JP4736560B2 - Epoxy resin composition - Google Patents

Description

  The present invention relates to an epoxy resin composition containing a fluorine atom and an epoxy resin in which a part of an aromatic ring is hydrogenated and a curing agent for epoxy resin. The cured product obtained from the epoxy resin composition of the present invention is colorless and transparent, and is excellent in heat resistance, light resistance, and moisture resistance, so it is used for electrical / electronic insulating materials, adhesives, semiconductor encapsulants, resist materials, etc. In particular, it is useful for applications related to optical semiconductors such as LEDs and CCDs.

  Epoxy resins are excellent in heat resistance, adhesion, water resistance, mechanical strength, electrical properties, etc., so they are used in various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electrical and electronic parts, etc. in use. As the normal temperature or heat curable epoxy resin, aromatic epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, phenol or cresol novolac type epoxy resin are generally used.

  In recent years, light emitting devices such as optical semiconductors (LEDs) that have been put to practical use in various display boards, image reading light sources, traffic signals, large display units, and the like are mostly manufactured by resin sealing. The sealing resin used here generally contains the above aromatic epoxy resin and an alicyclic acid anhydride as a curing agent.

  In addition, with the rapid progress of today's LEDs, higher output and shorter wavelengths of LED elements are rapidly becoming a reality. In particular, LEDs using nitride semiconductors emit light with a short wavelength and high output. Is being put to practical use. However, when an LED element using a nitride semiconductor is encapsulated with the above-described aromatic epoxy resin, the aromatic ring absorbs light of a short wavelength, so that the encapsulated resin deteriorates over time, resulting in yellowing. There arises a problem that the light emission luminance is remarkably lowered.

  Therefore, an LED sealed with an alicyclic epoxy resin obtained by oxidizing a cyclic olefin, represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, has been proposed. (Patent Document 1, Patent Document 2). However, the cured products of these alicyclic epoxy resins are very brittle, are liable to cause cracking by the thermal cycle, and have extremely poor moisture resistance, so they are not suitable for applications requiring long-term reliability characteristics. .

  In view of this, there has been proposed an LED mainly composed of hydrogenated bisphenol A type epoxy resin, blended with an alicyclic epoxy resin and a phosphorus antioxidant, and sealed with a methylhexahydrophthalic anhydride curing agent (Patent Document). 3). However, this epoxy cured product is excellent in colorless transparency, but has the disadvantages of poor heat resistance and easy yellowing, so it is not suitable for LED device sealing applications that require heat resistance.

Furthermore, a method using a triazine derivative epoxy resin alone and an acid anhydride curing agent has also been proposed (Patent Document 4). In this cured product, the heat resistance is improved, but because it is very brittle, it is easy to cause crack fracture by the thermal cycle similar to the one using the alicyclic epoxy resin, and the moisture resistance is extremely bad, It is not suitable for applications that require long-term reliability.

In addition, a method has been proposed in which a fluorine-containing epoxy resin is subjected to a polyaddition reaction to be used as a resist material (Patent Document 5). It is stated that it is difficult to wake up. However, since this fluorine-containing epoxy resin is colored, it is a thin film when used as a resist material, so it can be used without any problem even if the epoxy resin is somewhat colored. There is a problem that it cannot be used for materials.
JP-A-9-213997 JP 2000-196151 A JP 2003-12896 A JP 2003-224305 A JP 2003-321409 A

  The present invention provides an epoxy resin composition that is colorless and transparent, can provide a cured product excellent in heat resistance, light resistance, and moisture resistance, and is particularly useful as a sealing material for LEDs that emit light of a short wavelength. With the goal.

  The present invention includes the following inventions.

[式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は各々独立に水素原子、炭素数１〜４のアルキル基又はハロゲン原子を示し、ｎは０〜４０の数を示す。]
（Ｂ）成分；エポキシ樹脂用硬化剤 [1] An epoxy resin composition comprising the following component (A) and component (B):
Component (A): an epoxy resin obtained by directly hydrogenating an aromatic epoxy resin represented by the following general formula (1), wherein the aromatic ring has a hydrogenation rate of 1 to 30 %

[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n represents a number from 0 to 40. ]
Component (B): epoxy resin curing agent

[2] The epoxy resin according to [1], wherein in the general formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, and n is a number from 0 to 20. Composition.

[ 3 ] The epoxy resin curing agent of component (B) is an amine, acid anhydride, polyphenol, imidazole, Bronsted acid salt, amine BF ₃ complex compound, organic acid hydrazide, dicyandiamide And the epoxy resin composition according to [1] or [ 2 ], which is one or more selected from the group consisting of polycarboxylic acids.

[ 4 ] The epoxy resin curing agent of component (B) is an acid anhydride and / or a cationic polymerization initiator, and is an epoxy resin composition for a light emitting device sealing material used as a sealing material for a light emitting device. The epoxy resin composition according to any one of [1] to [ 3 ].

[ 5 ] With respect to 10 to 90 parts by mass of the epoxy resin of component (A), 10 to 90 parts by mass of alicyclic epoxy resin are included so as to be 100 parts by mass in total. [4 ] The epoxy resin composition according to [ 4 ].

[ 6 ] The epoxy resin composition for a light emitting device sealing material for sealing a light emitting device having a main light emission peak at 350 to 550 nm in the light emitting layer, according to [ 4 ] or [ 5 ] Epoxy resin composition.

[ 7 ] The epoxy resin composition as described in [ 4 ] to [ 6 ], wherein the light-emitting element is a light-emitting diode (LED).

  The cured product obtained from the epoxy resin composition of the present invention is excellent in colorless transparency, heat resistance, and moisture resistance, and also in light resistance, so that it is a light emitting element, particularly a group III nitride that emits light of a short wavelength. It can be advantageously used as an epoxy resin composition for a light emitting device sealing material that seals an LED using a physical compound semiconductor.

[式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は各々独立に水素原子、炭素数１〜４のアルキル基又はハロゲン原子を示し、ｎは０〜４０の数を示す。] ((A) component; epoxy resin)
The (A) component epoxy resin contained in the epoxy resin composition of the present invention is an epoxy resin obtained by directly hydrogenating an aromatic epoxy resin represented by the following general formula (1). The aromatic epoxy resin represented by the following general formula (1) performs addition / ring-closing reaction of a corresponding bisphenol compound and epihalohydrin in the presence of a base such as an alkali metal hydroxide. It can obtain by using the manufacturing method of a well-known epoxy resin.

[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n represents a number from 0 to 40. ]

  Examples of the aromatic epoxy resin represented by the general formula (1) include an epoxy resin obtained from 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,2-bis (4-hydroxy-3- Epoxy resin obtained from methylphenyl) hexafluoropropane, epoxy resin obtained from 2,2-bis (3-ethyl-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3,5- Epoxy resin obtained from dimethylphenyl) hexafluoropropane, epoxy resin obtained from 2,2-bis (3-bromo-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3,5-dibromo-4- And an epoxy resin obtained from (hydroxyphenyl) hexafluoropropane. That is, the aromatic epoxy resin according to the present invention is preferably 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane, 2-bis (3-ethyl-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (3-bromo-4-) Bisphenol compounds composed of one or more of hydroxyphenyl) hexafluoropropane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) hexafluoropropane, and one or more of epihalohydrin It is produced by performing an addition / ring closure reaction in the presence of a base such as an alkali metal hydroxide.

Among these, an epoxy resin obtained from 2,2-bis (4-hydroxyphenyl) hexafluoropropane, in which R ¹ , R ² , R ³ and R ⁴ in the general formula (1) are hydrogen atoms, From the viewpoint of hydrogenation reaction and easy availability of raw materials.

  The number of n in the aromatic epoxy resin represented by the general formula (1) is preferably in the range of 0 to 40, more preferably in the range of 0 to 20. When n exceeds 40, the molecular weight increases, so the viscosity and the softening temperature increase, and the handleability deteriorates. The value of n can be controlled by the molar ratio of the epihalohydrin to the bisphenol compound during the production of the aromatic epoxy resin, but it is preferable that 10% or more of n is 0. When n is less than 10 mol%, the viscosity and softening temperature are increased, and the handleability is deteriorated. The average value of n is preferably 0 to 10, particularly preferably 0 to 5.

  The epoxy equivalent of the aromatic epoxy resin represented by the general formula (1) is preferably 224 to 2000. When the epoxy equivalent exceeds 2000, the softening temperature rises and the handleability deteriorates.

  The epoxy resin as component (A) is produced by hydrogenating the aromatic ring of the aromatic epoxy resin represented by the general formula (1) in the presence of a catalyst.

  As the hydrogenation catalyst, various heterogeneous catalysts or homogeneous catalysts can be used. Among them, a heterogeneous catalyst is preferable because of easy catalyst separation, and one of a nickel catalyst and a platinum group catalyst. Or 2 or more types are used preferably. The nickel-based catalyst can be used as a Raney catalyst or supported on a support such as diatomaceous earth or alumina, and the platinum group catalyst is mainly used as supported on a support.

  Among these hydrogenation catalysts, platinum group catalysts are particularly preferable, and among them, rhodium-based catalysts and / or ruthenium-based catalysts moderate carbon-carbon double bonds by suppressing hydrogenolysis of contained epoxy groups. It is preferable in that it can be hydrogenated under various conditions. As the catalyst carrier, carbon-based carriers such as activated carbon and graphite, and inorganic carriers such as silica and alumina are preferably used.

  A hydrogenation reaction solvent may be used during the hydrogenation reaction in order to dissolve the aromatic epoxy resin and allow the reaction to proceed smoothly. As the hydrogenation reaction solvent, an ether solvent or an ester solvent is preferably used because it is not easily affected by the solubility of the aromatic epoxy resin and the hydrogenation reaction. As the ether solvent, tetrahydrofuran, methyltetrahydrofuran, dioxane and the like can be used, and as the ester solvent, various solvents such as ethyl acetate, butyl acetate and methyl propionate can be used. These solvents may be used alone or in combination of two or more.

  In the hydrogenation reaction of the aromatic epoxy resin represented by the general formula (1), the aromatic ring can be hydrogenated at a desired hydrogenation rate by controlling the reaction conditions and the amount of hydrogen to be reacted. The hydrogenation reaction conditions depend on the catalyst used and the degree of hydrogenation of the required raw material aromatic epoxy resin, but the pressure is from normal pressure to 30 MPa, the temperature is from about 30 to 150 ° C., and the reaction time is 0.00. It is common to adjust in the range of about 5 to 20 hours.

  As an example of a more preferable reaction method, the aromatic epoxy resin represented by the general formula (1) is dissolved in an ester solvent and / or an ether solvent, and a platinum catalyst, preferably rhodium and / or ruthenium, is converted into graphite and And / or a hydrogenation method using a catalyst supported on activated carbon.

  After completion of the reaction, the catalyst is removed by filtration, and the solvent is distilled off under reduced pressure until it substantially disappears to obtain an epoxy resin as component (A).

  The epoxy resin of component (A) thus obtained has an aromatic ring hydrogenation rate of 0.5 to 50%, preferably 1 to 30% of the aromatic epoxy resin represented by the general formula (1). It is formed by hydrogenation. When the hydrogenation rate is less than 0.5%, the hue of the resulting epoxy resin cannot be improved, and when it exceeds 50%, the heat resistant colorability of the cured product is deteriorated.

  The hydrogenation rate of the aromatic ring can be measured by various methods such as absorbance and nuclear magnetic resonance spectrum. For example, it can be measured by obtaining a change in absorbance (wavelength: 275 nm) using a spectrophotometer.

  Moreover, it is preferable that the epoxy equivalent of the epoxy resin of (A) component is 230-2000 for the same reason as in an aromatic epoxy resin.

((B) component; epoxy resin curing agent)
As the curing agent for epoxy resin of the component (B) contained in the epoxy resin composition of the present invention, a general curing agent for epoxy resin is used, and examples thereof include the following.

  (1) Amines: bis (4-aminocyclohexyl) methane, bis (aminomethyl) cyclohexane, m-xylylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [ 5,5] Aliphatic and alicyclic amines such as undecane, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) pheno And tertiary amines such as 1,8-diazabicyclo- (5,4,0) -undecene-7, 1,5-azabicyclo- (4,3,0) -nonene-7 and salts thereof.

  (2) Acid anhydrides: aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahexan anhydride Cyclic aliphatic acid anhydrides such as hydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.

  (3) Multivalent phenols: catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolacs, cresol novolacs, bisphenol Divalent phenol novolacs such as A, trishydroxyphenylmethanes, aralkylpolyphenols, dicyclopentadiene polyphenols and the like.

(4) Others: imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; BF ₃ complex compounds of amines as described above; aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphonium salts, etc. Bronsted acid salts of: organic acid hydrazides such as adipic acid dihydrazide and phthalic acid dihydrazide; dicyandiamides; polycarboxylic acids such as adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl group-containing polyester.

  These epoxy resin curing agents may be used alone or in combination of two or more.

  Although the compounding quantity of the hardening | curing agent for epoxy resins changes also with the kind of hardening | curing agent for epoxy resins to be used, it is 0.01-200 mass parts normally with respect to 100 mass parts of epoxy resin components, Preferably it is 0.1-150 mass. Within the range of the part. Here, the “epoxy resin component” means not only the epoxy resin of the component (a) but also other alicyclic epoxy resins described later, and the epoxy resin of the component (a) and other alicyclic compounds. Refers to all epoxy resin components in the epoxy resin composition, including epoxy resins. The same applies to the following.

(Acid anhydrides and cationic polymerization initiators)
When the epoxy resin composition of the present invention is used particularly as a sealing material for a light emitting device, it is possible to use an acid anhydride and / or a cationic polymerization initiator as a curing agent for the epoxy resin, and a cured product with less coloring. Is preferable in that it can be obtained.

  Examples of acid anhydrides include aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl anhydride And cyclic aliphatic acid anhydrides such as hexahydrophthalic acid, methylendoethylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride. Among these, it is particularly preferable to use a hydrogenated cyclic aliphatic acid anhydride such as hexahydrophthalic anhydride or methylhexahydrophthalic anhydride.

  Moreover, when using acid anhydrides, a hardening accelerator can be mix | blended in order to accelerate | stimulate the hardening. Examples of the curing accelerator include tertiary soaps, imidazoles, organic phosphine compounds or salts thereof, and metal soaps such as zinc octylate and tin octylate.

  The use ratio of the acid anhydrides as the curing agent for the epoxy resin is preferably in the range of 5 to 200 parts by mass, particularly 10 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin component. When blending, it is preferable that the use ratio is 0.01 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin component.

  Further, as the cationic polymerization initiator, an active energy ray cationic polymerization initiator that generates a cationic species or a Lewis acid by active energy rays, or a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heat can be used. it can.

Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653; bis (perfluoroalkyls) as described in US Pat. No. 3,586,616. Sulfonyl) methane metal salts; aryldiazonium compounds as described in US Pat. No. 3,708,296; aromatic onium salts of group VIa elements as described in US Pat. No. 4,058,400; described in US Pat. Aromatic onium salts of Group Va elements such as: dicarbonyl chelates of Group IIIa to Va elements as described in US Pat. No. 4068091; thiopyrylium salts as described in US Pat. No. 4,139,655; US Pat. No. 4,161,478 MF ₆ as described in JP ^- anion (where M is Element selected from the group consisting of antimony and arsenic; arylsulfonium complex salts as described in US Pat. No. 4,231,951; aromatic iodonium complex salts and aromatic sulfonium complex salts as described in US Pat. No. 4,256,828 W .; R. Bis [4- (diphenyl) as described by Watt et al. In "Journal of Polymer Science, Polymer Chemistry Edition", Vol. 22, p. 1789 (1984). One or more of sulfonio) phenyl] sulfide-bis-hexafluorometal salts (for example, phosphate, arsenate, antimonate, etc.). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.

  Preferred active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, Group V and Group VI elements. Some of these salts are "FX-512" (3M Company), "UVR-6990" and "UVR-6974" {Union Carbide Company}, "UVE-1014" and "UVE-1016". "General Electric Company", "KI-85" {Degussa Company}, "SP-150" and "SP-170" (Asahi Denka) and "Sun-Aid SI-60L", " It can be obtained as a product as “Sun-Aid SI-80L” and “Sun-Aid SI-100L” (Sanshin Chemical Industry Co., Ltd.).

  Examples of the thermal cationic polymerization initiator include cationic or protonic acid catalysts such as a triflic acid salt, boron trifluoride ether complex compound, boron trifluoride, etc. Preferred thermal cationic polymerization initiators For example, diethylammonium triflate, triethylammonium triflate, diisopropylammonium triflate, ethyldiisopropylammonium triflate, etc. (many of these are R.I., triflates available from 3M as “FC-520”). R. Alm, described in Modern Coatings published October 1980). Moreover, among aromatic onium salts used as active energy ray cationic polymerization initiators, there are those that generate cationic species by heat, and these can also be used as thermal cationic polymerization initiators. Examples include “Sun-Aid SI-60L”, “Sun-Aid SI-80L” and “Sun-Aid SI-100L” (Sanshin Chemical Industry Co., Ltd.).

  Among these active energy rays and thermal cationic polymerization initiators, onium salts are preferable in that they are excellent in handleability and the balance between latency and curability, and among them, diazonium salts, iodonium salts, sulfonium salts, and phosphonium salts. A salt is particularly preferable in that it has an excellent balance between handleability and latency.

  The usage-amount of a cationic polymerization initiator becomes like this. Preferably it is 0.01-15 weight part with respect to 100 mass parts of epoxy resin components, More preferably, it is 0.05-5 weight part.

  Even when any curing agent for epoxy resin is used, if the amount of use is outside the preferred range, the balance of heat resistance, light resistance and moisture resistance of the cured epoxy resin is deteriorated.

(Other alicyclic epoxy resins)
In the epoxy resin composition of the present invention, as the epoxy resin component, only the epoxy resin of the component (A) may be used, or a mixture of this epoxy resin and another alicyclic epoxy resin may be used. .

  As this alicyclic epoxy resin, other hydrogenated epoxy resins or alicyclic epoxy resins obtained by epoxidizing olefins can be used, for example, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy. Resin, hydrogenated biphenol type epoxy resin, hydrogenated phenol novolak type epoxy resin, hydrogenated cresol novolak type epoxy resin, hydrogenated bisphenol A novolak type epoxy resin, hydrogenated naphthalenediol type epoxy resin and hydrogenated phenol dicyclopentadiene novolak type Hydrogenated epoxy resins such as epoxy resins, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-epoxy-vinylcyclohexylene, bis (3,4-epoxycyclohexylmethyl) Dipetate, 1-epoxyethyl-3,4-epoxycyclohexane, limonene diepoxide, 3,4-epoxycyclohexylmethanol, dicyclopentadiene diepoxide, oligomer type alicyclic epoxy resin (trade name of Daicel Chemical Industries; Epolide GT300, An alicyclic epoxy resin obtained by epoxidizing an olefin such as Epolide GT400 or EHPE-3150) can be used. Among these, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated biphenol type epoxy resin, and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate are obtained. It is particularly preferable in terms of balance of physical properties and handleability of the cured product.

  These other alicyclic epoxy resins may be used alone or in combination of two or more.

  When using together the epoxy resin of the said (A) component and another alicyclic epoxy resin as an epoxy resin, the mixture ratio is other fats with respect to 10 mass parts or more of the epoxy resin of the said (A) component. The cyclic epoxy resin is preferably 90 parts by mass or less, particularly 10 to 90 parts by mass of the other alicyclic epoxy resin with respect to 10 to 90 parts by mass of the epoxy resin of the component (A), especially the component (A). It is preferable to set it as 20-80 mass parts of other alicyclic epoxy resins with respect to 20-80 mass parts of epoxy resin (However, the sum total of the epoxy resin of said (A) component and other alicyclic epoxy resins) 100 parts by mass). The combined use of other alicyclic epoxy resins, particularly the above-mentioned preferred alicyclic epoxy resins, has the effect of improving light resistance. However, when the proportion of other alicyclic epoxy resins is too large, The improvement effect such as heat resistance by using the epoxy resin of component A) cannot be sufficiently obtained.

(Antioxidant)
The epoxy resin composition of the present invention, particularly the epoxy resin composition for a light emitting device sealing material, is preferably blended with an antioxidant to prevent oxidative deterioration during heating, in order to obtain a cured product with little coloration. .

  In this case, examples of the antioxidant that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. The amount is usually 0.01 to 1 part by mass with respect to 100 parts by mass of the epoxy resin component. Specific examples of the antioxidant that can be used include the following.

[Phenolic antioxidant]
Monophenols; 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate, etc. Bisphenols; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- { β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, etc. Polymer Phenols; 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-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 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S— Triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc.

[Sulfur-based antioxidants]
Dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, etc.

[Phosphorus antioxidant]
Phosphites; triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, Cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butyl) -4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. Oxaphosphaphenanthrene oxides; 9,10 - Dro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

  These antioxidants can be used alone, but it is particularly preferable to use a combination of two or more types such as phenol / sulfur or phenol / phosphorus.

(UV absorber)
In the epoxy resin composition of this invention, light resistance can further be improved by mix | blending a ultraviolet absorber. As the ultraviolet absorber that can be blended, general ultraviolet absorbers for plastics can be used, and examples thereof include the following.
It is preferable that the compounding quantity of a ultraviolet absorber shall be 0.1-10 mass parts with respect to 100 mass parts of epoxy resin components.

  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 Benzophenones such as -4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5 ′; -Di-tert-Buchi Phenyl) 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 ′, 3 ″, 4 '' 5 '', 6 ''-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole and other benzotriazoles; 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} methyl] hindered amines such as butyl malonate.

(Optional component)
In the epoxy resin composition of the present invention, the following components can be added and blended as necessary.
(1) Powdery reinforcing agents and fillers; for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, transparent fillers such as glass beads, and aluminum hydroxide Metal hydroxide, other, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc. The above component (1) is blended within a range that does not impair the transparency of the epoxy resin composition of the present invention. 100 mass parts or less, for example 10-100 mass parts is suitable with respect to a mass part.

(2) Colorant or pigment; for example, titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red and organic dyes
(3) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds
(4) Additives such as an ion adsorbent, a coupling agent, and a release agent When blending the above components (2) to (4), 30 parts by mass or less for each 100 parts by mass of the epoxy resin component, For example, 0.01-30 mass parts is mix | blended.

  Furthermore, the epoxy resin composition of the present invention can be blended with various curable monomers, oligomers and synthetic resins for the purpose of improving the properties of the epoxy cured product. Examples of such blends include one or more of a diluent for epoxy resins such as aliphatic epoxies, diols or triols, vinyl ethers, oxetane compounds, fluororesins, acrylic resins, silicone resins and the like. Can be mentioned. The compounding ratio of these compounds and resins is preferably 50 parts by mass or less with respect to an amount within a range not impairing the original properties of the epoxy resin composition of the present invention, for example, 100 parts by mass of the epoxy resin component.

(Hardened epoxy resin)
The method for curing the epoxy resin composition of the present invention is not particularly limited, but is cured by light, heat, etc. after mixing the epoxy resin and the epoxy resin curing agent and other components blended as necessary. A cured epoxy resin can be obtained by carrying out the reaction. The cured epoxy resin obtained from the epoxy resin composition of the present invention has tough performance, and has a low content of impurities such as hydrolyzable chlorine and basic compounds. For example, although it can be suitably used as an insulating material, etc., the cured epoxy resin of the present invention is excellent in transparency, heat resistance, light resistance, and moisture resistance. It is.

(Light emitting element)
Since the epoxy resin composition of the present invention is particularly excellent in light resistance, it is effective for sealing a light emitting device that emits light having a relatively short wavelength having a peak wavelength of 350 to 550 nm.

As such a light emitting device, a group III nitride compound semiconductor formed by metal organic chemical vapor deposition (MOCVD), molecular beam crystal growth (MBE), or halide vapor deposition (HVPE) is used. The general formula is represented by Al _X Ga _Y In _1-XY N (0 ≦ X ≦ 1, 0 ≦ Y ≦ 1, 0 ≦ X + Y ≦ 1), and so-called Al _X , GaN and InN. Included are so-called ternary systems of binary systems, Al _x Ga _1-X N, Al _x In _1-X N and Ga _x In _1-X N (where 0 ≦ X ≦ 1). Examples of the semiconductor structure include a homostructure, a heterostructure, or a double heterostructure having a MIS junction, a PIN junction, a pn junction, or the like. Various emission wavelengths can be selected depending on the material of the semiconductor layer and the degree of mixed crystal. In addition, a single quantum well structure or a multiple quantum well structure in which the semiconductor active layer is formed in a thin film in which a quantum effect is generated can be used.

  Hereinafter, the present invention will be described more specifically with reference to production examples, comparative production examples, examples and comparative examples. However, the present invention is not limited by the following examples unless it exceeds the gist. . In the following, “part” means “part by mass”.

Moreover, in each Example and the comparative example, evaluation of the obtained epoxy resin composition and epoxy resin hardened | cured material was performed with the following method.
<Gelification time>
It measured at 120 degreeC using the gel time tester by Yasuda Seiki.
<Glass transition temperature Tg (° C)>
According to the TMA method (heating rate 5 ° C./min).
<Hue>
The initial YI value (Yellowness Index) after curing was measured.
<UV resistance>
Using a metering weather meter (manufactured by Suga Test Instruments Co., Ltd.), the YI value (Yellowness Index) of the cured product was measured after irradiation with ultraviolet rays at an irradiation intensity of 0.4 kW / m ² and a black panel temperature of 63 ° C for 72 hours. .
<Heat resistance degradation>
The YI value (Yellowness Index) of the cured epoxy resin after heating at 150 ° C. for 72 hours was measured.
<Hygroscopic rate (%)>
The moisture absorption rate after leaving the disc-shaped epoxy resin cured product having a thickness of 3 mm and a diameter of 50 mm for 24 hours at 121 ° C. was measured.

Production Example 1
An aromatic epoxy resin obtained by using 2,2-bis (4-hydroxyphenyl) hexafluoropropane as a bisphenol compound in a 1 L autoclave (epoxy equivalent; 239, n represented by the general formula (1)) The number was 0 to 4, and on average 0.15) 150 g, ethyl acetate 300 g, and 5 wt% rhodium / graphite catalyst 1.5 g as a catalyst were charged, and the hydrogenation reaction was carried out at 110 ° C. and 8 MPa. Although hydrogen absorption was observed for about 3 hours after the start of the reaction, hydrogen absorption stopped, and after stirring for 30 minutes, depressurization and gas replacement were carried out, and the reaction solution was extracted.
Magnesium oxide powder ("AD100P" manufactured by Tomita Pharmaceutical Co., Ltd.) and a filter aid were added to the reaction solution, followed by filtration. Ethyl acetate was distilled off from the filtrate at 150 ° C. under reduced pressure to obtain a colorless transparent semi-solid epoxy resin.
When the obtained epoxy resin was analyzed by ¹ H-NMR, it was confirmed that the hydrogenation rate of the aromatic ring was 28%. Moreover, the epoxy equivalent of the obtained epoxy resin was 244, and APHA (hue) calculated | required from the spectrophotometer was 3.

Production Example 2
A hydrogenation reaction was carried out under the same reaction conditions as in Production Example 1 except that the amount of the hydrogenation catalyst was 0.75 g and the reaction time was 1 hour, to obtain a colorless transparent semi-solid epoxy resin.
The hydrogenation rate of the aromatic ring of the obtained epoxy resin was 6%, the epoxy equivalent was 240, and the APHA calculated from the spectrophotometer was 7.

Comparative production example 1
Hydrogenation was carried out under the same reaction conditions as in Production Example 1 except that the amount of the hydrogenation catalyst was 7.5 g and the reaction time was 5 hours to obtain a colorless and transparent epoxy resin.
The hydrogenation rate of the aromatic ring of the obtained epoxy resin was 79%, the epoxy equivalent was 264, and the APHA calculated from the spectrophotometer was 2.

Comparative production example 2
After dissolving 150 g of an aromatic epoxy resin obtained using 2,2-bis (4-hydroxyphenyl) hexafluoropropane as a bisphenol compound in 300 g of ethyl acetate, 6 g of activated carbon (“Taiko K” manufactured by Nimura Chemical Co., Ltd.) After stirring at room temperature for 1 hour, a filter aid was added and filtration was performed. From the filtrate, ethyl acetate was distilled off at 150 ° C. under reduced pressure to obtain a yellow transparent semi-solid epoxy resin having an epoxy equivalent of 239 and an APHA of 73.

Example 1
100 parts of the epoxy resin obtained in Production Example 1 and 70 parts of Ricacid MH-700 (trade name of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride) as an acid anhydride curing agent were mixed at a temperature of 60 ° C. until uniform. Then, 1 part of Hishicolin PX-4MP (Nippon Kagaku Kogyo Co., Ltd .; trade name: methyltributylphosphonium dimethyl phosphate) was added as a curing accelerator, stirred and dissolved to obtain an epoxy resin composition. The gel time of this epoxy resin composition is shown in Table 1.
The epoxy resin composition was degassed under reduced pressure, then poured into a mold, and heated in an oven at 100 ° C. for 3 hours and then at 140 ° C. for 3 hours to obtain a cured product.
The evaluation results of this cured epoxy resin are shown in Table 1.

Examples 2-5 and Comparative Examples 1-2
Except having used the epoxy resin, the alicyclic epoxy resin, the epoxy resin curing agent, and other components in the formulation shown in Table 1, the same operation as in Example 1 was performed to obtain an epoxy resin composition and a cured product. The evaluation results are shown in Table 1.

  From Table 1, it can be seen that according to the present invention, it is possible to obtain a cured epoxy resin which is colorless and transparent and excellent in light resistance, heat resistance and moisture resistance.

Claims (7)

An epoxy resin composition comprising the following component (A) and component (B):
Component (A): an epoxy resin obtained by directly hydrogenating an aromatic epoxy resin represented by the following general formula (1), wherein the aromatic ring has a hydrogenation rate of 1 to 30 %

[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n represents a number from 0 to 40. ]
Component (B): epoxy resin curing agent ^2. The epoxy resin composition according to claim 1, wherein in the general formula (1), R ¹ , R ² , R ^3, and R ⁴ are hydrogen atoms, and n is a number from 0 to 20. 5. (B) Component epoxy resin curing agent includes amines, acid anhydrides, polyhydric phenols, imidazoles, Bronsted acid salts, amine BF ₃ complex compounds, organic acid hydrazides, dicyandiamides, and poly The epoxy resin composition according to claim 1 or 2 , wherein the epoxy resin composition is one or more selected from the group consisting of carboxylic acids. The (B) component epoxy resin curing agent is an acid anhydride and / or a cationic polymerization initiator, and is an epoxy resin composition for a light emitting device sealing material used as a light emitting device sealing material. The epoxy resin composition according to any one of claims 1 to 3 . (A) the epoxy resin 10 to 90 parts by weight of the component, any one of claims 1, characterized in that it comprises as a 100 parts by 10 to 90 parts by weight alicyclic epoxy resins in total 4 2. The epoxy resin composition according to item 1. The epoxy resin composition according to claim 4 or 5 light-emitting layer, characterized in that a light-emitting element for encapsulation epoxy resin composition for sealing a light emitting element having a main emission peak in 350～550Nm. The epoxy resin composition according to any one of claims 4, wherein the light emitting element is a light emitting diode (LED) 6.