JP2015218332A - Cation curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cation curable resin composition which is hardenable by both irradiation of active energy rays and low-temperature heating.SOLUTION: A cation curable resin composition comprises ingredients (A) to (C). Ingredient (A): a compound having a cycloalkane skeleton and at least one glycidyl group. Ingredient (B): a compound having an alicyclic hydrocarbon skeleton, excluding ingredient (A) and compounds in which an electron-withdrawing group selected from (meth)acrylic, carboxy, imide, sulfo, cyano and nitro groups is bonded directly to a carbon atom of a cyclic structure. Ingredient (C): a cation initiator containing an iodonium salt.

Description

The present invention relates to a cationic curable resin composition that is cured by either irradiation of active energy rays or low temperature heating.

Conventionally, cationically polymerizable resin compositions containing an epoxy resin or the like have excellent adhesive strength, sealing properties, high strength, heat resistance, electrical properties, and chemical resistance, and thus adhesives, sealing agents, and potting agents. It has been used in various applications such as coating agents and conductive pastes. Moreover, the object is various, and in electronic devices, it is used for semiconductors, liquid crystal displays, organic electroluminescence, flat panel displays such as touch panels, hard disk devices, mobile terminal devices, and the like.

Patent Document 1 discloses a cationic photopolymerizable 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. The thing had the problem that the location which a light does not hit cannot be hardened. In order to solve this problem, it is possible to generate an acid from the cation initiator by heating to about 200 ° C. and cure it. However, since it is a too high curing condition, it is easily deformed by heat. There has been a problem that it is difficult to apply to plastics, liquid crystals and organic EL elements that are easily deteriorated by heat.

From such a background, Patent Document 2 discloses a low-temperature curable cationic curable resin composition containing an iodonium salt compound, a peroxide, and a cationic polymerizable substance.

JP 59-204676 JP 2011-116977 A

However, the cationic curable resin composition disclosed in Patent Document 2 utilizes thermal decomposition of peroxide, and the cured product of the corresponding adhesive is unreacted when exposed to high temperature environment. The peroxide is decomposed and the polymer of the cured product may be deteriorated by the generated radicals. In addition, as long as the results of differential scanning calorimetry are confirmed, even those with the lowest reaction heat peak are 101 ° C., and it is suitable for applications such as bonding plastic members and flat panel displays such as liquid crystal displays, organic electroluminescence, and touch panels. Considering this, lower temperature curability has been demanded.

An object of the present invention is to solve the above-mentioned problems, that is, to provide a cationic curable resin composition that is cured by either irradiation of active energy rays or low-temperature heating.

That is, as a result of intensive studies to achieve the object of the present invention, it was found that the object can be achieved by a specific cationic curable resin composition, and the present invention has been completed.
The gist of the present invention will be described next.
Cationic curable resin composition (A) comprising the following components (A) to (C): Compound (B) having cycloalkane skeleton and at least one glycidyl group: Alicyclic carbonization Compound having a hydrogen skeleton (provided that (A) component and an electron selected from the group consisting of (meth) acryl group, carboxy group, imide group, sulfo group, cyano group and nitro group on the carbon atom constituting the cyclic structure) (Excluding compounds with a direct suction group)
Component (C): a cationic initiator containing an iodonium salt

The cationic curable resin composition of the present invention is excellent in that it can be rapidly cured by either irradiation of active energy rays or low temperature heating. Further, according to the present invention, it is possible to cure evenly to the gaps in the details.

4 is a graph showing the measurement results of differential scanning calorific value of Example 1. 6 is a graph showing the results of differential scanning calorimetry measurement in Example 5. 10 is a graph showing the measurement results of differential scanning calorimetry in Example 6. 10 is a graph showing a measurement result of differential scanning calorific value of Comparative Example 3. 10 is a graph showing a measurement result of differential scanning calorific value of Comparative Example 4. 10 is a graph showing a measurement result of differential scanning calorific value of Comparative Example 5.

The present invention realizes low-temperature curability by focusing on the decomposition temperature of the cationic polymerization initiator. That is, in general, the thermal decomposition temperature of iodonium-based cationic initiators often exceeds 200 ° C. and is stable to heat. However, it has been found that when the iodonium-based cation initiator is dissolved in the mixture of the components (A) and (B) of the present invention, the thermal decomposition temperature of the iodonium-based cation initiator is remarkably lowered.

The present invention will be described in detail below.
<(A) component>
The component (A) in the cationic curable resin composition of the present invention is not particularly limited as long as it is a compound having a cycloalkane skeleton and at least one glycidyl group. It can be used alone or in admixture of two or more. Here, the cycloalkane skeleton of the component (A) means a structure of an alicyclic hydrocarbon having 3 to 12 carbon atoms.

The component (A) is preferably liquid at 25 ° C. because it is excellent in workability and low-temperature curability. The viscosity at 25 ° C. is preferably from 0.1 to 30000 mPa · s, more preferably from 1 to 15000 mPa · s, and particularly preferably from 10 to 1000 mPa · s. Moreover, it is preferable that the epoxy equivalent of (A) component used for this invention is 500 or less, More preferably, it is 400 or less, Most preferably, it is 300 or less. When the epoxy equivalent of the component (A) exceeds 500, the low temperature curability may be lowered. The epoxy equivalent is measured by the method of JISK-7236.

Specific examples of the component (A) include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol A type alkylene oxide adduct diglycidyl ether, water Diglycidyl ether of alkylene oxide adduct of bisphenol F, hydrogenated phenol novolac epoxy resin, hydrogenated cresol novolac epoxy resin, epoxycyclohexane, pinene oxide, limonene dioxide, vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl ( 3 ′, 4′-epoxy) cyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, 1,4-cyclohexanedimethanol diglycidyl ether, epoxyethyldi Sulfonyl cyclohexane, diepoxy vinylcyclohexane, but 1,2,4-epoxy ethylcyclohexane, and the like are not limited thereto. Of these, excellent low-temperature curability is obtained, so hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin, epoxycyclohexane, pinene oxide, limonene dioxide, vinylcyclohexene Diepoxide, 3,4-epoxycyclohexylmethyl (3 ′, 4′-epoxy) cyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, 1,4-cyclohexanedimethanol diglycidyl ether, epoxyethyldivinylcyclohexane, Diepoxyvinylcyclohexane and 1,2,4-triepoxyethylcyclohexane are preferable, and hydrogenated bisphenol A type epoxy resin and hydrogenated bisphenol are particularly preferable because of low temperature curability. Le F type epoxy resins, and hydrogenated bisphenol E type epoxy resins.

The component (A) is produced by, for example, subjecting an aromatic epoxy resin to a hydrogenation reaction in the presence of a catalyst in which rhodium or ruthenium is supported on graphite using no solvent or an ether organic solvent such as tetrahydrofuran or dioxane. However, it is not limited to these. The hydrogen conversion rate of the component (A) is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more. If the hydrogen conversion is less than 50%, the low-temperature curability may be inferior.

Examples of commercially available components (A) include hydrogenated bisphenol A type epoxy resins, YX-8000, YX-8034 (Mitsubishi Chemical Corporation), EXA-7015 (DIC Corporation), ST-3000 (Nippon Steel). Sumikin Chemical Co., Ltd.), Rica Resin HBE-100 (New Nippon Rika Co., Ltd.), EX-252 (Nagase ChemteX Corporation), and the like. Moreover, as a commercial item of hydrogenated bisphenol F type epoxy resin, YL-6753 (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example. Examples of 1,4-cyclohexanedimethanol diglycidyl ether include, but are not limited to, licarresin DME-100 (Shin Nihon Rika Co., Ltd.) and the like.

<(B) component>
The component (B) of the present invention is a compound having an alicyclic hydrocarbon skeleton (provided that the (A) component and the carbon atom constituting the cyclic structure have a (meth) acryl group, a carboxy group, an imide group, a sulfo group, Except for compounds in which an electron-withdrawing group selected from a cyano group and a nitro group is directly bonded. As shown in Comparative Examples 4 and 5 to be described later, an electron withdrawing group selected from a (meth) acryl group, a carboxy group, an imide group, a sulfo group, a cyano group, and a nitro group as a carbon atom constituting the cyclic structure. When a compound in which is directly bonded is used, the low temperature curability is inferior. Examples of the alicyclic hydrocarbon skeleton include structures composed of 3 to 12 carbon atoms. Although the boiling point of (B) component is not specifically limited, 20 degreeC or more is preferable from a viewpoint of low-temperature curability and workability | operativity, More preferably, it is 30 degreeC or more, Especially preferably, it is 40 degreeC or more.

Component (B) is a carbon atom constituting the alicyclic hydrocarbon skeleton, each independently a hydrogen atom, a linear or branched alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, or a carbon number Although the compound etc. which 1-12 thiol, vinyl ether, or C1-C12 alcohol couple | bonds are mentioned, it is not this limitation.

Specific examples of the component (B) include cycloalkane derivatives having 3 to 12 carbon atoms, cycloalkene derivatives having 3 to 12 carbon atoms, norbornene derivatives, and preferably cycloalkanes having 3 to 12 carbon atoms. Derivatives and norbornene derivatives are exemplified, but not limited thereto.

Examples of the cycloalkane derivative having 3 to 12 carbon atoms corresponding to the component (B) include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, dicyclopentadiene, Examples include cyclohexyl vinyl ether, cyclohexane dimethanol, cyclohexane diethanol, cyclohexane dimethanol divinyl ale, 2-ethylhexyl butyl vinyl ether, chlorocyclohexyl, fluorocyclohexyl, trifluoromethylcyclohexyl and the like.

Examples of the norbornene derivative corresponding to the component (B) include norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidenenorbornene, dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tetracyclododecene, tricyclo Examples thereof include pentadiene and tetracyclopentadiene.

  Although the compounding quantity of (B) component in the cation curable resin composition of this invention is not restrict | limited in particular, The range of 0.01-95 mass parts with respect to a total of 100 mass parts of said (A) component and (B) component. It is preferably within the range, more preferably 0.1 to 50 parts by mass, and particularly preferably 0.5 to 30 parts by mass. If it is less than 0.01 part by mass, the low-temperature curability may not be obtained, and if it exceeds 90 parts by mass, the storage stability at room temperature may be adversely affected.

<(C) component>
The component (C) of the present invention is a cationic initiator and is an iodonium salt that generates an acid by irradiation with active energy rays or heating. In addition, it is preferable that the thermal decomposition temperature of (C) component is 200 degreeC or more from a viewpoint of the storage stability of a composition, More preferably, it is 220 degreeC or more. The thermal decomposition temperature is a value measured using a TG / DTA (thermal balance / differential thermal analysis) apparatus for the component (C). In addition, since the component (C) of the present invention is soluble in the component (A), the composition can be cured even in a fine gap of 10 μm or less.

（式中のＲ^１〜Ｒ^６は、水素原子、炭素数１〜２０の直鎖又は分岐アルキル基、炭素数１〜２０のアルコキシ基、ニトロ基、ハロゲン原子のいずれかを示し、それぞれのＲ^１〜Ｒ^６は互いに同一であっても異なっていてもよい。さらに、Ｘ⁻は、ＡｓＦ_６、ＳｂＦ_６ ⁻、ＢＦ_６、Ｂ（Ｃ_６Ｆ_５）_４ ⁻、Ｃ（ＣＦ_３ＳＯ_２）_３ ⁻又は［Ｐ（Ｒ^７）_ａ（Ｆ）_６−ａ］⁻（式中、Ｒ^７は炭素数１〜２０フッ素化アルキル基を示し、ａは０〜５の整数を示す。）であり、より低温硬化性に優れるという観点からＸ⁻は、Ｂ（Ｃ_６Ｆ_５）_４ ⁻、Ｃ（ＣＦ_３ＳＯ_２）_３ ⁻又は［Ｐ（Ｒ^６）_ａ（Ｆ）_６−ａ］⁻が好ましい。） Examples of the iodonium salt of the component (C) include those represented by the general formula (1).

(Wherein R ^{1 to} R ⁶ represent any ^one of a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, and a halogen atom, and each R ^{1 to} R ⁶ may be the same as or different from each other, and X ⁻ represents AsF ₆ , SbF ₆ ⁻ , BF ₆ , B (C ₆ F ₅ ) ₄ ⁻ , C (CF ₃ SO ₂ ). ₃ ^- or _{^{[P (R 7) a (}} F) 6-a] - ( wherein, ^{R 7} represents a C 1-20 fluorinated alkyl group having a carbon, a is an integer of 0-5.) be From the viewpoint of excellent low-temperature curability, X ⁻ represents B (C ₆ F ₅ ) ₄ ⁻ , C (CF ₃ SO ₂ ) ₃ ^— or [P (R ⁶ ) _a (F) _6-a ] ^−. preferable.)

Specific compounds of the component (C) of the present invention include, for example, diphenyliodonium-hexafluorophosphate, diphenyliodonium-hexafluoroantimonate, diphenyliodonium-tetrafluoroborate, diphenyliodonium-tetrakis (pentafluorophenyl) borate, diphenyl Iodonium-fluorinated alkyl fluorophosphoric acid, bis (dodecylphenyl) iodonium-hexafluorophosphate, bis (dodecylphenyl) iodonium-hexafluoroantimonate, bis (dodecylphenyl) iodonium-tetrafluoroborate, bis (dodecylphenyl) iodonium- Tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium-fluorinated alkyl group Orophosphoric acid, 4-methylphenyl-4- (1-methylethyl) phenyliodonium-hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium-hexafluoroantimonate, 4-methylphenyl-4 -(1-methylethyl) phenyliodonium-tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium-tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) ) Phenyliodonium-fluorinated alkyl fluorophosphate 4-methoxydiphenyliodonium-hexafluorophosphate, bis (4-methylphenyl) iodonium-hexafluorophosphate, bis (4-tert-butylpheny) ) Iodonium hexafluorophosphate, bis (4-methylphenyl) iodonium - although such fluorinated alkyl fluorophosphate acid, but it is not limited thereto. In addition, since it is excellent in low-temperature curability, among them, diphenyliodonium-tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium-tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methyl) is preferable. Ethyl) phenyliodonium-tetrakis (pentafluorophenyl) borate, diphenyliodonium-fluorinated alkylfluorophosphoric acid, bis (dodecylphenyl) iodonium-fluorinated alkylfluorophosphoric acid, 4-methylphenyl-4- (1-methylethyl) Examples thereof include phenyliodonium-fluorinated alkylfluorophosphoric acid and bis (4-methylphenyl) iodonium-fluorinated alkylfluorophosphoric acid.

  Although the compounding quantity of (C) component in the cation curable resin composition of this invention is not restrict | limited in particular, The range of 0.001-30 mass parts with respect to a total of 100 mass parts of said (A) component and (B) component. It is preferable that it is inside, More preferably, it is 0.1-10 mass parts. If less than 0.001 part by mass, low-temperature curability may not be obtained, and if it exceeds 30 parts by mass, it may be difficult to dissolve in the component (A) and the component (B).

<(D) component>
The silane coupling agent of the component (D) of the present invention is a compound that can improve the compatibility of the components (A) to (C) and improve the low temperature curability. Examples of the component (D) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyl. Glycidyl group-containing silane coupling agents such as trimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane, vinyl group-containing silane couplings such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane and vinyltrimethoxysilane Agent, (meth) acryl group-containing silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- Phenyl-γ-aminopro Amino group-containing silane coupling agents such as Le trimethoxysilane, other .gamma.-mercaptopropyltrimethoxysilane, .gamma.-chloropropyl trimethoxy silane, and the like. Among these, a glycidyl group-containing silane coupling agent is preferably used, and among the glycidyl group-containing silane coupling agents, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are preferable. These may be used independently and 2 or more types may be used together. Moreover, the compounding quantity of (D) component is although it does not specifically limit, It is 0.001-30 mass parts with respect to a total of 100 mass parts of (A) component of this invention, and (B) component. can give.

Furthermore, the cationic curable resin composition of the present invention includes an epoxy resin other than the component (A) of the present invention, an oxetane compound, a vinyl ether other than the component (A), and a photo radical initiator, as long as the characteristics of the present invention are not impaired. , Sensitizers, peroxides, thiol compounds, storage stabilizers, colorants such as pigments, dyes, calcium carbonate, magnesium carbonate, titanium oxide, magnesium hydroxide, talc, silica, alumina, glass, aluminum hydroxide, nitriding Inorganic fillers having an average particle diameter of 0.001 to 100 μm such as boron, aluminum nitride and magnesium oxide, conductive particles such as silver, flame retardant, acrylic rubber, silicon rubber, plasticizer, organic solvent, phenolic antioxidant , Antioxidants such as phosphorus antioxidants, light stabilizers, UV absorbers, antifoaming agents, foaming agents, mold release agents, leveling agents, Cure retarder such as ology control agent, tackifier, crown ether having cyclohexyl group (not applicable to component (A) of the present invention), polyimide resin, polyamide resin, phenoxy resin, cyanate ester, poly (meta ) A proper amount of additives such as polymers such as acrylate resins, polyurethane resins, polyurea resins, polyester resins, polyvinyl butyral resins, SBS, SEBS, and thermoplastic elastomers may be blended. By the addition of these, a cationic curable resin composition having excellent resin strength, adhesive strength, flame retardancy, thermal conductivity, workability, and the like, and a cured product thereof can be obtained.

Examples of the epoxy resin include aromatic bisphenol A type epoxy resin, aromatic bisphenol F type epoxy resin, aromatic bisphenol E type epoxy resin, aromatic bisphenol A type alkylene oxide adduct diglycidyl ether, and aromatic bisphenol F type. Diglycidyl ether of alkylene oxide adducts, diglycidyl ether of aromatic bisphenol E type alkylene oxide adducts, aromatic novolac epoxy resins, urethane-modified aromatic epoxy resins, nitrogen-containing aromatic epoxy resins, polybutadiene or nitrile butadiene Examples thereof include rubber-modified aromatic epoxy resins containing rubber (NBR) and the like.

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), EPICLON 830, 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 (stock) Made company ADEKA), Denacol EX614B, EX411, EX314, EX201, EX212, EX252 (manufactured by Nagase Chemtex Co., Ltd.) and the like can be mentioned but is not limited to these. These may be used alone or in admixture of two or more.

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-Oxetanyl Til) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether , Ethylene glycolose bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, trimethylol Propane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) Le) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether.

Examples of the vinyl ether compound include 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, and the like.

  Examples of the photo radical initiator include a benzyl ketal photo radical polymerization initiator, an α-hydroxyacetophenone photo radical polymerization initiator, a benzoin photo radical polymerization initiator, an aminoacetophenone photo initiator, and an oxime ketone photo radical polymerization. Initiators, acylphosphine oxide photoradical polymerization initiators, titanocene photoradical polymerization initiators, thiobenzoic acid S-phenyl polymerization initiators, benzophenone photoradical initiators, thioxanthone photoradical polymerization initiators, anthraquinone photoinitiators Agents, benzoylformic acid and the like. 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 hydroxyacetophenone-based photoradical polymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, but in the present invention, this compound is treated as a photoradical initiator instead of the component (B).

Examples of the sensitizer include 9-fluorenone, anthrone, dibenzosuberone, fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2-iodofluorene, and 2-fluoreneamine. , 9-fluorenol, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7-diaminofluorene, 9,9′-spirobi [9H-fluorene], 2-fluorenecarboxaldehyde, 9-fluorenylmethanol , 2-acetylfluorene, nitro compounds, dyes and the like. The addition amount is not particularly limited, but it is necessary to refer to the absorption wavelength and the molar extinction coefficient.

The cationic curable resin composition of the present invention can be cured by either irradiation of active energy rays or low-temperature heating, but the present invention is particularly characterized by being cured only by low-temperature heat.

As a curing method of the cationic curable resin composition of the present invention, the heating condition is preferably a temperature of 45 to 120 ° C, more preferably 50 to 100 ° C. Moreover, it can harden | cure by active energy ray irradiation. Examples of the active energy ray in this case include ultraviolet rays, electron beams, and visible rays, but are not particularly limited. The integrated light quantity of the active energy ray is preferably 300 to 100,000 mJ / cm ² , and the wavelength of the active energy ray is preferably 150 to 830 nm, more preferably 200 to 400 nm.

The reaction start temperature of the present invention is a value determined by differential scanning calorimetry (DSC) measurement for the cationic curable resin composition, and specifically, at the baseline and peak inflection points of the DSC measurement result graph. This is the temperature at the intersection with the tangent. Moreover, the low temperature curability of the present invention means that the reaction start temperature is 90 ° C. or lower.

  Applications of the cationic curable resin composition of the present invention include adhesives, sealants, potting agents, coating agents, conductive pastes, sheet-like adhesives, and the like. Specific targets for adhesives, sealants, potting agents, coating agents, conductive pastes, and sheet adhesives include switch parts, headlamps, engine internal parts, electrical components, drive engines, brake oil tanks, etc. Automotive field; Flat panel display field such as liquid crystal display, organic electroluminescence, touch panel, plasma display, light emitting diode display; Video disc, CD, DVD, MD, pickup lens, hard disk peripheral member; Recording field such as Blu-ray disc; Electronic materials such as electronic parts, electrical circuits, relays, sealing materials for electrical contacts or semiconductor elements, die bonding agents, conductive adhesives, anisotropic conductive adhesives, interlayer adhesives for multilayer substrates including build-up substrates, etc. Field: Li battery, manganese battery, a Battery field such as potassium battery, nickel-based battery, fuel cell, silicon-based solar cell, dye-sensitized solar cell, organic solar cell; optical switch periphery in optical communication system, optical fiber material around optical connector, optical passive component, Examples include optical component fields around optical circuit components and optoelectronic integrated circuits; mobile terminal devices; architectural fields; aviation fields.

In addition, since the cation-curable resin composition of the present invention can be cured evenly in the gaps of details at low temperatures, it is suitable for applications such as sealants for switch members such as relay parts and impregnation of coils. Used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the following examples. Moreover, the mixture ratio in the following table | surface is a mass reference | standard.

<Preparation of Examples and Comparative Examples>
In order to prepare the composition, the following components were prepared.

The materials used in the examples and comparative examples of the present invention are the following commercially available products or reagents.
<(A) component>
a1: Hydrogenated bisphenol A type epoxy resin, viscosity 1900 mPas, epoxy equivalent 205, trade name YX-8000, manufactured by Mitsubishi Chemical Corporation a2: Hydrogenated bisphenol F type epoxy resin, viscosity 200 mPas, epoxy equivalent 180, trade name YL-6753 Manufactured by Mitsubishi Chemical Co., Ltd. <Comparison of component (A)>
a′1: Mixture of aromatic bisphenol A type epoxy resin and aromatic bisphenol F type epoxy resin, viscosity 2250 mPas, epoxy equivalent 165, trade name EXA-835LV, manufactured by DIC Corporation <component (B)>
b1: cyclohexane, boiling point 81 ° C.
b2: cyclopentane, boiling point 49 ° C
b3: 2-norbornene, boiling point 96 ° C.
b4: cyclohexyl vinyl ether, boiling point 147 ° C.
b5: cyclohexanedimethanol, boiling point 283 ° C
b6: cyclohexanedimethanol divinyl ether, boiling point 104 ° C., trade name CHDVE, Nippon Carbide Industries Co., Ltd. b7: methylcyclohexane, boiling point 101 ° C.
<Comparison component of component (B)>
b′1: N-acryloyloxyethyl hexahydrophthalimide (compound having an alicyclic hydrocarbon skeleton in which an imide group as an electron-withdrawing group is directly bonded to a carbon atom constituting a cyclic structure)
b′2: cyclohexyl acrylate (a compound having an alicyclic hydrocarbon skeleton in which a (meth) acryl group which is an electron withdrawing group is directly bonded to a carbon atom constituting a cyclic structure), boiling point 183 ° C.
<(C) component>
c1: 4-methylphenyl-4- (1-methylethyl) phenyliodonium-fluorinated alkyl fluorophosphoric acid, thermal decomposition temperature 247 ° C.
c2: 4-methylphenyl-4- (1-methylethyl) phenyliodonium-tetrakis (pentafluorophenyl) borate, trade name Photoinitiator 2074, manufactured by Rhodia, thermal decomposition temperature 252 ° C.
<(D) component>
d1: 3-glycidoxypropyltrimethoxysilane

[Preparation of Cationic Curable Resin Compositions of Examples 1-12 and Comparative Examples 1-5]
Components (A) to (D) were added in the weight ratios shown in Tables 1 and 2, and the mixture was stirred and mixed at 25 ° C. in a light-shielding environment to prepare a cation curable resin composition.

<Measurement of reaction start temperature>
Regarding the low temperature curability of each cationic curable resin composition, the reaction initiation temperature was measured using differential scanning calorimetry (DSC), and the results are shown in Tables 1 and 2. The DSC measurement was performed using a DSC 110 manufactured by Seiko Instruments Inc., and the temperature was increased from 30 to 200 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. The reaction start temperature was defined as the intersection of the baseline of the DSC measurement result graph and the tangent at the peak inflection point. In addition, about the graph of the measurement result of the differential scanning calorie | heat amount of Example 1, 5, 6 and Comparative Examples 3-5, it shows in FIGS.

<Confirmation of active energy ray curability>
0.01 g of each cation-curable resin composition of Examples 1 to 12 is dropped on a slide glass, and a test piece in which the cation-curable composition is sandwiched between the glass as a thin film by covering with a cover glass is prepared. Next, after irradiating photoactive energy with an integrated light quantity of 30 kJ / m ^{2 with} an ultraviolet irradiator, a test was performed to confirm that the glasses were bonded together and could not be moved by hand.
The test results confirmed that all the cationic curable resin compositions of Examples 1 to 12 were adhered and had active energy ray curability.

[Comparative Example 6]
In Example 1, instead of c1, it was prepared in the same manner as in Example 1 except that a latent curing agent (product name PN-23J, manufactured by Ajinomoto Fine Techno Co., Ltd.) having an average particle size of 3 μm was used. Example 6 was obtained.

<Detailed gap curability test>
After two glass slides are stacked and fixed at both ends with a pinch, the glass slide is placed vertically with the overlapping end faces facing up. The curable compositions of Example 1 and Comparative Example 6 are dropped onto the overlapping portion at the center of the upper end face, and left in a high temperature bath at 100 ° C. for 1 hour. The cured glass was peeled off, and a case where there was a liquid portion was indicated as “X”, and a case where there was no liquid was indicated as “◯”.
The test result was “◯” when Example 1 was used, and “X” when Comparative Example 6 was used.

From the results of Examples in Table 1, it can be seen that the reaction start temperature is lower than that of Comparative Examples.

From the results of Comparative Example 1 in Table 2, the composition using the epoxy resin that does not contain the component (B) of the present invention and is not the component (A) of the present invention is compared with the examples of the present invention. In addition, it can be seen that the reaction start temperature is high and the low-temperature curability is poor. Moreover, from the result of Comparative Example 2, in the composition using the epoxy resin that is not the component (A) of the present invention, the reaction start temperature is high and the low-temperature curability is inferior compared with the Examples of the present invention. I understand that. From the results of Comparative Example 3, it can be seen that in the composition not containing the component (B) of the present invention, the reaction start temperature is high and the low-temperature curability is inferior compared with the Examples of the present invention. Further, from the result of Comparative Example 4, N-acryloyloxyethylhexahydrophthalimide (an oil in which an imide group as an electron withdrawing group is directly bonded to a carbon atom constituting a cyclic structure) instead of the component (B) of the present invention. It can be seen that the composition containing the compound having a cyclic hydrocarbon skeleton has a higher reaction start temperature and inferior low-temperature curability as compared with the examples of the present invention. Further, from the result of Comparative Example 5, cyclohexyl acrylate (an alicyclic carbonization in which a (meth) acryl group as an electron withdrawing group is directly bonded to a carbon atom constituting a cyclic structure) instead of the component (B) of the present invention. It can be seen that the composition containing the compound having a hydrogen skeleton has a high reaction initiation temperature and is inferior in low-temperature curability as compared with the examples of the present invention.

Since the cationic curable resin composition of the present invention can be quickly cured by either irradiation of active energy rays or low temperature heating, an adhesive, a sealant, a potting agent, a coating agent, a conductive paste, a sheet-like adhesive It is industrially useful because it can be applied to a wide range of fields. Furthermore, since the cation curable resin composition of the present invention can be cured evenly in the gaps of details at low temperatures, it is suitable for applications such as sealants for switch members such as relay parts and impregnation of coils. Used.

Claims (9)

A cationic curable resin composition comprising the following components (A) to (C):
(A) component: a compound having a cycloalkane skeleton and at least one glycidyl group (B) component: a compound having an alicyclic hydrocarbon skeleton (provided that (A) and carbon atoms constituting the cyclic structure are ) Excludes compounds in which an electron withdrawing group selected from the group consisting of an acrylic group, a carboxy group, an imide group, a sulfo group, a cyano group and a nitro group is directly bonded)
Component (C): a cationic initiator containing an iodonium salt (B) The carbon atoms constituting the alicyclic hydrocarbon of the component are each independently a hydrogen atom, a linear or branched alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, or 1 carbon. The cation-curable resin composition according to claim 1, which is a compound in which at least one of ˜12 thiol, vinyl ether, and alcohol having 1 to 12 carbon atoms is directly bonded. The component (B) is any one of a cycloalkane derivative having 3 to 12 carbon atoms, a cycloalkene derivative having 3 to 12 carbon atoms, and a norbornene derivative, according to any one of claims 1 and 2. Cationic curable resin composition. (A) Component is hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin, epoxycyclohexane, pinene oxide, limonene dioxide, vinylcyclohexene diepoxide, 3,4-epoxy It is selected from the group consisting of cyclohexylmethyl (3 ′, 4′-epoxy) cyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, 1,4-cyclohexanedimethanol diglycidyl ether The cation-curable resin composition according to any one of claims 1 to 3. The cation-curable resin composition according to any one of claims 1 to 4, wherein the component (C) is a cation initiator containing an iodonium salt represented by the general formula (1). .

(Wherein R ^{1 to} R ⁶ represent any ^one of a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, and a halogen atom, and each R ^{1 to} R ⁶ may be the same as or different from each other, and X ⁻ is AsF ₆ , SbF ₆ ⁻ , BF ₆ , B (C ₆ F ₅ ) ₄ ⁻ , C (CF ₃ SO ₂ ). ₃ ^- or _{^{[P (R 7) a (}} F) 6-a] - ( wherein, ^{R 7} represents a fluorinated alkyl group having 1 to 20 carbon atoms, a is an integer of 0-5.) The component (B) contains 0.01 to 95 parts by mass and the component (C) contains 0.001 to 30 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). The cation-curable resin composition according to any one of claims 1 to 5. Furthermore, a silane coupling agent is contained as (D) component, The cation curable resin composition of any one of Claims 1-6 characterized by the above-mentioned. The cation curable resin composition according to any one of claims 1 to 7, wherein the cation curable resin composition is cured only by heat. A curing method comprising curing the cationic curable resin composition according to any one of claims 1 to 7 at a temperature of 50 to 100 ° C.

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