JP2011001447A - Epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing a semiconductor that exhibits flame retardancy without using flame retardants, such as a halogen compound and an antimony compound.SOLUTION: The epoxy resin composition contains an epoxy resin, a phenol resin-based curing agent, and an inorganic filler as essential components. The epoxy resin is obtained from a reaction of a phenol compound represented by formula (1), wherein A is a 5-15C alkylidene group having a cyclo ring; and a plurality of substituents Rs are each a hydrogen atom or a methyl group, with epihalohydrin.

Description

  The present invention relates to an epoxy resin composition for semiconductor encapsulation that gives a cured product having excellent flame retardancy.

  Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.

However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), thinning is becoming more and more sophisticated year by year, and heat resistance as well as flexibility is required as a characteristic required for materials. . Furthermore, in recent years, halogen-based epoxy resins and antimony trioxide are frequently used as flame retardants for electrical and electronic parts as flame retardants due to environmental problems. It has been pointed out that it contributes to the generation of toxic substances such as
As one method for solving the above problem, an epoxy resin having a phosphorus atom in the skeleton has been proposed. In particular, since a normal phosphate ester type compound has low stability, a cyclic phosphate compound having good stability is used. Even if a phosphoric acid ester compound is not used, those having excellent flame retardancy compared to conventional epoxy resins have been developed by selecting a resin skeleton. However, at present, particularly in the field of semiconductor encapsulants, development of a system that can be made flame retardant without using phosphorus flame retardants is being studied, and flame retardant properties generally referred to as non-halogen, non-antimony, and non-phosphorus. Is required.
As common knowledge of this flame retardant material, it is believed that the greater the content of aliphatic hydrocarbon groups in the structure, the lower the flame retardancy. For example, based on CFT (thermal decomposition residue rate), which is generally known as a theoretical index, it is suggested that the larger the CFT, the greater the proportion that contributes to the formation of a carbonized layer during combustion, which makes it difficult to burn. Compared to resins with high aromatic density, aliphatic hydrocarbons basically make a negative contribution in this CFT, and are generally judged to be inferior in flame retardancy compared to other aromatic epoxy resins. Is a general view (Non-Patent Document 1).
In the prior art, epoxy resins having a cyclo ring that can be used in the present invention are often produced by using acid anhydrides or amine-based curing agents, and reports focusing on their flame retardancy Is not seen. For example, an epoxy resin of a bisphenol compound having a trimethylcyclohexane structure is known, and a flame-retardant cured product can be produced. However, a flame retardant is insufficient in a composition containing this resin, so that it is necessary to add a flame retardant. .

Incombustibility of polymer Hitoshi Nishizawa (Taisei) p53-57

Japanese Patent Laid-Open No. 02-229181 Japanese Patent Laid-Open No. 2003-082061

  The present invention provides an epoxy resin composition and a semiconductor device that impart flame retardancy to a cured product and have excellent fluidity and heat resistance without using a flame retardant such as a halogen compound, an antimony compound, or a phosphorus compound. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

（式中Ａはシクロ環を有する炭素数５以上１５未満のアルキリデン基である。また複数存在する置換基Ｒは水素原子、あるいはメチル基を表す。）
で表されるフェノール化合物とエピハロヒドリンとの反応によって得られるエポキシ樹脂とフェノール樹脂系硬化剤、無機充填材を必須成分として含有する組成物において無機充填材の含有量が外割で７０〜９５質量％であることを特徴とするエポキシ樹脂組成物、
（２）Ａがシクロヘプタン構造、シクロヘキサン構造、ノルボルネン構造、オクタヒドロメタノインデン構造、アダマンタン構造を有する基のいずれか一種であることを特徴とする前項（１）に記載のエポキシ樹脂組成物、
（３）Ｒが水素原子であり、Ａが炭素数７〜１０のアルキリデン基でかつ、シクロヘキサン構造、ノルボルネン構造、オクタヒドロメタノインデン構造を有する基のいずれか一種であることを特徴とする前項（１）、（２）いずれか一項に記載のエポキシ樹脂組成物、
（４）硬化剤が、フェノールアラルキル樹脂であることを特徴とする前項（１）〜（３）のいずれか一項に記載のエポキシ樹脂組成物、
（５）硬化剤の軟化点が５０〜７５℃であることを特徴とする前項（４）記載のエポキシ樹脂組成物、
に関する。 That is, the present invention relates to (1) formula (1)

(In the formula, A is an alkylidene group having a cyclo ring and having 5 or more and less than 15 carbon atoms. A plurality of substituents R each represent a hydrogen atom or a methyl group.)
In the composition containing an epoxy resin obtained by reaction of a phenol compound represented by the formula and an epihalohydrin, a phenol resin-based curing agent, and an inorganic filler as essential components, the content of the inorganic filler is 70 to 95% by mass in the outer ratio. An epoxy resin composition, characterized in that
(2) The epoxy resin composition according to the above item (1), wherein A is any one of groups having a cycloheptane structure, a cyclohexane structure, a norbornene structure, an octahydromethanoindene structure, and an adamantane structure,
(3) R is a hydrogen atom, A is an alkylidene group having 7 to 10 carbon atoms, and is any one of groups having a cyclohexane structure, a norbornene structure, and an octahydromethanoindene structure 1) The epoxy resin composition according to any one of (2),
(4) The epoxy resin composition according to any one of (1) to (3), wherein the curing agent is a phenol aralkyl resin,
(5) The epoxy resin composition according to the above item (4), wherein the softening point of the curing agent is 50 to 75 ° C,
About.

  The epoxy resin composition of the present invention is an epoxy resin that exhibits flame retardancy without using a flame retardant and a phosphorus compound, and contributes to the reduction of the flame retardant and phosphorus compound in the composition. This is useful for various insulating materials and laminates (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, and the like. In particular, it is extremely useful for a semiconductor sealing material for protecting a semiconductor element.

  The epoxy resin composition of the present invention is suitable for a semiconductor sealing material, and its composition is an epoxy resin composition containing an epoxy resin, a curing agent, and an inorganic filler as essential components.

  The epoxy resin which is an essential component in the epoxy resin composition of the present invention has the formula (1)

（式中Ａはシクロ環を有する炭素数５以上１５未満のアルキリデン基である。また複数存在する置換基Ｒは水素原子、あるいはメチル基を表す。）
で表されるフェノール化合物とエピハロヒドリンとの反応によって得られる。
以下、このエポキシ樹脂を便宜上「本発明のエポキシ樹脂」と表記する。

(In the formula, A is an alkylidene group having a cyclo ring and having 5 or more and less than 15 carbon atoms. A plurality of substituents R each represent a hydrogen atom or a methyl group.)
It is obtained by the reaction of a phenol compound represented by the formula and epihalohydrin.
Hereinafter, this epoxy resin is referred to as “the epoxy resin of the present invention” for convenience.

The phenol compound used as the raw material of the epoxy resin of the present invention can be obtained by reacting the corresponding cyclic aliphatic ketones with phenols.
Specific examples of the compound include the following compounds.

The phenol compound is commercially available, for example, BisP-CP, BisP-Z, BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisP -TCD, BisOC-CDE, Bis26X-CDE, BisP-CHEP, BisP-COCT, BisP-CPeDE (all manufactured by Honshu Chemical Industry), TCDBP (manufactured by METOROPORITA EXIMCHEM LTD), and the like.

Further, as an example of the production method, it can be obtained by reacting the corresponding cycloalkyl ketone and phenol under an acidic condition or a basic condition, followed by treatment such as recrystallization.
In the present invention, a particularly preferred phenol compound is preferably an alkylidene group having a carbon number of 7 to 10 in the formula (1), particularly a cyclohexane structure (for example, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, isopropylcyclohexane, etc.), norbornene It is preferably any one of a group having a structure (eg, norbornene, methylnorbornene, trimethylnorbornene, etc.), an octahydromethanoindene structure (octahydromethanoindene, methyloctahydromethanoindene, etc.), or an adamantane structure (eg, adamantane). . Further, the substituent R is preferably a methyl group or hydrogen, and in the present invention, it is particularly preferred that all are hydrogen atoms.

  Examples of the epihalohydrin used in the reaction of the phenol compound with epihalohydrin include epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin, and the like. In the present invention, epichlorohydrin that is easily available industrially is used. Is preferred. The usage-amount of epihalohydrin is 3-20 mol normally with respect to 1 mol of hydroxyl groups of a raw material phenolic compound, Preferably it is 4-10 mol.

  In the epoxidation reaction, an alkali metal hydroxide is preferably used. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. The alkali metal hydroxide may be used as a solid or an aqueous solution thereof. For example, when alkali metal hydroxide is used as an aqueous solution, an aqueous solution of alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or normal pressure. Then, liquid separation is performed to remove water, and the epoxidation reaction can be carried out by continuously returning the epihalohydrin to the reaction system. Moreover, when using solid, it is preferable to use a flaky thing from problems, such as the ease of handling and solubility. The usage-amount of an alkali metal hydroxide is 0.90-1.5 mol normally with respect to 1 mol of hydroxyl groups of a raw material phenolic compound, Preferably it is 0.95-1.25 mol, More preferably, it is 0.00. 99 to 1.15 mol.

  In the epoxidation reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst in order to accelerate the reaction. The usage-amount of a quaternary ammonium salt is 0.1-15g normally with respect to 1 mol of hydroxyl groups of a raw material phenolic compound, Preferably it is 0.2-10g.

In the epoxidation reaction, it is preferable to carry out the reaction by adding an alcohol such as methanol, ethanol or isopropyl alcohol, an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran or dioxane.
When using the said alcohol, the usage-amount is 2-50 mass% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-20 mass%. On the other hand, when using the said aprotic polar solvent, the usage-amount is 5-100 mass% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 10-80 mass%.

In the epoxidation reaction, the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. On the other hand, reaction time is 0.5 to 10 hours normally, Preferably it is 1 to 8 hours. The reaction product of these epoxidation reactions can be purified by removing epihalohydrin, a solvent, or the like under heating and reduced pressure after washing with water or without washing with water. In addition, in order to make an epoxy resin with less hydrolyzable halogen, the recovered reaction product is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is prepared. In addition, a ring closure reaction of the by-product can be performed to ensure the ring closure of the by-product halohydrin.
In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 mol of the hydroxyl group of the starting phenol compound used for epoxidation. It is. Moreover, reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.

  In the epoxidation reaction, after the completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain an epoxy resin that can be used in the present invention.

In the epoxy resin composition of the present invention, the proportion of the epoxy resin of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more in the total epoxy resin.
Examples of the other epoxy resins include novolac type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. In particular, the addition of a phenol aralkyl type epoxy resin is preferable because the effect of inhibiting the flame retardancy of the epoxy resin composition of the present invention is small. Epoxy compounds of halogenated phenol compounds (or phenol resins) are not preferred because of environmental problems and electrical characteristics (deteriorating electrical characteristics). Even if they are used, 5% by mass or less in all epoxy resins , Preferably 2% by mass or less, more preferably 5000 ppm or less.

  Specific examples of other epoxy resins that can be used include thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, Phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetopheno O-hydroxyacetophenone, tricyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4 -Polycondensates with bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc., and their modified products, halogenated bisphenols such as tetrabromobisphenol A, and glycidyl ethers derived from alcohols And solid or liquid epoxy resins such as alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like, but are not limited thereto. These may be used alone or in combination of two or more.

Examples of the curing agent contained in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, carboxylic acid compounds, and the like. Specific examples of curing agents that can be used include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, and isophoronediamine; amides such as polyamide resins synthesized from dimers of dicyandiamide and linolenic acid and ethylenediamine Compounds: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Acid anhydride compounds; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-te Tramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) Ethane and phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxy Novolac resin, polycondensate of acetophenone and furfural, phenol or cresol and phenylenedimethylol, dimethoxymethyl or methyl halide Or a reaction product of phenol or cresol with bischloromethylbiphenyl, bismethoxymethylbiphenyl or bishydroxymethylbiphenyl, or phenol with benzenediisopropanol, benzenediisopropanoldimethylether or benzenebis (chloroisopropane) Phenol aralkyl resins which are reactants and their modified products, phenolic compounds such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols, imidazoles, trifluoroborane-amine complexes, guanidine derivatives However, it is not limited to these. These may be used alone or in combination of two or more.
In the present invention, from the viewpoint of heat resistance, chemical resistance, and electrical reliability, it is preferable to use a phenolic compound as a curing agent. Phenol aralkyl resins are preferred. Particularly preferred is a phenol aralkyl resin. Moreover, in this invention, it is preferable to use the phenol aralkyl resin whose softening point is 50-100 degreeC. A lower softening point tends to improve fluidity and flame retardancy, but it is preferable to use a higher softening point in order to increase heat resistance.

  In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.8 to 1.1 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.8 equivalent or more than 1.1 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained. In the present invention, a preferable combination of an epoxy resin and a curing agent is an epoxy resin having a softening point of 45 to 70 degrees (more preferably 50 to 65 ° C) and a softening point of 50 to 100 ° C (preferably 50 to 85 ° C, more preferably. 50 to 75 ° C.). A resin composition having balanced properties in terms of fluidity, flame retardancy, and heat resistance is obtained.

  The epoxy resin composition of the present invention may contain a curing accelerator. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- And tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. As for a hardening accelerator, 0.1-5.0 mass parts is used as needed with respect to 100 mass parts of epoxy resins.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid ester compounds such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9- Phosphanes such as oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; activity of epoxy resin and said phosphanes Phosphorus obtained by reacting with hydrogen -Containing epoxy compounds, red phosphorus, etc., but phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylyl). Renyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
However, the amount of the phosphoric acid ester compound as described above is preferably phosphoric acid ester compound / epoxy resin ≦ 0.1 (mass ratio) because of environmental problems and concerns about electrical characteristics. More preferably, it is 0.05 or less. It is particularly preferable not to add a phosphorus compound except that it is added as a curing accelerator.

  The epoxy resin composition of the present invention contains an inorganic filler. Inorganic fillers include fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, titanium oxide, aluminum nitride, silicon nitride, and nitride Examples thereof include boron, mica, glass, quartz, and mica. Further, it is also preferable to use a metal hydroxide such as magnesium hydroxide or aluminum hydroxide in order to impart a flame retardant effect. However, it is not limited to these. Two or more kinds may be mixed and used. Of these inorganic fillers, silicas such as fused silica and crystalline silica are preferred because of low cost and good electrical reliability. In the epoxy resin composition of the present invention, the amount of the inorganic filler used is usually 70% by mass to 95% by mass, and preferably 75% by mass to 90% by mass. If the amount is too small, the flame retardant effect cannot be obtained. If the amount is too large, when the semiconductor element to be sealed is mounted on a copper lead frame, the linear expansion coefficient of the sealing resin and the frame does not match, and heat shock, etc. There is a possibility that a problem due to thermal stress will occur.

  A release agent can be blended in the epoxy resin composition of the present invention in order to improve the release from the mold during molding. Any conventionally known release agent can be used, for example, ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid, and metal salts thereof, polyolefins such as polyethylene oxide and non-oxidized polyethylene And waxes. These may be used alone or in combination of two or more. As for the compounding quantity of these mold release agents, 0.5-3 mass% is preferable with respect to all the organic components. If the amount is too small, release from the mold is poor, and if the amount is too large, adhesion to the lead frame and the like is poor.

  In the epoxy resin composition of the present invention, a coupling agent can be blended in order to enhance the adhesion between the inorganic filler and the resin component. Any conventionally known coupling agent can be used. For example, vinyl alkoxy silane, epoxy alkoxy silane, styryl alkoxy silane, methacryloxy alkoxy silane, acryloxy alkoxy silane, amino alkoxy silane, mercapto alkoxy silane, isocyanate alkoxy Examples include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more. The coupling agent may be added by treating the surface of the inorganic filler with the coupling agent in advance and then kneading with the resin, or mixing the coupling agent with the resin and then kneading the inorganic filler. .

  Furthermore, a known additive can be blended in the epoxy resin composition of the present invention as necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, and silicone oil. And colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

  The epoxy resin composition of the present invention can be produced by any conventionally known technique capable of uniformly dispersing and mixing each component. For example, all the components are pulverized and pulverized, mixed with a Henschel mixer, etc., then melt kneaded with a heating roll, melt kneaded with a kneader, mixed with a special mixer, or an appropriate combination of these methods. The semiconductor device of the present invention can be manufactured by resin-sealing a semiconductor element mounted on a lead frame or the like by transfer molding or the like using the epoxy resin composition of the present invention.

  The semiconductor device of the present invention has a cured product of the epoxy resin composition of the present invention such as the one sealed with the epoxy resin composition of the present invention. As semiconductor devices, for example, DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package).

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the following, “part” means “part by mass”.

Synthesis example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while the following formula (2)

で表されるフェノール化合物（本州化学工業株式会社製、ＢｉｓＰ−ＴＭＣ）１５５部エピクロロヒドリン５５５部、メタノール５６部を加え、撹拌下で溶解し、還流（約７０℃）にまで昇温した。次いでフレーク状の水酸化ナトリウム４１部を９０分かけて分割添加した後、更に７０℃で３時間反応を行った。反応終了後，水２００部で水洗を行い、油層からロータリーエバポレーターを用いて１４０℃で減圧下、過剰のエピクロルヒドリン等の溶剤類を留去した。残留物にメチルイソブチルケトン８００部を加え溶解し、７０℃にまで昇温した。撹拌下で３０質量％の水酸化ナトリウム水溶液１０部を加え、１時間反応を行った後、油層の洗浄水が中性になるまで水洗を行い、得られた溶液から、ロータリーエバポレーターを用いて１６０℃で減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂（ＥＰ１）２０１部を得た。得られたエポキシ樹脂のエポキシ当量は２１９ｇ／ｅｑ．軟化点４７℃、１５０℃における溶融粘度（ＩＣＩ溶融粘度 コーン＃３）は０．０３Ｐａ・ｓであった。

155 parts epichlorohydrin (55 parts by Honshu Chemical Industry Co., Ltd., BisP-TMC) and 56 parts of methanol were added, dissolved under stirring, and heated to reflux (about 70 ° C.). . Next, after adding 41 parts of flaky sodium hydroxide over 90 minutes, the reaction was further carried out at 70 ° C. for 3 hours. After completion of the reaction, water was washed with 200 parts of water, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 800 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 10 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water for the oil layer became neutral. From the resulting solution, 160 parts were used using a rotary evaporator. By distilling off methyl isobutyl ketone and the like under reduced pressure at ° C, 201 parts of the epoxy resin (EP1) of the present invention was obtained. The epoxy equivalent of the obtained epoxy resin is 219 g / eq. The melt viscosity (ICI melt viscosity cone # 3) at a softening point of 47 ° C. and 150 ° C. was 0.03 Pa · s.

Synthesis example 2
155 parts of epichlorohydrin 277 represented by the above formula (2) (BisP-TMC, manufactured by Honshu Chemical Industry Co., Ltd.) while purging nitrogen in a flask equipped with a stirrer, a reflux condenser, and a stirrer And 93 parts of dimethyl sulfoxide were added, dissolved under stirring, and the temperature was raised to 45 ° C. Next, 41 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. Excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure at 150 ° C. using a rotary evaporator. To the residue, 800 parts of methyl isobutyl ketone was added and dissolved, washed with 200 parts of water, and the resulting organic layer was heated to 70 ° C. Under stirring, 10 parts of a 30% by weight sodium hydroxide aqueous solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water of the oil layer became neutral. From the resulting solution, 190 was used using a rotary evaporator. By distilling off methyl isobutyl ketone and the like under reduced pressure at ° C, 205 parts of the epoxy resin (EP2) of the present invention was obtained. The epoxy equivalent of the obtained epoxy resin was 233 g / eq. The melt viscosity (ICI melt viscosity cone # 3) at a softening point of 53 ° C. and 150 ° C. was 0.05 Pa · s.

Synthesis example 3
In Synthesis Example 1, the phenol compound is represented by the formula (3)

で表されるフェノール化合物（ＭＥＴＲＯＰＯＲＩＴＡＮ ＣＨＥＭ製）１６０部とした以外は同様の操作で合成を行った。得られたエポキシ樹脂（ＥＰ３）はエポキシ当量２３１ｇ／ｅｑ．軟化点６１℃、１５０℃における溶融粘度（ＩＣＩ溶融粘度 コーン＃３）は０．０７Ｐａ・ｓであった。

The synthesis was performed in the same manner except that 160 parts of a phenol compound (manufactured by METROPORITA CHEM) represented by the formula: The resulting epoxy resin (EP3) had an epoxy equivalent of 231 g / eq. The melt viscosity (ICI melt viscosity cone # 3) at a softening point of 61 ° C. and 150 ° C. was 0.07 Pa · s.

Examples 1-5 and Comparative Examples 1-3
<Flame retardance test>
The epoxy resin obtained above was blended in the proportions (parts by mass) shown in Table 1, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation. The flame retardant test results are also shown in Table 1.
In addition, the physical property of hardened | cured material was measured in the following ways.
Flame retardance: Performed according to UL94. However, the test was conducted with a sample size of 12.5 mm wide × 150 mm long and a thickness of 0.8 mm.
・ Afterflame time: Total afterflame time after 10 times contact with 5 samples

In the table (EP4): bisphenol A type epoxy resin (trade name: jER-834, manufactured by Japan Epoxy Resin Co., Ltd., shape, semi-solid, epoxy equivalent 250 g / eq)
(H1): Phenol aralkyl type phenol resin (trade name: Millex XLC-3L, Mitsui Chemicals, softening point 71 ° C., hydroxyl equivalent 172 g / eq)
(H2): Phenol aralkyl-type phenol resin (trade name: KAYAHARD GPH-65, Nippon Kayaku softening point 65 ° C., hydroxyl equivalent 198 g / eq)
(H3): phenol novolak (trade name: H-1 Meiwa Kasei Kogyo, softening point 83 ° C., hydroxyl group equivalent 106 g / eq)

Curing accelerator: Triphenylphosphine (manufactured by Hokuko Chemical)
Inorganic filler: fused silica (trade name: MSR-2212, manufactured by Tatsumori)
Mold release agent: Carnauba wax No. 1 (manufactured by Celerica Noda)
Coupling agent: KBM-303 (manufactured by Shin-Etsu Chemical)

From Table 1, it is clear that the epoxy resin composition of the present invention can give a cured product excellent in flame retardancy without using a flame retardant such as a halogen or an antimony compound.
That is, the epoxy resin composition of the present invention containing a phenol aralkyl resin (H1, H2) as a curing agent and an inorganic filler for a bisphenol epoxidized product having a cycloalkyl group having 6 or more carbon atoms as an epoxy resin. The combustion time is short, and in the combustion test based on UL-94, when compared under the same conditions, both are V-1 or V-0 level, and at least the afterflame time is less than 100 seconds. Yes. On the other hand, when a comparative bisphenol A type epoxy resin having no cycloalkyl group was used, the afterflame time was 100 seconds or longer, the combustion time was long, and the result was that it was completely burned. Further, when the curing agent was a resin (H3) other than the phenol aralkyl resin, the flame retardancy was not exhibited, and the afterflame time was 100 seconds or longer and the combustion time was long.

Claims (5)

Formula (1)

(In the formula, A is an alkylidene group having a cyclo ring and having 5 or more and less than 15 carbon atoms. A plurality of substituents R each represent a hydrogen atom or a methyl group.)
In the composition containing an epoxy resin obtained by reaction of a phenol compound represented by the formula and an epihalohydrin, a phenol resin-based curing agent, and an inorganic filler as essential components, the content of the inorganic filler is 70 to 95% by mass in the outer ratio. An epoxy resin composition characterized by the above. The epoxy resin composition according to claim 1, wherein A is any one of groups having a cycloheptane structure, a cyclohexane structure, a norbornene structure, an octahydromethanoindene structure, or an adamantane structure. R is a hydrogen atom, A is an alkylidene group having 7 to 10 carbon atoms, and is any one of groups having a cyclohexane structure, a norbornene structure, or an octahydromethanoindene structure. The epoxy resin composition as described in any one. The epoxy resin composition according to any one of claims 1 to 3, wherein the curing agent comprises a phenol aralkyl resin as an essential component. The epoxy resin composition according to claim 4, wherein the curing agent has a softening point of 50 to 75 ° C.