containing silane coupling agents, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are preferred. These may be used alone or in combination of two or more. As the polyol compound, it may be added to adjust the curing rate or further enhance the adhesive strength. Examples of the polyol compound include aliphatic polyols such as ethylene glycol, propylene glycol, 1,4 - butanediol, 1,3 - butanediol, 1,9 - nonanediol, neopentyl glycol, tricyclodecane dimethylol, cyclohexane dimethylol, trimethylolpropane, glycerin, hydrogenated polybutadiene polyol, and hydrogenated dimer diol; (poly)ether polyols having one or more ether bonds such as diethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane polyethoxytriol, glycerin polypropoxytriol, bisphenol A polyethoxydiol, bisphenol F polyethoxydiol, and ditrimethylolpropane; polyester polyol compounds; polycaprolactone polyol compounds; polyol compounds having phenolic hydroxyl groups; and polycarbonate polyols such as polycarbonate diol, etc. <Curing of the cation - curable resin composition> The cation - curable resin composition of the present invention can be cured by irradiation with active energy rays (photo - curable). Also, the cation - curable resin composition of the present invention can be cured at low temperatures (low - temperature curability). Furthermore, the cation - curable resin composition of the present invention can be cured by irradiation with active energy rays and at low temperatures. Here, as described in the explanation of the above component (A), examples of the active energy rays include ultraviolet rays, electron beams, visible light, etc. The integrated light quantity of the active energy rays is, for example, 300 - 100000 mJ / cm 2 , preferably 500 - 50000 mJ / cm 2 , more preferably 1000 - 10000 mJ / cm 2 , still more preferably 2000 - 5000 mJ / cm 2 , even more preferably about 3000 mJ / cm 2It is appropriate that the wavelength of the active energy ray is preferably 150 to 830 nm, more preferably 200 to 600 nm, and still more preferably 250 to 380 nm. In addition, the above "low temperature" means that the curable temperature of the cation-curable resin composition of the present invention is low, and actually corresponds to the heating conditions of the curing method of the cation-curable resin composition of the present invention. The heating conditions (curable temperature) are not particularly limited. For example, a temperature of 45°C or higher and lower than 100°C is preferable, more preferably 50°C or higher and lower than 95°C, still more preferably 55°C or higher and lower than 90°C, and even more preferably 80°C ± 5°C. It can also be cured by irradiation with active energy rays. Examples of the active energy rays in this case include ultraviolet rays, electron beams, visible light, etc., but are not particularly limited. The integrated light quantity of the active energy ray is, for example, 300 to 100000 mJ / cm 2 and preferably 500 to 50000 mJ / cm 2 more preferably 1000 to 10000 mJ / cm 2 even more preferably 2000 to 5000 mJ / cm 2 and even more preferably about 3000 mJ / cm 2 It is appropriate that the wavelength of the active energy ray is preferably 150 to 830 nm, more preferably 200 to 400 nm, and still more preferably 250 to 350 nm. <Adhesion method> The cation-curable resin composition of the present invention can be further used for adhesion of adherends. Specific adhesion methods include, for example, step 1 of disposing the cation-curable resin composition of the present invention between a pair of adherends, step 2 of irradiating the cation-curable resin composition with active energy rays, and step 3 of heating at a temperature of 45°C or higher and lower than 100°C after the irradiation. An adhesion method of the adherend having these steps can be mentioned. Hereinafter, each step will be described. [Step 1] The cation-curable resin composition of the present invention is disposed between a pair of adherends. Specifically, for example, the cation-curable resin composition is dropped or applied to one of the adherends and then the other adherend is placed on the disposed cation-curable resin composition, and the positions of the pair of adherends are optionally aligned. For the application, for example, known coating methods for sealants or adhesives may be used. For example, methods such as dispensing using an automatic coater, spraying, inkjet, screen printing, gravure printing, dipping, and spin coating can be used. As the adherend, for example, glass, plastic, etc. can be used, but preferably, it is a flat plate material that is transparent or translucent and has light transmissivity. [Step 2] The disposed cation-curable resin composition is irradiated with active energy rays, the curing of the cation-curable resin composition proceeds, and the pair of adherends are temporarily adhered. The curing of the cation-curable resin composition by the irradiation of active energy rays proceeds particularly on the surface of the composition and in its vicinity. The irradiation may be performed directly on the disposed cation-curable resin composition, or particularly when the adherend is transparent or translucent, it may be performed indirectly through the adherend. The preferred type of active energy rays, the preferred integrated light quantity of the active energy rays, and the preferred wavelength of the active energy rays are as described in the explanation of the component (A) above. [Step 3] After the irradiation of the active energy rays, the disposed cation-curable resin composition is further heated at a predetermined temperature, the cation-curable resin composition is completely cured, and the pair of adherends are completely adhered (primary adhesion). The curing of the cation-curable resin composition by heating proceeds particularly inside the composition other than the surface of the composition and its vicinity. By performing the curing reaction by irradiation in Step 2 above prior to the curing reaction by heating in Step 3, the curing (crosslinking) reaction of the resin composition is promptly initiated, and then the reaction inside the resin composition that is not irradiated by the active energy rays proceeds promptly by the subsequent curing reaction by heating in Step 3, achieving complete curing of the resin composition. The heating temperature is, for example, 45°C to 100°C, preferably 45°C or higher and less than 100°C, more preferably 50°C or higher and less than 95°C, still more preferably 55°C or higher and less than 90°C, and even more preferably 80°C ± 5°C. <Use of the cation-curable resin composition> The uses of the cation-curable resin composition of the present invention include adhesives, sealants, potting agents, coating agents, conductive pastes, sheet adhesives, and the like. Specific uses of adhesives, sealants, potting agents, coating agents, conductive pastes, and sheet adhesives include automotive fields such as switch parts, headlamps, engine internal parts, electrical components, drive engines, brake oil tanks, etc.; flat panel display fields such as liquid crystal displays, organic electroluminescence, touch panels, plasma displays, light-emitting diode display devices, etc.; recording fields such as video discs, CDs, DVDs, MDs, pickup lenses, hard disk peripheral members, Blu-ray discs, etc.; electronic materials fields such as encapsulating materials, die bonding agents, conductive adhesives, anisotropic conductive adhesives, and interlayer adhesives for multilayer substrates including build-up substrates for electronic components, electric circuits, relays, electrical contacts, or semiconductor elements, etc.; camera modules such as CMOS image sensors, etc.; battery fields such as Li batteries, manganese batteries, alkaline batteries, nickel-based batteries, fuel cells, silicon-based solar cells, dye-sensitized solar cells, organic solar cells, etc.; optical component fields such as around optical switches and around optical connectors in optical communication systems, optical fiber materials, optical passive components, optical circuit components, around optoelectronic integrated circuits, etc.; mobile terminal devices; construction fields; aviation fields, etc. Particularly preferred uses include CMOS image sensors, assembly adhesives for housings and lenses, etc., sealants for liquid crystal displays for the purpose of preventing light leakage of backlights and preventing entry of external light, etc. The present invention will be specifically described below with reference to examples, but the present invention is not limited by the following examples. <Preparation of the cation-curable resin composition> ・Example 1 As component (A), 100 parts by mass of a hydrogenated bisphenol A type epoxy resin (a1) (YX-8000, manufactured by Mitsubishi Chemical Corporation) having a viscosity of 1900 mPa·s at 25°C, and as component (B), 4-methylphenyl-4-(1-methylethyl)phenyl iodonium-tetrakis(pentafluorophenyl)borate (b1) (PI-2074, manufactured by Rhodia) 3 parts by mass, and as component (C), 1 part by mass of a thermal cationic polymerization initiator (c1) (CX C-1821, manufactured by King Industries) containing a salt composed of a quaternary ammonium cation and a borate anion were added, and they were mixed with a planetary mixer at room temperature (25°C) for 60 minutes under light shielding to obtain Example 1, which is a cation-curable resin composition. - Example 2 Example 2 was obtained in the same manner as Example 1, except that 1 part by mass of component c1 was changed to 2 parts by mass. - Example 3 Example 3 was obtained in the same manner as Example 1, except that 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (a2) (Celoxide 2021P) having a viscosity of 300 mPa·s at 25°C was used instead of component a1. - Example 4 Example 4 was obtained in the same manner as Example 1, except that 1 part by mass of component c1 was changed to 2 parts by mass in Example 3. - Example 5 Example 5 was obtained in the same manner as Example 1, except that 100 parts by mass of component a1 was changed to 50 parts by mass and further changed to contain 50 parts by mass of component a2. - Example 6 Example 6 was obtained in the same manner as Example 1, except that the thermal cationic polymerization initiator (c2) (CX C-1612, manufactured by King Industries) containing a salt composed of a quaternary ammonium cation and an antimony anion was used instead of component c1. - Comparative Example 1 In Example 1, except that the thermal cationic polymerization initiator (c'1) (SI-B2A, manufactured by Sanshin Chemical Industry Co., Ltd.) containing a salt composed of an aromatic sulfonium cation and a borate anion was used instead of the c1 component, it was prepared in the same manner as in Example 1 to obtain Comparative Example 1. ・ Comparative Example 2 In Example 1, except that the thermal cationic polymerization initiator (c'2) (SI-110L, manufactured by Sanshin Chemical Industry Co., Ltd.) containing a salt composed of an aromatic sulfonium cation and a phosphate anion was used instead of the c1 component, it was prepared in the same manner as in Example 1 to obtain Comparative Example 2. ・ Comparative Example 3 In Example 1, except that the thermal cationic polymerization initiator (c'3) (SI-80L, manufactured by Sanshin Chemical Industry Co., Ltd.) containing a salt composed of an aromatic sulfonium cation and an antimony anion was used instead of the c1 component, it was prepared in the same manner as in Example 1 to obtain Comparative Example 3. ・ Comparative Example 4 In Example 1, except that the c1 component was removed, it was prepared in the same manner as in Example 1 to obtain Comparative Example 4. ・ Comparative Example 5 In Example 1, except that the b1 component was removed, it was prepared in the same manner as in Example 1 to obtain Comparative Example 5. <Storage Stability> The cation-curable resin compositions prepared in each example and comparative example were placed in a 15-ml plastic container, allowed to stand for 30 days in an environment at a temperature of 25°C, and then contacted with a pointed rod and evaluated based on the following evaluation criteria. [Evaluation Criteria] OK: Gelation was not confirmed and it was confirmed to be liquid. NG: Gelation was confirmed. <Photocuring Test> 0.01 g of the cation-curable resin composition prepared in each of the examples and comparative examples was dropped and applied onto a slide glass as one adherend, and then covered with a cover glass as the other adherend to prepare a test piece in which the cation-curable composition was sandwiched between a pair of glasses as a thin film. Next, an ultraviolet irradiation machine (manufactured by Jatec Co., Ltd., model number: JUL-M-433AN-05, ultraviolet wavelength: 365 nm) was used to irradiate active energy rays with an integrated light amount of 3000 mJ / cm 2 After irradiation, a test was conducted to confirm that the pair of glasses adhered to each other and could not be moved by hand. <Low-temperature curability test> 0.1 g of the cation-curable resin composition prepared in each of the examples and comparative examples was dropped onto a hot plate set at 80°C, and after 30 minutes, it was contacted with a rod with a pointed tip to evaluate the presence or absence of curing of the composition. From Examples 1 to 6, it can be seen that the present invention has excellent storage stability while maintaining photocurability and low-temperature (less than 100°C) curability. Comparative Example 1 is a composition using a thermal cationic polymerization initiator containing a salt composed of an aromatic sulfonium cation and a borate anion, which is not the component (C) of the present invention, and it can be seen that its storage stability is poor. Further, Comparative Example 2 is a composition using a thermal cationic polymerization initiator containing a salt composed of an aromatic sulfonium cation and a phosphate anion, which is not the component (C) of the present invention, and it can be seen that its storage stability and low-temperature curability are poor. Further, Comparative Example 3 is a composition using a thermal cationic polymerization initiator containing a salt composed of an aromatic sulfonium cation and an antimony anion, which is not the component (C) of the present invention, and it can be seen that its photocurability is poor. Further, Comparative Example 4 is a composition excluding the component (C) of the present invention, and it can be seen that its low-temperature curability is poor. Further, Comparative Example 5 is a composition excluding the component (B) of the present invention, and it can be seen that its photocurability is poor. Subsequently, a test was conducted to evaluate the hiding property of the cation-curable resin composition of the present invention. - Example 7 In Example 1, Example 7 was obtained in the same manner as in Example 1, except that 1 part by mass of carbon black (SRB Black T-04, manufactured by Mikuni Shikiso Co., Ltd.) as a black pigment was further added as component (D). <Concealability Test> The cation-curable resin composition of Example 7 was stretched to a thickness of 0.2 mm to prepare a test piece with a smooth surface, and the integrated light quantity was 3000 mJ / cm by an ultraviolet irradiation machine (manufactured by Jatec Co., Ltd., model number: JUL-M-433AN-05, ultraviolet wavelength: 365 nm). 2 The light was irradiated with photoactive energy. Then, the test piece was further heated in a constant temperature bath at 80°C for 30 minutes to obtain a cured product. The transmittance of the green light with a wavelength of 550 nm of the cured product was measured with a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation). The transmittance was less than 1%, and it was confirmed that the concealability of the cured product was excellent. Since the cation-curable resin composition of the present invention has excellent storage stability while maintaining photocurability and low-temperature (less than 100°C) curability, it is industrially useful because it can be applied to a wide range of fields such as adhesives, sealants, potting agents, coating agents, conductive pastes, and sheet adhesives.

Claims

Page 1 of 2 pages Claims 1. A cationic resin composition consisting of the following components (A)-(C): Component (A): A compound with cationic polymerization properties; Component (B): A photocatalytic cationic polymerization initiator; Component (C): A thermocatalytic cationic polymerization initiator containing an amine salt.

2. A cationic resin composition specified in Claims 1, which is characterized by such component (C) being a thermocatalytic cationic polymerization initiator containing a salt containing a quaternary ammonium cation.

3. A cationic resin composition specified in Claims 1 or 2, which is characterized by such component (C) being one or more types selected from the group of salts derived from quaternary ammonium cation and borate anion, salts derived from quaternary ammonium cation and antimony anion, salts derived from quaternary ammonium cation and phosphate anion. 4.One of the cationic resin components specified in any of the claims 1-3, which is characterized by one or more components (C) selected from the group derived from quaternary ammonium cation and borate anion salts, quaternary ammonium cation and antimony anion salts; 5. One of the cationic resin components specified in any of the claims 1-4, which is characterized by one or more components (A) selected from the group derived from epoxy resins, compounds, 6. One cationic resin composition specified in any one of the claims 1-5, which is characterized by the presence of 0.1-30 parts by mass of component (B) and 0.1-30 parts by mass of component (C) to 100 parts by mass of such component (A).

7. One cationic resin composition specified in any one of the claims 1-6, which is characterized by the presence of at least one such component (B) containing either an aromatic iodochium salt or an aromatic sulfonium salt. Page 2 of 2, Page 8.

1. A cationic resin composition specified in one of the claims 1-7, which is characterized by the addition of a coloring agent as a component. (D)9. A bonding method with process 1 in which one of the claims 1-8, cationic resin compositions is placed between a pair of bonded objects, and process 2 in which the cationic resin composition is irradiated with an activation energy, and process 3 in which the temperature is heated to 45 °C or lower than 100 °C after such irradiation.

10. A hardener obtained by hardening one of the cationic resin compositions shown in one of the claims 1-8;