JP2011099086A - Epoxy resin composition, and electronic component device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-component epoxy resin composition, which can be used in a homogeneous system with high latency while maintaining rapid hardenability equal to that of a conventional hardening accelerator. <P>SOLUTION: The epoxy resin composition includes: (A) an epoxy resin having two or more epoxy groups in one molecule; (B) a hardener having two or more phenolic hydroxyl groups or acid anhydrides in one molecule; and (C) a triaryl borane-amine complex having boron-nitrogen bond energy between -35 and -70 kJ/mol, which is determined by MOPAC Ver1.01 AM1. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an epoxy resin composition suitable as a molding material, a laminate or an adhesive material, and an electronic component device obtained by bonding, molding or sealing with the composition.

Epoxy resins are excellent in heat resistance, moisture resistance, electrical properties and adhesiveness, and are used in a wide range of fields such as electrical insulating materials, paints, and adhesives. Many of these epoxy resin products are required to have stability and standing stability in heating processes such as kneading and drying during the manufacturing process. On the other hand, shortening of the curing time is required for improving the productivity, and it is necessary to achieve both the manufacturing process and the potential during storage and fast curing.
The use of latent curing accelerators has been proposed in order to solve the problem of both latency and fast curability. In many cases, the latent curing accelerator is a method in which a curing accelerator is started by dispersing an incompatible curing accelerator in an epoxy resin and dissolving it in the epoxy resin by heating. Examples include a microcapsule type, a tetra-substituted borate salt, an epoxy-amine adduct, and the like.
Since microcapsules, epoxy-amine adducts, and the like are used in a dispersed state in an epoxy resin, there are problems such as a reduction in solvent resistance and uncured transparency. Moreover, although the tetra-substituted borate salt can be used even in a uniform state, there is a need for a uniform curing accelerator that has low fast curability and can achieve both latency and fast curability.
On the other hand, with recent improvements in computational chemistry and computer performance, the structure and properties of molecules can be predicted to some extent by theoretical calculations, and it can be used easily by non-computational chemistry experts and is used for molecular design. It became so.

Japanese Patent No. 1699430 Japanese Patent No. 1981639 JP-A-62-245925 Japanese Patent Laid-Open No. 7-10893 JP-A-3-139517 JP-A-3-296525 JP-A-8-311023

J. et al. Am. Chem. Soc. , Vol. 107, 3902 (1985)

  The present invention has been made as a result of various studies in order to solve the problem of compatibility between the conventional potential and the fast curability, and has a uniform and high potential while maintaining the same fast curability as a conventional curing accelerator. A one-pack type epoxy resin composition that can be used in a system is provided.

The present invention is as follows.
(1) (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent having two or more phenolic hydroxyl groups or acid anhydrides in one molecule, (C) MOPAC Ver1. An epoxy resin composition comprising a triarylborane-amine complex having a boron-nitrogen bond energy of -35 or less and -70 kJ / mol or more determined by the 01AM1 method.
(2) The epoxy resin composition according to (1), wherein the (C) triarylborane-amine complex is represented by the following general formula (I) or (II).

（式中のＲ_１〜Ｒ_４は同一でも異なっていても良く、水素、アルキル基、アリール基、アルコキシ基又はハロゲン原子を示す。Ｘは水素、アルキル基、ハロゲン原子、アルコキシ基、アミノ基を示す。）

(In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkoxy group, or a halogen atom. X represents hydrogen, an alkyl group, a halogen atom, an alkoxy group, or an amino group. Show.)

(3) The epoxy resin composition according to (1) or (2), wherein (C) the triarylborane-amine complex is contained in an amount of 0.1 to 20% by mass relative to the total amount of the epoxy resin.
(4) An electronic component device comprising a member sealed, molded or connected by the epoxy resin composition according to any one of (1) to (3).

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition with the high potential which can be used by a homogeneous system can be provided, maintaining the quick curability equivalent to an imidazole series hardening accelerator in an epoxy-phenol hardening system.

  As the epoxy resin having two or more epoxy groups in one molecule (A) in the epoxy resin composition of the present invention, known resins can be used without any particular limitation. Examples of such epoxy resins include glycidyl ethers of phenols such as bisphenol A, bisphenol F, bisphenol S, phenol novolak, cresol novolak, and resorcinol novolak, glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol, and phthalic acid. Glycidyl esters of carboxylic acids such as isophthalic acid and tetrahydrophthalic acid, glycidyl type (including methyl glycidyl type) epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as aniline and isocyanuric acid is substituted with a glycidyl group, Vinylcyclohexene epoxide obtained by epoxidizing an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Xylates, alicyclic epoxy resins such as 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, epoxidized products of bis (4-hydroxy) thioether, paraxylylene Glycidyl ether of modified phenolic resin, glycidyl ether of metaxylylene / paraxylylene modified phenolic resin, glycidyl ether of terpene modified phenolic resin, glycidyl ether of dicyclopentadiene modified phenolic resin, glycidyl ether of cyclopentadiene modified phenolic resin, polycyclic aromatic ring modified phenol Glycidyl ether of resin, glycidyl ether of phenol resin containing naphthalene ring, stilbene type epoxy resin, biphenyl type epoxy resin, halogenated phenol novolak Epoxy resins. These epoxy resins can be used alone or in admixture of two or more.

  As the phenol resin having two or more phenolic hydroxyl groups in one molecule (B) in the epoxy resin composition of the present invention, a known phenol resin can be used without particular limitation. For example, phenols such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. Resins obtained by condensation or cocondensation with aldehydes under acidic catalyst, biphenyl skeleton type phenol resin, paraxylylene modified phenol resin, metaxylylene / paraxylylene modified phenol resin, melamine modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified Phenol resin, cyclopentadiene modified phenol resin, polycyclic aromatic ring modified phenol resin, xylylene modified naphthol Resin etc. are mentioned, It can use individually or in mixture of 2 or more types.

  In the present invention, the blending ratio of the epoxy resin (A) and the phenol resin (B) is such that the ratio of the hydroxyl equivalent of the phenol resin to the epoxy equivalent of the epoxy resin is set in the range of 0.5 to 2.0. Is preferable, more preferably 0.7 to 1.5, and still more preferably 0.8 to 1.3. If it is less than 0.5, curing of the epoxy resin is insufficient, and the heat resistance, strength, etc. of the cured product tends to be inferior. On the other hand, if it exceeds 2.0, the phenol resin component remains, and the heat resistance, strength, etc. of the cured product are likely to be inferior.

  The (C) triarylborane-amine complex in the epoxy resin composition of the present invention serves as a curing accelerator for the epoxy resin (A) and the phenol resin (B), and is generally a sodium tetraphenylborate salt. Manufactured from various amine compounds. In such a compound, the boron-nitrogen bond is considered to be broken by heating. For this reason, curing acceleration is low at low temperatures, but amines are generated by the cleavage of boron-nitrogen bonds during heating, so that fast curability is manifested, and it is possible to achieve both low-temperature potential and rapid curability during heating. Conceivable.

As the amine compound of the (C) triarylborane-amine complex used in the present invention, a known compound can be used without particular limitation as long as it is a compound having Lewis basicity. Examples thereof include nitrogen-containing heterocyclic compounds such as aliphatic or aromatic primary, secondary, and tertiary amines, pyridine, imidazole, and pyrazole. Specifically, methylamine, methylamine, etheramine, ethylamine, trimethylamine, triethylamine, triethanolamine, N, N-diisopropylethylamine, piperidine, piperazine, morpholine, quinuclidine, 1,4-diazabicyclo [2.2.2. ] Octane, pyridine, 4-dimethylaminopyridine, ethylenediamine, tetramethylethylenediamine, hexamethylenediamine, aniline, catecholamine, phenethylamine, 1,8-bis (dimethylamino) naphthalene (proton sponge), amino acid, amantadine, spermidine, spermine, etc. Is mentioned.
In particular, from the viewpoint of the thermal decomposition temperature of the borane complex and the curing promoting action of the amine compound to be formed, imidazole compounds represented by the general formulas (I) and (II) can be preferably used.

（式中のＲ_１〜Ｒ_４は同一でも異なっていても良く、水素、アルキル基、アリール基、アルコキシ基又はハロゲン原子を示す。Ｘは水素、アルキル基、ハロゲン原子、アルコキシ基、アミノ基を示す。）

(In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkoxy group, or a halogen atom. X represents hydrogen, an alkyl group, a halogen atom, an alkoxy group, or an amino group. Show.)

Furthermore, a substituent having a small steric hindrance such that R ₂ in the general formulas (I) and (II) is a hydrogen atom, a methyl group or an ethyl group can be used more suitably. This is because the presence of a bulky substituent such as a phenyl group in R _{2 to} R ₄ of the general formulas (I) and (II) makes it easy to cleave the boron-nitrogen bond due to steric repulsion with triarylborane. This is because the property decreases. In addition, an electron-withdrawing substituent such as a chlorine atom or a fluorine atom can be more suitably used for X in the general formula (I). This is because the Lewis acidity of the boron atom increases and the boron-nitrogen bond is not easily cleaved, thereby further improving the potential. Specific examples include compounds (1), (2) and (3) represented by the following general formula.

（式（１）中のＲ_１は水素原子または炭素数１〜１０のアルキル基、フェニル基、ベンジル基、シアノエチル基、Ｒ_２は水素原子、メチル基またはエチル基、Ｒ_３は水素原子、メチル基またはエチル基を示す。）

(R ₁ in formula (1) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, phenyl group, benzyl group, cyanoethyl group, R ₂ is a hydrogen atom, methyl group or ethyl group, R ₃ is a hydrogen atom, methyl Group or ethyl group.)

（式（３）中のＲ_１は水素原子または炭素数１〜１０のアルキル基、フェニル基、ベンジル基、シアノエチル基、Ｒ_２は水素原子、メチル基またはエチル基、Ｒ_３は水素原子、メチル基またはエチル基を示す。Ｘは水素原子、炭素数１〜１０のアルキル基、塩素原子、フッ素原子を示す。）

(In formula (3), R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, phenyl group, benzyl group, cyanoethyl group, R ₂ is a hydrogen atom, methyl group or ethyl group, R ₃ is a hydrogen atom, methyl And X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a chlorine atom, or a fluorine atom.)

Furthermore, the strength of the boron-nitrogen bond can be predicted by theoretical calculation. By calculating the difference in heat of formation before and after the borane complex formation, the boron-nitrogen bond energy can be obtained. Specifically, it can be calculated by the following formula (1).
Boron-nitrogen bond energy = (borane complex formation heat)-((triarylborane formation heat) + amine compound formation heat)) (1)
The boron-nitrogen bond energy value determined by semi-empirical molecular orbital calculation in the present invention is −35 to −70 kJ / mol, preferably −40 to −65 kJ / mol, and more preferably −45 to 55 kJ. / Mol. If the value of the boron-nitrogen bond energy is greater than -35 kJ / mol, the bond is weak, so that it partially decomposes in solution or during long-term storage, and if it is less than -70 kJ / mol, the bond is too strong to obtain catalytic activity. Moreover, when it is larger than −40 kJ / mol, sufficient potential cannot be obtained, and when it is less than −65 kJ / mol, sufficient rapid curability cannot be obtained. Furthermore, in the range of −40 to −65 kJ / mol, the balance between the latency and the fast curability is good and more preferable.
As a calculation method, the ab initio molecular orbital method (ab initio molecular orbital method) has high calculation accuracy, but the calculation time is long and the software is expensive. On the other hand, the semi-empirical molecular orbital method can be easily used although the calculation accuracy is reduced. As a result of the study, in the present invention, it is possible to sufficiently measure the strength of the boron-nitrogen bond even with an accuracy equivalent to that of a semi-empirical molecular orbital method. In the present invention, the calculation was performed by the MOPAC AM1 calculation method.
In order to increase the calculation accuracy, an ab initio molecular orbital method or other semi-empirical molecular orbital methods with higher accuracy can be applied. At that time, since the absolute value of the bond energy varies depending on the calculation method, it is necessary to reset the optimum threshold value of the boron-nitrogen bond energy by the calculation method.
The molecular structure and energy after structure optimization calculation may vary depending on the initial structure before optimization calculation. Therefore, it is preferable to perform optimization calculation from a plurality of initial structures and to make the most stable structure the most stable structure.

The addition amount of the (C) triarylborane-amine complex in the epoxy resin composition of the present invention is usually 0.1 to 20% by mass, preferably 1 to 15% by mass, based on the total amount of the epoxy resin. More preferably, it is 2-8 mass%. If the addition amount is less than 0.1% by mass, the effect as a curing accelerator cannot be obtained, and if it exceeds 20% by mass, phase separation may occur with the epoxy resin. Further, if the addition amount is less than 1% by mass, sufficient fast curability may not be obtained, and if it exceeds 15% by mass, sufficient potential may not be obtained. Furthermore, when the addition amount is in the range of 2 to 8% by mass, it is particularly easy to achieve both latency and fast curability.
These triarylborane-amine complexes may be used alone or in admixture of two or more compounds. In that case, you may mix and use with another well-known hardening accelerator.

The organic solvent used in the synthesis (production) of the triarylborane-amine complex desirably dissolves the raw material or the reaction product, but may be in a dispersed state. The organic solvent to be used is preferably a triarylborane-amine complex and a product that does not have reactivity with the product triarylborane or amine. Specifically, aromatic hydrocarbon compounds such as toluene, xylene and mesitylene, amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidinone, diethylene glycol dimethyl ether, triethylene A polyether compound such as glycol dimethyl ether is preferred, but is not limited thereto. A plurality of organic solvents may be mixed for the purpose of adjusting the boiling point and solubility.
Moreover, since the triarylborane to be generated is unstable to oxygen, it is preferably performed in an inert gas atmosphere such as nitrogen or argon.

  A thermoplastic resin may be used in combination with the epoxy resin composition of the present invention for the purpose of adjusting the film formability and the crosslinking density. Specifically, known materials such as polyimides, polyamides, phenoxy resins, poly (meth) acrylates, polyimides, polyurethanes, polyesters, polyester urethanes, and polyvinyl butyrals can be used without particular limitation. These can be used alone or in admixture of two or more.

  The epoxy resin composition of the present invention may be used in combination with a rubber component for the purpose of stress relaxation and adhesion improvement. Specifically, polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, Hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group-containing acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxy Examples include silyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, and poly-ε-caprolactone. These compounds may be used alone or in admixture of two or more compounds.

  In the epoxy resin composition of the present invention, an inorganic filler may be used in combination for the purpose of adjusting the viscosity, reducing the linear expansion coefficient, and improving the thermal conductivity. Specifically, known materials such as fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, and graphite can be used without particular limitation. These compounds may be used alone or in admixture of two or more compounds.

  The epoxy resin composition of this invention is used suitably for a general electronic component apparatus. For example, it is used in the fields of electrical insulating materials, paints, molding materials, laminates, adhesives, etc., and the electronic component device may include a member sealed, molded or connected by the epoxy resin composition of the present invention. That's fine.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. Hereinafter, a triarylborane-amine complex is abbreviated as a borane complex.
(Synthesis method)
(Synthesis of borane complex 1)
Tetraphenylborate sodium salt (product name: Hokuboron Na, manufactured by Hokuko Chemical Co., Ltd.) in a three-necked flask, 10 g of tetrahydrofuran (Wako Pure Chemical Industries, Ltd., special grade reagent) and 5 g of toluene (Wako Pure Chemical) Industrial Co., Ltd., special grade reagent) was added and dissolved. A three-way cock and a dropping funnel were attached, and degassing of dissolved oxygen and nitrogen substitution were performed by repeating decompression (attainment pressure 200 Pa) and nitrogen substitution four times using a diaphragm pump (ULVAC, Inc., DTU-20). To the dropping funnel, 3.7 g (10 mmol) of 10% aqueous hydrochloric acid was added, and the mixture was added dropwise at 25 ° C. over 1 hour, followed by further stirring at 25 ° C. for 2 hours. A solution obtained by diluting 1.1 g (10 mmol) of an imidazole compound (product name: 2PZ (2-phenylimidazole), Shikoku Kasei Kogyo Co., Ltd.) with 10 g of toluene was added dropwise at 25 ° C. over 30 minutes. After the addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the reaction solution was extracted with toluene and washed with water four times. The toluene phase was recovered, concentrated and dried with a rotary evaporator, and the resulting white solid was washed with a small amount of toluene to obtain borane complex 1 in a yield of 58%.
The synthesized borane complex 1 has the structure represented by the general formula (I), wherein X is a hydrogen atom, R ₁ is a hydrogen atom, R ₂ is a phenyl group, and R ₃ is a hydrogen atom. And R ₄ is a hydrogen atom.

(Synthesis of borane complex 2)
The imidazole compound was synthesized according to the method for synthesizing borane complex 1 except that 1.2 g (10 mmol) of 2PZ-CN (Shikoku Kasei Kogyo Co., Ltd.) was used instead of 2PZ. The yield of borane complex 2 was 75%.
The synthesized borane complex 2 has the structure represented by the general formula (I), wherein X is a hydrogen atom, R ₁ is a 2-cyanoethyl group, R ₂ is a phenyl group, and R ₃ is a hydrogen atom. An atom, and R ₄ is a hydrogen atom.

(Synthesis of borane complex 3)
Instead of 2PZ as an imidazole compound, 1.2 g (10 mmol) of 2E4MZ (Shikoku Chemical Industry Co., Ltd.) was used, and tetrakis (4-methoxyphenyl) borate sodium salt (Wako Pure Chemical Industries, Ltd.) was used as a borate. The borane complex 1 was synthesized according to the synthesis method. The yield of borane complex 3 was 45%.

(Synthesis of borane complex 4)
Instead of 2PZ as an imidazole compound, 1.2 g (10 mmol) of benzylamine (Wako Pure Chemical Industries, Ltd.) was used, and tetrakis (4-fluorophenyl) borate sodium salt (Wako Pure Chemical Industries, Ltd.) was used as a borate. Except for the above, it was synthesized according to the synthesis method of borane complex 1. The yield of borane complex 4 was 94%.

(Synthesis of borane complex 5)
The imidazole compound was synthesized according to the method for synthesizing borane complex 1 except that 1.2 g (10 mmol) of 2E4MZ (Shikoku Kasei Kogyo Co., Ltd.) was used instead of 2PZ. The yield of borane complex 2 was 81%.
The synthesized borane complex 5 has the structure represented by the general formula (I), wherein X is a hydrogen atom, R ₁ is a hydrogen atom, R ₂ is an ethyl group, and R ₃ is a hydrogen atom. And R ₄ is a methyl group.

(Synthesis of borane complex 6)
The imidazole compound was synthesized according to the synthesis method of borane complex 1 except that 1.2 g (10 mmol) of 1-butylimidazole (Tokyo Chemical Industry Co., Ltd.) was used instead of 2PZ. The yield of borane complex 2 was 84%.
The synthesized borane complex 6 has a structure represented by the general formula (I), wherein X is a hydrogen atom, R ₁ is an n-butyl group, R ₂ is a hydrogen atom, and R ₃ is a hydrogen atom. An atom, and R ₄ is a hydrogen atom.

(Synthesis of borane complex 7)
Instead of 2PZ as an imidazole compound, 1.2 g (10 mmol) of 2E4MZ (Shikoku Chemical Industry Co., Ltd.) was used, and tetrakis (4-fluorophenyl) borate sodium salt (Wako Pure Chemical Industries, Ltd.) was used as a borate. The borane complex 1 was synthesized according to the synthesis method. The yield of borane complex 7 was 64%.
The synthesized borane complex 7 has the structure represented by the general formula (I), wherein X is a fluorine atom, R ₁ is a hydrogen atom, R ₂ is an ethyl group, and R ₃ is a hydrogen atom. And R ₄ is a methyl group.

(Preparation of epoxy resin composition)
As the epoxy resin, a bisphenol F type epoxy resin (product name; YDF-8170C, manufactured by Toto Kasei Co., Ltd.) was used. As the phenolic resin, bisphenol A novolac type phenolic resin (product name: LF4871C, manufactured by DIC Corporation, solid content 60 mass% MEK solution) was used. As the acrylic rubber, a copolymer of butyl acrylate, ethyl acrylate and acrylonitrile (product name: WS-023, manufactured by Nagase ChemteX Corporation, solid content 23 mass% toluene / ethyl acetate solution) was used. As the curing accelerator, borane complexes 1 to 7 synthesized by the above synthesis method and an imidazole compound (product name: 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) were used.

  It mix | blends as shown in Table 1 and Table 2 by solid mass ratio, and it apply | coats it using a coating apparatus (apparatus name: SNC-S3.0, the Yasui Seiki Co., Ltd. product) on the fluororesin film of thickness 80micrometer. Film-like epoxy resin compositions of Examples 1 to 9 and Comparative Examples 1 to 15 having an adhesive layer thickness of 20 μm were prepared by drying with hot air at 10 ° C. for 10 minutes.

The following characteristic evaluation was performed about the epoxy resin composition obtained by the Example and the comparative example. The results are shown in Table 3.
(1) Curing temperature The epoxy resin composition was measured at a heating rate of 10 ° C / min under nitrogen using a differential scanning calorimeter (DSC7 PERKIN ELMER), and the exothermic peak temperature was taken as the curing temperature.
(2) Epoxy reaction rate The epoxy reaction rate α is calculated from the reaction heat ΔH1 (J / g) immediately after the preparation of the epoxy resin composition and the reaction heat ΔH2 (J / g) after standing at 40 ° C. for 5 days by the equation (2). Calculated.
α = (1−ΔH2 / ΔH1) × 100 (2)
The reaction heat of the epoxy resin composition was measured using a differential scanning calorimeter (DSC7 PERKIN ELMER) under nitrogen at a heating rate of 10 ° C./min, calculated from the exothermic peak area, and exothermic per gram of epoxy resin composition. Amount (J / g).
(3) Film appearance Regarding the epoxy resin composition in the form of film (Examples 1 to 9, Comparative Examples 1 to 15), if the epoxy resin composition film after standing at 40 ° C. for 5 days can be bent at 25 ° C., it becomes brittle When it broke, it was set as x.
In addition, the smaller the epoxy reaction rate, the better the storage stability.
(4) Nitrogen boron bond energy Using MOPAC2002 Ver1.01, using the heat of formation (Final Heat of Formation) obtained by optimizing the structure of imidazole borane complex, imidazole compound, and triarylborane compound by AM1 calculation, the following formula The boron-nitrogen bond energy was calculated according to (3).

When the imidazole compound is complexed with borane (Comparative Examples 4 to 12, Examples 1 to 9), the storage stability after standing at 40 ° C. for 5 days is compared with the case where it is not complexed with borane (Comparative Examples 1 to 3). The epoxy reaction rate was small and improved.
However, in the case of a borane complex having a low boron-nitrogen bond energy (Comparative Examples 4 to 12), when the addition amount is increased and the curing temperature is lowered, the epoxy reaction rate increases and the storage stability decreases (Comparative Example 6). To 9, Comparative Example 12).
On the other hand, in the case of a borane complex having a strong boron-nitrogen bond energy (Comparative Examples 4 to 12), the increase in the epoxy reaction rate is small even if the addition amount is increased to lower the curing temperature. Further, in the case of a borane complex having a significantly strong boron-nitrogen bond energy (Comparative Examples 13 to 15), the curing temperature is very high and almost no catalytic activity is observed.
Further, when compared at a curing temperature equivalent to a borane complex having a weak boron-nitrogen bond energy (Example 2, Comparative Example 6), (Example 2, Comparative Example 12), (Example 6, Comparative Example 8), (Example 8, Comparative Example 6), (Example 8, Comparative Example 12), and borane complexation improved only the storage stability while maintaining the same rapid curability as the corresponding imidazole compound. Further, in the case of a borane complex having a high boron-nitrogen bond energy even if the epoxy reaction rate is the same, the appearance change of the film after standing is less and the storage stability is excellent (Example 6, Comparative Example 5).

Claims (4)

  (A) Epoxy resin having two or more epoxy groups in one molecule, (B) Curing agent having two or more phenolic hydroxyl groups or acid anhydrides in one molecule, (C) MOPAC Ver1.01AM1 An epoxy resin composition comprising a triarylborane-amine complex having a calculated boron-nitrogen bond energy of -35 or less and -70 kJ / mol or more. The epoxy resin composition according to claim 1, wherein the (C) triarylborane-amine complex is represented by the following general formula (I) or (II).

(In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkoxy group, or a halogen atom. X represents hydrogen, an alkyl group, a halogen atom, an alkoxy group, or an amino group. Show.)   (C) 0.1-20 mass% of triaryl borane-amine complexes are contained with respect to the total amount of epoxy resins, The epoxy resin composition of Claim 1 or 2 characterized by the above-mentioned.   An electronic component device comprising a member sealed, molded or connected by the epoxy resin composition according to claim 1.