TW201130877A - Epoxy resin composition, curable resin composition, and cured object obtained therefrom - Google Patents

Abstract

Disclosed is an epoxy resin composition comprising an epoxy resin obtained by oxidizing an olefin compound represented by formula (1) and an epoxy resin obtained by oxidizing an olefin compound represented by formula (2), wherein the ratio of the epoxy resin derived from the compound of formula (1) to the epoxy resin derived from the compound of formula (2) is 10/90 to 90/10 by weight.

Description

201130877 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an epoxy resin composition suitable for use in electrical and electronic materials, particularly for optical semiconductor applications. Further, the present invention relates to a curable resin composition containing the epoxy resin composition and a cured product thereof. Further, the present invention relates to an optical semiconductor device obtained by curing and sealing with the above hard composition.先前 [Prior Art] Epoxy resin is a cured product that is excellent in water, chemical resistance, heat resistance, electrical properties, etc., by curing with various curing agents, and is excellent in adhesion, adhesion, coating, and lamination. A wide range of fields such as plates, forming materials, casting materials, and resists. ^ Among them, in the field of optoelectronics, especially in recent years, the highly informative 1 has effectively utilized the optical signal technology to replace the previous signal transmission using electrical wiring. In the field of optical components such as light materials, blue LEDs, and optical semiconductors, development of resins excellent in transparency is expected. In particular, in the field of optical parts such as LED products, a cured product obtained by hardening an epoxy resin with a curing agent such as an acid anhydride is often used. The epoxy resin used as a sealing material for optical semiconductor elements such as such LED products has been widely used for its excellent balance of heat resistance, transparency, and mechanical properties. (IV) Glycidyl ether type represented by A-type epoxy resin Epoxy resin composition. However, the short-wavelength of the illuminating wavelength of the illuminating element used in the LED product is 201130877 (mainly the blue color below 480 nm is generated by ^fll). The result of the evolution of short-wavelength light is caused by ^ ^ 4 materials on the LED chip: color problem. If the above sealing material is colored, the illuminance of the product is lowered. Therefore, in terms of transparency, the alicyclic epoxy resin represented by 3,4·epoxycyclohexylcarboxylic acid-3,4,_hexyl methacrylate has an aromatic ring = glycerol "epoxy resin Since the composition is excellent, it is actively studied as (10) sealing material (patent document 丨, ]). ... ★ Face of LED products in recent years, in order to be suitable for lighting or τν 4 light source, etc., and further to the ancient temple YL, + ancient + retrogressive 彺 冗 冗 冗 冗 , , LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED LED Therefore, it has been reported that even if a resin composition of the alicyclic:lact resin is used, coloring is caused on the LED wafer, which eventually leads to a decrease in illuminance of the LED article. Therefore, the alicyclic epoxy resin needs to be improved in durability against light or heat (Patent Document 3). Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A resin which is introduced into a skeleton of a cerium oxide pit (specifically, a skeleton having a Si_〇 bond), which is represented by an oxygen ester or a polyoxygen-modified cyclic oxime resin, is used as a density: Research (Patent Document 3) ^, usually It is known that the resin into which the stone-oxygen skeleton is introduced is more stable to heat and light than the epoxy resin 201130877. Therefore, in the case of application to a sealing material for an LED product, the resin introduced into the skeleton of the xenon chamber is more excellent in durability than the epoxy resin from the viewpoint of coloring on the LED wafer. However, the resin having the skeleton of the Shixia oxygen institute has a poor gas permeability resistance compared with the epoxy resin, so when using a polyphthalocyanine resin or a polyoxymethylene-modified epoxy resin as the LED sealing material, The coloring on the led wafer is not a problem, but there is still a problem in that the silver component (silver plating for improving the reflectance) on the metal lead frame of the constituent member in the (four) package body is discolored or blackened, and finally The performance as a result of LED products is reduced. So on the market, an epoxy resin composition is sought which has a structure in which the above-mentioned gas permeability is not problematic, and (4) a prior epoxy resin composition phase containing an alicyclic epoxy resin is obtained. Durable [ED products. /,.,,, Therefore, the present invention has been made in view of the above problems of the prior art, and aims to provide

Li can obtain an epoxy resin group and a product of a cured product excellent in light or heat. The inventors of the present invention have intensively studied the invention in view of the above-described actual circumstances. The present invention relates to: (1) A cyclic oxime resin composition characterized by: _ a diene compound represented by the following formula (1) and an olefin compound represented by the following formula (2) The constitutive mixture is oxidized, and the ratio of the epoxy resin derived from the compound of the formula (1) to the epoxy resin derived from the formula 201130877 is 丨〇/9〇~9〇/ ι by weight.

(wherein a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; 卩 represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent)

(2) (wherein a plurality of Rs each independently represent an alkyl group having an inverse number of 1 to 6 of a hydrogen rough); ^ (2) An epoxy resin composition characterized in that: fat and == indicate: The epoxy compound obtained by oxidizing the olefin compound, the epoxy resin obtained by oxidizing the epoxy compound, the ratio of the epoxy resin derived from the compound of the formula (1) to the epoxy resin, and the oxygen resin and the formula (7) The weight ratio is 10/90~9〇/10, 201130877

R mountain (wherein a plurality of R independently represent a hydrogen atom or a carbon number of 6; and p represents a cyclohexyl ring or a norbornane ring which may have a methyl group as a substituent)

(wherein a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms); (3) an epoxy resin composition according to item (1) or (2) above, Wherein the substituent R of the formula (1) and the substituent R of the formula (2) are a hydrogen atom and the linking group P is selected from the group consisting of a methylcyclohexane ring, a cyclohexane ring, a methylnorzane ring and One or more of the decane rings; (4) The epoxy resin group of the item (4) to (3) above, wherein the oxidation is carried out by using hydrogen peroxide; (5) The epoxy resin is a curable resin composition characterized by comprising: the above-mentioned items (1) to (4), the composition of the curing agent and/or the hardening accelerator; (6) The curable resin composition of the above item (5), which is an acid anhydride and/or a poly-acid retardant; C 7) k U ; the hardened resin composition of the article is hardened; (8) - an optical semiconductor device It is obtained by sealing with the curable resin composition of the above item (5) or (4). (2) The curable resin composition of the invention is highly resistant to light and heat. Therefore, it is extremely useful as an optical material, particularly as a light semiconductive substrate or a sealing material. [Embodiment] The curable resin composition of the present invention is disclosed. The epoxy resin composition of the two types of hair is at least an epoxy resin obtained by oxidizing a dilute compound of the following formulas (1) and (2) as an essential component.

A plurality of R having a carbon number of 1 ^ 6 independently represent a hydrogen atom, or a ring or a decane ring, and a cyclohexane having no fluorenyl group as a substituent, 201130877, further, a hydrogen atom of the formula (1) It is made up of a residue of a cesium atom. P in the following formula (2) means that the two structures are removed from cyclohexane or norbornane (generally, the radicals are removed from different carbon atoms). The residues may also have a f group as a substituent.

(wherein a plurality of R atoms independently of the alkyl group having 1 to 6 carbon atoms or, if by I: a dimer, can be produced by a known method, and the compound (or a derivative thereof) ) and cycloheximide methanol street bio-reaction as cyclohexane methanol derivative, no special cyclohexene f alcohol, 2·methyl_3_cyclohexene + methanol, enumeration: 3-methanol, 3-ethyl- 3. cyclohexanol + sterol, 3-methyl-3-3 cyclohexene = hexene-bu 3 - cyclohexyl-3-cyclohexanol, etc., preferably 3-cyclohexanol A = can be used alone, Two or more types may be used in combination. The 4 is a dicarboxylic acid (or a derivative thereof), and examples thereof include a dicarboxylic acid, a cyclohexane-12-dicarboxylic anhydride, and a cyclohexane]2:hexane. , 2· cyclohexane-i,2-dicarboxylic acid diethyl acetonate, cyclohexane < dimethyl vinegar, hexane dicarboxylic acid dicyclohexyl vinegar, cyclohexane: methyl /: ..., ring (cyclohexane-! ^^ 10 201130877 Cyclohexane-l, 2-dicarboxylic dibromide, cyclohexane-1,3-didecanoic acid, cyclohexane-1,3-dicarboxylic acid dinonyl ester, cyclohexane-1,3-di Diethyl decanoate, dipropyl cyclohexane-1,3-dicarboxylate, cyclohexane-1,3-didecanoic acid dicyclohexyl ester, cyclohexane- 1,3-dimethylhydrazine, cyclohexane-1,3-dibromo bromide, cyclohexane-1,4-didecanoic acid, dimethyl cyclohexane-1,2-dicarboxylate, cyclohexyl Dialkyl-1,4-didecanoate, dicyclodecyl-cyclohexane-1,4-dicarboxylate, dipropyl cyclohexane-1,4-dicarboxylate, cyclohexane-1,4- Dicyclohexyl dicarboxylate, cyclohexane-l,4-dimethylhydrazine, cyclohexanyl--1,4-diguana bromide, hydrogenated nadic acid, hydrogenated acid anhydride, Hydrogenated dimethyl dimethyl sulphate, hydrogenated dimethyl sulphate, hydrogenated dipropyl sulphate, hydrogenated dicyclohexyl ester, hydrogenated ceric acid diterpene, hydrogenated ceric acid diterpene, hydrogenation Sulfhydric acid, hydrogenated decyl benzoic acid anhydride, hydrogenated methyl dysenteric acid diterpene ester, hydrogenated decyl benzoic acid diethylene glycol, hydrogenated decyl phthalic acid dipropyl ester, hydrogenated methyl dysonic acid Cyclohexanone, hydrogenated fluorenyl ruthenium dibenzoate, hydrogenated fluorenyl ruthenium dichloride, bismuth decanoic acid, decane, 2,5-dioxanoic acid, norbornane-2 , dimethyl bis-dicarboxylate, diethyl decane-2,5-dicarboxylate, dipropyl decano-2,5-didecanoate, 2'5-one Dicyclohexyl ester, norbornane-2,5_dioxane, phlegm-one-5, formazan, jiangmengyan, 2,6•dicarboxylic acid, dimethyl benzoate Vinegar, reduced appearance, 2,6. dicarboxylic acid, diethyl acetonate, reduced alkane 2,6-dicarboxylic acid 2:: norbornane-2,6-didecanoic acid dicyclohexyl ester, norbornane·2 , 6_二曱醯气, "'甲甲醯〉臭, etc. 'but not limited to these. These can be used alone or in combination of two or more. As the cycloheximide reaction, the usual esterified alcohol derivative method is suitable for use with a dicarboxylic acid (or a derivative thereof). Specifically, the usual 11 201130877 applies.

The acetation reaction may, for example, be a Fischer esterification using an acid catalyst, a reaction of caries under an alkaline condition, an alcohol reaction, a condensation reaction using various condensing agents, etc. (ADVANCED ORGANIC CHEMISTRY

PartB: Reaction and Synthesis pl35, 145-147, 151, etc.). Further, as a specific example, it is also possible to utilize an esterification reaction of an alcohol with a carboxylic acid (Tetrahedron ν〇1·36 ρ·2409 (1980), Tetrahedron Letter P. 4475 (1980)), and further utilize a citric acid vinegar. It is produced by a vinegar exchange reaction (Japanese Patent Laid-Open No. 2006-052187). The diene compound of the above formula (1) synthesized in this manner is preferably a compound of any one of a nitrogen atom and a methyl group in the above formula (1), in terms of ease of availability. Preferably, R is a compound of a gas atom. Further, P is preferably selected from the group consisting of a methylcyclohexane ring, a cyclohexane ring, a fluorenyl-reduced alkane ring, and a reduced ring, and more preferably does not have a degree of availability. Substitute, especially for the ring of the ring. The diene compound of the above formula (2) can be produced by a known method, and examples thereof include dimerization of a cyclohexenal derivative (TiShchenk0 reaction, patent document: JP-A-2-2) 3_ι7〇〇59, JP-A-2004.262871, etc., or a cyclohexene carboxylic acid derivative obtained by reacting a cyclohexene carboxylic acid derivative with a cyclohexene sterol derivative (Reference: Tetrahednon V〇1, 36 p 24〇9 (丨98〇),

A compound such as the method described in Tetrahedron Letter p. 4475 (1980), ^ # F, 2006.052! Examples of the cyclohexenal derivative include 3-cyclohexenefurfural and 2-mercapto 3 cyclohexene methyl K-methyl-3.cyclohexene, but are not limited thereto. 12 201130877 These may be used alone or in combination of two or more. Specific examples of the cyclohexene carboxylic acid derivative include cyclohexenecarboxylic acid, methyl cyclohexenecarboxylate, and cyclohexylcarbazide.旨, propyl cyclohexene methacrylate, butyl cyclohexene decanoate, cyclohexyl hexyl hexyl ester, cyclohexene carboxylic acid (cyclohexenyl methyl) thio, cyclohexene carboxylic acid octyl ester, cyclohexene Methane, cyclohexene, guanidinium bromide, decyl cyclohexenecarboxylic acid, decyl ring = olefinic acid methyl vinegar, decyl cyclohexene decanoic acid ethyl vinegar, methylcyclohexene oxime, propionate methyl %hexenecarboxylic acid (methylcyclohexenylmethyl) ester, methylcyclohexene rolling, etc., but is not limited thereto. These may be used singly or in combination of two. The methanol derivative may, for example, be the above-mentioned compound. The epoxy resin composition of the present invention is obtained by oxidizing a mixture of the above compounds (1) and (2). The method of oxidizing the compound of the formula (1) and the formula is obtained by separately oxidizing the obtained epoxy resin. As a method of oxidizing, it is a method of oxidizing by using a peracid such as peracetic acid. Hydrogen peroxide water, the method of using the ruler to enter the sputum, the method of using air (oxygen), emulsification, etc. 'but is not limited to these. As a method of using the peracid gas 44 ^ ,, specifically The method described in 耜本本表 2007-5 10772, 耜Q χ, etc. The use of hydrogen peroxide water by 曰本特特2006-52187 is specifically applicable to 曰本特::匕之Various methods can be applied to the method, Q gamma No. 5, No. 5, No. 3, No. 5, No. 3, No. 5, 213, 919, Japanese Patent Laid-Open No. Hei No. 1-349579, and No. Gazette No. 33471, Sakamoto

IL 13 201130877 曰本特公平3-57-1102, and the like. In the present invention, hydrogen peroxide. In view of the low viscosity of the product, it is more preferred to use the following method for the epoxidation using hydrogen peroxide. First, in the state of an organic solvent or an aqueous solution of hydrogen peroxide, the above formula is used. 1) the dilute compound and the diene compound of the formula (7) alone or in a mixture thereof (hereinafter referred to as a dilute compound only), a polyacid and a quaternary ammonium salt Would prefer that a buffer can also be used for the reaction. The polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, and is preferably a polyacid containing tungsten or molybdenum, more preferably a polyacid containing tungsten, and particularly preferably a tungstate. Specific examples of the polyacid include a tungsten acid selected from the group consisting of tungstic acid, 12-tungstophosphoric acid, 12-tungstoboronic acid, 18-tungstophosphoric acid, and 12-tungstic acid, or a salt thereof, which is selected from the group consisting of acid turning Or a molybdenum acid or the like in phosphomolybdic acid or the like. Examples of the counter cation (c〇unter cati〇n) of a salt such as hydrazine include a money ion, a soil-based metal ion, a metal ion, and the like. Specific examples thereof include alkaline earth metal ions such as calcium ions and magnesium ions, and alkali metal ions such as potassium ions and absolute ions, but are not limited thereto. The best counter cations are sodium ions, unloading ions, doping ions, and ions. The amount of use of the polyacid is 〇.5~2〇 with respect to the diene compound 1 mol, in terms of 201130877 metal element (when the tungstic acid is the molar number of the tungsten atom, the moir number of the molybdenum atom). It is preferably 1 to 20 millimolar, more preferably 25 to 15 millimolar. As the quaternary ammonium salt, it is preferred to use a total carbon number of a. ^ 1 U or more, and to a 25-degree guanidine, more preferably 25 to 55 quaternary ammonium target, all of which are aliphatic chains. - "Specifically, for the alkyl group, tridecyl sulfhydryl ammonium salt, dihydroproline - lauryl monomethyl peroxide, dioctylmethyl naphtha, trialkyl methyl group (calcinyl group) a mixed type of a compound of an octyl group and a compound in which an alkyl group is a mercapto group) ^ ^ 钕盥, di-hexadecyl bauxite, dimethyl stearyl ammonium salt, tetraamyl ammonium salt, hexadecyl three Base money salt, sulfhydryl tributyl salt, twenty-six yard dimethyl ammonium salt:: 16 yards of methyl money salt, two hardened tallow base dimethyl record salt #, but not limited to In addition, the anion species of the salts are not particularly specific, and specific examples thereof include a tooth ion, a succinic acid ion, a sulfate ion, a sulfate ion acetate ion, and a carbonate ion, but they are not Limit to these, especially the acetate ion. If the right stone and the number exceeds 100 Å, the hydrophobicity becomes too strong, and the quaternary ammonium salt deteriorates in the cold solution of several layers. When the number is less than 10, the hydrophilicity becomes strong, and similarly, the quaternary ammonium salt deteriorates in compatibility with the organic layer, so that it is not preferable. The use of the four's and the salt is 5 The price of the acid is several times 0.0] 4. The amount of the field is more preferably 〜. 5~6 times the equivalent, more preferably 4~4 5 times the equivalent. Η汝 The right is tungstic acid, and the price is H2W04. Therefore, relative to 15 201130877: Γ〇 2 ears, the grade of the slow acid salt is preferably 〇.02 ~ "mole or 2.2 mole range. In addition, if it is Zhenxiu acid, it is better to have A _... 3 valence', so the same as two: 4 ears or 3.3~3 〇 Mo, if it is miscellaneous, Bay! is 4 valence, so it is better 〇 .〇4~3 2 Moor or 44~4〇 Mo Er. When the amount of the acid salt in the fourth stage is lower than the amount of the polyacid, it is difficult to carry out the epoxidation reaction (when the same, the time is also accelerated) and the by-product is easily formed. In the case of 1 G times equivalent, not only the subsequent treatment is troublesome, but also the effect of suppressing the reaction is unsatisfactory. As the buffer, any of the known buffers can be used, and in the present reaction, it is preferred to use an aqueous solution of the can acid. # ρΗ, preferably adjusted to between ρΗ4 and 10' is more preferably ρΗ5~9. When the ρ Η is less than 4, the hydrolysis reaction and polymerization reaction of the epoxy group are easily carried out. Further, in the case of the It shape exceeding Η), the reaction becomes extremely slow and the reaction time is too long. Particularly, in the case where the polyacid as a catalyst is dissolved in the present invention, p Η is preferably adjusted to be between 5 and 9. The method of using the buffer is, for example, a phosphate phosphate aqueous solution as a preferred buffer. The following method is used: 0.1 to 1 G mol% equivalent of acid (or (10) sodium dihydrogenate is used with respect to nitrogen peroxide. The dish salt) is a method of pH adjustment using a basic compound 16 (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, carbon gas, carbonic acid, etc.). Here, in terms of pH, when hydrogen peroxide is added, it is preferably added so as to have the above pH. In addition, it can also be adjusted by using sodium acid sodium hydride or acid gas sodium. Preferably, the concentration of the phosphate is 〇丨~6〇% by weight, 16 201130877 is preferably 1~'. In addition, the buffer may be used without adding p-sodium phosphate or sodium dihydrogen phosphate directly. Sodium phosphate, tri-salt (or its hydrate). It is preferred because it is directly added. At this time, the amount of ferrite used is preferably two to three moles/. : s. At this time, if it exceeds 5 mol% equivalent to hydrogen peroxide, it is necessary to adjust the pH. When it is not reached, it is easy to carry out m # and ear. /〇 equivalents, such as slow reaction, etc., the hydrolysis of the ruthenium compound formed by the reaction, or the reaction is epoxidized using chlorine peroxide. The hydrogen peroxide is used, and the operation is as simple as possible, and the reaction is carried out by an intercalation, preferably an aqueous solution having a peroxygen concentration of Η) to 40% by weight. When the concentration exceeds 4 〇 weight, it is difficult to operate except that the operation becomes difficult. The decomposition reaction of the fat is not good. Epoxy tree produced by hydrazine This reaction uses an organic solvent. As a result, it is preferable that the diuretic compound h == = ~1 〇' as the reaction substrate is preferably from 0.3 to 5'. When the weight is over 10, the progress of the reaction is extremely slow, and as a specific example of the usable organic solvent, it can be listed as a good one. Alkanes such as heptane, toluene, -methane oxime~, alkane, cyclohexane, ... Benben 4-party aromatic hydrocarbon compound, sterol ethylene glycol, isopropanol, butanol, hexanol, cyclohexanol Alcohol can also be used: methyl ethyl hydrazine, methyl isophthalene _ (deduction, etc., 4 ether, ketone, cyclohexanthine, dioxane, etc., 7 17 201130877 acid Ethyl acetate, acetonitrile, decyl phthalate, etc., acetonitrile, especially solvent A pβ Θ nitrile compound

- η, alkane such as calcined, cyclohexene, and heptane, P-A stupid, etc., a group of smog compounds, as a specific reaction method, for example, when the reaction is carried out, 1 is used as a human Batch reactor, linolecene compound, hydrogen peroxide (acid; (catalyst), buffer, quaternary salt and organic solvent: stick drop. The speed of the drop is not specified. Because of the addition of peroxidation ;: There are many cases of heat entering. Therefore, it is also possible to add a method for hydrogenation. X knife Jun slowly adds peroxygen. At this time: use the following method: add buffer (or water and phosphorus, poly The pH of the acid is adjusted to the 〇〇, 化合物, compound, double: di-record salt and organic solvent, diene double s stirring, and then add hydrogen peroxide. Or you can also use the following methods: water, organic In the process of solvent and compound, adding polyacids, phosphoric acid (or phosphate) for positive adjustment, then adding four-level recording, w雔si, du-di h ° nitrogen. ... double-layered into Fu' and then adding peroxygen The reaction temperature is not particularly limited, preferably 〇~9 (TC, more preferably 〇~ 75 CX is preferably 15 C~6Gt. When the reaction temperature is too high, the hydrolysis reaction is easy to proceed. 'When the reaction temperature is low', the reaction rate becomes extremely slow. In addition, the reaction time depends on the reaction temperature and the amount of catalyst. Etc. However, in terms of industrial production, the long-term reaction consumes a large amount of energy, so that the preferred range is from i to 48 hours, preferably from 3 to 36 hours, more preferably from 4 to 24 hours. After the end, the excess quenching of hydrogen peroxide is carried out (叩(3)“丨%) 18 201130877 Geography” The cold treatment is preferably carried out using an inspective compound. In addition, it is also preferred to use a reducing agent together with an inspective compound. A preferred treatment method is as follows: after the pH neutralization is adjusted to 6 to 1 Torr by using a basic compound, 'the residual hydrogen peroxide is quenched by using a reducing agent. When the rush is not up to 6 = the situation is excessive. The heat generated by the reduction of hydrogen peroxide is likely to cause decomposition products. Examples of the reducing agent include sodium sulfite, sodium thiosulfate, solution, hydrazine, vitamin C, etc. The amount of the reducing agent used is relative to excess In part: the molar number of the oxidizing gas 'usually 0. 01 to 20 times the molar, more preferably 005 10 times the molar, more preferably 0.05 to 3 times the molar. These are preferably added as an aqueous solution, The concentration is 0.5 to 30% by weight. The test compound can be exemplified by sodium hydroxide, potassium hydroxide, dihydric oxyhydroxide, etc., metal hydroxide, sodium carbonate, carbon

:;, sulphate, sulphate gas and other sulphate, material exchange resin and other basic solids. G is used in terms of its amount έ 'If it is dissolved in water or organic solvent: Ben: aromatic smoke compounds such as xylene, methyl isobutyl steel, methyl ethyl ketone and other ketones 'cyclohexane, heptane Hydrocarbons such as octane, alcohols such as methanol and ethanol propanol, etc. 4# m „, the number of moles of hydrogen peroxide: often, megamolar, more preferably? 5 20 moles, More preferably. - You; Yezhang 1 Gui A 0.05~3 times Mo. The solution of these organic solvents can be added in six or above, or can be added in a single way. In the case of a solid base in water or an organic solvent, the amount of hydrogen peroxide remaining in the system is preferably used in comparison with the amount of hydrogen peroxide remaining in the system, and is preferably a weight ratio of 1 to 5 〇〇. More preferably, it is 1 〇 to 纲. When using a solid base which is insoluble in water or an organic solvent, it can also be treated after separation of the aqueous layer and the organic layer described below. After cooling (or before quenching), when the organic layer and the aqueous layer are not separated, or when no organic solvent is used, The organic solvent is operated to extract the reaction product from the aqueous layer. The organic solvent used at this time is 〇 5 to 10 times, preferably 0.5 to 5 times by weight, based on the weight of the raw material olefin compound. The organic layer separated after several times of the above operation is repeatedly subjected to water washing and purification as needed. The obtained organic layer is activated by a borrowing material (especially a tannin, alumina, etc.), a composite metal salt (a clay thereof) Minerals (especially montmorillonite, which is the standard epoxy compound for water washing, transition, etc.. Oxidation resin or metal oxidation, activated carbon (especially especially in the chemical is alkaline alkaline metal salt) After removing the impurities, such as a layered clay mineral, the solvent is distilled off to obtain the y / β I ring-containing resin composition of the present invention obtained in this manner by the following formula (3) and the following formula (4) The indication is that the early Helmets of the Eighths 7 knives are the main component', but the compound of the formula r, τ卞仗 (1) or (2) may be present in a ratio of less than 15% by weight of the total amount. Unreacted matter, partial ring Compound, water Ms - Immature and ν λ surgery hydrolyzate of such impurities and degradation products thereof:

(3) 20 201130877 (where R&P represents the same meaning as equation (1))

(wherein 'the ruler has the same meaning as the formula (2)). When the mixtures are homogeneous, they are mostly liquid. Further, the ratio of the compound of the above formula (3) (and the above-mentioned impurities derived from the compound of the formula (与)) to the compound of the above formula (4) (and the above-mentioned impurities derived from the compound of the formula (7)) is 10/9〇~90/10. More preferably 25//75~8〇/2〇, especially 25/75~60/40 ‘best 25/75~50/50. The epoxy resin composition of the present invention may be a compound of the formula (1) and a compound of the formula (7): a compound obtained by mixing and epoxidizing, or a compound of the formula (3) obtained by epoxidizing the formula (1) (2) A compound of the formula (4) obtained by epoxidation is mixed and formed. In the case of the former, in order to set the above weight ratio, the compound of the formula (1) and the compound of the formula (7) are usually 1〇/90~9〇/1(), preferably 25/75~8()/2G. , especially for a 〆 〜 ~ 6 〇 / : 〇, the best range of 25 / 75 ~ 50 / 〇 混合 mixed and oxidized. The cured product obtained by mixing the epoxy compound contained in the epoxy resin composition in the above range exhibits an excellent effect on durability against light and heat. In particular, by mixing the compound of the formula (3) with the compound of the formula (4) in the range of 25/75 to 50/50, the decrease in transmittance due to coloring can be remarkably suppressed, and it is used for an optical semiconductor. In the case of the sealant 21, the high illuminance retention ratio can be achieved in the case of 201130877. In addition, in the present invention, the substituent R in the compound of the formula (7) and the compound (4) is a chlorine atom or A methyl group is particularly preferably a hydrogen atom. Further, P is preferably one or more selected from the group consisting of a methylcyclohexene ring, a cyclohexane ring, a methylnorbornane ring, and a norbornane ring, and is more preferably a non-substituent. More preferably, it is a ring-shaped ring. The curable resin composition of the present invention contains the epoxy resin composition, the curing agent and/or the hardening accelerator of the present invention. In the curable resin composition of the present invention, the epoxy resin composition of the present invention or the other epoxy resin (IV) may be used alone. In the case of m彡, the ratio of the oxygen-containing resin composition to the entire epoxy resin component is preferably 70% by weight or more, particularly preferably 80% by weight or more. Other epoxy resins which can be used in the curable resin composition of the present invention include novolak type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, and triphenylmethane type epoxy. Resin, phenol aralkyl type epoxy resin, and the like. Specific examples thereof include bisphenol A, bisphenol S, thiophenol, bisphenol, stilbene, 4,4'-biphenol, 2,2,-biphenol, 3,3', 5,5 ,-tetradecylbiphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2 -tetrakis(4-hydroxyphenyl)ethane, phenols (benzene, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde , benzaldehyde, p-hydroxybenzaldehyde ' o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4·-bis (gas thiol)-1,1 , _biphenyl, 4,4,-bis (methoxy 22 201130877: condensed benzene, M bis (chloro(7) benzene, 1, bis (decyloxymethyl) benzene) polycondensate and these changes Physique, four double bismuth... bismuth, glycidyl condensate derived from alcohol, alicyclic epoxy resin, glycidylamine epoxy resin, glycidol vinegar epoxy resin, sesquiterpene oxide A fire-retardant epoxy resin (in a chain, a ring, a ladder, or a mixture of at least two or more thereof) a solid or liquid epoxy resin such as an epoxy resin having a glycidyl group or an epoxy ring-pit structure in an oxy-oxygen structure, etc., etc. In particular, the curable resin composition of the present invention is used for When it is used for optical use, it is preferable to use an epoxy resin with a alicyclic epoxy resin and a sesquivalent-oxygen 1 structure. Especially in the case of an alicyclic epoxy resin, it is preferable to have a magnetic ring. The compound having a structural structure is preferably an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure. The human being as an epoxy resin such as 5 hai is exemplified by a group which can be produced by the following method. And the winners: ^ esterification of hexene carboxylic acid with alcohols or esterification of % hexene methanol with carboxylic acids (Tetrahedron v〇l 36 p.2409 ( ΙοχπΛ rp ), Tetrahedron Letter Ρ · 4475 ( 1980)

The method of loading), push; ^ 1 〇C and the transesterification reaction of % hexene carboxylate (Japanese No. 87, No. 87 (4), the name of the temple is opened as an alcohol, if it is an alcoholic hydroxyl group Listed ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1 S Λ·, _ _ , · 戍-fermentation, hexanediol, cyclohexane Sterols, κ-mercaptool, 2·ethyl-2 butyl-1,3-propanediol, neopentyl glycol, glycols such as methanol and dilute diol, glycerol, three rebels 23 201130877 diols such as phenylamine, trihydroxydecylpropane, trimethylolbutane, 2-hydroxyindole _14-butanediol, tetraols such as pentaerythritol and di-trimethylolpropane Wait. Further, examples of the slow acid include oxalic acid, cis-butyl diacid, anti-butene di-i, o-dicarboxylic acid 'isophthalic acid', adipic acid, and cyclohexane dicarboxylic acid, but are not limited thereto. this. Further, as another example of the compound having an epoxycyclohexane structure in the skeleton, an acid-reducing compound obtained by reacting a cyclohexenal derivative with an acetal of an alcohol can be mentioned. The reaction method can be produced by applying a usual reduction reaction, for example, a method in which a reaction solvent is used for azeotropic dehydration while using a solvent such as toluene or xylene (U.S. Patent No. 2945008); A method in which a phenol is slowly added to a polyhydric alcohol in a concentrated hydrochloric acid, and a reaction is carried out by a method of slowly adding an aldehyde (JP-A-48-96590 唬); a method of using water in a reaction medium (US Pat. No. 3,924, 〇); A method of using an organic solvent (Japanese Patent Laid-Open Publication No. Hei 7-215979); a method using a solid acid catalyst (Japanese Unexamined Patent Publication No. Hei No. Hei No. 7-23〇992). In terms of stability of the structure, a cyclic acetal structure is preferred. Specific examples of such epoxy resins include ERL-4299 (both of which are trade names, all manufactured by Dgw Chemieai) and E (four), all of which are Daicel, but are not limited to P76-85). GT4 (H, EHPE 3150, ehpe 3150CE (all trade name chemical = manufacturing) and dicyclopentadienyl diepoxide equal to these (Reference: General epoxy resin basics s Xuan et al. can be used alone In addition, two or more types may be used in combination. In addition, at least a semi-anthracene-based epoxy resin (such as a chain-like or ring-shaped ladder or a mixture of two or more kinds of structures having a condensation structure of 24) 201130877 Water-glycol-based, and/or cyclo-epoxy resin 敕 敕 敕 敕 敕 敕 环氧树脂 环氧树脂 环氧树脂 t t t t t 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体The curable resin has a reactive hardener. Benzoic anhydride, trimellitic anhydride, pyrome UUic anhydride, maleic acid needle, tetrahydrophthalic acid as the hardening Specific examples of the hardeners which can be used, for example, a pharmaceutically acceptable compound, a guanamine compound, and a phenolic compound are diethyltriamine, tris-ethyltetraketonediamine, dicyanodiamine, and a synthetic polymer. Nitrile-containing resin, etc. a compound, an acid anhydride-based compound, a carboxylic acid-based compound, etc., which may be mentioned as follows: diaminodiphenylmethane, amine, monoaminodiphenyl sulfonate, isophorol linolenic acid dimer and ethylenediamine The compound (amine, guanamine compound); o-quinone anhydride, mercapto tetrahydrophthalic anhydride, mercaptoic acid anhydride, nadic anhydride, hexahydrophthalic anhydride, A Hexahydrophthalic anhydride, butane tetraphthalic anhydride, bicyclo[2,2,1]heptane 2,3-diphthalic anhydride, indenylbicyclo[2,2,1]heptane·2,3 An acid anhydride such as dicarboxylic anhydride, cyclohexane-tridecanoic acid-1,2-anhydride; a carboxylic acid resin obtained by an addition reaction of various alcohols, methanol (carbinol) and polyoxo oxygen with the above acid anhydride; Bisphenol A, bisphenol F, bisphenol S, bismuth bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl [1, plant-biphenyl]-4,4·-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)decane, 1,1,2, 2-tetrakis(4-hydroxyphenyl)ethane, phenanthrene (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthalene , dihydroxybenzene, dihydroxynaphthalene, etc.) with brewing, acetaldehyde, benzofural, p. 25 201130877 hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxy acetophenone, dicyclopentadiene ,furfural, 4,4,_bis(chloromethyl)^,·biphenyl, 4,4,·bis(methoxymethyl)-1,1,·biphenyl, M,.bis (gas methyl) a polycondensate of benzene, M•bis(methoxymethyl)benzene, and the like, and a polyphenol such as a bisphenol, a condensate of cumene and a phenol; The imidazole, the boron trifluoride (tnfluoroborane)-amine complex, the compound of the anthracene derivative, and the like are not limited thereto. These may be used alone or in combination of two or more. In the present invention, a compound having an acid anhydride structure and/or a compound having a carboxylic acid structure represented by the above acid anhydride or carboxylic acid resin is particularly preferred. The acid anhydride forms a hardened product of high hardness, and a compound having a carboxylic acid structure is preferred because of its low volatility. More preferably, it is a compound having an acid anhydride structure and/or a compound having at least one divalent or higher carboxylic acid structure, and particularly preferably a mixture of the two. As the compound having an acid anhydride structure, it is particularly preferably: mercaptotetrahydro o-benzoic anhydride, mercapto-resistic acid anhydride, ceric anhydride hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and butyl Alkane tetraphthalic anhydride, bicyclic fluorene and hydrazine] heptane 2,3-dicarboxylic anhydride, fluorenylbicyclo[2,2,1]heptane-2,3·dicarboxylic anhydride, cyclohexane• 1,2, 4-dicarboxylic acid _ 1,2-acetic anhydride, etc., particularly preferably methylhexahydrophthalic anhydride, cyclohexane-1,2,4·tridecanoic acid-l,2-anhydride. The compound having a carboxylic acid structure (hereinafter referred to as a polycarboxylic acid) is preferably a 2 to 4 functional polycarboxylic acid, more preferably obtained by subjecting a 2 to 4 functional polyol to an acid anhydride addition reaction. Polycarboxylic acid. The 2~4-functional polyol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol 'oxime, 3-propylene glycol, 26 201130877, 2-butanol, and M-butylene. Alcohol, ... pentanediol, & hexanediol, cyclohexane: methanol, diethyl pentanediol, 2. ethyl·2·τ-based decanediol, neodymidine-alcohol, tricyclic terpine ", dicyclopentadienyl dimethanol, glycerol diols, glycerol, trimethyl bromide, trimethyl ketone, tris-methyl ketone, 2-passyl Triols such as m-alcohols, neopentyl alcohol: tetra-alcohols such as methyl propyl bromide. The preferred alcohols are cyclohexane dimethanol, 2,4-diethylpentanediol, 2-ethylpolybutyl·U·propanol: alcohol, neopentyl: alcohol, tricyclohexanethanol, dicyclopentan A dilute dimethyst, a branched chain or a cyclic aliphatic alcohol such as a dilute diol. As an acid anhydride for producing a polyacid, it is preferably methyltetrazole: needle, methyl dexamethasone, diarrhea, hexaphthalic acid needle, methyl dicarboxylic acid m tetracarboxylic anhydride, Double ring coffee (four) # diformate liver, methyl bicyclo [...] Gengyuan H anhydride, cyclohexane-1,2,4-dicarboxylic acid _1,2- anhydride. The conditions for the addition reaction are not particularly specified. For example, a method in which the polyol is heated and reacted at 4 to 15 under conditions of no catalyst or solvent is used, and the reaction is directly taken out after completion of the reaction. Anhydrides and polycysteines can be used in single-cat etched fields, m ^ early alone, or can be used in combination. In the case of Z, the ratio of 'acid needle to multiple' is 9〇; 2〇/80, especially preferably 8〇//2〇~3. /7〇. By setting the weight to 90, it is excellent in heat resistance and workability. If the amount of (4) exceeds 9% by weight, the volatility increases, which is not preferable. In the curable resin composition of the present invention, the curing agent is used in an amount of 1 equivalent to the epoxy group epoxy group, and is 0 '5 27 201130877 to 1.5 equivalents based on the functional group equivalent. More preferably, it is 7 to 1.1 equivalents, and particularly preferably 〇·8 to ι 〇. Further, in the case of use for optical use, it is preferably 1.0 equivalent or less, more preferably 〇, 7 to 〇.95 equivalent, more preferably 〇·7 to 0.85 equivalent. When the amount of the hardener used is less than 0.5 equivalents with respect to the epoxy group, or when it exceeds 1.5 equivalents, the hardening becomes incomplete and the good hardened physical properties cannot be obtained. In the curable resin composition of the present invention, a hardening accelerator may be used in combination with a curing agent, or a curing accelerator may be used alone without using a curing agent. Specific examples of the curing accelerator which can be used include: 2-methylimidazole '2-phenylimidazole, 2-undecylimidazole, 2-heptadecyl oxazole, and 2-benyl-4-methyl Basic taste. Sit, 1-benzyl-2-phenyl β m. Sit, 1-benzyl-2-indenyl hydrazine, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-fluoroethyl-2- Undecylimidazole, 2,4-diamino-6(2,-methylimidazolium(1,))ethyl-symmetric trimorphine, 2,4-diamino-6(2'-undecane Imidazolium (1,)) ethyl-symmetric triammine =, 2,4-diamino-6 (2'-ethyl-4-methylimidazolium (1,)) ethyl-symmetric triammine: 2,4 -Diamine- 6 (2'-nonylimidazolium) ethyl-symmetric trimorphine-isocyanuric acid adduct, 2-mercaptoimidazole isocyanuric acid 2:3 adduct , 2-phenylimidazole. Sitting on isomeric cyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl•4-hydroxyindolyl-5-mercaptoimidazole, 1-cyanoethyl_2 Various imidazoles such as phenyl·3,5·dicyanoethoxymethylimidazole, and the imidazoles and phthalic acid bismuth, m-dicarboxylic acid, terephthalic acid, and trimellitic acid , salts of polycarboxylic acids such as pyromellitic acid, naphthalic acid, maleic acid, oxalic acid, and guanamines such as dicyanodiamine, 1,8-diazabicyclo (5.4.0) a salt of a nonaza compound such as undecene-7 and a salt of a phenyl sulfonate, a benzoic varnish, etc., and a polycarboxylic acid or phosphinic acid (Ph〇sphinic acid) Salts of the class, tetrabutylammonium, hexadecanyl tridecyl bromide, trioctyl fluorenyl evolution, etc., triphenylphosphine, tris(tolylmethyl)phosphine, tetraphenyl Bromine scale, phosphine or ruthenium compound such as tetraphenylphosphonium tetraphenylborate, 2,4,6-triaminomethylbenzene, metal compound, tin octylate and other metal compounds Waiting 'and making these hardening accelerators into micro A microcapsule type hardening accelerator for capsules, and the like. Which one of the curing accelerators is used is appropriately selected depending on the properties required for the obtained transparent resin composition such as transparency, curing rate, and working conditions. The hardening accelerator is usually used in an amount of from 0.001 to 15 parts by weight based on 100 parts by weight of the epoxy resin component. The curable resin composition of the present invention may further contain a scaly compound as a flame retardancy imparting component. As the phosphorus-containing compound, it may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include tridecyl phosphate, triethyl phosphate, tricresyl Phosphate, trixylylenyl phosphate, and dish @夂toluene. creSyl diphenyl phosphate 'cresyl-2,6-dixylylenyl phosphate, 1,3-extended bis(diphenylene) phosphate ), 丨, 4_ phenyl bis(di(diphenylene) phosphate vinegar), 4,4,-biphenyl (di(dimethyl) phosphate) (4'4-biphenyl (dixylylenyl phosphate) Acid esters; 9,10-diox-9-oxa-10-phosphaphenanthrene-10-oxide (9,1 〇-Dihydro-9-oxa-1 〇-phosphaphenanthrene 10-oxide), 1〇 ( Phosphorus such as 2,5-dihydroxyphenyl)-10Η·9-oxa-10-phosphaphenanthrene-10-oxide

S 29 201130877 phosphanes; phosphorus-containing epoxy compounds, red phosphorus, etc. obtained by reacting an epoxy resin with active hydrogens of the above phosphanes; preferably phosphates, phosphines or phosphorus Epoxy compound, especially 1,3-phenylene bis(di(biphenylene) phosphate), 1,4-phenylene bis(di(biphenylene) phosphate), 4,4,- Biphenyl (bis(biphenylene) phosphate) or phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a compound-containing compound/epoxy resin = 0 _ 1 to (X (weight ratio). When the amount is less than 0.1, the flame retardancy is insufficient; if it exceeds 〇. 6, there is a cured product. Further, in the curable resin composition of the present invention, the binder resin may be blended as needed. Examples of the binder resin include a butyral resin and a shrinkage system. Resin, acrylic resin, epoxy-nylon resin, NBR (Nitdle Butadiene Rubber)-phenolic resin, epoxy-nbr resin, polyamine resin, polyimide resin, Although it is not limited to such a polysulfide resin, the amount of the binder resin is preferably such that it does not impair the flame retardancy and heat resistance of the cured product, and is relative to the epoxy resin component and the hardener. In general, 100 parts by weight, and usually 5 to 5 parts by weight, is preferably used, preferably 5 to 20 parts by weight. In the curable resin composition of the present invention, an inorganic filler may be added as needed. As the inorganic filler, crystal cerium oxide, Molten cerium oxide, aluminum oxide, bismuth, calcium silicate, calcium carbonate, tantalum carbide, tantalum nitride 'boron nitride, cerium oxide, forsterite, talc, large sun stone, titanium dioxide, talc, etc. The filler or the like may be used alone or in combination, and the filler may be used singly or in combination of two or more. The content of the inorganic filler is used in the hardening of the present invention. In the composition of the curable resin of the present invention, a decane coupling agent, stearic acid, palmitic acid, zinc stearate, and stearic acid may be added. a mold release agent such as calcium acid, various preparation agents such as pigments, and various thermosetting resins. When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor sealant, the above may be used. The inorganic filler material used has a particle size of a nanometer-level filler material to enhance mechanical strength without hindering transparency, etc. From the viewpoint of transparency, the standard of the nanometer level is preferably an average of use. grain It is preferable to use a filler having an average particle diameter of 200 nm or less for a filler of 500 nm or less. When the curable resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, it may be added as needed. A phosphor system having a function of emitting wavelength-converted yellow light to absorb white light, for example, by absorbing a portion of blue light emitted from a blue LED element. The phosphor is pre-dispersed in a curable resin. The sealed photo-semiconductor phosphor is not particularly limited, and a conventionally known phosphor can be used. For example, an aluminate of a rare earth element or a thi〇gaUic acid salt of protopanatocin can be exemplified. Salt, etc. More specifically, it can be exemplified: YAG (YUnum

Aluminium Garnet, Jishao Stone Folding Stone) Crab Light, Tag (Dingzhou _

Aluminum Garnet, yttrium aluminum garnet) phosphors such as phosphors, orthosilicate phosphors, thiogallate phosphors, sulfide phosphors, etc. are exemplified by YAl〇3 : Ce ' Y3A15012 : Ce Sr5 (P〇4) 3Cl : Eu > (SrEu)O . Using a particle size well known in the 5H field, Υ4Α12〇9 · Ce 'Y202S : Eu > ai2o3荨. The particle diameter of the phosphor is preferably from 1 to 2 5 ο 31 201130877 em, and particularly preferably from 2 to 50 #m. In the case of using these phosphors, the amount thereof is preferably from 1 to 80 parts by weight, more preferably from 5 to 60 parts by weight, per 100 parts by weight of the above resin component. When the curable resin composition of the present invention is used for an optical material, particularly in the case of an optical semiconductor encapsulant, it is possible to add a silica dioxide powder (also known as Aerosil) in order to prevent settling of various phosphors during hardening. Or Aerosol) is a representative thixotropy-imparting agent. As the above-mentioned disulfide powder, for example, Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300 > Aerosil 380 'Aerosil 0X50 > Aerosil TT600 '

Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, RY200, RX200 (manufactured by Aerosil Corporation of Japan) and the like. When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, 'for preventing coloring' may contain an amine compound as a photostabilizer or a phosphorus-based compound as an antioxidant material and Phenolic compounds. As the above amine compound, for example, 1,2,3,4-butane tetradecanoic acid can be cited.

Piperidinyl ester, bismuth di 1.2.3.4-butane tetradecanoic acid tetra2.3.4-butane tetradecanoic acid and 3,9-bis(2-hydroxy-1, b-dimethyl ethoxyspiro[5 · 5] mixed esterified product of undecane; amidodisuccinic acid) sebacate, bis(1-undecyloxypiperidinyl-4-yl) carbonate 2,2, 6,6-tetradecyl-4-oxime double (2,2,6,6-tetramethyl_4_0 bottom 0) ester, azelaic acid 32 201130877 double (1,2,2,6,6- Pentamethyl-4-piperidinyl vinegar, 4-phenylhydrazineoxy-2,2,6,6·tetramethylpiperidine, 1-[2-[3-(3,5-di· Tributyl-4-hydroxyphenyl)propanoxy]ethyl]-4-[3-(3,5-di-t-butyl-4-yl)-phenylphenylpropanoxy]-2 , 2,6,6-tetraf-piperidinyl, meth, 2,2,6,6-pentamethyl-4-piperidyl ester, {[3,5-bis(1,1-di) Methyl ethyl) 4-hydroxyphenyl] methyl butyl butyl malonate bis (1,2,2,6,6-pentamethyl-4-pyridyl) ester, azelaic acid bis (2, 2,6,6-tetramethyl-1-(octyloxy)-4-»endridinyl) vinegar, 1,1-dimethylethylhydroperoxide and Xinyuan reaction product; ,1^,,1^",1^,''-tetra-(4,6-bis(butyl-(^[-methyl-2,2,6,6- Nonylpiperidine _4_yl)amino)_trin-2-yl)-4,7-diazepine-1,10-diamine, dibutylamine-1,3,5_three tillage Ν,Ν,-bis(2,2,6,6-tetramethyl-4-pine. Stationary-oxime, 6-tetramethylenediamine and ;^-(2,2,6,6-tetramethyl -4_0辰咬基) Polyamine polycondensate 'poly{[6-(l,l,3,3-tetradecylbutyl)amino-1,3,5·3 1f - a group][(2 , 2,6,6-tetradecyl-4-0-bottom base)imido]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imide; )}, a polymer of dinonyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetradecyl _20_ (call -lauryloxycarbonyl)ethyl_7_oxa-3,20-diazabispiro[5·1.11·2]di-----21-one, cold-alanine, Ν·(2 , 2,6,6-tetradecyl-4-0 bottom bite)-dodecyl ester/tetradecyl ester, Ν_ethinyl_3-dodecyl_1_(2,2, 6,6-tetradecyl-4-piperidinyl)<»Byrrolidine-2,5-dione, 2,2,4,4-tetramethyloxa-3,20-diaza Spiro[5,1,11,2] twenty-one burnt-21-_, 2,2,4,4-tetramethyl-21-oxa-3,20-diazabicyclo-[5,1, 11,2] _ twenty-one burning 20-propionic acid 12-cavity ester / fourteen burning Ester, malonic acid, [(4-methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidyl), 2,2, Higher fatty acid ester of 6,6-tetradecyl-4-piperidinol, hydrazine, 3-phenylenediamine 33 201130877 (l,3,benzenediearb()xamide), N,N,j(2,2 , 6,6,^4n base) and other hindered amines such as octabenzophenone and other benzophenone-based compounds, 2_(2h benzo^^^^)^-(1,1,3,3-tetramethyl Butyl), phenol, 2-(2-carbyl-5-methylphenyl)benzo-indole 2-[2·carbyl·3·(3,4,5,6·tetrahydro-o-phenylene Brewed imine _ methyl + yl). 5 _ methyl stupyl] benzotriene. Sit, 2_(3_t-butyl·2_radio-5-methylphenyl)-5·gas benzotrisole, 2·(2_carbyl·3,5_di-p-pentylbenzene Benzo), benzotriene, 3·(3_(2Η·benzotriazole. sit 2·yl)_5_t-butyl-o-phenyl)propionic acid, A, a reaction product with polyethylene glycol, 2·( a benzotriazole compound such as 2? stupotriazole I group)·6·dodecyl-4-methyl phenol, μ·di·t-butylphenyl-3,5-a-third a benzoate such as a _4-hydroxybenzoate, a triterpene compound such as 2_(4,6-diphenyltriphthyl-2-yl)-5_[(hexyl)oxy]benzene, etc. It is a hindered amine compound. As the amine compound of the above-mentioned photostabilizing material, a commercially available product as shown below can be used. The commercially available amine-based compound is not particularly limited, and examples thereof include TinuWn 765 ^ Tinuvin 770df > Tinuvin 144 ^ Tinuvin 123 ^ Tinuvin 6221d, Tinuvin 152, Chimassorb 944, manufactured by dba Specialty Chemicals Co., Ltd. ' LA_52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, La_82, LA 87, etc. manufactured by Adeca. The phosphorus compound is not particularly limited, and examples thereof include 1,1'3-bis(2-mercapto-4-di(tridecyl)phosphite·5·t-butylphenyl). Butane (mtrisP-methylW-ditridecylphosphito-St-butylphenyl) butane), distearyl pentaerythritol diphosphite, bis (2 4_ 34 201130877 a _ second butyl styl) pentaerythritol Dish acid g, bis(2,6-di- rr butyl-4-methylphenyl)neopentitol diphosphite, phenyl bisphenol octaerythritol mono tartaric acid from θ, Monocyclohexyl neopentyl alcohol disubcaprate, tris(diethylphenyl) sulfite, tris(di-isopropylphenyl) phosphite, tris(di-n-butylphenyl) phosphite ) vinegar, tris(2,4-di-t-butylphenyl) phosphite, bis(2,6-di-t-butylphenyl) phosphite, sub-filled acid three (2,6_ Di-tert-butylphenyl)ester, 2,2··methylenebis(4,6-di-t-butylphenyl)(2,4-di-t-butylphenyl)phosphite , 2,2'-fluorenylene bis(4,6-di-tert-butylphenyl)(2-butylbutyl-4-mercaptophenyl) dialoate, 2,2 '·Alkenylene bis(4-indolyl-6-t-butylphenyl)(2-t-butyl-4-indolylphenyl)phosphite, 2,2'-ethylene bis ( 4-mercapto-6-t-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)·4 ,4,-t-butyl diphosphonate (tetrakis(2,4-di-tert-butylphenyl) _4,4'-biphenylenephosphonite), tetrakis(2,4-di-t-butylphenyl)- 4,3'-Exbiphenyl bisphosphonate g, tetrakis(2,4-di-t-butylphenyl)-3,3'-extended phenyldiphosphinic acid vinegar, four (2 ,6-di-t-butylphenyl)-4,4'-extended biphenyl diphosphinate, tetrakis(2,6-di-t-butylphenyl)-4,3'- Biphenyl diphosphinic acid vinegar, tetrakis(2,6-di-t-butylphenyl)-3,3'-extended biphenyl diphosphinate, bis (2,4-di-third Butyl phenyl)-4-phenyl-phenylphosphinate, bis(2,4-di-t-butylphenyl)-3-phenyl-phenylphosphinate, bis (2, 6-di-n-butylphenyl)-3-phenyl-phenylphosphinate, bis(2,6-di-t-butylphenyl)-4-phenyl-phenylphosphinic acid Purpose, double (2,6 - two - Tert-butylphenyl)_3-phenyl-phenylphosphinic acid g, tetrakis(2,4-di-t-butyl-5-fluorenyl)-4,4'-extension Diphosphonite, tributyl phosphate, phosphoric acid 35 201130877 Trimethyl ester, triplesyl phosphate, triphenyl phosphate, triphenyl phosphate, triethyl phosphate, cresyl diphenyl phosphate Diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyacetate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like. Commercially available products can also be used as the phosphorus compound. The commercially available phosphorus-based compound is not particularly limited, and examples thereof include Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-3 6, Adekastab HP-10, Adekastab 2112, Adekastab manufactured by Adeca. 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP. The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-nonylphenol and 3-(3,5-di-t-butyl-4-hydroxyphenyl)propane. N-octadecyl acid, tetrakis[methylene_3_(3,5-di-t-butyl-4-hydroxyphenyl)propionate]decane, 2,4-di-t-butyl _6_nonylphenol, hydrazine, 6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], three (3,5_two _ tert-butyl-4-hydroxybenzyl)-isocyanate, hydrazine, 3,5-trimethyl 2,4,6_ tris(3,5-di-t-butyl-4- Hydroxybenzyl)benzene, pentaerythritol-tetrakis[3_(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9_bis-{2-[3-( 3-tert-butyl-4-hydroxy-5-mercaptophenyl)-propenyloxy]-^-dimethylethylhydrazine-2,4,8,1〇_tetraoxaspiro[5, 5] undecane, triethylene glycol, bis[3_(3_t-butyl-5-nonyl-4-hydroxyphenyl)propionate], 2,2,-butylene bis (4,6 _Di-tert-butylphenol), 4,4·-butylidene bis(3-methyl·6_t-butylphenol), 2,2,·methylene 36 201130877 Double (4-mercapto- 6-tert-butylphenol), 2,2'-indenylene bis (4-B -6-tert-butylphenol), 2-t-butyl-6-(3-tert-butyl-2-hydroxy-5-nonylbenzyl)-4·decyl phenol acrylate, hydroxyl _3,5_di-triptylamyl)ethyl]-4,6-di-third amyl phenyl acrylate, 4,4,-thiobis(3-indolyl-6 -T-butyl phenol), 4,4,-butylidene bis (3-methyl-6-t-butyl phenol), 2-tert-butyl-4-methylphenol, 2,4- Di-tert-butylphenol, 2,4-di-p-pentylphenol, 4,4,-thiobis(3-mercapto-6-tert-butylphenol), 4.4-butylene bis (3) - mercapto-6-t-butylbenzene), bis[3,3-bis(4'-carbyl-3-t-butylphenyl)-butyric acid]-diol g, 2, 4 -di-t-butylbenzene, 2.4-di-p-pentylphenol, 2-[1-(2-hydroxy-3,5-di-p-pentylphenyl)ethyl]-4,6 - di-p-pentyl phenyl acrylate, bis[3,3.bis(4,-hydroxy-3,_t-butylphenyl)-butyric acid]-glycol ester, and the like. Commercially available products can also be used as the above-mentioned compound. The commercially available lanthanide compound is not particularly limited, and examples thereof include those manufactured by Ciba Specialty Chemicals Co., Ltd.

Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135,

Irganox 245'Irganox 259'Irganox 295'Irganox 3114'Irganox 1098, Irganox 1520L, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60 'Adekastab AO-70 by Adeca Adekastab AO-80, Adekastab AO-90, Adekastab AO-330, Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumi 1 izer GS (F), Sumilizer GP, etc. manufactured by Sumitomo Chemical Industries . In addition to this, a commercially available additive may be used as the anti-coloring agent for the resin. For example, Tinuvin 328, 37 201130877 manufactured by Ciba Specialty Chemicals Co., Ltd.

Tinuvin 234^ Tinuvin 326^ Tinuvin 120> Tinuvin 477^ Tinuvin 479, Chimassorb 2020FDL, Chimassorb 119Fl, etc. It is preferable that at least one of the above-mentioned phosphorus-based compound, amine compound, and 16-based compound is contained, and the amount thereof is not particularly limited, and it is 〇·〇〇5 to 5 相对 with respect to the curable resin composition. weight. , the scope. In the case where the curable resin composition of the present invention is used for an optical material, particularly in the case of a photo-semiconductor encapsulant, it is preferred to add a zinc salt and/or a zinc complex to improve stability. The zinc salt is preferably a salt and/or a complex of a zinc ion as a central element, and has a structure of a phthalate or a carbonate which is a counter ion and/or a ligand. Particularly preferred is a zinc salt and/or a zinc complex which is a carboxylic acid, a sulphuric acid having a carbon number of 1 to 30 (single g, a diacetate, a triacetate or a mixture thereof). Specific examples of the alkane and limb of the phosphate of 1 to 30; examples of the pot _ can be exemplified by methyl, isopropyl, butyl '2-ethylhexyl' sin, lysine, and fluorene. Isostearyl, decanyl, hexadecyl, etc. In the present invention, it is particularly preferred to be a sour vinegar having a carbon number of 3 to 15, and the vinegar may be mixed or a single product. It is preferably a phosphate monoester. Especially in the phosphate esters contained, the molar ratio of the monoester body, the 栌 栌, the 肢 一 S S, and the diester body (replaced by the purity of gas chromatography, 1 φ, Λ μ # In the middle, the difference in sensitivity is required, and _ ^; in the stage of the dimethylation treatment, the amount of the single S is preferably 5 G% or more. The can acid ester compound can be obtained by using a cake, a phosphorus pentoxide, a phosphorus oxychloride, a trichlorosilane, or the like as a dish acidifying agent, in addition to the powder, and the phosphoric acid is obtained by, for example, It is obtained by reacting with zinc carbonate, hydrogen and oxygen, and the like (European Patent Application No. 699,708, filed on Jun.

As the details of the zinc salt or zinc complex of the above-mentioned phosphoric acid vinegar, the ratio of the atom of the dish to the zinc atom (Ρ/Ζη) is preferably 〜, more preferably U = 2·0 / especially preferably U 丨 · 9. That is, in the form of Yu Jia, it is preferred that the phosphate (or phosphoric acid) is 丨.9 mol, relative to the zinc ion, and not a simple ion structure, but has several molecules by ion ^ The structure associated with the ^ key. As the above-mentioned compound, commercially available zinc carboxylate can be exemplified by ζη_^, 602, Zn-St Nz, zs_3, zs_6, zs_8, ZS 8, ZS 7 m ZS-5, ZS-14, ZS_16 (Nitto Kasei Industrial manufacturing), χκ_6ΐ4 ((4) manufactured by InduStry), 18% 〇ct〇pe Zn, 12% & 8% 〇 〇 ^

Zn (manufactured by H〇pe Pharmaceutical Co., Ltd.); as the acid-curing S and/or zinc-disc, there are mentioned: LBT-2_B (manufactured by Sc Organic Chemicals), and xc_92()6 ((four) (four) is manufactured). Here, the ratio of the epoxy resin component to the zinc salt and/or the zinc complex is 0.01 to 8% by weight based on the weight ratio of the epoxy resin to the zinc salt and/or the zinc complex. More preferably, it is 5 to 5 wt% 〇 1 to 4 wt%. When it is more than 8% by weight, the application period as a curable resin composition becomes a problem, and when it is less than G Q1% by weight, the effect is not remarkable. The curable resin composition of the present invention is obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily formed into a cured product by the same method as previously known. For example, the curable resin composition of the present invention, which is required to be added by an extruder, a kneader, a roll-crossing type C7, etc., and a curing agent and/or a hardening accelerator, see 39 201130877 The phosphorus compound, the binder resin, the inorganic filler, and the formulation are thoroughly mixed until they become uniform. In addition, as a curing method, a method of "potting" or "easting" the curable resin composition into a substrate when the curable resin composition is in a liquid state is exemplified. The curable resin composition is introduced into a mold and cast into a shape, and is hardened by heating. In the case of a solid state, it is molded by a casting or a transfer molding machine after melting, and is then hardened by heating. The hardening temperature is 80 to 200 t, and the hardening time is 2 to ι hr. As the hardening method, the secondary solidification can be carried out at a high temperature, but it is preferred to carry out the hardening reaction by gradually increasing the temperature. Specifically, the initial hardening is performed between 8 〇 and 15 〇 t, and the post-hardening is performed between 10 〇 t and 20 (r). As the hardening stage, it is preferably divided into 2 to 8 stages for temperature rise, preferably. In addition, the curable resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, decyl isobutyl ketone, dimethylformamide, dimercapto B. In a solvent such as guanamine or N-methylpyrrolidone, a curable resin composition varnish is formed and impregnated into a substrate such as glass fiber, carbon fiber 'polyester fiber, polyamide fiber, alumina fiber, or paper, and heated. Drying, the obtained prepreg is hot-pressed, whereby a cured product of the curable resin composition of the present invention can be formed. The solvent at this time is used in a mixture of the curable resin composition of the present invention and the solvent. The amount of 丨〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Hardened material. The curable resin composition of the present invention can also be used as a film type 40 201130877 sealing composition. The film type resin composition may be exemplified by first forming the curable resin composition of the present invention as described above. The curable resin composition varnish is applied onto a release film, and the solvent is removed by heating, and then B-staged; thereby obtaining a film-type resin composition as a sheet-like adhesive. The sheet-like adhesive can be used. The interlayer insulating layer of the multilayer substrate or the like and the collective film sealing of the optical semiconductor. The epoxy resin composition of the present invention can also be suitably used as a sealing material or a solid crystal material for a photo-semiconductor. When it is used as a sealing material or a solid crystal material of a light semiconductor such as a high-brightness white coffee, the epoxy resin composition of the present invention is used as an acid anhydride and/or a polysulfide of a curing agent (hardener composition). An additive such as a hardening accelerator, a coupling material, an antioxidant, a light stabilizer, and the like is prepared by fully mixing the squeegee to prepare a curable resin composition. As a mixing method, % 4 ^ _ Female W with kneading machine, two-roll mill, universal mixer, planetary mixer 'homogeneous.,. χ J贞 into a machine, uniform disperser, bead mill, etc. 'mixed at room temperature or heated That is, the hardened resin composition that can be used can be used for the sealing material, and it can be used for both the solid crystal material and the sealing material once for the cathode. The high-brightness white LED and other Guangfeng Road brand - the cattle conductor 7L is usually used. Subsequent agent C solid crystal material)' makes the layered on the blue 窨x,. a *... gems, spines, Sic, Sl, Zn0 temple GaAs, GaP, GpiAiAa wide

GaAlAs, GaAsp, A1Ga inp, GaN,

Semiconductors such as InN, AIN, and InGaN are formed on a lead frame or a heat release plate or a package. There are also ^ ^ m ^ ^ types that are connected to a wire such as a metal wire. The semi-conducting 艚 θ 祖 甘 甘 甘 甘 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The sealing wire 杻 total sealing material is used to protect the semiconductor wafer from the heat of the lens, and to play the role of the lens. The curable f-fat composition of the present invention can be used as the above-mentioned sealing material or solid crystal material. In the step 5, it is preferred to use the curable resin composition of the present invention for both the die bonding material and the sealing material. ^ As a method of attaching a semiconductor wafer to a substrate using the curable resin composition of the present invention, the curable resin composition of the present invention is applied onto a substrate by dispenser, infusion or screen printing. Thereafter, a semiconductor wafer is placed on the curable resin composition and heat-hardened. By this method, the semiconductor wafer can be attached to the substrate. Hot air circulation type, infrared ray, high frequency wave, etc. can be used for heating. The heating condition is, for example, preferably 80 to 23 (rc 'i minutes to 24 hours or so.) To reduce the internal stress generated during heat curing, for example, after pre-hardening for 30 minutes to 5 hours at 8 Torr to 12 hours, Post-hardening is carried out under the conditions of 12 〇 to 18 代 and μ minutes to 10 hours. As a method of forming a sealing material, it is used in the mold frame of the substrate in which the semiconductor wafer is entangled in the above-mentioned manner; After the sealing material is introduced, the injection molding method is performed by heat-hardening, and the sealing material is preliminarily injected into the mold to impregnate the semiconductor wafer fixed on the substrate, and then heat-hardened, and then subjected to compression molding from the mold. Examples of the injection method include a dispenser, transfer molding, etc. The hot air circulation type and the heat condition can be, for example, preferably 80 to 230. The internal stress generated by heat curing and the like, infrared rays, high frequency waves, and the like are added. Minutes ~ 24 hours or so. For the drop 'for example, can be carried out under 80~120t 42 201130877 3〇 minutes~5 hours pre-hardening, after 12〇~l8〇t)c, 3〇 minutes 〇 hours After curing conditions. Further, the use of the curable resin composition of the present invention is not limited to the above, and can be applied to a general use of a curable resin such as an epoxy resin. Specifically, 'except adhesives, coatings, coating agents, molding materials (including sheets, films, FRP (Fiber Reinf〇rced pias Hcs, fiber reinforced plastic), etc.), insulating materials (including printed substrates, wire coating, etc.), In addition to the sealing material, a cyanate resin composition for a substrate, an additive for a resist for curing, and the like in an other resin such as an acrylate resin may be used. Examples of the adhesive include an adhesive for electronic materials other than civil engineering, construction, automotive, general-purpose, and medical adhesives. Examples of the adhesive for electronic materials include an interlayer adhesive for a multilayer substrate such as a build-up substrate, a semiconductor adhesive such as a die bond or a primer, and a BGA (Ball Grid Array). Array) A primer for encapsulation such as a primer, an anisotropic conductive film (ACF, an anisotropic conductive film), or an anisotropic conductive paste (ACP 'Anisotropic Conductive Paste). Examples of the sealant include a filling, impregnation, and transfer molding seal used for a capacitor, a transistor, a diode, a light-emitting diode, a 1C, an LSI (Large Scale Integration), and the like, 1C or LSI. Infusion sealing, flip chip (Chip on Board), C0F (Chip 〇n FUm), TAB (Tape Automated Bonding) Flip chip), etc., QFP (Plastic Quad Flat Package), 43 201130877 BGA and CSP (Chip Scale pa package for sealing (including _ = chip size package), etc. 1 (4),匕祜 Strengthen the primer and so on. The hardened material obtained in the present invention can be used for various purposes represented by the material of the prior art. The term "optical material" rr is a material used to make infrared, ultraviolet, X-ray, and laser (4) lasers pass through the material. More specifically, in addition to the LED sealing material such as a lamp type or a soil 5MD (surface mount device), the following may be mentioned. A material for a liquid crystal display device such as a substrate material such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a phase difference plate, a viewing angle correction film, an adhesive, or a polarizing element protective film in the field of liquid crystal display. In addition, a sealing material, an antireflection film, an optical correction film, an outer casing material, a protective film for a front glass, a front glass substitute material, and an adhesive for a color PDP (electropolymer display) of a lower-generation flat panel display are desired. (4) The molding material of the LED used in the display device, the sealing material of the LED, the protective film of the front glass, the replacement material of the moon 'J plate glass, the adhesive, and the plasma-addressed liquid crystal (PALC,

Plasma Address Liquid Crystal ) substrate material in the display, light guide plate 'strip, polarizer, phase difference plate, viewing angle correction film, adhesive, polarizing element protective film, and the front plate in organic EL (electroluminescence) display The glass protective film 'front plate glass is used as a substitute material and an adhesive. In addition, various film substrates in the FED (Field Emission Display), a protective film for the front plate glass, a front plate glass substitute material, and an adhesive are used. In the field of optical recording, VD (Video Disc), CD/CD-R〇M, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase change disc), optical disc substrate material for optical card , CD player to read the lens, protect the 臈, seal 201130877 materials, adhesives and so on. In the field of optical equipment, it is a lens material for a static camera, a finder prism, a finder c〇ver, and a light-receiving sensor unit. In addition, the camera lens and viewfinder of the camera. In addition, a projection lens, a protective film, a sealing material, an adhesive, and the like of a projection television. The material for the lens of the light sensing machine, the sealing material, the adhesive, the film, and the like. In the field of optical components, it is a fiber material, a lens, a waveguide, a sealing material for a component, an adhesive, etc. around the optical switch in an optical communication system. Optical fiber material around the optical connector, ferrule, sealing material, adhesive, and the like. In the passive parts of the light and the parts of the photoelectric circuit, it is a sealing material, an adhesive, etc. of a lens, a waveguide, an LED seal, a material, a pled device. (〇EIC> Optoelectronic Integrated Circuit) Substrate materials, fiber materials, sealing materials for components, and adhesives. In the field of optical fiber, it is used for lighting, light guide tubes, etc. for decorative displays, industrial applications: sensors, display/identification, etc., as well as communication infrastructure and digital fiber for connecting digital devices in the court. In the periphery of the semiconductor integrated circuit, it is an anti-synthesis material for LSI and ultra-LSI materials. In the field of automobile/transporter, it is a lamp reflector for automobile, bearing retainer, gear part, corrosion resistant coating, switch part, headlight, engine parts, electrical parts, various internal and external equipment, drive engine, brake Oil tank, anti-iron steel plate for automobile, guide for interior use (4) interior materials, protection/bundling, ", fuel hose, car lamp, glass substitute. In addition, the road = layer of glass. In addition, the aircraft The material imparting agent for the structural material, the peripheral member, the wire bundle for protection/bundling, and the anti-slip coating. It is replaced by the material for inner skirt/processing and the cover glass in the field of building 45 201130877.... Solar cell peripheral material sheet The material 'glass interlayer film, cover film. As the next-generation light, electricity, agricultural use, it is the surrounding material of the greenhouse cover, organic...1 machine material, is the organic el yuan large component, the optical transport 笪i勹 nine conversion device The material of the light release material, the density of the element (4) the substrate material around the p, the fiber 1 dry sealant, the adhesive, etc. The embodiment is described in more detail by way of examples, as long as there is no special Say , Then "part ^ ^ J to reset the part." Furthermore, the invention is not limited to the embodiments. In the other three examples, the physical property values were measured by the following methods. • Epoxy equivalent: measured according to JIS KJ236 • Viscosity: measured with a £-type viscometer at 251 • Gas Chromatography (hereinafter referred to as GC): Analytical conditions Separation column: HP5-MS (〇 .25mmI.D.xl5m, film thickness 〇25 β m) B-column heater temperature: set the initial temperature to 1 and heat up at a rate of 15 °C per minute. Hold at 30 (TC for 25 minutes). : Gel Permeation Chromatography (hereinafter referred to as GPC): Column: Shodex SYSTEM-21 column (KF-803L, KF-802.5 (x2 root), KF-802) 46 201130877

Linked dissolving solution: tetrahydrofuran 'flow rate is 1 m1 〆 min Column temperature: 40 ° C Detection: UV (ultraviolet 'ultraviolet light) (254 nm) Calibration curve · Shodex standard polystyrene synthesis example 1 with mixer, reflux Adding dimethyl 1,4-cyclohexanedicarboxylate (DMCD-pt) 140 parts, 3-ring in a cooling tube, a stirring device, and a flask of a Ding Stark tube while performing nitrogen purge. 314 parts of hexene-nonyl sterol and 0.07 parts of tetrabutoxytitanium titanate, 1 hour at i20 °C, 1 hour at 150 °C, 1 hour at 170 °C, 1 9 〇 X; under the conditions of 12 hours, the reaction is carried out while removing the sterol formed by the reaction. After the reaction was carried out by GC, it was cooled to 5 (TC. After cooling, 347 parts of toluene was added and homogenized, and then the reaction solution was washed 3 times with 10% by weight of a 10% by weight aqueous sodium hydroxide solution, and further water. 100 parts/times of repeated washing until the wastewater becomes neutral. Distillation of toluene and unreacted 3-cyclohexene-1-methyl by heating under reduced pressure using a rotary evaporator

240 parts. Formula (5)

47 201130877 Synthesis Example 2 In a flask equipped with a stirrer and a reflux cooling tube 'stirring device, one side was purged with nitrogen - 15 parts of water was added. ' 12% of 嫣 〇 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Hardened tallow alkyl dimethyl ammonium acetate 27 parts (manufactured by Li〇n AkZ〇, 5% by weight of the solution of Arquad 2HT-Acetate), 180 parts of toluene, 118 parts of the dilute compound obtained in the synthesis example i Further, the mixture was stirred again to prepare a solution in an emulsion state. The solution was heated to 50 t: the surface was vigorously mixed, and 70 parts by weight of 35 wt% of hydrogen peroxide water was added in an hour, and in this state, it was stirred at 5 ° for 13 hours. The progress of the reaction was confirmed by gas chromatography, and as a result, the raw material ridge value disappeared 0, and then, after neutralization with a 1% by weight aqueous sodium hydroxide solution, 25 parts by weight of a 2% by weight aqueous sodium thiosulfate solution was added and stirred. 3 minutes and stand still. The organic layer separated into two layers was taken out, and activated carbon (Ajin〇m〇t〇Fine-Techno, CP1), 2 parts, and bentonite (manufactured by H〇jun, SH) 20 parts were added thereto. ! Filter after an hour. 100 parts of the obtained filtrate was washed with water three times, and the obtained organic layer was evaporated to remove toluene, thereby obtaining an epoxy resin (Ερ_丨) [丨9 parts which was liquid at normal temperature. The epoxy equivalent of the obtained epoxy resin was 217 g/eq. Synthesis Example 3 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 15 parts of water, 12-tungstenium phosphate, 9 parts, monosodium hydrogen phosphate 1_6 wound, and dihardened tallow alkyl dioxime were added while performing nitrogen purge. Ammonium acetate 4 4 parts (Li〇n 0 system 〇 5 〇 weight % of hexane solution 'Arquad2HT-Acetate), 48 201130877 曱 benzene 160 parts, 3-cyclohexene decanoic acid 3 · cyclohexene brewing The mash was further stirred again to thereby prepare a solution in an emulsion state. The solution was heated to ?c' while 70 parts by weight of 35% by weight of peroxidic feng shui was added in an hour, and in this state, it was grasped and mixed for 2 hours. The progress of the reaction was confirmed by gas chromatography, and as a result, the peak of the starting material disappeared. Then, after neutralization with a 1% by weight aqueous solution of sodium hydroxide, 25 parts of a 2% by weight aqueous solution of sodium thiosulfate was added, and the mixture was allowed to stand for 3 minutes and allowed to stand. The organic layer separated into two layers was taken out, and 40 parts of activated carbon (manufactured by Ajin〇m〇t〇'Μ110, CP1) and 40 parts of bentonite (manufactured by H〇JUn, Bengel SH) were added thereto, and η was mixed at room temperature. Filter afterwards. The obtained liquid was subjected to water hydration three times with 100 parts of water, and the acetaminophen (Ερ_2) ιι〇 part was obtained by distilling off the obtained organic layer from the obtained organic layer by π ^ human water washing. The epoxy equivalent of the obtained epoxy resin was 13 〇g/eq. ^ Synthesis Example 4 - In a flask equipped with a blender, a reflux cooling tube, and a device, a dicyclopentadiene dimethanol (7) phthalic acid needle and a methyl hexanitro phthalate needle were added while performing a nitrogen purge. The mixture (made in the new 曰 理 理 , , , , , , , , , R R R R R R R R R R R R R R R , , , , R R R R R R R R R R R R R R R R R R R R R R R R The ene, and, see + Αβττ alcohol lost 4, thereby obtaining 60 parts of the hardener composition as a mixture of the acid and the acid anhydride. The obtained hardener composition is a colorless liquid resin, and the purity obtained by GPC is: the area of the polyacid is 51 area%, and the methylhexahydroorthophenone: the formic acid needle and the hexahydrophthalic anhydride The total amount is 49 area%. In addition, the official 49 201130877 energy base equivalent is 201 g / eq. Further, 'the saponin composition of the obtained hardener composition was added with 丨2^-acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., H_TMAn:: 12 parts of cyclohexane) to prepare a hardener composition (B). ~ Lower called H·2)

The weight ratio (theoretical value) of the hardening agent (B-1) of Jr' Ain f X> 1 \ is polydecanoic acid, 'H_1 is 48.9%' and the anhydride H-2 is 10.7%. .夂野合成例5 In a blender, a reflux cooling tube, a stirring device, and a bottle, a nitrogen-fluorinated side is added with 1 part of dicyclopentadienyldiamine, hexahydrophthalic anhydride and Mixture of methylhexahydrophthalic anhydride (New Day = manufactured by Physicochemical Co., Ltd., Rikacid MH-700, hereinafter referred to as anhydride H1) 5 parts, heat search under the condition of i hour under the boot and i hour under the arm. The disappearance of the dicyclopentadienyl dimethanol was confirmed by GPC, whereby 6 parts of a hardener composition as a mixture of polyoxoic acid and an acid anhydride was obtained. The obtained hardener composition is a colorless liquid resin, and the purity obtained by GPC is: the structure of the polycarboxylic acid is 5 丨 area%, and the total of decyl hexahydrophthalic acid anhydride and hexahydrophthalic anhydride The amount is 49 area%. In addition, the official base equivalent is 201 g/eq. Further, 'the weight ratio (theoretical value) of the hardener composition (B-2) obtained by adding 6 parts of the acid anhydride (H 2 ) to the obtained hardener composition to obtain a uniform hardener composition (B 2 ) The carboxylic acid was 42.6%, the anhydride η-1 was 5 1.7%, and the anhydride H-2 was 5.6%. Example 1 16 parts of the epoxy resin (Ep_1) obtained in Synthesis Example 2 and the obtained product of Synthesis Example 3 50 201130877 were combined to obtain the present invention (F-1). Examples 2 and 3, Comparative Example 丨~4 The obtained epoxy resin composition (using the curing agent composition (B-., as a promoter) of Synthesis Example 4 and _·., .s Example 4 The fourth grade bismuth salt (manufactured by Sakamoto Chemical Industry, HlshlC0lin PX4MP, hereinafter referred to as catalyst θ VIII, w _ _ 21 Table 1 does not match the ratio (heavy I: paste line configuration) for 2 minutes defoaming. After the obtained curable resin product was subjected to vacuum defoaming for 2 minutes, it was slowly formed into a barrier glass ((4) on a glass substrate by a heat-resistant tape so as to be 30 mm x 2 mm mm. After 12 hours of pre-hardening, it was hardened by 150 〇 C x 1 hour to obtain a test piece for the penetration of the thickness imm. The obtained test piece was heat-treated at 150 C for 1 hour by heat. The degree of coloration was evaluated by the course (the retention rate of the penetration rate of (10) was measured and compared) [Table 1]

Composition of epoxy resin (ΕΡ-2) 6.50 Hardener-scientifier composition (Β-1) 9.20 9.20 9.20 Hardener composition (Β-2) 6.50 9.59 9.59 9.59 Hardening catalyst|hardened contact rC-Π 400 Percentage of penetration of nm (%) 0.02 ~ 89.2 0.02 84.4 0.02 89.5 0.02 0.02 0.02 90.5 82.5 89.2 According to the above results, the epoxy resin composition of the present invention (F-1) 51 201130877 is used. Regardless of whether or not the epoxy resin (EP-1) or (EP_2) was mixed, the retention of the transmittance equal to or higher than that of the epoxy resin (EP-2) was exhibited. Example 4 'Comparative Examples 5 and 6 For epoxy resin composition (F-1) and epoxy resin (EP-2), commercially available alicyclic epoxy resin (manufactured by Daicel Chemical Industry, Celloxide 2021P, hereinafter referred to as In the case of EP-3), the hardener composition (B-1) obtained in Synthesis Example 4 and the quaternary scale salt (C-1) as a hardening catalyst were used, and the blending ratio (parts by weight) shown in Table 2 below was used. The preparation was carried out for 20 minutes of defoaming (the composition thereof is shown in Table 2). These were filled in a syringe and cast into a surface mount type LED package having an outer diameter of 5 mm square with a center light-emitting wave of 465 nm (with an inner diameter of 4.4 mm and an outer wall height of 1.25 mm) using a precision discharge device. . The cast material was placed in a heating furnace, and hardened at 1 to 20 ° C for 1 hour, and further hardened at 15 ° C for 3 hours to prepare an LED package. After the LED was packaged, the LED was lit under the following conditions, and the illuminance was measured. The results are shown in Table 2. Detailed conditions for lighting Light-emitting wavelength: 465 nm Drive method: Constant current mode, 60 mA (light-emitting element specified current is 30 mA)

Driving environment: 85 ° C, 85% RH Driving time: 200 hours Evaluation: Illuminance retention after lighting for 200 hours 52 201130877 [Table 2] Example 4 Comparative Example 5 Comparative Example 6 Composition of a cyclic resin composition (F- 1) 7.7 Epoxy Resin (EP-2) 6.5 Epoxy Resin (EP-3) 6.5 Hardener Composition (B-1) 9.2 9.2 9.2 Hardening Catalyst (C-1) 0.02 0.02 0.02 LED Lighting Test Illumination Rate (%) 89.7 79.5 80.3 According to the above results, it is understood that the curable resin composition using the epoxy resin composition (F-1) of the present invention can be obtained as an LED as compared with the epoxy resin (Ep_2) and (ep_3). More excellent hardened material. Synthesis Example 6 In a flask equipped with a mixer, a reflux cooling tube, a sowing device, and a Ding Stark tube, a nitrogen purge was carried out while adding hydrazine, 4_cyclohexanedicarboxylic acid II. methyl vinegar (rock valley) Manufactured by gas, DMCD-pt) 14 parts, 314 parts of 3_cyclohexene_丨_sterol, tetrabutyl titanate 〇. 〇 7 parts 'at 1 hour at 12〇t, 1 hour under 15〇艽, The reaction was carried out while removing the sterol formed by the reaction under the conditions of 20 hours under 170 C. After the reaction was carried out by GC, it was cooled to 5 Torr. Hey. After the completion of the cooling, 347 parts of toluene was added and homogenized, and then the reaction solution was washed three times with 10 parts by weight of a 10% by weight aqueous sodium hydroxide solution, and further washed with water in 100 parts/time until the wastewater became neutral. Chemically activated activated carbon (manufactured by Ajinomoto Fine-Techno, ZN1) 5 g was added, and after the temperature: _ i hours, the activated carbon was removed by the transition. The terpene and the unreacted 3_cyclohexene decyl alcohol were distilled off under heating and reduced pressure by a rotary rotator to obtain 235 parts of the diene compound represented by the above formula (5). 53 201130877 Synthesis Example 7 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen citrate, and trioctyl thioglycolic acid were added while performing nitrogen purge. 2,7 parts of ammonium (manufactured by u〇n Akz〇, 50 parts by weight of hexane solution, TOMAC-50), 17 parts of hydrazine, 1 part of the diene compound obtained in Example 6, and then again Stirring is carried out to prepare a solution in an emulsion state. The solution was heated to 5 ° C, and while vigorously searching for one side, 7 wt% of peroxidic water was added in an amount of 7 liters per hour, and the mixture was stirred at 50 ° C for 14 hours. Then, 20 weights were added after being made into a ρΗι〇 by a 30% by weight aqueous sodium hydroxide solution. /. 25 parts of an aqueous solution of sodium thiosulfate, which was dropped for 3 minutes and allowed to stand. The organic layer separated into two layers was taken out, and 8 parts of active 1 (manufactured by Ajinomoto Fine. Techn0, CPi) and 10 parts of montmorillonite (manufactured by K.K.) were added thereto, and stirred at room temperature for 3 hours, followed by filtration. . Further, the wet cake was rinsed with 50 parts of toluene and mixed with the previous liquid. From the obtained filtrate, the methyl ester was distilled off, whereby 120 parts of the epoxy resin (EP-4) which was usually liquid was obtained. The resulting epoxy resin had an oxygen equivalent weight of 212 g/eq. Coating Synthesis Example 8 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a nitrogen purge was performed while adding 15 parts of water, 0.9 parts of 12 g pigeon phosphoric acid, 1.5 parts of sodium phosphate pigeon, and disodium hydrogen phosphate. ·6 parts, ammonium trioctylmethylacetate (manufactured by U〇n Akzo, 50% by weight in hexane solution, TOMAC-50) ^ 160 parts of toluene, 3-cyclohexenyl ester of 3-cyclohexenecarboxylic acid u 177 延延54 201130877 Stir again, to make an emulsion-like solution, 〇r, a solution of J. The solution was heated to (4), and the surface was mixed for 3 minutes to add "% by weight of peroxidized ^ 7 parts, and in this state, it was mixed at 46 ° C for 16 hours. By gas chromatography. After confirming the progress of the reaction, the result was a peak of the raw material. After the weight % of the aqueous sodium hydroxide solution was made into ρΗι〇, 5 parts by weight of an aqueous sodium thiosulfate solution was added, and the mixture was dropped for 3 minutes and allowed to stand. The organic layer separated into two layers was taken out, and activated carbon (_. fine. Fine_Teehn. Manufacture 'cpi) was added thereto, and 5 parts of montmorillonite industrial product 'KunipiaF' 1G part was stirred at room temperature for 1 hour, and then subjected to hydrazine. The obtained filtrate was washed with water 3 times in 7 jc (9) portions, and toluene was evaporated from the obtained organic layer to obtain 109 parts of epoxy resin (EP-5) which was liquid at normal temperature. The epoxy equivalent was I" v eq· ° Synthesis Example 9 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 24 parts of dicyclopentadiene dimethanol and methyl hexaazaphthalene were added while performing nitrogen purge. Hepatic acid liver (made by New Japan Physical and Chemical Co., Ltd.), called RikacndM H anhydride H-3) 146 parts, anhydride (Η·2) 3 parts, 4 〇 <t! The mixture was heated and stirred at an hour and 70 ° C for 1 hour to obtain a hardener composition (B-3 ) as a mixture of a polycarboxylic acid and an acid anhydride. The obtained hardener composition was a colorless liquid resin, and the purity obtained by GPC was: a structure of a polycarboxylic acid of 55 area%, an acid anhydride (H_3) of 35 area%, and an acid anhydride (H-2) of 10 area%. Further, the functional group equivalent was 178 g/eq· 〇55 201130877. Synthesis Example ίο In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, while nitrogen gas was purged, 2,4-diethylpentanediol was added (Concord) Manufactured by fermentation chemistry, Ky〇Wadiol PD_9) 24 parts, methylhexahydrophthalic anhydride (manufactured by Shinji Ryo Chemical Co., Ltd., called Rikacid MH Anhydride H-3) 146 parts, acid anhydride (H-2) 30 parts, 1 hour at 40 ° C, 70. (: The next one hour condition was heated and mixed, thereby obtaining 200 parts of a hardener composition (Β·4 ) as a mixture of polyphenolic acid and an acid anhydride. The resulting hardener composition was a colorless liquid resin by Gpc The purity obtained is: the structure of the polycarboxylic acid is 5 Å area%, the acid anhydride (H 3 ) is 40 area/〇, and the acid anhydride (H-2) is 1 〇 area. In addition, the functional group equivalent is 1 7 8 g / e q. Example 5-8, Comparative Example 7 The epoxy resin (EP_4) obtained in Synthesis Example 7 and (EP-5) obtained in Synthesis Example 8 were uniformly mixed at the following mixing ratios. The % oxygen resin composition (F-2) to (F-5) of the present invention were obtained. The epoxy resin composition obtained in the same manner was used as the hardener composition obtained in Synthesis Example 9 (Β_3) 〇8 molar equivalent. As a hardening catalyst, an alkylphosphonium sulphate zinc catalyst (manufactured by Mirage Industries, XC-92〇6, hereinafter referred to as c_2) is used for the resin 2 jaws, and the compounding ratio shown in Table 3 below is The parts by weight are prepared and defoamed in minutes. The obtained curable resin composition is vacuum defoamed for 2 minutes, and then slowly cast. The glass substrate of the barrier is formed by a heat-resistant tape at a height of 30 mm x 20 mmx and a height of 1 mm. After the pre-hardening of the above-mentioned cast material for 2 〇 ° C for 3 hours, it is hardened by 15 〇 t x l hours to obtain a thickness of 56 201130877 degrees. The penetration rate of 1 mm was compared by the test. The penetration rate of each hardened material at 400 nm was compared. The test piece of 150 〇c was used for the treatment of the toothpaste. The test piece of Shishishi was treated for 96 hours and evaluated by thermal history. The degree of ..., Ba (measured and maintained by the penetration rate of 4〇〇nm) [Table 3] Epoxy resin composition F-2 Composition EP-4 EP-5 5 ' 15 Hardener hardening Catalyst B-3 C-2 Γ 19 0.08 400 nm penetration rate 91 penetration rate protection rate 90 Example 6 0.08 0.07 0.07 Example 9~1 5 : _ Example 7 epoxy resin (Ερ 4) The (() obtained in Synthesis Example 8 was uniformly mixed with the following compounding ratios to obtain the epoxy resin compositions (F_6) to (8) of the present invention. The epoxy resin composition obtained by the use of the hardener compositions (B-3) and (B4) obtained in Synthesis Examples 9 and 10, as a hardening catalyst, a quaternary phosphonium salt (c_i), an alkyl phosphate Ester _, octyl phosphate (Hope Pharmaceuticals, 〇 ctope Zn, hereinafter referred to as C 3 1 'one' as an additive phosphorus compound (Sanguang Co., Ltd., hereinafter referred to as C-4), phosphorus compound (Adeca Manufacture, Adeca 260) , hereinafter referred to as C-5), hindered amine (Adeca sex, LA-62, hereinafter referred to as C-5), formulated with the following 袅4 μ - ratio (parts by weight), 20 minutes in /Shaw bubble (the composition is described in Table 4). These were filled in a syringe, and were cast into a surface mount type LED having an outer diameter of 5 mm square, which was mounted on a wafer 57 with a central light-emitting wave of 465 nm, using a precision discharge device. The package (inner _ hair mm 'outer wall south degree is 1.25 mm). The cast material is put into a heating furnace and hardened at 110 ° C for 2 hours, and then made into an LED at i5 (3 times hardening treatment under TC). After encapsulating the LED, the LED is lit under τ and conditioned conditions, and the illuminance is measured. The result is shown in the table. 4 shows the detailed conditions of lighting. illuminating wavelength: 465 nm driving method: constant current mode, 60 mA (lighting component specified, axe 30 mA) Driving environment: 85 ° C, 85% RH driving time: 400 hours Evaluation: 200 hours, illuminance retention rate after lighting for 400 hours 58 201130877 [Inch Example 15 as ϋπ ΓΛ 0.90 0.06 0.06 0.06 00 Example 14 Os Uh 〇\ \〇m 0.90 0.06 0.06 | 0.06 | m 00 (N Ό Example 13 00 Ua 〇 0.90 0.06 0.06 Ο ON H VC Example 12 00 t-lH as (N 0.75 0.05 0.05 < N Os Example 11 __________ ____1 00 ΓΟ 0.80 0.06 0.06 0.06 Example 10 op Uh On m 0.80 0.06 0.06 0.06 m 〇\ !〇Example 9 Bu 0.80 0.06 0.06 ^T) VO EP-4 EP-5 B-3 Β-4 1 ^ 〇H 余田田 ^ tt ό ό ό C-2 C-3 C-4 C-5 C-6 200 hr after (%) 400 hr after (%) composition of hardener hardening catalyst scale compound hindered amine illuminance retention rate 201130877 According to the above results can be named. Learning characteristics (illuminance retention ° rate: J · The epoxy resin composition of the invention is hardened by light . ΤExcellent, can be paid as an LED. This application is based on the 曰 寻 申 申 安 安 安 安 安 安 安 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( It is incorporated in its entirety as a whole. [Simple diagram description] None [Main component symbol description] None

Claims (1)

201130877 VII. Patent application scope: 1. An epoxy resin composition, which is obtained by oxidizing a mixture of a diene compound represented by the following formula (1) and a diene compound represented by the following formula (7). The ratio of the epoxy resin derived from the compound of the formula (1) to the epoxy resin derived from the compound of the formula (2) is 1 G/9 G to 9 Å/1 Torr in a weight ratio. There are a plurality of formulas in the formula, and the cutters independently represent a hydrogen atom, a burnt group of 驭~6; p represents a cyclohexane 4 norbornane ring which may have a methylidene methyl group as a substituent. Number 1: 1:? A plurality of epoxy resin compositions, which are represented by the following formula: (1) The ratio of the ratio of the epoxy resin of the compound of the formula (1) to the epoxy resin of the compound of the formula (2) by weight of the diene compound represented by the following formula (2) The ratio is (〇 / 9 〇~9 〇 / i 〇: P meaning 0) (wherein R is plural), each independently represents a hydrogen atom or a carbon number of 1 to 6 represents a cyclohexyl ring or a norbornane ring which may have a methyl group as a substituent. (wherein a plurality of alkyl groups having an R number of 1 to 6 are present). The epoxy resin composition of the first or second item of the patent money, the substituent R and the substitution of the formula (2) are respectively a hydrogen atom, a hydrogen group, a nuking group. And P is one or more selected from the group consisting of a methylcyclohexane ring, a methylnorbornane ring, and a norbornane ring. The coating is as shown in any one of claims 1 to 3. 'Where' is oxidized by hydrogen peroxide. Epoxy resin 5. A curable resin composition characterized by: Epoxy tree 62 201130877 grease containing one of items 1 to 4 of the patent application scope The composition and the hardener and/or the hardening accelerator. 6. The curable resin composition according to claim 5, wherein the hardener is phthalic anhydride and/or polyacid. 7·- hardened material The curable resin composition of the fifth or sixth aspect of the patent application is obtained by hardening. The optical semiconductor device is obtained by sealing with the patented article. 'It is characterized by: hardening of the fifth or sixth item Resin group VIII, schema: (none) 63