JP5397265B2 - Epoxy resin composition, cured product thereof, optical semiconductor sealing resin composition, optical semiconductor device, fiber reinforced composite material, and fiber reinforced resin molded product - Google Patents

Description

  The present invention relates to an epoxy resin composition suitable for an optical semiconductor sealing resin composition, a cured product thereof, an optical semiconductor sealing resin composition, and an optical semiconductor device.

  An epoxy resin composition containing an epoxy resin and its curing agent as essential components is excellent in various physical properties such as high heat resistance, moisture resistance, and dimensional stability, so that it is a semiconductor encapsulant, a printed wiring board, a build-up board, a resist ink. Electronic parts such as, conductive adhesives such as conductive paste and other adhesives, liquid sealing materials such as underfill, sealing materials for optical semiconductor devices such as LEDs, photocouplers, optical sensors, semiconductor lasers, image sensors, Widely used in liquid crystal sealing materials, flexible substrate coverlays, build-up adhesive films, paints, photoresist materials, developer materials, fiber reinforced composite materials, and the like.

  Among these, in particular, as an encapsulating material for optical semiconductor devices such as LEDs, photocouplers, optical sensors, semiconductor lasers, image sensors, etc., a combination of an aromatic epoxy resin and an acid anhydride curing agent 2 A liquid curing agent is used because it is excellent in molding processability and transparency.

  However, the sealing material using the above-described aromatic epoxy resin as a main agent tends to cause yellowing of a cured product due to absorption of an aromatic ring in the resin, and particularly in the LED field, the output of the LED element is increased and shortened. As the wavelength has progressed, the aromatic epoxy resin easily absorbs light of this short wavelength, causing yellowing of the optical semiconductor element and a decrease in light extraction efficiency.

  Therefore, aliphatic cyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate as an optical semiconductor encapsulating material with little yellowing of the cured product and excellent strength and heat resistance As a main agent, a technique using acid anhydride as a main curing agent is known (see Patent Document 1).

  However, a sealing material containing the aliphatic cyclic epoxy compound as a main component and an acid anhydride as a curing agent has a drawback that a suitable strength cannot be obtained because the cured product is hard and brittle. In addition, as a means of improving this solid and brittle property, there is a method of blending a flexible resin component, but in this case, the heat resistance of the cured product is inevitably lowered and usually has both heat resistance and strength. It was difficult to do.

  On the other hand, in the field of fiber reinforced thermosetting plastics, curable compositions that cure bisphenol-type epoxy resins with acid anhydrides are commonly used, but in this case as well, the cured products are similarly hard and brittle. It was difficult to combine heat resistance and strength.

JP 2009-114390 A

  Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition which is remarkably excellent in heat resistance and strength of a cured product.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have added an aliphatic ester bond or an aliphatic carbonate bond to a curable resin composition containing an epoxy resin and a curing agent for an acid anhydride epoxy resin as essential components. By compounding the acid group-containing radically polymerizable monomer, it was found that the strength of the cured product was drastically improved while maintaining excellent heat resistance, and the present invention was completed.

  That is, the present invention essentially comprises an epoxy resin (A), a curing agent for acid anhydride epoxy resin (B), and an acid group-containing radical polymerizable monomer (C) having an aliphatic ester bond or an aliphatic carbonate bond. It is related with the epoxy resin composition characterized by making it a component.

  The present invention further relates to an optical semiconductor sealing resin composition comprising the above epoxy resin composition.

  The present invention further relates to an optical semiconductor device comprising an optical semiconductor sealed with the epoxy resin composition.

  The present invention further relates to a fiber-reinforced composite material containing the above epoxy resin composition and reinforcing fibers as essential components.

  The present invention further relates to a fiber reinforced resin molded product comprising a cured product of the above epoxy resin composition and reinforcing fibers as essential components.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which is remarkably excellent in the heat resistance and intensity | strength of hardened | cured material can be provided.

Hereinafter, the present invention will be described in detail.
As described above, the epoxy resin composition of the present invention includes an epoxy resin (A), methacrylic acid (B), an acid group-containing radical polymerizable monomer (C) having an aliphatic ester bond or an aliphatic carbonate bond, and The radical polymerization initiator (D) is an essential component, and this is reacted at once, that is, the reaction between the epoxy group and the acid group and the polymerization reaction of the radical polymerizable group are distinguished as reaction steps. It is characterized in that both reactions are carried out simultaneously or continuously without being carried out. It is worthy of special mention that the heat-resistant yellowing and strength of the cured product are dramatically improved by curing by such an in-situ reaction.

  The epoxy resin (A) used in the present invention is a bisphenol type epoxy resin such as bisphenol A type epoxy resin or bisphenol F type epoxy resin; a hydrogenated bisphenol type such as hydrogenated bisphenol A type epoxy resin or hydrogenated bisphenol F type epoxy resin. Epoxy resins; Novolak type epoxy resins such as phenol novolac resin type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin; polyglycidyl esters of polychloric acids such as phthalic acid and dimer acid; diaminodiphenylmethane, isocyanuric acid, etc. Glycidylamine-type epoxy resin obtained by reacting polyamines of the above with epichlorohydrin; butyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neopen Linear aliphatic epoxy resins such as glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, polypropylene glycol glycidyl ether, trimethylolpropane triglycidyl ether; 2- (3,4-epoxy) cyclohexyl-5,5-spiro -(3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6 -Methylcyclohexanecarboxylate, vinylcyclohexane dioxide, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, exo -Exobis (2,3-epoxycyclopentyl) ether, 2,2-bis (4- (2,3-epoxypropyl) cyclohexyl) propane, 2,6-bis (2,3-epoxypropoxycyclohexyl-p-dioxane), 2,6-bis (2,3-epoxypropoxy) norbornene, diglycidyl ether of linoleic acid dimer, limonene dioxide, 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene dioxide, o- (2,3-epoxy) cyclopentylphenyl-2,3-epoxypropyl ether, 1,2-bis [5- (1,2-epoxy) -4,7-hexahydromethanoindanxyl] ethane, cyclohexanediol Rings such as diglycidyl ether and diglycidyl hexahydrophthalate Epoxy resins having an aliphatic structure.

  Among these, from the viewpoint of preventing yellowing of the cured product, an epoxy equivalent of 150 to 1,000 g / eq. Of low molecular weight, linear aliphatic epoxy resin, hydrogenated bisphenol type epoxy resin, and epoxy resin having a cyclic aliphatic structure are preferred, and an epoxy equivalent of 150 to 500 g / eq. The bisphenol type epoxy resin and the epoxy resin having a cycloaliphatic structure are preferred.

  Examples of the curing agent (B) for the acid anhydride type epoxy resin used in the present invention include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylendoethylenetetrahydrophthalic anhydride. Cyclic aliphatic acid anhydrides such as acid, trialkyltetrahydrophthalic anhydride and methylnadic anhydride; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; unsaturated such as maleic anhydride Examples thereof include carboxylic acid anhydrides. Among these, cycloaliphatic acid anhydrides are preferable from the viewpoint of excellent transparency of the cured product, and acid anhydrides having a viscosity at 25 ° C. of 500 mPa · s or less from the viewpoint of excellent fluidity when the composition is melted. It is preferable that

  The acid group-containing radical polymerizable monomer (C) having an aliphatic ester bond or an aliphatic carbonate bond used in the present invention improves the light extraction efficiency by improving the transparency of the cured product and is suitable for the cured product. It is an essential component for imparting flexibility and improving strength. The acid group-containing radical polymerizable monomer (C) is specifically represented by the following structural formula (1) from the viewpoint of compatibility with the epoxy resin (A).

（式中、Ｒ^１は炭素原子数２〜１０の脂肪族炭化水素基、Ｘはエステル結合又はカーボネート結合、Ｒ^２は炭素原子数２〜１０の脂肪族炭化水素基を表し、ｎは１〜５の整数を示す。）で表されるものが好ましい。

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms, X represents an ester bond or a carbonate bond, R ² represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and n represents 1 to 1) An integer of 5 is preferred).

  Here, as the compound having an ester bond as X in the structural formula (1), a compound obtained by reacting a hydroxyalkyl (meth) acrylate with an aliphatic polycarboxylic acid having 2 to 10 carbon atoms, And the compound obtained by making a hydroxyalkyl (meth) acrylate, a C2-C10 aliphatic diol, and a C2-C10 aliphatic polycarboxylic acid react is mentioned.

  Here, examples of the hydroxyalkyl (meth) acrylate include β-hydroxyethyl methacrylate and β-hydroxyethyl acrylate. Examples of the aliphatic polyvalent carboxylic acid include succinic anhydride, adipic acid, maleic anhydride, tetrahydrophthalic acid, and cyclohexanedicarboxylic acid.

  Furthermore, as the aliphatic diol having 2 to 10 carbon atoms, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propane Diol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediethanol, 1,3-cyclohexanedie Nord, 1,4-cyclohexane diethanol, and the like. Of these, butanediol, pentanediol, hexanediol, cyclohexanediol, and cyclohexanedimethanol having 4 to 8 carbon atoms are preferred from the viewpoint of excellent compatibility with the epoxy resin (A).

  Moreover, as what has a carbonate bond as X in the said Structural formula (1), after obtaining polycarbonate diol by transesterification of C2-C10 aliphatic diol and dialkyl carbonate, for example, (meth) acryl The compound obtained by making it react with an acid or its derivative (s) is mentioned.

Here, examples of the aliphatic diol having 2 to 10 carbon atoms used when X is a carbonate bond include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, , 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propane Diol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2 -Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, B hexane diethanol, 1,3-cyclohexane diethanol, those having 3 to 10 carbon atoms such as 1,4-cyclohexane diethanol, and the like. Of these, butanediol, pentanediol, hexanediol, cyclohexanediol, and cyclohexanedimethanol having 4 to 8 carbon atoms are preferred from the viewpoint of excellent compatibility with the epoxy resin (A).
On the other hand, the dialkyl carbonate used when X is a carbonate bond includes dimethyl carbonate from the viewpoint of reactivity.

  Among these, X is preferably an ester bond in the structural formula (1) from the viewpoint that moderate hardness can be imparted to the cured product, in particular, β-hydroxyethyl methacrylate and succinic anhydride. Preference is given to 3-[[2- (methacryloyloxy) ethoxy] carbonyl] propionic acid which is an adduct, and 2-methacryloyloxyethyl hexahydrophthalic acid which is an adduct of β-hydroxyethyl methacrylate and hexahydrophthalic acid.

  The compounding of the epoxy resin (A) detailed above, the curing agent for acid anhydride epoxy resin (B), and the acid group-containing radical polymerizable monomer (C) having an aliphatic ester bond or an aliphatic carbonate bond The ratio is such that the mass ratio [(A) / (C)] of the epoxy resin (A) and the acid group-containing radical polymerizable monomer (C) is 65/35 to 95/5, And the equivalent ratio [acid anhydride group / epoxy group] of the acid anhydride group in the curing agent for acid anhydride epoxy resin (B) to the epoxy group of the epoxy resin (A) is 0.40 / 1. A ratio of 0.0 to 1.10 / 1.0 is preferable from the standpoint of remarkable effects of improving heat resistance and strength.

  The epoxy resin composition of the present invention preferably contains an epoxy group-containing olefin polymer (D) in addition to the components (A) to (C) described above from the viewpoint of further improving the strength. .

  Examples of the epoxy group-containing olefin polymer (D) used here include a copolymer of an epoxy group-containing vinyl monomer and another polymerizable vinyl monomer. Examples of the epoxy group-containing vinyl monomer used here include various glycidyl esters of (meth) acrylic acid such as glycidyl (meth) acrylate or β-methylglycidyl (meth) acrylate, and (meth) allyl. Examples include allyl glycidyl ethers such as glycidyl ether and (meth) allylmethyl glycidyl ether, and various alicyclic epoxy group-containing vinyl monomers such as 3,4-cyclohexyl acrylate and 3,4-cyclohexyl methacrylate. It is done.

  Examples of other vinyl monomers copolymerizable with these epoxy group-containing monomers include, for example, various acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and cyclohexyl acrylate; methyl methacrylate, ethyl Various methacrylates such as methacrylate, butyl methacrylate, cyclohexyl methacrylate, benzyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( Various waters such as meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate Group-containing (meth) acrylates; or the main component of addition reaction of these (meth) acrylates and ε-caprolactone; various carboxyl groups such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid Mono- or diesters of various monomers containing polyvalent carboxyl groups such as itaconic acid, maleic acid, fumaric acid and the like, and monoalkyl alcohols having 1 to 18 carbon atoms; or N-dimethyl Various amino group-containing amide unsaturated monomers such as aminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-diethylaminopropyl (meth) acrylamide; Dimethylaminoethyl (meth) acrylate, diethylamino Various dialkylaminoalkyl (meth) acrylates such as noethyl (meth) acrylate; tertiary (tert-) butylaminoethyl (meth) acrylate, tert-butylaminopropyl (meth) acrylate, aziridinylethyl (meth) ) Various amino group-containing monomers such as acrylates, pyrrolidinylethyl (meth) acrylates, piperidinylethyl (meth) acrylates, various α-olefins such as ethylene, propylene, butene 1; fluoroolefins such as vinyl chloride and vinylidene chloride Various halogenated olefins except styrene; various aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxy Various hydrolyzable silyl group-containing monomers such as silane and γ- (meth) acryloyloxypropylmethyldimethoxysilane; vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoro Various fluorine-containing α-olefins such as ethylene, pentafluoropropylene and hexafluoropropylene; various perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether and heptafluoroethyl trifluorovinyl ether , Fluorine-containing vinyl monomers such as (per) fluoroalkyl vinyl ether (alkyl group having 1 to 18 carbon atoms); vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, cap Various aliphatic carboxylates such as vinyl acetate, vinyl caprate, vinyl caprate, vinyl laurate, branched aliphatic carboxylate having 9 to 11 carbon atoms, vinyl stearate; vinyl cyclohexanecarboxylate, methylcyclohexane Various vinyl esters of carboxylic acid having a cyclic structure such as vinyl carboxylate, vinyl benzoate, vinyl p-tert-butylbenzoate, and the like can be mentioned, and these can be used alone or as a mixture of two or more.

  The polymerization ratio of the epoxy group-containing vinyl monomer and the other vinyl monomers described above is the mass ratio of the monomer at the time of production [epoxy group-containing vinyl monomer / other vinyl monomers. The body] is preferably in a ratio of 20/80 to 60/40 from the viewpoint of excellent effect of improving the strength of the cured product.

  In addition, the epoxy group-containing olefin polymer (D) has a softening point of 80 by the ring and ball method (5 ° C./min temperature raising method) from the viewpoint of excellent balance between the fluidity at the time of melting the composition and the strength of the cured product. What is in the range of -120 degreeC is preferable. Furthermore, the epoxy equivalent of the epoxy group-containing olefin polymer (D) is 300 to 600 g / eq. It is preferable that it exists in the range.

  When using the above-mentioned epoxy group-containing olefin polymer (D), the blending ratio of the components (A) to (D) is as follows: epoxy resin (A) and acid group-containing radical polymerizable monomer (C). And the epoxy group-containing olefin polymer (D) at a mass ratio [(A) / (C) / (D)] of 60/35/5 to 65/5/30, and the epoxy Equivalent ratio of acid anhydride group in acid anhydride epoxy resin curing agent (B) to epoxy group of resin (A) and epoxy group-containing olefin polymer (D) [acid anhydride group / epoxy group] Is preferably in a ratio of 0.40 / 1.0 to 1.10 / 1.0 from the viewpoint that the effect of improving heat resistance and strength becomes remarkable.

  In the epoxy resin composition of the present invention, in addition to the above components, a radical polymerization initiator (F) may be used in combination. The radical polymerization initiator (F) that can be used here may be any one that can be used as a thermal radical polymerization initiator. For example, methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1, 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) ) Cyclododecane, n-butyl 4,4-bis (t-butyl per) Xyl) valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α '-Bis (t-butylperoxy) diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, Isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide Side, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxy Dicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl- 1-Me -Ruethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5- Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2 -Ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoe T-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t- Hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, t-butylperoxyallyl monocarbonate, 3,3 ′, 4 , 4′-tetra (t-butylperoxycarbonyl) benzophenone and the like. The radical polymerization initiator (F) is preferably used in an amount of 0.001% by mass or more and 2% by mass or less in the epoxy resin composition.

  The transparent epoxy resin composition of the present invention further improves the light resistance and heat yellowing of a cured product by using a reactive silicone (G) in addition to the above-described components for use in an optical semiconductor encapsulant. Can be made. Such reactive silicone (G) has an amino group, an epoxy group, an alicyclic epoxy group, a carbinol-based hydroxyl group, a silanol-based hydroxyl group, a methacryloyl group, a polyether alcohol group, a mercapto group, and a carboxyl in a part of the polysiloxane structure. And those containing a reactive functional group selected from the group.

  More specifically, the following structural formula (2)

ここで、上記式（２）中、Ｒ^１及びＲ^２は、それぞれ独立的にメチル基又は水素原子を表す。また、上記式（２）中、Ｘ、Ｘ’、及びＸ”は、それぞれ独立的に、下記構造式ａ〜ｈからなる群から選択される反応性基、又は、メチル基又は水素原子を表し、ｘ及びｙは１以上の整数である。また、ｘ及びｙの合計は２〜１００となる範囲である。

Here, in said formula (2), R < ¹ > and R < ² > represents a methyl group or a hydrogen atom each independently. In the formula (2), X, X ′, and X ″ each independently represent a reactive group selected from the group consisting of the following structural formulas a to h, a methyl group, or a hydrogen atom. , X and y are integers of 1 or more, and the total of x and y is in the range of 2-100.

  Here, X, X ′, and X ″ are the reactive groups, and R in the structural formulas a to g represents an alkylene group having 1 to 4 carbon atoms.

  Among these, a polysiloxane having an epoxy group, a carboxyl group, or a methacryloyl group is particularly preferable from the viewpoint of excellent reactivity.

  The amount of the reactive silicone (G) used is preferably 5 to 30% by mass in the solid content of the epoxy resin composition of the present invention, from the viewpoint of further improving light resistance and heat yellowing resistance.

  The epoxy resin composition of the present invention can further use a curing accelerator as appropriate. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as an optical semiconductor sealing material application, from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., phosphorous compounds are triphenylphosphine, and tertiary amines are 1,8- Diazabicyclo- [5.4.0] -undecene (DBU) is preferred.

  In addition to the above components, the epoxy resin composition of the present invention can prevent oxidative deterioration when heated by adding an antioxidant, and a cured product having excellent transparency can be used for optical semiconductor sealing materials. It is preferable at the point obtained.

  Examples of the antioxidant that can be used here include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and stearyl-β. -(3,5-di-t-butyl-4-hydroxyphenyl) propionate, monophenols such as 4-methoxynaphthol, hydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2 , 2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-) Butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl Bisphenols such as 2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl) -4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 Phenols represented by polyfunctional phenols such as', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol System antioxidants; -Quinone antioxidants typified by benzoquinone, tolquinone, naphthoquinone; dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropio Sulfur-based antioxidants such as nitrates; triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butyl Phenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4- J-t-B Phosphites such as til-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene Examples thereof include phosphorus-based antioxidants typified by oxaphosphaphenanthrene oxides such as -10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. It is preferable that the usage-amount of above-mentioned antioxidant is the range used as 0.005-1 mass part with respect to 100 mass parts of all the hardening components.

  The epoxy resin composition of the present invention can be further improved in light resistance by further blending an ultraviolet absorber for use in an optical semiconductor sealing material. Examples of ultraviolet absorbers that can be blended include salicylic acids such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy- Benzophenones such as 5-sulfobenzophenone; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3 ', '-Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-3 ′ Benzotriazoles such as 3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole; bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3 5- bis (1,1-dimethylethyl) -4-hydrido hydroxyphenyl} hindered amines such as methyl] butyl malonate and the like. It is preferable that the compounding quantity of these ultraviolet absorbers shall be 0.1-10 mass parts with respect to 100 mass parts of all the hardening components.

  In addition to the above components, a colorant, a coupling agent, a leveling agent, a release agent, a lubricant, and the like can be appropriately added to the epoxy resin composition of the present invention depending on the purpose.

  The colorant is not particularly limited. Inorganic pigments such as chrome vermilion, valve shell, cobalt violet, bitumen, ultramarine, carbon black, chrome green, chromium oxide, cobalt green and the like can be mentioned.

  Examples of the leveling agent include oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil, and titanium coupling agent. Etc. Examples of the lubricant include hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid, stearylamide, palmitylamide Higher fatty acid amide lubricants such as oleylamide, methylenebisstearamide, ethylenebisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri-, or tetra -) Higher fatty acid ester lubricants such as stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, arachidin , Behenic acid, ricinoleic acid, such as magnesium naphthenate, calcium, metal soaps is cadmium, barium, zinc, metal salts such as lead, carnauba wax, candelilla wax, beeswax, and natural waxes such as montan wax.

  As the coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , Vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylto Silane coupling agents such as limethoxysilane, isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neo Titanium coupling agents such as alkoxytri (p-N- (β-aminoethyl) aminophenyl) titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodecanoyl Zirconate, Neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, Neoalkoxytris (ethylenediaminoethyl) zirconate, Neoalkoxytris (m-aminophenyl) Rukoneto, ammonium zirconyl Niu arm carbonate, Al- acetylacetonate, Al- methacrylate, zirconium or the like Al- propionate, or Aluminum-based coupling agents is preferably silicon-based coupling agent. By using a coupling agent, moisture-reliability is excellent, and a cured product with little decrease in adhesive strength after moisture absorption can be obtained.

  Release agents include hydrocarbon lubricants such as paraffin wax, microwax, polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, stearylamide, palmityl. Higher fatty acid amide type lubricants such as amide, oleylamide, methylene bisstearamide, ethylene bisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri-, or Higher fatty acid ester lubricants such as tetra-) stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, Metallic soaps such as magnesium, calcium, cadmium, barium, zinc, lead and other metal salts such as hemonic acid, ricinoleic acid, naphthenic acid, and natural waxes such as carnauba wax, candelilla wax, beeswax, and montan wax are preferable. Higher fatty acid esters, higher fatty acid amides, higher fatty acids, metal soaps, hydrocarbon lubricants, more preferably zinc stearate, magnesium stearate, stearic acid, pentaerythritol (mono-, di-, tri-, Or tetra-) stearate.

  The epoxy resin composition of the present invention can be easily obtained by uniformly stirring the above-described components.

  The curing reaction of the epoxy resin composition of the present invention is preferably in the temperature range of 100 to 170 ° C, for example.

  As described above, the composition of the present invention described above is excellent in fluidity and excellent in transparency and strength of the cured product. Therefore, various compositions such as LED, phototransistor, photodiode, photocoupler, CCD, EPROM, and photosensor are available. It is useful as a sealing material for an optical semiconductor device, and particularly useful as a sealing material for a high-brightness LED element that generates significant heat during light emission. Here, the high-brightness LED element means an element having a luminous flux of 100 lumens (1 m) or more.

  As the high-brightness LED, a blue to white LED having a main light emission peak at a wavelength of 350 to 550 nm and a compound semiconductor composed of four elements of aluminum, gallium, indium, and phosphorus are used, and the element composition is adjusted. And quaternary LEDs that enable red, orange, yellow, and yellow-green color development.

As the application of the former blue to white LED having a main emission peak at a wavelength of 350 to 550 nm, it is used for a backlight source for liquid crystal panels used in portable DVD players, car navigation systems, laptop computers, etc. 10 -17 type liquid crystal panel backlight light source, automobile headlamp light source, and the like.
On the other hand, the use of quaternary LEDs includes outdoor displays, rear lamps and interior lighting of automobiles, backlights of liquid crystal displays of thin televisions and personal computers.

  The optical semiconductor device of the present invention is, for example, transfer molded or casted with the epoxy resin composition of the present invention to the above-mentioned epoxy resin composition that has been sufficiently degassed, for example, an optical semiconductor to which an electrode such as a lead wire is attached. Examples thereof include a method of sealing and curing by a molding method, a method of previously mounting an optical semiconductor on a circuit board, sealing it with the epoxy resin composition of the present invention, and curing. Specifically, it can be obtained by pouring into a mold set with an optical semiconductor element, followed by heat curing under the above temperature conditions.

  The optical semiconductor device of the present invention includes various optical semiconductor devices enumerated as applications of the above-described epoxy resin composition, specifically, light receiving elements such as LEDs, phototransistors, photodiodes, photocouplers, CCDs, EPROMs, and photosensors. And an optical semiconductor device in which a light emitting element or the like is sealed. Among these, LED devices, particularly high-intensity LED devices are particularly preferable, and blue to white LED devices having a main emission peak at a wavelength of 350 to 550 nm and quaternary LED devices are particularly preferable.

  Moreover, the epoxy resin composition of the present invention is used for the optical semiconductor sealing material described above, as well as a laminated board for a printed wiring board, an interlayer insulating material for a buildup board, an adhesive film for buildup, a semiconductor sealing material, and a die attach. Resin materials used for electronic circuit boards such as adhesives, flip-chip mounting underfill materials, grab top materials, liquid sealing materials for TCP, conductive adhesives, liquid crystal sealing materials, flexible substrate coverlays, resist inks, etc. It can be applied to various applications such as optical materials such as waveguides and optical films, resin casting materials, coating materials such as adhesives and insulating paints, and fiber reinforced plastic members. Among these, because of its particularly excellent high heat resistance, other uses for optical semiconductor encapsulating materials include laminates for printed wiring boards, interlayer insulation materials for build-up boards, adhesive films for build-up, and fiber reinforcement. Plastic members are preferred.

  When the epoxy resin composition of the present invention is used as a varnish for a printed circuit board, a composition in which the above-described components are blended into a varnish is used as a paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving. A prepreg which is a cured product can be obtained by impregnating various fiber base materials such as cloth and heating at a heating temperature according to the solvent type used, preferably 50 to 170 ° C. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this epoxy resin composition, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and it is under pressure of 1-10 MPa. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours.

  When the epoxy resin composition of the present invention is used as a varnish for a fiber reinforced plastic member, an epoxy equivalent of 150 to 1000 g / eq. Bisphenol type epoxy resin (A), acid group-containing radical polymerizable monomer (B), radical polymerization initiator (C), and other varnish obtained by blending the above-described components as necessary, The target fiber-reinforced plastic member can be obtained by processing according to various applications described in detail below.

  Here, as the reinforcing fiber constituting the fiber base material used for the fiber reinforced plastic member, it is preferable to use carbon fiber because of its excellent mechanical strength and durability, but as other reinforcing fiber, moderately adhesive The glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, etc., which have been subjected to surface treatment to increase the viscosity can be used, and two or more of these fibers can be used in combination. The carbon fibers include so-called graphite fibers, and specifically, various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Among them, a polyacrylonitrile-based one that can easily obtain a high-strength carbon fiber is preferably used.

  The reinforcing fiber may be any of twisted yarn, untwisted yarn, or untwisted yarn, but the untwisted yarn and untwisted yarn are preferable because both the formability and mechanical strength of the fiber-reinforced plastic member are compatible. Furthermore, the form of a reinforced fiber can use what the fiber direction arranged in one direction, and a textile fabric. The woven fabric can be freely selected from plain weaving, satin weaving, and the like according to the site and use.

  Moreover, it is preferable to use a carbon fiber having a high elastic modulus so that a sufficient amount of material can be produced with a small amount of material in order to produce sports equipment such as a light fishing rod and golf shaft. From this viewpoint, the tensile elastic modulus of the carbon fiber is preferably 200 to 800 GPa, more preferably 225 to 800 GPa.

  Moreover, the amount of the fiber base material in the member in the fiber reinforced plastic member use is not particularly limited, but is in the range of 40 to 70% by mass, and in particular, 50 to 70% by mass in terms of strength. It is preferable that it is the range of these.

  Various known methods are used to manufacture a fiber reinforced plastic member from the epoxy resin composition of the present invention, and a hand in which a fiber aggregate is laid on a mold and the epoxy resin composition of the present invention is laminated in layers. Lay-up method, spray-up method, SMC press method in which an epoxy resin composition containing aggregate in advance is made into a sheet form by compression molding with a mold, RTM that injects an epoxy resin composition into a mating die laid with fibers And a method in which a reinforcing fiber is impregnated with an epoxy resin composition to produce a prepreg, which is baked and hardened in a large autoclave.

  Here, specific uses of the fiber reinforced plastic member include fishing rods, golf shafts, sports equipment such as bicycle frames, automobiles, aircraft frames or body materials, wind power generator blades, and the like.

  When using the epoxy resin composition of this invention as resist ink, after apply | coating this epoxy resin composition on a printed circuit board by a screen printing system, the method of setting it as a resist ink hardened | cured material is mentioned, for example.

  In order to produce a buildup substrate using the epoxy resin composition of the present invention as an interlayer insulating material for a buildup substrate, for example, a circuit was formed by using the epoxy resin composition of the present invention appropriately blended with rubber, filler, etc. It is cured after being applied to the wiring board using a spray coating method, a curtain coating method, or the like. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

When the epoxy resin composition of the present invention is used as an underfill material for semiconductor encapsulating materials or flip chip mounting, silica is usually used as a filler, but the filling rate is per 100 parts by mass of the epoxy resin composition. In addition, it is preferable to use a filler in the range of 30 to 95% by mass. Among them, in order to improve flame retardancy, moisture resistance and solder crack resistance, and to reduce the linear expansion coefficient, 70 parts by mass or more is particularly preferable. Preferably, 80 parts by mass or more can further enhance the effect in order to significantly increase the effect.
As semiconductor package molding, the composition is molded by casting, using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours. A semiconductor device can be obtained.

  On the other hand, as a flip chip mounting method, a plurality of electrodes on an IC chip are aligned with predetermined electrodes on a circuit board through metal bumps, and then electrical connection between these electrodes is performed. Insulating underfill material between IC chip and circuit board, heat curing method, reflow simultaneous curing method that cures sealing resin simultaneously with electrode connection through metal bump, circuit board surface After the liquid epoxy resin is applied to the IC chip, the IC chip is placed on the epoxy resin coating layer and heated and pressed from the back of the IC chip to perform electrode connection and curing of the sealing resin in one step. .

  The method for producing an adhesive film for buildup from the epoxy resin composition of the present invention is, for example, applied to the support film by forming the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of using an adhesive film is mentioned.

  When the epoxy resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, It is important to show fluidity (resin flow) capable of filling the via hole or through hole in the substrate, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like epoxy resin composition of the present invention, coating the varnish-like composition on the surface of the support film (Y), and further It can be manufactured by forming a layer (X) of the epoxy resin composition by curing by heating or hot air blowing.

  The thickness of the formed layer (X) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the layer (X) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (X) is protected by a protective film, after peeling these layers ( X) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C., a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

  When the epoxy resin composition of the present invention is used as a die attach material, for example, a method of dispersing fine conductive particles in the epoxy resin composition to form a composition for an anisotropic conductive film, which is liquid at room temperature. Examples thereof include a paste resin composition for circuit connection and an anisotropic conductive adhesive.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified.
1) Glass transition temperature: Measured by using a viscoelasticity measuring device (solid rheometric measuring device “RSAII” manufactured by Rheometric Co., Ltd., double currant lever method; frequency 1 Hz, heating rate 3 ° C./min).
2) Initial transmittance: Measured using a spectrophotometer “UV-3150” (manufactured by Shimadzu Corporation).
3) Transmittance after heat resistance test: The light transmittance at a wavelength of 400 nm of the cured epoxy resin after heating at 150 ° C. for 72 hours was measured.
4) Bending strength, flexural modulus, strain: compliant with JIS6911.

Examples 1-4, Comparative Examples 1 and 2
According to the formulation shown in Table 1 below, each component was blended to obtain an epoxy resin composition. Varnish viscosity and storage stability were evaluated using this epoxy resin composition.
Also, this epoxy resin composition was poured into a mold gap in which a spacer (silicone tube) having a thickness of 3 mm was sandwiched between glass plates, cured at 120 ° C. for 1 hour, further heated to 160 ° C. and heated to 160 ° C. After reaching, the cured product was obtained by holding at that temperature for 2 hours, and various evaluation tests were performed using this as a test piece. The results are shown in Table 1.

In addition, each component shown in the said Table 1 is as follows.
BPA type epoxy resin: Bisphenol A type epoxy resin (“Epiclon 850S” epoxy equivalent 188 g / eq. Manufactured by DIC Corporation)
Alicyclic epoxy resin: (3,4-epoxycyclohexane) methyl-3 ′, 4′-epoxycyclohexyl-carboxylate (trade name “Celoxide 2021P”, epoxy equivalent 131 g / eq., Manufactured by Daicel Chemical Industries, Ltd.)
Epoxy group-containing olefin polymer: copolymer of glycidyl methacrylate and methyl methacrylate (epoxy equivalent: 430 g / eq.)
Acid anhydride: Methylhexahydrophthalic anhydride (HN-5500E manufactured by Hitachi Chemical Co., Ltd.)
BHT: Dibutylhydroxytoluene HCA: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide JP-202: diethyl phosphite Perhexa HC manufactured by Johoku Chemical Industry Co., Ltd .: 1,1-di (t- Hexylperoxy) cyclohexane (trade name “Perhexa HC” manufactured by NOF Corporation)
PX-4MP: Methyltributylphosphonium dimethyl phosphate (trade name “Hishicolin PX-4MP” manufactured by Nippon Chemical Industry Co., Ltd.)

Claims (12)

Epoxy resin (A), acid anhydride epoxy resin curing agent (B), acid group-containing radical polymerizable monomer (C) having an aliphatic ester bond or an aliphatic carbonate bond, and an epoxy group-containing olefin polymer ( D) is an essential component, and the epoxy group-containing olefin polymer (D) is a copolymer of (meth) acrylic acid glycidyl ester and other vinyl monomers, . The acid group-containing radical polymerizable monomer (C) having an aliphatic ester bond or an aliphatic carbonate bond is represented by the following structural formula (1).

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms, X represents an ester bond or a carbonate bond, R ² represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and n represents 1 to 1) Indicates an integer of 5.)
The epoxy resin composition according to claim 1, which is represented by: The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin (A) is an epoxy resin having a cyclic aliphatic structure. The epoxy resin (A) has an epoxy equivalent of 150 to 1,000 g / eq. The epoxy resin composition according to claim 1, which is a bisphenol type epoxy resin. The compounding ratio of the epoxy resin (A), the curing agent for acid anhydride epoxy resin (B), and the acid group-containing radical polymerizable monomer (C) having an aliphatic ester bond or an aliphatic carbonate bond is an epoxy resin. The mass ratio [(A) / (C)] of (A) to the acid group-containing radical polymerizable monomer (C) is a ratio of 65/35 to 95/5, and
The equivalent ratio [acid anhydride group / epoxy group] of acid anhydride group in the acid anhydride epoxy resin curing agent (B) to the epoxy group of the epoxy resin (A) is 0.40 / 1.0. The epoxy resin composition according to claim 1, which has a ratio of ˜1.10 / 1.0. The blending ratio of the components (A) to (D) is a mass ratio of the epoxy resin (A), the acid group-containing radical polymerizable monomer (C), and the epoxy group-containing olefin polymer (D) [ (A) / (C) / (D)] is a ratio of 60/35/5 to 65/5/30, and
Equivalent ratio of acid anhydride group in the curing agent for acid anhydride epoxy resin (B) to the epoxy group of the epoxy resin (A) and the epoxy group-containing olefin polymer (D) [acid anhydride group / epoxy group] is claim 1 epoxy resin composition wherein the ratio of the 0.40 / 1.0 to 1.10 / 1.0. It consists of the epoxy resin composition as described in any one of Claims 1-6, The resin composition for optical semiconductor sealing characterized by the above-mentioned. The composition according to claim 7, which is a material for encapsulating a high-brightness LED element. An optical semiconductor device comprising an optical semiconductor sealed with the epoxy resin composition according to claim 1. The fiber reinforced composite material which uses the epoxy resin composition as described in any one of Claims 1-6, and a reinforced fiber as an essential component. The fiber-reinforced composite material according to claim 10, wherein the volume content of the reinforcing fibers is in the range of 40 to 85%. A fiber-reinforced resin molded product comprising a cured product of the epoxy resin composition according to any one of claims 1 to 6 and a reinforcing fiber as essential components.