JP4674112B2 - Epoxy resin composition and optical electronic member using the same - Google Patents

Description

  The present invention relates to an epoxy resin composition used for an optical semiconductor encapsulant, an electronic circuit encapsulant, an optical waveguide, an optical communication lens, an organic EL element encapsulant, an optical film, and the like. More specifically, the present invention relates to an epoxy resin composition containing a specific adamantane-based epoxy compound and an optical electronic member using the same.

In recent years, flat panel displays using liquid crystal, organic EL, etc. have higher definition, higher viewing angle, higher image quality, and light sources with light emitting diodes (optical semiconductors) such as LEDs have higher brightness, shorter wavelength, and whitening. Furthermore, high performance and improvement studies of optical and electronic components are being promoted, such as higher frequency of electronic circuits and circuits / communication using light.
As an improvement method, research and development of basic materials such as liquid crystal materials and light emitting materials for organic EL has been carried out. However, improvement in performance of resins such as coating materials or sealing materials used with these materials has also been studied. ing.
Various thermosetting resins, photo-curing resins, or thermoplastic resins are applied as coating materials for optical and electronic parts and as resins for sealing materials. They are applied according to characteristics such as heat resistance, transparency, solubility and adhesion of the resin alone.

For example, in the field of LEDs where performance is advancing, proposals and practical applications for lighting and lights using white LEDs composed of near-ultraviolet and blue light-emitting elements have been promoted. Expansion to automobiles is expected. LED elements are sealed with a resin containing a phosphor in an inorganic semiconductor. However, conventional thermosetting resins such as bisphenol A type epoxy resins have limitations in heat resistance and light resistance, and satisfy the required characteristics. There is a demand for a stopper (see, for example, Non-Patent Document 1).
In the display field, organic EL elements excellent in small size, high definition, and energy saving are used, and a top emission type or the like is employed. Along with that, as a sealing resin for organic EL elements, in addition to the function of bonding a sealing substrate such as conventional stainless steel and a glass substrate and the function of gas barrier properties, the sealing resin itself has transparency and light resistance, Heat resistance, mechanical strength, etc. are demanded more (for example, refer nonpatent literature 2).

  In addition, with the advancement of the information society, electronic circuits integrated with semiconductors, etc., have increased information volumes and communication speeds, and miniaturized devices, requiring circuit miniaturization, integration, and higher frequencies. It has become. Furthermore, an optical circuit using an optical waveguide or the like that enables higher-speed processing has been studied. Conventionally used bisphenol A type epoxy resins as sealing resins and films or lenses used in these applications have high dielectric constants in electronic circuits, transparency in optical waveguides, etc. There is a problem.

  A polymer compound having an adamantane skeleton has good heat resistance. For example, polyesters and polycarbonates using adamantanediol are known. Further, it has been proposed to use an epoxy resin composition made of 2,2-bis (glycidyloxyphenyl) adamantane as an electronic component sealing resin (see, for example, Patent Document 1). This adamantane derivative has a high glass transition temperature (Tg) and excellent heat resistance, but there is no description of transparency, long-term reliability and durability required for optical materials and electronic materials.

Published by Technical Information Association: Monthly “Material Stage” June 2003, pages 20-24 Published by Technical Information Association: Monthly “Material Stage” March 2003, pages 52-64 JP-A-10-130371

  From the above situation, the present invention is an optical electronic member such as an optical semiconductor encapsulant, an electronic circuit encapsulant, an optical waveguide, an optical communication lens, an organic EL element encapsulant, and an optical film. An object of the present invention is to provide an epoxy resin composition that provides a cured product having excellent optical properties such as transparency and light resistance, long-term heat resistance, and electrical properties such as dielectric constant.

  As a result of intensive studies to achieve the above object, the present inventors have solved the above problems by using 1,3-bis (glycidyloxyphenyl) adamantanes as the epoxy resin component, and optical It discovered that the resin composition which gives the hardened | cured material excellent as an electronic member is obtained. The present invention has been completed based on such knowledge.

That is, the present invention provides the following epoxy resin composition and optical electronic member.
(1) 1,3-bis (glycidyloxyphenyl) adamantane represented by the general formula (I) and selected from hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride An epoxy resin composition containing an acid anhydride curing agent composed of at least one compound and a curing accelerator, which can react with an epoxy group in the curing agent with respect to 1 equivalent of the epoxy group in the epoxy resin An epoxy resin composition, wherein the active group is 0.5 to 1.5 equivalents, and the content of the curing accelerator is 0.01 to 8.0% by mass with respect to the epoxy resin.

Wherein R ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl-substituted alkyl group having 7 to 13 carbon atoms and a carbon number represents a group selected from the group consisting of 1-6 fluoroalkyl group, when R ¹ is a plurality, the plural R ¹ s are the same as each other, may be different .n is an integer of 0-4.)
(2) A sealing compound for optical semiconductors using the epoxy resin composition of (1) .
(3) An electronic circuit sealant comprising the epoxy resin composition of (1) .
(4) An optical waveguide using the epoxy resin composition according to (1) .
(5) A lens for optical communication using the epoxy resin composition according to (1) .
(6) A sealant for an organic EL device using the epoxy resin composition according to (1) .
(7) An optical film using the epoxy resin composition according to (1) .

The epoxy resin composition containing 1,3-bis (glycidyloxyphenyl) adamantanes represented by the general formula (I) of the present invention has optical properties such as transparency and light resistance, long-term heat resistance, dielectric constant, and the like. Suitable for optical electronic members such as optical semiconductor encapsulants, electronic circuit encapsulants, optical waveguides, optical communication lenses, organic EL element encapsulants, and optical films. Can be used.
That is, in the present invention, by introducing a glycidyl group into an adamantane compound having excellent heat resistance and further reacting with a specific curing agent, in addition to long-term heat resistance, transparency, light resistance, and dielectric constant are improved. In addition, it is more excellent in solubility in a curing agent and a diluting solvent than 2,2-bis (glycidyloxyphenyl) adamantane.
Thereby, the epoxy resin composition containing 1,3-bis (glycidyloxyphenyl) adamantanes excellent in transparency, heat resistance and strength can be used for a sealant, an adhesive, a coating agent, Transparency, light resistance, long-term heat resistance, and electrical characteristics can be improved.
Accordingly, the epoxy resin composition of the present invention can be used for lighting applications using displays such as organic EL elements and LEDs, or for information communication members such as electronic circuits and optical circuits, sealing agents and adhesives, It is useful as an optical film or a lens for optical communication.

  First, the epoxy resin composition of the present invention is characterized by containing 1,3-bis (glycidyloxyphenyl) adamantanes represented by the following general formula (I).

In the formula, R ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl-substituted alkyl group having 7 to 13 carbon atoms, and 1 carbon atom. It represents a group selected from the group of 6 fluoroalkyl groups, when R ¹ is plural, R ¹ is also the same as each other or may be different. n is an integer of 0-4.
Examples of the halogen atom for R ¹ include fluorine, chlorine, bromine and iodine, and the alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group, and examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the fluoroalkyl group include groups in which one or more hydrogen atoms of the alkyl group are substituted with fluorine atoms, such as a trifluoromethyl group, and examples of the aryl-substituted alkyl group include benzyl group and phenethyl group. It is done.

  Specific examples of 1,3-bis (glycidyloxyphenyl) adamantanes include 1,3-bis (4-glycidyloxyphenyl) adamantane, 1,3-bis (3-methyl-4-glycidyloxyphenyl) adamantane, 1,3-bis (3,5-dimethyl-4-glycidyloxyphenyl) adamantane, 1,3-bis (3-chloro-4-glycidyloxyphenyl) adamantane, 1,3-bis (2-methyl-4-) Examples thereof include glycidyloxyphenyl) adamantane, 1,3-bis (3-cyclohexyl-4-glycidyloxyphenyl) adamantane, and 1,3-bis (3-phenyl-4-glycidyloxyphenyl) adamantane.

As the epoxy resin in the epoxy resin composition of the present invention, only the above 1,3-bis (glycidyloxyphenyl) adamantanes may be used, but those mixed with other known epoxy resins are also applicable. Known epoxy resins that can be used as a mixture include, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin (bisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated) Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol G diglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol AF diglycidyl ether, bisphenol C diglycidyl ether, etc.), phenol novolac type epoxy resin and cresol novolac type epoxy Novolac type epoxy resin such as resin, alicyclic epoxy resin, triglycidyl isocyanurate, Nitrogen-containing heterocyclic epoxy resins such as dantoin epoxy resin, aliphatic epoxy resins, glycidyl ether type epoxy resins, biphenyl type epoxy resins, dicyclo ring type epoxy resins, naphthalene type epoxy which are the mainstream of low water absorption hardened type Examples thereof include resins. These may be used alone or in combination of two or more.
Among these epoxy resins, a suitable one is selected depending on the application to be used, such as transparency, light resistance, heat resistance, and mechanical strength.

  The epoxy resin may be solid or liquid at normal temperature, but generally, the epoxy resin used preferably has an average epoxy equivalent of 200 to 2000. If the epoxy equivalent is less than 200, the cured product of the epoxy resin composition may become brittle. Moreover, when an epoxy equivalent exceeds 2000, the glass transition temperature (Tg) of the hardening body may become low.

The epoxy resin composition of the present invention can be cured by a known method such as cationic polymerization, reaction using a curing agent such as acid anhydride or amine, and thermal curing or ultraviolet curing.
Any cationic polymerization initiator may be used as long as it reacts with an epoxy group by heat or ultraviolet rays. For example, aromatic diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, aromatics such as triphenylsulfonium hexafluorophosphate, and the like. Aromatic sulfonium salts, aromatic iodonium salts such as diphenyliodonium hexafluorophosphate, aromatic iodosyl salts, aromatic sulfoxonium salts, metallocene compounds, and the like. Of these, aromatic sulfonium salts such as triphenylsulfonium hexafluorophosphate and aromatic iodonium salts such as diphenyliodonium hexafluorophosphate are optimal.
It is preferable that the content rate of a cationic polymerization initiator is 0.01-5.0 mass% with respect to the said epoxy resin, More preferably, it is 0.1-3.0 mass%. By setting the content of the initiator within the above range, physical properties such as good polymerization and optical properties can be expressed.

As the curing agent, an acid anhydride curing agent, a phenol curing agent, an amine curing agent or the like may be used in combination according to the purpose.
Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride. Examples include acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like.
Examples of the phenolic curing agent include phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, triazine-modified phenol novolak resin, and the like. Examples of amine-based curing agents include dicyandiamide, aromatic diamines such as m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and m-xylylenediamine. Two or more of these curing agents may be used in combination.
Among these curing agents, acid anhydride curing agents are preferred from the viewpoint of physical properties such as transparency of the cured resin. Among them, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, Methyltetrahydrophthalic anhydride is optimal.

  The mixing ratio of the epoxy resin and the curing agent is such that the active group (an acid anhydride group, hydroxyl group, etc.) capable of reacting with the epoxy group in the curing agent is 0.5 to 1 with respect to 1 equivalent of the epoxy group in the epoxy resin. The ratio is preferably 5 equivalents, and more preferably 0.7 to 1.2 equivalents. By setting the blending ratio of the epoxy resin and the curing agent in the above range, the curing rate of the epoxy resin composition is not slowed, the glass transition temperature of the cured resin is not lowered, and the moisture resistance is lowered. This is preferable.

In addition, the epoxy resin composition of the present invention, if necessary, is conventionally used, for example, a curing accelerator, a deterioration inhibitor, a modifier, a silane coupling agent, a defoaming agent, an inorganic powder, a solvent. Various known additives such as leveling agents, mold release agents, dyes and pigments may be appropriately blended.

The curing accelerator is not particularly limited. For example, 1,8-diaza-bicyclo (5.4.0) undecene-7, triethylenediamine, tris (2,4,6-dimethylaminomethyl) Tertiary amines such as phenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o , O-diethyl phosphorodithioate and the like phosphorus compounds, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination. Among these curing accelerators, it is preferable to use tertiary amines, imidazoles, and phosphorus compounds.
It is preferable that the content rate of a hardening accelerator is 0.01-8.0 mass% with respect to the said epoxy resin, More preferably, it is 0.1-3.0 mass%. By making the content rate of a hardening accelerator into the said range, sufficient hardening acceleration effect can be acquired and discoloration is not seen in the hardened | cured material obtained.

Examples of the deterioration preventing agent include conventionally known deterioration preventing agents such as phenol compounds, amine compounds, organic sulfur compounds, and phosphorus compounds.
Examples of phenolic compounds include Irganox 1010 (Irganox 1010, Ciba Specialty Chemicals, Inc.), Irganox 1076 (Irganox 1076, Ciba Specialty Chemicals, Inc.), Irganox 1330 (Irganox 1330, Ciba Specialty Chemicals, Inc.) Irganox 3114 (Irganox 3114, Ciba Specialty Chemicals, Trademark), Irganox 3125 (Irganox 3125, Ciba Specialty Chemicals, Trademark), Irganox 3790 (Irganox 3790, Ciba Specialty Chemicals, Trademark) BHT, Cyanos 1790 Cyanox 1790, Cyanamid Co., Ltd.), Sumilizer GA-80 (S milizerGA-80, Sumitomo Chemical Co., Ltd., trademark) can be mentioned a commercially available product, such as.

Examples of amine compounds include Irgastab FS042 (Ciba Specialty Chemicals, Trademark), GENOX EP (Crimpton, Trademark, Compound Name; Dialkyl-N-methylamine oxide), and a hindered amine product manufactured by Asahi Denka Co., Ltd. ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82, LA-87, LA-94, Tinuvin 123, 144 manufactured by CSC 440, 662, Chimassorb 2020, 119, 944, Hostavin N30 from Hoechst, Cyasorb UV-3346, UV-3526 from Cytec, Uval 299 from GLC, SanduvorPR-31 from Clariant, etc. it can.
Examples of organic sulfur compounds include DSTP (Yoshitomi, Trademark), DLTP (Yoshitomi, Trademark), DLTOIB (Yoshitomi, Trademark), DMTP (Yoshitomi, Trademark), Seeox 412S. (Cypro Kasei Co., Ltd., Trademark), Cyanox 1212 (Cyanamide Co., Ltd., Trademark), and other commercial products.

  Examples of the modifying agent include conventionally known modifying agents such as glycols, silicones, and alcohols. Examples of the silane coupling agent include conventionally known silane coupling agents such as silane and titanate. Examples of the defoaming agent include conventionally known defoaming agents such as silicone. As the inorganic powder, those having a particle size of several nanometers to 10 μm can be used depending on the application, and examples thereof include known inorganic powders such as glass powder, silica powder, titania, zinc oxide, and alumina. As the solvent, when the epoxy resin is powder, or as a diluent solvent for coating, an aromatic solvent such as toluene or xylene, or a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone can be used.

The epoxy resin composition of the present invention is a mixture of the above-mentioned epoxy resin component and curing agent and various additives, and into a desired shape such as a film by injection into a mold to be molded (resin mold) or coating, Heat cure. The curing temperature is 50 to 200 ° C, preferably 100 to 180 ° C. Setting it to 50 ° C. or higher does not cause curing failure, and setting it to 200 ° C. or lower prevents coloring and the like from occurring. The curing time varies depending on the epoxy resin, curing agent, accelerator and initiator used, but 0.5 to 6 hours are preferred.
The molding method is not particularly limited, such as injection molding, blow molding, press molding, and the like, but it is preferably manufactured by injection molding using a pellet-shaped resin composition in an injection molding machine.

The resin obtained by curing the epoxy resin composition of the present invention is excellent in heat resistance and transparency, and has a total light transmittance of 70% or more. In addition, as shown in the following examples, the melting temperature is low, so the processability is excellent, the glass transition temperature is high, the durability is excellent (heat resistance and light resistance), and the electrical properties such as dielectric constant are also excellent. Cured product is obtained.
Thus, since the epoxy resin composition of the present invention has excellent characteristics, it is a resin (encapsulation) for optical semiconductors (LEDs, etc.), flat panel displays (organic EL elements, etc.), electronic circuits, and optical circuits (optical waveguides). (Stopping agent, adhesive), optical communication lenses such as optical communication lenses and optical films, and the like.

  For this reason, the epoxy resin composition of the present invention is a semiconductor element / integrated circuit (IC, etc.), individual semiconductor (diode, transistor, thermistor, etc.), LED (LED lamp, chip LED, light receiving element, optical semiconductor lens, etc.) , Sensors (temperature sensors, optical sensors, magnetic sensors), passive components (high-frequency devices, resistors, capacitors, etc.), mechanical components (connectors, switches, relays, etc.), automotive components (circuit systems, control systems, sensors, lamps) Seals, etc.), adhesives (optical components, optical discs, pickup lenses, etc.), etc., and also for optical films, etc. for surface coating.

Accordingly, the present invention provides an optical semiconductor encapsulant, an electronic circuit encapsulant, an optical waveguide, an optical communication lens, an organic EL element encapsulant, and an optical, each of which uses the above-described epoxy resin composition of the present invention. Films are also provided.
The structure when used as a sealant for optical semiconductors (LEDs, etc.) can be applied to elements such as a shell type or surface mount (SMT) type, and adheres well to semiconductors such as GaN formed on metal or polyamide. Further, it can also be used by dispersing a fluorescent dye such as YAG. Further, it can be used for a surface coating agent of a bullet type LED, a lens of an SMT type LED, and the like.
The organic EL device has a structure in which an anode / hole injection layer / light emitting layer / electron injection layer / cathode are sequentially provided on a transparent substrate such as general glass or transparent resin. It can be applied to an EL element. As an organic EL device sealing material, an adhesive for covering a metal can, a metal sheet, or a coated resin film such as SiN on the EL device, or an inorganic material for imparting gas barrier properties to the epoxy resin of the present invention It is also possible to directly seal the EL element by dispersing the filler or the like. As a display method, it is currently applicable to the mainstream bottom emission type, but by applying it to the top emission type which is expected in the light extraction efficiency, etc., the epoxy resin composition of the present invention is transparent. The effect of heat resistance and heat can be utilized.
The configuration applied to the electronic circuit can be applied as an interlayer insulating film, an adhesive between polyimide and copper for a flexible printed board, or a resin for a substrate.
The configuration used in an optical circuit can be applied to a single-mode or multi-mode thermo-optic switch, arrayed waveguide grating, multiplexer / demultiplexer, wavelength tunable filter, or optical fiber core material or cladding material. Further, the present invention can be applied to a microlens array for condensing light in a waveguide or a mirror of a MEMS type optical switch. Moreover, it is applicable also to the pigment | dye binder etc. of a photoelectric conversion element.
When used as an optical film, the structure is applied to a film substrate for liquid crystal, a film substrate for organic EL, or a color conversion film by dispersing a light diffusion film, an antireflection film, a fluorescent pigment, etc. Is possible.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these examples.
In the following examples and comparative examples, the obtained resins were evaluated as follows.

(1) Dissolution temperature The temperature at which the epoxy resin, the curing agent, and the solvent were uniformly dissolved was measured.

(2) Glass transition temperature Using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a sample was held at 50 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 20 ° C./min. The discontinuity point observed in the obtained heat flux curve was defined as the glass transition temperature Tg.

(3) Total light transmittance It measured based on JISK7105 using the test piece of thickness 3mm as a sample (unit%). A spectrophotometer UV-3100S manufactured by Shimadzu Corporation was used as a measuring apparatus.

(4) Light resistance test
Using Ltd. Toyo Seiki Seisakusho SUNTEST CPS +, the samples were irradiated for 500 hours light at 60 ° C., it was measured change in light transmittance of 400nm before and after the irradiation.

(5) Long-term heat resistance test The sample was placed in a constant temperature bath at 140 ° C for 100 hours, and the change in light transmittance at 400 nm before and after the test was measured.

(6) Dielectric Constant Using a dielectric loss measuring device TR-10C manufactured by Ando Electric Co., Ltd., measurement was performed at 1 MHz and 23 ° C. in accordance with IEC60250.

(7) Light loss evaluation About the sample of Example 2 and Comparative Example 2, the transparent thin film layer with a thickness of 10 micrometers which formed the thermosetting (film formation) on the silicon substrate was formed. About this thin film sample, light having a wavelength of 850 nm was incident using a prism coupler to propagate the light into the thin film. At that time, the detector was scanned along the propagation light to detect the scattered light from the sample, and the light loss of the thin film propagation light was calculated from the attenuation of the intensity.

Production Example 1
In a 300 mL four-necked flask, 1,3-bis (4′-hydroxyphenyl) adamantane [14 g, 43.7 milmol], epichlorohydrin [32.4 g, 350 milmol], dimethyl sulfoxide 40 g, methyl 20 g of isobutyl ketone and 0.4 g of water were charged and the temperature was raised to 45 ° C. Flaked caustic soda [3.5 g, 87.5 mmol] was added to the resulting solution in small portions over 1.5 hours. After completion of the addition, the reaction temperature was raised to 63 ° C., and the reaction was carried out at 65 to 75 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, 50 ml of water and 50 g of methyl isobutyl ketone were added and stirred. Next, the solution was transferred to a separatory funnel so as to prevent insoluble matter from entering as much as possible, and the aqueous layer was removed. The organic layer was transferred to an eggplant flask while filtering insoluble matter, and unreacted epichlorohydrin and methyl isobutyl ketone were distilled off by an evaporator to obtain 23 g of pale yellow crystals. The pale yellow crystals were recrystallized with a mixed solvent of TFP and isopropyl ether to obtain white crystals of 1,3-bis (4′-glycidyloxyphenyl) adamantane (actual yield 17 g, 39 mmol, yield 89%). .

Example 1
1 g of 1,3-bis (4-glycidyloxyphenyl) adamantane represented by the following chemical formula obtained in Production Example 1 and methyl hexahydrophthalic anhydride as an acid anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name MH700) ) 0.63 g and 0.01 g of 2-ethyl-4-methyl-imidazole as an accelerator were mixed by heating at 70 ° C. and heated at 100 ° C. for 2 hours and then at 140 ° C. for 2 hours to obtain a cured resin. The obtained cured resin (sheet having a thickness of 3 mm) was produced. The melting temperature, glass transition temperature, total light transmittance, and dielectric constant of the obtained cured resin were measured, and a light resistance test and a long-term heat resistance test were further performed. The evaluation results are shown in Table 1.

Reference example 1
To 1 g of 1,3-bis (4-glycidyloxyphenyl) adamantane, iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate (1-) (Ciba 0.02 g of trade name IRGACURE250 manufactured by Specialty Chemicals Co., Ltd. and 2 g of methyl ethyl ketone were added, dissolved by heating at 80 ° C., and then cast on a Teflon petri dish. The cast film was irradiated with an ultraviolet irradiation device (UL200 manufactured by HOYA-SCHOTT Co., Ltd.) at an intensity of 2000 mJ / cm ² to produce a cured resin. About the obtained cured resin, the same measurement as Example 1 was performed, and also optical loss evaluation was performed. The results are shown in Table 1.

Reference example 2
1 g of 1,3-bis (4-glycidyloxyphenyl) adamantane, 0.45 g of phenol resin and 0.01 g of tetraphenylphosphine are heated at 80 ° C. for 1 hour to dissolve uniformly, and then cured at 180 ° C. for 4 hours. did. A cured resin was produced. About the obtained cured resin, the same measurement as Example 1 was performed. The results are shown in Table 1.

Example 2
Curing was conducted in the same manner except that 1 g of 1,3-bis (glycidyloxyphenyl) adamantane of Example 1 was changed to 0.5 g of 1,3-bis (glycidyloxyphenyl) adamantane and 0.45 g of bisphenol A glycidyl ether. Reaction and measurement were performed. The results are shown in Table 1.

Comparative Example 1
A cured resin was produced in the same manner as in Example 1, except that 1 g of 1,3-bis (4-glycidyloxyphenyl) adamantane was changed to 0.9 g of bisphenol A glycidyl ether. About the obtained cured resin, the same measurement as Example 1 was performed. The results are shown in Table 1.

Comparative Example 2
A cured resin was produced in the same manner as in Example 2, except that 1 g of 1,3-bis (4-glycidyloxyphenyl) adamantane was changed to 0.9 g of bisphenol A glycidyl ether. About the obtained cured resin, the same measurement as Example 1 was performed, and also optical loss evaluation was performed. The results are shown in Table 1.

Comparative Example 3
A cured resin was produced in the same manner as in Example 3 except that 1 g of 1,3-bis (4-glycidyloxyphenyl) adamantane was changed to 0.9 g of bisphenol A glycidyl ether. The same measurement as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 4
1,2-bis (4-glycidyloxyphenyl) adamantane (1 g), phenol resin (0.45 g) and triphenylphosphine (0.01 g) were heated and mixed at 180 ° C. and cured for 5 hours. About the obtained cured resin, the same measurement as Example 1 was performed. The results are shown in Table 1.

  From Table 1, the cured resin by the epoxy resin composition of the present invention is superior in the glass transition temperature, long-term heat resistance, etc. as compared to the commonly used bisphenol A type epoxy resin, and has a small optical loss. It can be seen that it is advantageously used in the member. Moreover, since it is excellent in solubility compared with 2,2-bis (glycidyloxyphenyl) adamantane used in the examples of Patent Document 1, it is advantageous in processing and is excellent in transparency and the like. It turns out that it is advantageously used for an electronic member.

Claims (7)

1,3-bis (glycidyloxyphenyl) adamantanes represented by general formula (I) and at least one selected from hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride An epoxy resin composition containing an acid anhydride-based curing agent and a curing accelerator comprising a compound of the above, wherein an active group capable of reacting with an epoxy group in the curing agent is equivalent to 1 equivalent of an epoxy group in the epoxy resin. It is 0.5-1.5 equivalent, and the content rate of a hardening accelerator is 0.01-8.0 mass% with respect to an epoxy resin, The epoxy resin composition characterized by the above-mentioned.

Wherein R ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl-substituted alkyl group having 7 to 13 carbon atoms and a carbon number represents a group selected from the group consisting of 1-6 fluoroalkyl group, when R ¹ is a plurality, the plural R ¹ s are the same as each other, may be different .n is an integer of 0-4.)   The sealing compound for optical semiconductors which uses the epoxy resin composition of Claim 1.   The sealing agent for electronic circuits which uses the epoxy resin composition of Claim 1.   An optical waveguide using the epoxy resin composition according to claim 1.   An optical communication lens comprising the epoxy resin composition according to claim 1.   The sealing agent for organic EL elements formed using the epoxy resin composition of Claim 1.   An optical film comprising the epoxy resin composition according to claim 1.