TW201008960A - Epoxy resin composition, the cured article thereof, light-semiconductor sealing material, and light-semiconductor device - Google Patents

Abstract

The subject of the present invention provides an epoxy resin composition showing the excellent liquidity in the state of the varnish, in the meantime, showing the excellent heat-yellowing resistance, and further showing the excellent performance in the strength of the cured article. An epoxy resin composition is characterized in that comprises epoxy resin (A), having 150 to 500g/eq. of epoxy equivalent of biphenol type epoxy resin or cyclic aliphatic structure; methacrylic acid (B); radical polymerization monomer having acid groups that contains aliphatic ester bonds or aliphatic carbonate (C), and radical polymerization initiator (D) as the essential components.

Description

201008960 VI. Description of the Invention: [Technical Field] The present invention relates to an epoxy resin composition suitable for an optical semiconductor sealing material, a cured product thereof, an optical semiconductor sealing material, and an optical semiconductor device. [Prior Art] In recent years, an optical semiconductor device such as an LED, a photocoupler, a photosensor, a semiconductor laser, or an image sensor has been widely used as a light-emitting element or an optical transmission device, and an aromatic epoxy resin and an acid anhydride-based hardener are combined. In the case of the liquid-type hardener, it is used as a resin material for sealing the photo-semiconductor factor because it is excellent in moldability and transparency. However, since the aromatic epoxy resin is used as the sealing material of the main component, the absorption of the aromatic ring in the resin tends to cause yellowing of the cured product, and in particular, in the field of LEDs, the LED element is highly exported. In the case of shortening the wavelength, the aromatic epoxy resin easily absorbs the short-wavelength light, resulting in yellowing of the optical semiconductor element and a decrease in light output efficiency. An optical semiconductor sealing material having less yellowing of a cured product, for example, an aliphatic cyclic epoxy compound such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate is used. The technique of the main agent (refer to Patent Document 1). However, even for such non-aromatic compounds, yellowing due to the thermal history of the cured product cannot be avoided, and in particular, it is not required to have a high-output type high-brightness LED sealing material which has been in high demand in recent years. Thermal stability. Further, the photo-semiconductor sealing material needs to have moderate flexibility, and the above-mentioned aliphatic cyclic epoxide is mainly used as a sealing material, and since the hardened material is hard and brittle, it does not have moderate strength, which is a disadvantage. Moreover, such an epoxy hardening type sealing material has a long-term hardening reaction due to -4-201008960, so the productivity of the optical semiconductor device is low, and the hardening speed is increased, and the excessive curing after the hardening reaction is still caused by the hardened material. The color. Therefore, from the viewpoint of excellent heat resistance and moisture resistance of the cured product and curing in a short time, an ultraviolet curing type sealing material is used, for example, a vinyl ester compound of the above aliphatic cyclic epoxy compound is used. A method of curing by radical polymerization (refer to Patent Document 2 below). However, when a vinyl ester compound is used, a step of reacting an aliphatic cyclic epoxy compound with methyl Φ acrylic acid is required, and for industrial production, In order to be a suitable method, and the reaction product of the aliphatic cyclic epoxy compound and methacrylic acid is solid, when it is used as a photo-semiconductor sealing material, it must be adjusted into a solution-like varnish, and the design of the limited material is not easy to cope with. A significant expansion in the use of optical semiconductor devices in recent years. Moreover, the color of the cured product itself is also conspicuous, and the light output efficiency is low, and it is difficult to achieve practical use of the LED sealing material. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2006-332262. [Patent Document 2] JP-A-2006-332262A SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION Accordingly, the object of the present invention is to provide a varnish state. An epoxy resin composition which is excellent in fluidity, excellent in transparency of a cured product, and excellent in heat-resistant yellowing after heat history, and excellent in strength of a cured product. Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a composition of a free '201008960-based polymerizable monomer having an epoxy resin, methacrylic acid, and a specific acid group is blended. The reaction is hardened, that is, hardened by an in situ reaction, whereby not only excellent fluidity before hardening but also excellent transparency, heat yellowing resistance and strength after hardening are obtained. The present invention has been completed. That is, the present invention relates to an acid group-containing radical polymerizable monomer (C) containing an epoxy resin (A), methacrylic acid (B), and having an aliphatic ester bond or an aliphatic carbonate bond. And the radical polymerization initiator (D) is an epoxy resin composition of an essential component. β An optical semiconductor sealing material formed of the above epoxy resin composition. Further, the present invention relates to a cured product which is cured by heating or irradiating an active energy ray after the above transparent epoxy resin composition is formed. Further, the present invention relates to a method for producing a cured product which is cured by heating or irradiating an active energy ray after the transparent epoxy resin composition is formed. The present invention is more related to an optical semiconductor device in which an optical semiconductor is sealed by the above-described transparent epoxy resin composition. EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an epoxy resin composition which is excellent in fluidity in a varnish state, and which has a heat-resistant yellowing property after heat treatment, and which has excellent mechanical strength and excellent properties. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The epoxy resin composition of the present invention, as described above, is an epoxy resin 201008960 (A), methacrylic acid (B), and an acid group-containing radical polymerization having an aliphatic ester bond or an aliphatic carbonate bond. The monomer (C) and the radical polymerization initiator (D) are essential components, and the reaction of the epoxy group with the acid group and the polymerization of the radical polymerizable group are carried out continuously or simultaneously. Thus, by hardening it by in-situ reaction, the fluidity of the epoxy resin composition containing an epoxy resin and a hardener as an essential component before hardening can be improved, and at the same time, the heat-resistant yellowing of the cured product is remarkably enhanced. Strength, this is its characteristic. The epoxy resin (A) used in the present invention, for example, a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin; a hydrogenated bisphenol A type epoxy resin and a hydrogenation double Hydrogenated bisphenol type epoxy resin such as phenol F type epoxy resin; phenol novolak resin type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, etc. Polyglycidyl ester of polychloric acid such as phthalic acid or dimer acid; glycidylamine type epoxy obtained by reacting polyamines such as diaminodiphenylmethane and trimeric isocyanic acid with epichlorohydrin Resin; butyl glycidyl ether, i, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, polypropylene glycol glycidyl ether, trimethylolpropane a linear aliphatic epoxy resin such as triglycidyl ether; having 2-(3,4-epoxy)cyclohexyl-5,5-spiro-(3,4-epoxy)cyclohexane-m-dioxin Alkane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6 -methylcyclohexane Acid ester, ethylene cyclohexane dioxide, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate Ester, exo-ring-exo-bis(2,3-epoxycyclopentyl)ether, 2,2-bis(4-(2,3-epoxypropyl)cyclohexyl)propane, 2,6-201008960 double (2,3-glycidoxycyclohexyl-p-dioxane), 2,6-bis(2,3·epoxypropoxy)norzene, diglycidyl ether of linoleic acid dimer, Limonene dioxide, 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene dioxide, o-(2,3-epoxy)cyclopentylphenyl-2,3 -glycidyl ether, 1,2-bis[5-(1,2-epoxy)-4,7-hexahydromethane oxime]ethane, cyclohexanediol diglycidyl ether and diglycidyl hexahydro An epoxy resin having a cyclic aliphatic structure such as phthalic acid ester. Among them, from the viewpoint of preventing yellowing of the cured product, it is preferably a low molecular weight body having an epoxy equivalent of 150 to 1,000 g/eq., or a linear aliphatic epoxy resin, in the bisphenol epoxy resin. The hydrogenated bisphenol type epoxy resin and the epoxy resin having a cyclic aliphatic structure, in particular, from the viewpoint of forming a varnish excellent in fluidity, it is preferably a bisphenol type epoxy resin having an epoxy equivalent of 150 to 500 g/eq. An epoxy resin containing a cyclic aliphatic structure. Next, the methacrylic acid (B) used in the present invention is reacted with the epoxy resin (A) as described above, and polymerization of an acrylonitrile group is carried out by radical polymerization. The present invention can significantly enhance the heat-resistant yellowing by performing the hardening by the in-situ reaction. The acid group-containing radical polymerizable monomer (C) containing an aliphatic ester bond or an aliphatic carbonate bond used in the present invention is a type which enhances the light output efficiency while improving the transparency of the cured product while imparting hardening The necessary softness to increase the strength of the ingredients. 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). 201008960 ο

(wherein R1 represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms' χ is an ester bond or a carbonate bond' R2 represents an aliphatic hydrocarbon group having a carbon number of 2 to 10' η is an integer of 1 to 5) In the structural formula (1), a compound represented by a hydrazine-containing hydrazine bond, for example, a trans-group (meth) acrylate and an aliphatic polyvalent carboxylic acid having 2 to 10 carbon atoms, and a hydroxyalkyl group A compound obtained by reacting a (meth) acrylate and an aliphatic diol having 2 to 10 carbon atoms with an aliphatic polyvalent carboxylic acid having 10 carbon atoms. Among them, a hydroxyalkyl (meth) acrylate such as /S-hydroxyethyl methacrylate or /3-hydroxyethyl acrylate. Further, the aliphatic polyvalent carboxylic acid is succinic anhydride, adipic acid, maleic anhydride, tetrahydrophthalic acid or cyclohexane dicarboxylic acid. Further, an aliphatic diol having 2 to 10 carbon atoms, such as 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, ίο-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl Base-1,% propylene glycol, 3-methyl-indole, pentanediol, hydrazine, 2-cyclohexanediol, 1,3-cyclohexanediol, hydrazine, 4-cyclohexanediol, 1 , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, iota, 4-cyclohexanedimethanol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, ι , 4-cyclohexane diethanol, and the like. Among them, it is preferred that the butylene glycol, pentanediol, hexanediol, cyclohexanediol, and cyclohexyl dimethanol having a carbon number of 4 to 8 are excellent in compatibility with an epoxy resin (Α). Preferably. 201008960 The above structural formula (in the case of a carbonate-containing bond represented by ruthenium, for example, an aliphatic diol having 2 to 10 carbon atoms and a dialkyl carbonate obtained by transesterification to obtain a polycarbonate diol, a compound obtained by reacting acrylic acid or a derivative thereof, wherein an aliphatic diol having 2 to 10 carbon atoms, such as 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-propanediol, 3-methyl-1,5-pentanediol, 1,2-O cyclohexanediol, 1,3-cyclohexane Alkanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexane Alkane diethanol, 1,3-cyclohexane diethanol, 1,4-cyclohexane diethanol, etc., such as 3 to 10 carbon atoms, among which, it is preferably a butanediol having a carbon number of 4 to 8, and a pentanediol. Alcohol, hexanediol, cyclohexanediol, and cyclohexanedimethanol are excellent in compatibility with the epoxy resin (A). On the other hand, from the viewpoint of reactivity, carbon The acid dialkyl group is preferably dimethyl carbonate. Among them, in particular, from the viewpoint that the cured product has moderate flexibility, it is preferred that X in the above structural formula (1) is an ester bond, especially /5. 3-[[2-(Methacryloxy)ethoxy]carbonyl]propionic acid, hydroxyethyl methacrylate and hexahydrophthalic acid as an addition to hydroxyethyl methacrylate and succinic anhydride The addition of 2-methylpropenyloxyethyl hexahydrophthalic acid. The epoxy resin (A), methacrylic acid (B), and the aliphatic ester bond or aliphatic carbonate bond described above are contained. The mixing ratio of the acid group-containing radical polymerizable monomer (C) is from the viewpoint of a good balance between the heat-resistant yellowing resistance of the cured product and the strength of -10-201008960, specifically, 100 parts by mass relative to the total amount, It is preferable to mix 10 to 60 parts by mass of the above epoxy resin (A), 1 to 35 parts by mass of the above methacrylic acid (B), and 5 to 50 parts by mass of the above-mentioned one having an aliphatic ester bond or an aliphatic carbonate bond. Acid-based radical polymerizable monomer (C). The radical polymerization initiator (D) used in the present invention is used as The thermal radical polymerization initiator may be, for example, methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl ethyl hydrazine acetate peroxide, acetamidine acetone peroxide, 1, 1-double (Third butylperoxy) 3,3,5-trimethylcyclohexane, Φ 1,1-bis(Third hexylperoxy)cyclohexane, 1,1-double (Third hexyl Oxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-butyl Peroxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl 4,4-bis(t-butylperoxy)pentyl ester, 2,2 - bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, tert-butyl hydroperoxide, p-decane hydrogen Peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, third hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2, 5-bis(tertiary tributylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, tert-butyl cumyl peroxide, di- Tertiary butyl peroxidation , 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyl hydrazine peroxide, 3,3,5-trimethylhexyl peroxide , octyl peroxide, laurel peroxide, lauric acid peroxide, meta-toluene peroxide, benzamidine peroxide, diisopropyl peroxydicarbonate, double (4-third Cyclohexyl)peroxydicarbonate, bis-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-second butyl peroxydicarbonate, -11- 201008960 bis(3-methyl-3-methoxybutyl)peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, α,α'·double (peroxygen) Neodecyl)diisopropylbenzene, peroxycumene neodecyl ester, 1,1,3,3-tetramethylbutyl peroxy neodecyl ester, 1-cyclohexyl-1-methyl Base peroxy neodecyl ester, third hexyl peroxy neodecyl ester, tert-butyl peroxy neodecyl ester, third hexyl peroxytrimethyl acetate, tert-butyl peroxy trimethyl Acetate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, third hexyl peroxy-2-ethylhexanoate, tert-butylperoxy- 2-ethylhexanoate, tert-butylperoxy isobutyl ester, tert-butylperoxymaleic acid, tert-butylperoxylaurate, tert-butylperoxy-3,5,5 -trimethylhexanoate, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethylhexylmonocarbonate, 2,5-dimethyl-2,5-double (benzimidoxime)hexane, tert-butylperoxyacetate, third hexylperoxybenzyl ester, tert-butylperoxy-m-tolylbenzyl ester, third butoxyperoxide Benzyl methyl ester, bis(t-butylperoxy)isophthalate, tert-butylperoxyallyl monocarbonate, 3,3',4,4'-tetra (t-butyl Peroxycarbonyl) benzophenone and the like. The amount of the radical polymerization initiator (D) to be used is preferably 0.001% by mass or more and 2% by mass or less based on the total mass of the radical polymerizable component and the total mass of the radical polymerization initiator (D). In the epoxy resin composition of the present invention, in addition to the above components, it is preferred to further use a monomethacrylate compound (E) having an aliphatic cyclic structure, because the heat-resistant yellowing of the cured product can be further enhanced. Monocyclic methacrylate compound (E) having an aliphatic cyclic structure, specifically, -12-201008960 such as dicyclopentyl methacrylate, dicyclopentyloxyethyl methacrylate, 1, 2 -Epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, isobornyl methacrylate Ester and the like. Among them, it is particularly preferably selected from the group consisting of dicyclopentyl methacrylate, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, cyclohexyl methacrylate And a compound of the group consisting of isobornyl methacrylate or the like is because the mechanical strength of the cured product is further enhanced. © The above-mentioned ratio of the monomethacrylate compound (E) containing an aliphatic cyclic structure, relative to the epoxy resin (A), methacrylic acid (B), containing an aliphatic ester bond or an aliphatic carbonate bond 100 parts by mass of the acid group-containing radical polymerizable monomer (C) and the monocyclic methacrylate compound (E) having an aliphatic cyclic structure, in a ratio of 20 to 70 parts by mass, from hardening The viewpoint of the strength of the material is particularly suitable for a ratio of 40 to 60 parts by mass. In the transparent epoxy resin composition of the present invention, in addition to the above-mentioned respective components, the light resistance and heat yellowing resistance of the cured product can be further improved by using the reactive ruthenium (F). The reactive hydrazine (F), for example, in a part of the polyoxyalkylene structure, contains an amine group, an epoxy group, an alicyclic epoxy group, a methanol-based hydroxyl group, a stanol-based hydroxyl group, a methacryl fluorenyl group, A reactive functional group of a group consisting of a polyether alcohol group, a hydrogenthio group, and a carboxyl group. More specifically, the following structural formula (2)

In the above formula (2), R1 and R2 are each independently a methyl group or a hydrogen atom. Further, in the above formula (2), X, X' and X" are each independently a reactive group selected from the group consisting of the following structural formulae a to h, a methyl group or a hydrogen atom, X and y. It is an integer of 1 or more. The total of X and y is in the range of 2 to 100. —RNH2 ab

-R-CH—CHj Ο

c —ROH d —RSH c -RCOOH f

O

II —ROC—C=CH 2 g ❹ CH 3 —OH h X, X′ and X′′ are the above-mentioned reactive groups, and R′ in the above structural formula a to g is represented by an alkylene group having 1 to 4 carbon atoms. The polyoxyalkylene containing an epoxy group, a carboxyl group and a methacryloyl group is particularly suitable because of its excellent reactivity. The amount of the above reactive hydrazine (F) is relative to the epoxy resin (A) and methacrylic acid ( B), a radical polymerizable monomer (C) containing an aliphatic ester bond or an aliphatic carbonate bond, and a total of 100 parts by mass of the above reactive hydrazine (F), preferably 5~ In the range of 30 parts by mass, the light-resistant property and the heat-resistant yellowing resistance are further improved. The epoxy resin composition of the present invention can be suitably used as a curing accelerator. The above-mentioned curing accelerator can be used in various types, for example, a phosphorus system. a compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid, an amine complex salt, etc., particularly when used as a photo-semiconductor sealing material, due to hardenability, heat resistance, electrical properties, moisture resistance, etc. Excellent, the phosphorus compound should be ® triphenylphosphine hydrogen, and the third amine should be 1,8-two Bicyclo [5.4.0]-undecene (DBU). The epoxy resin composition of the present invention may be suitably used as a radical polymerizable polyfunctional monomer, and the physical properties of the cured product may be improved by adjusting the heat resistance of the cured product. Balanced, wherein a radically polymerizable polyfunctional monomer is used, such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate , neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, ethylene diamine tetramethacrylate, hexane diacrylate vinegar, dipentaerythritol pentavinyl ester. Such free radical polymerizable multifunctional single The amount of the body is preferably in the range of from 1 to 10% by mass in the composition. The epoxy resin composition of the present invention, in addition to the above components, is preferably formulated with an antioxidant to prevent oxidative degradation upon heating. A cured product excellent in transparency. The antioxidants used above, such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl- Correct -ethylphenol, hard -15- 201008960 a phenol, hydroquinone such as bismuth-s-(3,5-di-t-butyl-4-hydroxyphenyl)propionate or 4-methoxynaphthol , 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4 , 4'-thiobis(3-methyl-6_t-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-double [1,1-Dimethyl-2-{ yS-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy}ethyl]2,4,8,10-tetra Bisphenols such as oxaspiro[5,5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5 -trimethyl-2,4,6-tris(3,5-di-© tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di -T-butyl-4-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate], 1,3,5-tris(3',5'-di-t-butyl-4-hydroxybenzyl)-S-three-plow-2,4,6-(1Η,3Η,5Η)trione, fertility a phenolic antioxidant represented by a polyfunctional phenol such as phenol; p-benzoquinone, A Anthraquinone and naphthoquinone represented by lanthanide; dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl sulfonate a sulfur-based antioxidant such as -3,3'-thio-dipropionate; triphenyl phosphate, diphenylisodecyl phosphoric acid ester, phenyl diisodecyl phosphate, tris(nonylphenyl) Phosphate ester, diisodecyl pentaerythritol phosphate, tris(2,4-di-t-butylphenyl) phosphate, cyclopentane tetrakis(bis-octadecyl) phosphate, cyclopentane tetrayl Bis(2,4-di-t-butylphenyl)phosphate, cyclopentanetetrakis(2,4-di-t-butyl-4-methylphenyl)phosphate, bis[2 - Phosphate esters such as tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphate, 9,10-dihydro-9-oxa-10 - phosphophenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxidation A phosphorus-based antioxidant represented by an oxaphosphorus oxide such as -10-201008960 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. The amount of the antioxidant to be used is preferably in the range of 0.005 to 1 part by mass based on 100 parts by mass of the total hardening component. The epoxy resin composition of the present invention can further improve light resistance by further blending the ultraviolet absorber. UV absorbers which can be combined, such as phenyl salicylate, p-t-butylphenyl salicylate, p-octylphenyl salicylate, etc.; 2,4-dihydroxy Benzene, 2-hydroxy-4-methoxypyrbenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecylbenzophenone, 2, 2-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonate Benzophenones such as benzophenone; 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl Benzotriazine, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2·(2'-hydroxy-3'-tert-butyl-5 '-Methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3',5'-di-p-pentylphenyl)

W benzotriazole, 2-{( 2 '-hydroxy-3 ', 3", 4", 5", 6"-tetrahydrofurfurimide methylmethylphenyl} benzotriazole and other benzo Triazoles; bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl Azelaic acid ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[{3,5-bis(1,1-dimethylethyl)-4-oxime A hindered amine such as a oxyphenyl}methyl]butyl propylene dicarboxylate. The amount of such an ultraviolet absorber is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total hardening component. In the resin composition, in addition to the above-mentioned respective components, a coloring agent, a coupling agent, a flat lubricant, or the like may be appropriately added depending on the purpose. The coloring agent is not particularly limited, for example, phthalocyanine or袅quinacridone, anthraquinone, xanthone, ketone, perene, diterpene, methine, various organic pigments, titanium oxide, lead sulfate yellow, chrome vermilion, iron oxide red, cobalt violet, Prussian Inorganic pigments such as blue, group chrome green, chrome oxide, cobalt green, etc. Used as a leveling agent, for example, ethyl propyl An acrylate type β 4000 to 12000 oligomer such as an acid ester, an oxime ester or a 2-ethylhexyl acrylate, an epoxidized soybean fatty acid, an alcohol, a hydrogenated castor oil, an oxime coupling agent, etc. Hydrocarbon-based lubricants such as crystalline wax and polyethylene wax, lubricating lubricants such as dodecanoic acid, palmitic acid, octadecanoic acid, eicosanoic acid, behenic acid, octadecylamine, and hexadecane Higher fatty acids such as amine, decylamine, decylamine, ethylene distearamide, amide amine I ramie oil, butyl stearate, ethylene glycol monostearate (single, two, Three or four) higher fatty acid esters such as stearate, alcohols such as stearyl alcohol, polyethylene glycol, and polyglycerol are lubricated with tetradecanoic acid, palmitic acid, octadecanoic acid, icosonic acid, and a metal such as magnesium, calcium, cadmium, strontium, zinc or lead such as dodecanoic acid, a coupling agent such as carnauba wax, candelilla wax, beeswax or montan wax, such as 3-glycidoxypropyltrimethyl Oxalyl oxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyl decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy phthalocyanine Agent, non-diazo, condensed azo, chrome yellow, zinc cyanide, carbon black, butyl acrylate, molecular weight epoxidized rosin such as paraffin, micro-tetradecanoic acid, ten higher fatty acid methylene di-hard lubricant, Hard ester, pentaerythritol, hexadecane, dodecanoic acid, ricinoleic acid, salt, natural soap, etc. :, 3-epoxypropyldimethoxy, Ν- ( 2- Amine-18- 201008960 ethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-hydrothiopropyltrimethoxydecane, ethylene trimethoxydecane , N-(2-(vinylbenzylamine)ethyl)3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, 3-chloropropylmethyl a decane coupling agent such as dimethoxy decane or 3-chloropropyltrimethoxy decane, isopropyl (N-ethylamine ethylamine) titanate, isopropyl triisostearyl strontium titanate, Titanium di(dioctyl pyrophosphate) oxyacetate, tetraisopropylbis(dioctylphosphite) titanate, neoalkoxy tris(p-N-(no-amineethyl) © Titanium couples such as amine phenyl) titanate Mixture, chrome-acetamidine, pin-methacrylate, pin-propionate, neoalkoxy chromate, neoalkoxytrimethylsulfonate, neoalkoxy III Benzosulfonium zirconate, neoalkoxytris(ethylenediamineethyl)chromate, neoalkoxytris(m-aminophenyl)zirconate, ammonium zirconium carbonate, aluminum-acetonitrile A zirconium or aluminum coupling agent such as an oxime ester, an aluminum-methacrylate or an aluminum-propionate, which is preferably a lanthanide coupling agent. By using a coupling agent, it is possible to obtain a cured product which is excellent in moisture resistance and has little reduction in adhesion strength after moisture absorption. Release agents such as paraffin wax, microcrystalline wax, polyethylene wax and other hydrocarbon-based lubricants, dodecanoic acid, myristic acid, palmitic acid, octadecanoic acid, eicosanoic acid, behenic acid, etc. Terpene fatty acid-based lubricant, octadecylamine, hexadecaneamine, decylamine, methylene distearylamine, ethylene distearylamine, and other higher fatty acid amide-based lubricants, hardened castor oil Higher fatty acid ester lubricants such as butyl stearate, ethylene glycol monostearate, pentaerythritol (mono, di, tri or tetra) stearate, cetyl alcohol, stearyl alcohol, polyethyl b Alcohol-based lubricants such as diols and polyglycerols, dodecanoic acid, tetradecanoic acid, palmitic acid, octadecanoic acid, di-19-201008960, octanoic acid, behenic acid, ricinoleic acid, naphthenic acid, etc. A natural wax such as a metal soap of a metal salt such as zinc or lead, a Brazilian brown beeswax or a montan wax, and preferably a higher fatty acid amide. Higher fatty acid, metal soap zinc octadecanoate, magnesium octadecanoate, octadecanoic acid, tri or tetra) stearate. The epoxy resin composition of the present invention can be obtained by stirring, and a liquid photo-semiconductor sealing material can be obtained. The curing of the epoxy resin composition of the present invention does not specifically react the epoxy group with the acid group. The free reaction is distinguished by the reaction step, but is hardened at the same time or even by in situ reaction. Specifically; a temperature range of 50 to 200 ° C, particularly preferably 50 to 100 ° C after the wrinkle-like cured product, more than 120 to 180 ° C, the composition of the present invention detailed above, such as ^ and It is excellent in yellowing resistance, especially heat-resistant yellowing, and is suitable for various light and semi-materials such as LED, phototransistor, photoelectric two-g CCD, EPROM, and photoelectric sensor. It is especially suitable for high-temperature materials with remarkable heat generation during illuminating. High-brightness LED elements refer to those having a beam of more than 100. The above high-brightness LED, for example, at a wavelength of 35 (a blue or even white LED of a crest, and a compound semiconductor formed using four elements, by adjusting magnesium, calcium, cadmium, strontium, palm wax, candelilla wax, Grade fatty acid esters, high, hydrocarbon-based slip agents, especially pentaerythritol (single and second, the above components are uniformly conjugated, as described above, the polymerization of the base polymerizable group continues to carry out two reactions, the hydrazine hardening temperature is preferably For the purpose of curing, it is treated under the conditions of the degree of curing. In the above, the fluidity before curing, the photocoupler, the sealing device for the brightness of the LED device for the conductor device is sealed (lm) • 550nm has a main luminescence consisting of aluminum, gallium, indium, and phosphorous elements, and can emit -20- 201008960. Red, orange, yellow, and yellow-green quaternary LEDs. The above has a main illuminating peak at a wavelength of 3 50 to 550 nm. For blue or even white LEDs, for example, backlights for liquid crystal panels such as portable DVD projectors or satellite navigation, backlights for 10 to 17 inch LCD panels used in notebook computers, and automotive headlights. The light source, etc. On the other hand, the use of the quaternary LED, such as an outdoor display, a backlight of a car or an interior illumination, a backlight of a thin television or a liquid crystal display of a computer, etc. 光 The optical semiconductor device of the present invention is The photo-semiconductor and the electrode component bonded to the photo-semiconductor are sealed by the epoxy resin composition. Specifically, for example, by molding, casting, and the like using the epoxy resin composition of the present invention. In the plastic method, a method of sealing or hardening the above-mentioned epoxy resin composition which has been sufficiently defoamed to an optical semiconductor to which an electrode component such as a wire is attached, or mounting an optical semiconductor on a circuit substrate in advance, and using the epoxy resin of the present invention A method of sealing and hardening a composition, etc. Specifically, it is obtained by flowing into a mold in which a light-emitting semiconductor element is provided, and then heat-hardening under the above-described temperature conditions. The optical semiconductor device of the present invention is a series of the above-mentioned epoxy. Various optical semiconductor devices for the use of the resin composition include, for example, LEDs, phototransistors, photodiodes, photocouplers, CCDs, EPROMs, An optical semiconductor device sealed by a light-receiving element such as an electric sensor or a light-emitting element, etc., preferably an LED device, particularly a high-brightness LED device, particularly having a blue or even white color of a main illuminating peak at a wavelength of 3 50 to 550 nm. - - - - - - - - - - 1) varnish viscosity: measured at 25 ° C using an E-type viscometer (Euro machine production system) "TV-20" corn plate type. 2) Light transmittance: using a spectrophotometer " UV-3150" (made by the island company). 0 3) Thermal deterioration resistance: The light transmittance of the cured product of the ring after heating for 72 hours at a wavelength of 400 nm was measured at 150 °C. 4) UV resistance: using a color fader (SUGA tester) to measure the light intensity of 490 W/m2, the black panel temperature of 63 °C and the ultraviolet light after the ultraviolet light is transmitted at a wavelength of 400 nm. 5) Bending strength, Flexural modulus: according to JIS6911. 6) Storage stability: After varnish was stored at 25 ° C for 2 weeks, the examples 1 to 8 and Comparative Examples 3 and 4 were measured. According to the combination shown in Table 1 or Table 2 below, a blender resin and various carboxylic acids were used. An acid, a polymerizable compound, a radical polymerization initiation accelerator, and the like are mixed to obtain an epoxy resin composition. Using this fat composition, the varnish viscosity and storage stability were evaluated. Further, this epoxy resin composition was poured into a gap formed by sandwiching a thick spacer (tank tube) on a glass plate, and the mixture was allowed to stand at 80 ° C for 2 hours, and the cured product was taken out from the molding to confirm the formation of no The wrinkle is heated to 16 (TC, and after maintaining the temperature at 160 ° C for 2 hours, the cured product is used as a test piece for various evaluation tests, but the price is based on! System), U 1000 rate 〇 viscosity. After the epoxy resin and the hard epoxy resin are hardened by 3 mm, they are further produced.结-22- 201008960 The results are shown in Tables 1 and 2. Comparative Examples 1 and 2 According to the blending shown in Table 2 below, the components were blended and mixed using a stirrer to obtain an epoxy resin composition. Using this epoxy resin composition, the varnish viscosity and storage stability were evaluated. Further, this epoxy resin composition was poured into the gap of the molding used in Example 1, and it was hardened at 110 ° C for 2 hours, and the cured product was taken out from the molding, and further heated to 165 ° C to reach 165 °. After C was maintained at this temperature for 2 hours, a hardened material was obtained, and the cured product was used as a test piece to carry out various evaluation tests. The results are shown in Table 2. Table 1 Example 1 2 3 4 5 6 7 8 compounded epoxy resin 25 27 22 fiber bisphenol A type ring resin 32 35 16 16 28 hydrogenated bisphenol A type ring grease 16 16 methacrylic acid 8 12 7 10 8 7 9 8 HO-MS 16 15 20 13 12 HO-HH 27 24 24 Dicyclopentyl methacrylate Cool 40 45 37 40 40 37 36 32 Brewing cut 20 20 methyl hexahydrophthalic acid Liver peroxide 1 1 1 1 1 1 1 1 Hardening agent 1 1 1 1 1 1 1 1 Cleanliness (mPaS) 52 24 100 56 63 109 21 31 Hardening conditions 80〇C/2h+160°C/2h Evaluation result Light transmittance (400 biliary) 83.6 83.1 79.7 81.3 82 81.2 80.2 83.5 Resistance to heat deterioration (150 〇C72h) 74.1 72.4 70.4 72.8 70.3 70.2 72.8 75.7 External linear 1000h 81.8 81.9 77.5 78.3 78.9 79.3 79.2 83.5 Flexural strength (MPa) 125 130 144 147 140 140 119 108 Elasticity (MPa) 3700 3700 3500 3300 3300 3500 2500 2690 Storage safety (25 ° C) 2 weeks later 〇〇〇〇〇〇〇〇-23- 201008960 Table 2 Comparative Example 1 2 3 4 compounding composition 44 30 30 phenolic type A toroidal grease 53 hydrogenated bisphenol A type Face fat methyl propylene acid 20 HO-MS HO-HH 40 Dicyclopentyl methacrylate 50 30 Reactive 矽 4* methyl hexahydrophthalic anhydride 56 47 Peroxide 1 1 Hardening agent 0.4 0.5 1 1 Qingshi (mPaS) 120 736 20 56 Hard 'condition not/3h+165t:/2i S0°C/7h+mX:/7h Evaluation result Guanglin over rate (400nra) 82.6 83 85 66.4 Resistance to heat deterioration Face 150. . 73〇60.2 42.2 62.7 20 UV resistance l〇〇〇h 81.5 73.5 82 55.3 Flexural strength (MPa) 70 139 80 120 Elasticity (MPa) 3400 3000 2800 3200 Storage safety (25. 〇 2 weeks later XX 〇〇 above table In Tables 1 and 2, the "storage stability" is adjusted to a composition of 瓌 胃 胃 胃 胃 , , 2 2 2 2 2 2 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 ^ Further, the components shown in the above Tables 1 and 2 are as follows. Alicyclic epoxy resin: (3,4-epoxycyclohexane)methyl_3', 4'-epoxy Cyclohexyl-carboxylate (trade name "Sirokitet 202 1 P", manufactured by Daisy Chemical Industry Co., Ltd.) Bisphenol A type epoxy resin: bisphenol A type with epoxy equivalent weight 188 g/eq. Epoxy resin (trade name "EPICLON 850S", manufactured by DIC) Hydrogenated bisphenol A epoxy resin: Hydrogenated bisphenol A epoxy resin (Shang-24- 201008960 Product name "EPICLON EXA-7015" ring Oxygen equivalent: 200g/eq, DIC (manufactured by DIC) HO-MS: 3-[[2-(methacryloxy)ethoxy]carbonyl]propionic acid (trade name "Lite ester HO-MS", Kyoeisha Chemical (share) system) HO- HH: 2-Methyl propylene oxiranyl hexahydro phthalic acid (trade name "Lite ester HO-HH", manufactured by Kyoeisha Chemical Co., Ltd.) Dicyclopentyl methacrylate: trade name "Imitation FAFA-513M" 曰立化成工业(股) 〇Responsive 矽: methacrylate-containing eucalyptus oil (Shin-Etsu Chemical's trade name "X-22- 1 64A") Peroxide: 1,1-two (Second hexylperoxy) Cyclohexanin (trade name "Pahex HC", manufactured by Nippon Oil Co., Ltd.) Hardening accelerator: methyltributyl squamous dimethyl phosphate (trade name "Pi Xi Ke" Lin PX-4MP" manufactured by Nippon Chemical Industry Co., Ltd.) Comparative Example 5 27 parts by mass of the above alicyclic epoxy resin [(3,4-epoxycyclohexyl)methyl-3,, 4'- Epoxycyclohexyl carboxylate ("Sirokitet 2021P" manufactured by Daisy Chemical Industry Co., Ltd.)], 0.027 parts by mass of hydroquinone was placed in a reaction vessel, and the temperature was raised to 7 (TC dissolved hydrogen after dissolution) '1 丨·8 parts by mass of methacrylic acid and 16 parts by mass of 3-[[2-(methacryl oxime) ethoxy) carbonyl] propionic acid (Lyme ester manufactured by Kyoeisha Chemical Co., Ltd.) H0-MS"), relative to Further, in the case of triphenylphosphine of 100 ppm by weight, 22.7 parts by mass of dicyclopentyl methacrylate ("Flush FA_513M" manufactured by Hitachi Chemical Co., Ltd.) was added as a solvent, and the nonvolatile content was adjusted to 70% by mass. Secondly, 'heat up to 80 -25-201008960 °C, maintain at 90 °C for 7.5 hours. Here, in the reaction system, triphenylphosphine in an amount of 100 ppm relative to the solid content was intermittently added. After the reaction was completed, 22.6 parts by mass of dicyclopentyl methacrylate was added to obtain a varnish. The varnish viscosity of the obtained varnish was 890 mPa · s. Next, 1,1-di(Third-hexylperoxy)cyclohexane ("Haihes HC" manufactured by Nippon Oil Co., Ltd.) and methyltributyl dimethyl dimethyl hydride were added to the obtained varnish. Phosphate ("Pixicolin® PX-4MP" manufactured by Nippon Chemical Industry Co., Ltd.) each has 1 PHR as a curing catalyst. Thereafter, the gap of the molding used in Example 1 was injected, and it was cured at 100 ° C for 1 hour, and the cured product was taken out from the molding, heated to 170 ° C, and maintained at this temperature for 1 hour. Hardened material. The obtained cured product was colored in brown color, and the light transmittance (400 nm) was 52.2%. [Simple description of the diagram] None. [Description of main component symbols] φ Zero is not available. -26-

Claims (1)

201008960 VII. Patent application scope: 1. An epoxy resin composition characterized by epoxy resin (A), methacrylic acid (B), acid group containing aliphatic ester bond or aliphatic carbonate bond The radical polymerizable monomer (C) and the radical polymerization initiator (D) are essential components. The present invention relates to an epoxy resin composition according to claim 1, wherein the acid group-containing radical polymer (C) containing a fatty ester bond or an aliphatic carbonate bond is of the formula (1). ) shown (1) (wherein R1 represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms, X is an ester bond or a carbonate bond, R2 represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and η is 1 to 5 Integer). 3. The epoxy resin composition according to claim 1, wherein the epoxy resin is an epoxy resin having a cyclic aliphatic structure. Φ 4. The epoxy resin composition according to claim 1, wherein the epoxy resin is an epoxide type epoxy resin having an epoxy equivalent of 150 to 1, 〇〇〇g/eq. 5. The epoxy resin composition of claim 1 of the invention, wherein the epoxy resin (A), methacrylic acid (B), and an acid group-containing radical polymerization containing an aliphatic ester bond or an aliphatic carbonate bond In a total of 1 part by mass of the monomer (C), the epoxy resin (A) is contained in a ratio of 1 to 35 parts by mass, and the methacrylic acid (B) is contained in a ratio of 1 to 35 parts by mass. ) -27- 201008960 The acid group-containing radical polymerizable monomer (C) containing the aliphatic ester bond or the aliphatic carbonate bond is contained in an amount of 5 to 50 parts by mass. 6. The epoxy resin composition of claim 1 is free of epoxy resin (Α), methacrylic acid (Β), acid group containing aliphatic ester bond or aliphatic carbonate bond. In addition to each component of the radical polymerizable monomer (C) and the radical polymerization initiator (D), a monomethacrylate compound having an aliphatic cyclic structure is further contained. 7. The epoxy resin composition of claim 6 of the patent scope, in which the epoxy group (Α), methacrylic acid (Β), an aliphatic ester bond or an aliphatic carbonate bond-containing free radical 100 parts by mass of the synthetic mass of the radical polymerizable monomer (C) and the monomethacrylate compound (E) having an alicyclic structure, the aliphatic cyclic structure is contained in a ratio of 20 to 70 parts by mass. Monomethacrylate compound (E). 8. An optical semiconductor sealing material formed by the epoxy resin composition of claim 1 of the patent application. Λ 9. A cured product which is a hardened product which is hardened by an in-situ reaction after the epoxy resin composition of the first application of the patent application is formed. A method for producing a cured product which is obtained in a molding machine to harden an epoxy resin composition as in the first item of Patent Application No. 1 by an in-situ reaction. An optical semiconductor device formed by sealing an optical semiconductor and an electrode member bonded to the optical semiconductor by the epoxy resin composition of claim 1 of the patent application. -28- 201008960 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: