JP2018070682A - Epoxy resin composition and epoxy resin cured product using the same, and electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition which easily obtains a stacking effect by reaction of an epoxy resin as a main agent and a curing agent and has high thermal conductivity; an epoxy resin cured product using the same; and an electronic component device having an element sealed by the epoxy resin cured product.SOLUTION: There are provided an epoxy resin composition which contains (A) a phenol compound represented by structural formula (1), (B) an epoxy resin and (C) a hardening accelerator, preferably contains (D) a phenol resin excluding the phenol compound represented by the structural formula (1), preferably further contains (E) an inorganic filler; an epoxy resin cured product formed by curing the epoxy resin composition; and an electronic component device in which an element is sealed with the epoxy resin composition.SELECTED DRAWING: None

Description

  The present invention relates to an epoxy resin composition that provides a cured product excellent in thermal conductivity, an epoxy resin cured product using the same, and an electronic component device.

Conventionally, curable resins such as epoxy resins have been widely used in the fields of molding materials, laminates and adhesives, various electronic and electrical parts, paints and ink materials. In particular, epoxy resin compositions are widely used as sealing materials in the field related to sealing technology for electronic component elements such as transistors and ICs. This is because epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.
On the other hand, in recent years, in the field of electronic components, speeding up and density increase have progressed, and accordingly, heat generation of electronic components has become remarkable. In addition, electronic components that operate at high temperatures are also increasing. For this reason, high thermal conductivity is required for plastics used for electronic parts, particularly epoxy resin cured products.
In order to improve the thermal conductivity of the cured epoxy resin, the use of a crystalline epoxy resin has been reported (for example, see Patent Documents 1 to 3).

JP-A-11-323162 Japanese Patent Laid-Open No. 2016-23227 JP2015-212367A

  The problem of the present invention is that the main epoxy resin and the curing agent react to maintain a high flatness and easily obtain a stacking effect, and an epoxy resin cured product using the same, An electronic component device including an element sealed with a resin composition is provided.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have obtained an epoxy containing a phenol compound having a mesogenic group obtained by synthesis from pyromellitic dianhydride and 4-aminophenol as a curing agent. It has been found that an epoxy resin composition having a desired high thermal conductivity can be provided by using the resin composition, and the present invention has been completed.
The present invention is as follows.

[1] An epoxy resin composition comprising (A) a phenol compound represented by the following structural formula (1), (B) an epoxy resin, and (C) a curing accelerator.

［２］ 更に上記［１］に記載の構造式（１）で示すフェノール化合物を除く（Ｄ）フェノール樹脂を含有する上記［１］に記載のエポキシ樹脂組成物。
［３］ 更に（Ｅ）無機充填剤を含有する上記［１］又は［２］に記載のエポキシ樹脂組成物。
［４］ (Ｅ)無機充填剤の含有含有率が、エポキシ樹脂組成物の全量に対して５５〜９０体積％である上記［３］に記載のエポキシ樹脂組成物。
［５］ 上記［１］〜［４］のいずれか一項に記載のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物。
［６］ 上記［１］〜［４］のいずれか一項に記載のエポキシ樹脂組成物で、素子を封止した電子部品装置。

[2] The epoxy resin composition according to the above [1], further comprising (D) a phenol resin excluding the phenol compound represented by the structural formula (1) according to the above [1].
[3] The epoxy resin composition according to the above [1] or [2], further comprising (E) an inorganic filler.
[4] The epoxy resin composition according to the above [3], wherein the content of the (E) inorganic filler is 55 to 90% by volume with respect to the total amount of the epoxy resin composition.
[5] A cured epoxy resin obtained by curing the epoxy resin composition according to any one of [1] to [4].
[6] An electronic component device in which an element is sealed with the epoxy resin composition according to any one of [1] to [4].

  In the epoxy resin composition of the present invention, stacking of the epoxy resin is easily formed by using the phenol compound represented by the structural formula (1) as the curing agent, and as a result, the thermal conductivity is excellent. Using such an epoxy resin composition, it has become possible to provide electronic component devices such as ICs and LSIs having excellent thermal conductivity.

[(A) Phenol compound represented by formula (1)]
The phenol compound represented by the structural formula (1) used in the present invention is obtained by reacting pyromellitic dianhydride (structural formula (2)) with 4-aminophenol (structural formula (3)). The amic acid represented by Structural Formula (4), the amic acid represented by Structural Formula (5), or a mixture of both can be synthesized by an imide reaction.

[Synthesis of Amic Acid represented by Structural Formulas (4) and (5)]
Although it does not specifically limit as a solvent used at the time of reaction with pyromellitic dianhydride (Structural formula (2)) and 4-aminophenol (Structural formula (3)), For example, N, N-dimethylacetamide, N , N-diethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy-N , N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert- Butoxy-N, N-dimethylpropylamide, hexamethylphosphoramide, dimethyl sulfoxide, γ-butyro T, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2-methoxyethyl) ether, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, acetone, chloroform, toluene, xylene, etc. And aprotic solvents such as phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, and p-chlorophenol. These solvents may be used alone or in combination of two or more.

  The proportion of pyromellitic dianhydride (structural formula (2)) and 4-aminophenol (structural formula (3)) is a mass ratio (molar ratio) of pyromellitic dianhydride: 4-aminophenol = 1. : 3 is preferable, and 1: 2 is more preferable from the viewpoint of determination at the end of the reaction and ease of purification of the synthesized amic acid (Structural Formulas (4) and (5)).

  The reaction temperature is -20 to 100 ° C, preferably 20 to 60 ° C. The time when the starting 4-aminophenol was not detected by thin layer chromatography (TLC), nuclear magnetic resonance measurement (NMR measurement) or the like was defined as the reaction completion time.

  The imidation reaction for obtaining the phenol compound of Structural formula (1) described later as it is or after diluting the reaction solution of the amic acid represented by Structural Formulas (4) and (5) generated after completion of the reaction Can be used for Alternatively, the polyamic acids of the structural formulas (4) and (5) collected by precipitation from the reaction solution can be redissolved in an appropriate solvent and used in an imidation reaction to obtain a phenol compound of the structural formula (1). . The solvent used for dilution and re-dissolution is not particularly limited as long as it can dissolve the obtained polyamic acid. For example, m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3- Propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone, etc. . These solvents may be used alone or in combination of two or more.

[Synthesis of phenolic compound represented by structural formula (1) by dehydrating and ring-closing an amic acid]
The phenolic compound represented by the structural formula (1) can be obtained by dehydrating and ring-closing (thermal imidation) the amic acid (structural formulas (4) and (5)) synthesized as described above by heating. At this time, the amic acid is converted into an imide in a solvent. Moreover, the method of chemically ring-closing using a well-known dehydration ring-closing catalyst is also employable. The method by heating can be performed at an arbitrary temperature of 100 to 500 ° C, preferably 120 to 450 ° C. The method of chemically cyclizing can be performed, for example, in the presence of pyridine, triethylamine, and the like, and acetic anhydride, and the temperature at this time can be selected from -20 to 200 ° C. .

  In the dehydration ring closure reaction by heating the amic acid, an azeotropic solvent may be used so that water generated separately from the reaction solvent can be efficiently removed. For example, toluene, xylene, mesitylene, cumene and the like can be mentioned.

  When the raw material amic acid (structural formulas (4) and (5)) is no longer detected by thin layer chromatography (TLC) or nuclear magnetic resonance measurement (NMR measurement) or after 24 hours from the start of the reaction End time.

  In the present invention, the obtained phenol compound of the structural formula (1) can be used as a resin composition as it is or diluted with the reaction solution, or a poor solvent such as methanol, ethanol, isopropyl alcohol or the like in the reaction solution. The phenol compound precipitated and recovered by re-dissolving can be redissolved in an appropriate solvent and used as a resin composition. The solvent used for dilution and re-dissolution is not particularly limited as long as it dissolves the obtained phenol compound. For example, m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3- Propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone and the like. These solvents may be used alone or in combination of two or more.

[Epoxy resin composition]
The epoxy resin composition of the present invention contains (A) a phenol compound represented by the structural formula (1), (B) an epoxy resin, and (C) a curing accelerator.

[(B) Epoxy resin]
The (B) epoxy resin used in the present invention includes an epoxy resin having two or more epoxy groups in one molecule. Examples of epoxy resins having two or more epoxy groups in one molecule include biphenylene type epoxy resins, stilbene type epoxy resins, sulfur atom-containing epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, and salicylaldehyde type epoxy resins. And at least one selected from the group consisting of copolymerized epoxy resins of naphthols and phenols, aralkyl-type epoxy resins, diphenylmethane-type epoxy resins, and triphenylmethane-type epoxy resins. The epoxy resin mentioned here is also called a specific epoxy resin. A specific epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  (B) The epoxy resin may contain other epoxy resins other than the specific epoxy resin. Examples of other epoxy resins include epoxy resins that are commonly used in the field. For example, an epoxy-silica hybrid resin having a functional group or a skeleton modified to improve flexibility and adhesiveness, or a flexible tough liquid. An epoxy resin can be mentioned.

  (B) When using a specific epoxy resin as an epoxy resin, the total content of the specific epoxy resin in the total amount of the epoxy resin is preferably 60% by mass or more from the viewpoint of exhibiting the respective performances of the specific epoxy resin. It is more preferably 75% by mass or more, and further preferably 90% by mass or more.

  The epoxy equivalent of the epoxy resin is not particularly limited. Among these, from the viewpoint of balance of various properties such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq. .

  The softening point or melting point of the epoxy resin is not particularly limited. Among these, from the viewpoint of moldability and reflow resistance, the softening point or melting point is preferably 40 ° C. to 180 ° C., and more preferably 50 ° C. to 150 ° C. from the viewpoint of handleability in producing a cured product.

  From the viewpoint of improving thermal conductivity, an epoxy resin having a mesogen skeleton is preferable. Examples of the mesogenic skeleton include a biphenyl skeleton, a naphthalene skeleton, an anthracene skeleton, a benzophenone, and a stilbene skeleton.

[(A) Phenol compound represented by structural formula (1)]
As the curing agent for the epoxy resin composition of the present invention, (A) a phenol compound represented by the structural formula (1) is used.
(A) The phenol compound represented by the structural formula (1) is also referred to as a specific phenol curing agent. A specific phenol hardening | curing agent may be used individually by 1 type, or may be used in combination of 2 or more type.

[(D) Phenol resin ((A) excluding phenol compound represented by structural formula (1))]
(A) The phenolic resin other than the phenolic compound represented by the structural formula (1) used as the specific phenol curing agent may be any phenolic resin having two or more phenolic hydroxyl groups in one molecule. It is not limited. For example, biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, copolymer type resin of benzaldehyde type phenol resin and aralkyl type phenol resin, triphenylmethane type phenol resin, novolac type phenol resin and the like can be mentioned. .

  (D) When using the phenol resin and the phenol compound (specific phenol resin) represented by the structural formula (1), from the viewpoint of exhibiting the performance of the specific phenol resin, the total content of the specific phenol resin in the total amount of the phenol resin is: It is preferably 60% by mass or more, more preferably 75% by mass or more, and still more preferably 90% by mass or more.

  (A) The content ratio of the phenol compound represented by Structural Formula (1) and (B) the epoxy resin is such that the ratio of the hydroxyl equivalent of the phenol resin to the epoxy equivalent of the epoxy resin (hydroxyl equivalent / epoxy equivalent) is 0.5 to 0.5. It is preferable to set in the range of 2, more preferably 0.7 to 1.5, and still more preferably 0.8 to 1.3. When the ratio is 0.5 or more, the epoxy resin is sufficiently cured and the cured product tends to have excellent heat resistance, moisture resistance, and electrical characteristics. Moreover, when the ratio is 2 or less, the amount of phenolic hydroxyl groups remaining in the cured resin is suppressed, and the electrical characteristics and moisture resistance tend to be excellent.

[(C) Curing accelerator]
The curing accelerator is not particularly limited, and examples thereof include 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, and 5,6. -Tertiary amines such as dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like Derivatives, imidazoles such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole and derivatives thereof, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine And these maleated phosphines , Benzoquinone, diazophenylmethane and the like, phosphorus compounds having intramolecular polarization, tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenyl Examples thereof include borate, N-methyltetraphenylphosphonium-tetraphenylborate, an adduct of triphenylphosphine and benzoquinone, an adduct of tripalatolylphosphine and benzoquinone, and triphenylphosphonium-triphenylborane.

  The blending amount of the (C) curing accelerator in the epoxy resin composition of the present invention is not particularly limited as long as a curing acceleration effect can be achieved. From the viewpoint of improving the curability and fluidity at the time of moisture absorption of the epoxy resin composition, the total amount of (C) the curing accelerator is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total (B) epoxy resin. Part is preferable, and 1 part by mass to 15 parts by mass is more preferable. When the content of the curing accelerator is 0.1 parts by mass or more, the composition tends to be cured well in a short time, and when it is 30 parts by mass or less, a curing rate is not too high and a good molded product tends to be obtained. It is in.

[(E) Inorganic filler]
The epoxy resin composition preferably contains (E) an inorganic filler. By containing the inorganic filler, it is possible to improve the thermal linear expansion coefficient, thermal conductivity, elastic modulus and the like of the cured product.

  As the inorganic filler, those generally used for sealing molding materials can be appropriately selected and used, and are not particularly limited. Inorganic fillers include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, magnesium oxide, calcium silicate, silicon nitride, aluminum nitride, boron nitride, silicon carbide, industrial diamond, beryllia, zirconia, Particles such as zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, mica; beads formed by spheroidizing these may be mentioned.

  Moreover, you may use the inorganic filler which has a flame-retardant effect. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as composite hydroxide of magnesium and zinc, and particles such as zinc borate. Among these, fused silica particles are preferable from the viewpoint of reducing the linear expansion coefficient, and alumina particles and magnesium oxide are preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.

  The content of the inorganic filler is not particularly limited as long as the effect of the present invention is obtained, and is preferably in the range of 55% by volume to 90% by volume with respect to the total amount of the resin composition. If the content of the inorganic filler is 55% by volume or more, the cured product tends to have excellent thermal linear expansion coefficient, thermal conductivity, elastic modulus and the like, and if it is 90% by volume or less, the viscosity of the resin composition increases. Is suppressed, the fluidity is excellent, and the package tends to be easily molded.

  The average particle size of the inorganic filler is preferably 0.1 μm to 80 μm, and more preferably 0.3 μm to 50 μm. When the average particle size of the inorganic filler is 0.1 μm or more, an increase in the viscosity of the resin composition is easily suppressed, and when the average particle size is 80 μm or less, the mixing property between the resin composition and the inorganic filler is improved and cured. The package obtained by the above tends to be uniform, variation in characteristics is suppressed, and the filling property to a narrow region tends to be improved. The particle size can be measured using a dry particle size distribution system or a slurry in which an inorganic filler is dispersed in water or an organic solvent using a wet particle size distribution measuring device.

  From the viewpoint of fluidity, the particle shape of the inorganic filler is preferably spherical rather than rectangular, and the particle size distribution of the inorganic filler is preferably distributed over a wide range. For example, when the inorganic filler is contained in an amount of 75% by volume or more, 70% by mass or more of the particles are spherical particles, and the particle size of the spherical particles is preferably distributed in a wide range of 0.1 μm to 80 μm. Since such an inorganic filler can easily form a close-packed structure, even if the content of the inorganic filler is increased, the viscosity of the resin composition is small and a resin composition excellent in fluidity can be obtained. .

[Various additives]
In addition to the above-described components, the epoxy resin composition may further contain various additives such as coupling agents, ion exchangers, mold release agents, stress relaxation agents, flame retardants, and colorants exemplified below. . In addition to the additives exemplified below, the resin composition may contain various additives well known in the art as needed.

(Coupling agent)
The resin composition of the present invention may contain a coupling agent as necessary in order to enhance the adhesion between the resin component and the inorganic filler. As coupling agents, various known silane compounds such as epoxy silane, mercaptosilane, aminosilane, alkyl silane, ureido silane, vinyl silane, and acid silane; titanium compounds; aluminum chelate compounds; aluminum / zirconium compounds; Of coupling agents.

  When the resin composition contains a coupling agent, the content of the coupling agent in the resin composition is preferably 0.05% by mass to 5% by mass with respect to the inorganic filler, and 0.1% by mass. % To 2.5% by mass is more preferable. When the content is 0.05% by mass or more, the adhesion between the resin component and the inorganic filler tends to be further improved, and when it is 5% by mass or less, the moldability of the package tends to be further improved. is there.

(Ion exchanger)
The epoxy resin composition of the present invention may contain an ion exchanger as necessary. In particular, when the epoxy resin composition is used as a molding material for sealing, it is preferable to contain an ion exchanger from the viewpoint of improving the moisture resistance and high temperature storage characteristics of an electronic component device including an element to be sealed. . There is no restriction | limiting in particular as an ion exchanger, A conventionally well-known thing can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. These ion exchangers can be used singly or in combination of two or more. Especially, the hydrotalcite shown by the following general formula (A) is preferable.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (A)
(0 <X ≦ 0.5, m is a positive number)

  When the epoxy resin composition contains an ion exchanger, the content is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferable that it is 0.1 mass%-30 mass% with respect to (B) epoxy resin, and it is more preferable that it is 1 mass%-5 mass%.

(Release agent)
The epoxy resin composition of the present invention may contain a release agent from the viewpoint of obtaining good releasability from the mold during molding. There is no restriction | limiting in particular as a mold release agent, A conventionally well-known thing can be used. Specific examples include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. These release agents may be used alone or in combination of two or more. Of these, carnauba wax is preferred. Examples of the polyolefin wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst.

  When the epoxy resin composition contains a release agent, the content is preferably 0.01% by mass to 10% by mass, and 0.1% by mass to 5% by mass with respect to the total amount of (B) epoxy resin. More preferred. If the content of the release agent is 0.01% by mass or more, sufficient release property tends to be obtained, and if it is 10% by mass or less, better adhesiveness tends to be obtained.

(Stress relaxation agent)
The epoxy resin composition of the present invention may contain a stress relaxation agent such as silicone oil or silicone rubber powder as necessary. By containing the stress relaxation agent, warpage deformation of the package and generation of package cracks can be further reduced. As a stress relaxation agent, if it is a well-known flexible agent (stress relaxation agent) generally used, it will not specifically limit. Specifically, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic Rubber particles such as rubber, urethane rubber and silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer Examples thereof include rubber particles having a structure. These flexible agents may be used alone or in combination of two or more. Of these, silicone-based flexible agents are preferred. Examples of the silicone-based flexible agent include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

(Flame retardants)
The epoxy resin composition of the present invention may contain a flame retardant as necessary from the viewpoint of imparting flame retardancy. There is no restriction | limiting in particular as a flame retardant, It can select suitably from the well-known flame retardant generally used. Specific examples include known organic or inorganic compounds containing a halogen atom, antimony atom, nitrogen atom or phosphorus atom, metal hydroxides, and the like. These flame retardants may be used alone or in combination of two or more. When the epoxy resin composition contains a flame retardant, the content is not particularly limited as long as the flame retardant effect is achieved. For example, 1 mass%-30 mass% are preferable with respect to the total amount of (B) epoxy resin, and 2 mass%-15 mass% are more preferable.

(Coloring agent)
The epoxy resin composition of the present invention may further contain a colorant as required. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, pitch, red lead, and bengara. The content of the colorant can be appropriately selected according to the purpose and the like.

[Method for preparing epoxy resin composition]
The preparation method of the epoxy resin composition is not particularly limited, and any method can be used as long as various components can be sufficiently dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized. More specifically, for example, a predetermined amount of the above-mentioned components are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, etc., heated to 70 ° C. to 140 ° C. in advance, cooled, and pulverized. Can be obtained. The epoxy resin composition is easy to handle if it is tableted with dimensions and mass that match the molding conditions of the package.

[Electronic component equipment]
The electronic component device of the present invention includes an element and a cured product of the epoxy resin composition that seals the element. Examples of the electronic component device include a device in which an element such as an active element or a passive element is mounted on a support member, and the element is sealed with the epoxy resin composition of the present invention. Examples of the support member include a lead frame, a wired tape carrier, a wiring board, glass, and a silicon wafer. Examples of the active element include a semiconductor chip, a transistor, a diode, and a thyristor. Examples of the passive element include a capacitor, a resistor, and a coil.

  More specifically, for example, a semiconductor element is fixed on a lead frame, the terminal part of the element such as a bonding pad and the lead part are connected by wire bonding or bump, and then transferred using the resin composition of the present invention. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small) Outline Package), general resin-encapsulated ICs such as TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) in which a semiconductor chip connected to a tape carrier with bumps is encapsulated with the resin composition of the present invention; Semiconductor chips and transistors connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module, hybrid IC, multi-chip module in which active elements such as capacitors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the epoxy resin composition of the present invention; The element is mounted on the surface of the organic substrate on which the terminals for connecting the wiring board are formed on the back surface, and after connecting the element and the wiring formed on the organic substrate by bump or wire bonding, the element is formed with the epoxy resin composition of the present invention. Sealed BGA (Ball Grid Array), CSP (Chip Size Package), etc. are mentioned. The epoxy resin composition of the present invention can also be used effectively for printed circuit boards.

  A method for sealing an electronic component device using the epoxy resin composition of the present invention is not particularly limited, and methods known in the art can be applied. For example, although a low pressure transfer molding method is common, an injection molding method, a compression molding method, or the like may be used.

  The epoxy resin composition of this invention is excellent in the fluidity | liquidity at the time of shaping | molding, and the heat conductivity of hardened | cured material. Using such an epoxy resin composition, it becomes possible to provide electronic component devices such as IC and LSI, and their industrial value is high.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the examples shown below.

[Synthesis of Amic Acid represented by Structural Formulas (4) and (5)]
In order to synthesize the amic acid represented by the structural formulas (4) and (5), the following were prepared.
・ Pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 4-Aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Tetrahydrofuran (Wako Pure Chemical Industries, Ltd., reagent grade)

  In a 500 mL separable flask, 15.3 g (0.0700 mol) of pyromellitic dianhydride is dissolved in 350 mL of tetrahydrofuran, and 4-aminophenol 15.3 (0.140 mol) manufactured by Tokyo Chemical Industry Co., Ltd. is added thereto. did. Then, it was made to react at 50 degreeC for 1 hour. The resulting precipitate of amic acid was removed by filtration and dried to obtain 29.3 g (0.0671 mol, yield 96%) of amic acid.

In order to synthesize the phenol compound represented by the structural formula (1), the following was prepared.
・ N-methyl-2-pyrrolidone (manufactured by BASF Japan Ltd.)
・ Mesitylene (Wako Pure Chemical Industries, Wako Special Grade)
・ Isopropyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Synthesis of phenol compound represented by structural formula (1)]
In a 500 mL separable flask, 27.1 g (0.0621 mol) of the amic acid formed above was dissolved in 270 mL of N-methyl-2-pyrrolidone, and 30 mL of mesitylene was added thereto. Thereafter, a Dean-Stark tube was connected, and the reaction was carried out for 5 hours while removing water produced at 230 ° C. Thereafter, the mixture was stirred at 0 ° C. for 1 hour, and the resulting phenol compound precipitate added with isopropyl alcohol was filtered off and dried to obtain 20.2 g (0.0505 mol, yield 81%) of the phenol compound. It was.

(Examples 1-6 and Comparative Examples 1-2)
Each component shown below is blended in parts by mass shown in Table 1 and melt-mixed under the conditions of a kneading temperature of 150 ° C. and a kneading time of 2 minutes, whereby Examples 1 to 6 and Comparative Examples 1 and 2 respectively. A resin composition was obtained. The recipe is shown in Table 1.

(Preparation of epoxy resin composition)
The following were prepared as epoxy resins.
Biphenyl type epoxy resin; epoxy equivalent 175 g / eq, melting point 120 ° C. (Mitsubishi Chemical Corporation, trade name: jER YL-6121H)
Bis F type epoxy resin; epoxy equivalent 195 g / eq, melting point 79 ° C. (tetramethylbisphenol F type epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd., trade name: YSLV-80XY)

The following was prepared as a phenol curing agent.
Triphenylmethane type phenol resin; Triphenylmethane type phenol resin having a hydroxyl group equivalent of 103 g / eq and a softening point of 68 ° C. (trade name: HE-910-09, manufactured by Air Water Co., Ltd.)

The following were prepared as the curing accelerator according to the present invention.
Triphenylphosphine; (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Evaluation of thermal conductivity of epoxy resin composition]
The epoxy resin composition obtained by Examples 1-6 and Comparative Examples 1-2 was evaluated by the test method shown below. The evaluation results are shown in Table 2. The resin composition for measuring thermal conductivity was molded using a vacuum hand press molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 10 minutes. Further, post-curing was performed at 175 ° C. for 6 hours.

[Measurement of thermal conductivity]
The thermal diffusivity in the thickness direction of the cured product molded 1 cm in length and 1 cm in width by the above method was measured. The thermal diffusivity and specific heat were measured by a laser flash method (apparatus: LFA447 / 2, manufactured by NETZSCH). Pulse light irradiation was performed under the conditions of a pulse width of 0.1 (ms) and an applied voltage of 247V. The measurement was performed at an ambient temperature of 25 ° C. ± 1 ° C. Subsequently, the value of thermal conductivity was obtained by multiplying the thermal diffusivity by specific heat and density using the following formula (1). The density was measured by a specific gravity measuring device using an electronic balance.
λ = α · Cp · ρ Formula (1)
In formula (1), λ is thermal conductivity (W / mK), α is thermal diffusivity (m ² / s), Cp is specific heat (J / kg · K), and ρ is density (d: g / cm ³ ) Respectively.

  As shown in Table 2, the resin compositions (Examples 1 to 6) containing the phenol compound represented by the structural formula (1) according to the present invention exhibit higher thermal conductivity than Comparative Examples 1 and 2. As a result.

Claims (6)

(A) An epoxy resin composition comprising a phenol compound represented by the following structural formula (1), (B) an epoxy resin, and (C) a curing accelerator.

  Furthermore, the epoxy resin composition of Claim 1 containing the phenol resin except the phenolic compound shown by Structural formula (1) of Claim 1 (D).   The epoxy resin composition according to claim 1 or 2, further comprising (E) an inorganic filler.   (E) The epoxy resin composition according to claim 3, wherein the content of the inorganic filler is 55 to 90% by volume with respect to the total amount of the epoxy resin composition.   The epoxy resin hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-4.   The electronic component apparatus which sealed the element with the epoxy resin composition as described in any one of Claims 1-4.