TW201233726A - Curable epoxy resin composition - Google Patents

Abstract

The present invention provides a curable epoxy resin composition. The curable epoxy resin composition can obtain cured products which have high transparency, heat resistance, light resistance and crack resistance. The curable epoxy resin composition is characterized by containing alicyclic epoxy compounds (A), monoallyl diglycidyl isocyanurate compounds (B) represented by following formula (1), alicyclic polyester resins (C), curing agents (D) and curing accelerators (E). [In the formula, R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

Description

.201233726 VI. [Technical Field] The present invention relates to a curable epoxy resin composition, a cured product obtained by hardening the curable epoxy resin composition, and a curable epoxy resin composition. A resin composition for optical semiconductor sealing which is formed of a material, and an optical semiconductor device in which an optical semiconductor element is sealed by using the resin composition for optical semiconductor sealing. [Prior Art] In recent years, the high output of optical semiconductor devices has progressed, and resins used in optical semiconductor devices require high heat resistance and light resistance. For example, in the sealing material (sealing resin) for blue and white light semiconductors, the light emitted from the optical semiconductor element and the yellow of the sealing resin caused by heat become a problem. The yellowing sealing resin lowers the luminosity of light output from the optical semiconductor device with time as it absorbs light emitted from the optical semiconductor device. Heretofore, a highly heat-resistant sealing resin has been known to contain a composition of isomeric glyceryl monoallyl diglycidyl ester and a bisphenol A type epoxy resin (see Patent Document 1). However, when the cured product is used as a high-output blue sealing resin for white light semiconductors, coloring occurs due to light and heat generated by the optical semiconductor element, and light that should originally be taken out is absorbed. The problem that the luminosity of light output by the optical semiconductor device decreases with time. [Technical Problem to be Solved by the Invention] In terms of a sealing resin having high heat resistance and light resistance and not easily yellowing, the sealing resin is not disclosed. 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, 14-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylic acid A liquid alicyclic epoxy resin having an alicyclic skeleton such as an adduct of ester and _caprolactone, or 1,2,8,9-diepoxylimene. However, the cured product of the alicyclic epoxy resin is not resistant to various stresses, and when thermal shock such as heating and cooling (reverse heating and cooling) is applied, cracks (cracks) or the like may occur. The current situation is that the output of an optical semiconductor device (especially an optical semiconductor device having a high-output, high-intensity optical semiconductor device) is required to have high heat resistance, light resistance, and turtle resistance. Cracked transparent sealing resin. Therefore, an object of the present invention is to provide a curable epoxy resin composition capable of imparting a cured product having high transparency, heat resistance, light resistance, and crack resistance. Further, another object of the present invention is to provide a cured product which is obtained by curing the curable epoxy resin composition and having high transparency, heat resistance, richness, and timely cracking. -1 π 1 hexagram patrols the composition of the hardened epoxy resin, which constitutes a 树脂 先 先 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体 导体Device. Further, the present invention is directed to providing an optical semiconductor device which is sealed by a cured product which is highly resistant to light, transparency, and cracking resistance: an optical semiconductor device in which the reduction in luminosity between % is suppressed. It is obtained by sealing the optical semiconductor element using the resin composition for optical semiconductor sealing of the above -5 - 201233726. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have intensively studied and found that the compound containing an alicyclic epoxy compound, isomeric cyanuric acid monoallyl propylene oxide, and a fat j Resin as an essential component, and further contains a stone modifier, a hardening accelerator, or a hardening epoxy resin composition of a curing catalyst, which provides excellent heat resistance, light resistance, transparency, and crack resistance. The cured product in which the optical semiconductor device obtained by sealing the optical semiconductor device with the cured product is not easily deteriorated over time, has completed the present invention. That is, the present invention provides a curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (Α) and an eight-t fl mono-propyl-propyl acrylate-S represented by the following formula (丨) a compound (B), an alicyclic polyester ruthenium (C), a hardener (7), and a hardening accelerator (E);

Further, the present invention provides a curable epoxy resin composition comprising 3 % 曰 % %, an oxygen compound (A), and an iso-cyanuric acid mono-cyanate- ρ $ &; - 虱 虱 S S compound (Β), and alicyclic polyester resin (C), and hardening catalyst (F); (1) 201233726 [the above-mentioned alicyclic ring again]

Provided is a hardenable epoxy resin composition as described above, wherein the alicyclic epoxy group of the epoxy compound (A) is hexylene oxide. Provided is a hardenable epoxy resin composition as described above, wherein the epoxy compound (A) is represented by the following formula:

(I-1) In addition, the alicyclic polyester and the rubber particles are further formed into a hard, constitutive light, which is semi-conductive to provide a hardening epoxy resin composition as described above, (4) (C) The main chain has an alicyclic alicyclic polyester. The crucible epoxy resin composition further contains 〇. The present invention provides the hardening of the composition of the above-mentioned attack-hardening nuclear oxygen resin. The present invention provides "white rice, +, Λ, 匕, 匕 3" as a curable epoxy resin composition and a resin composition for conductor sealing. The present invention provides an optical semiconductor device obtained by sealing a resin composition for sealing a light semiconducting ytterbium conductor. In the case of the above-described structure, the curable epoxy resin composition of the present invention has a high transparency and is heated, And crack resistant hardened material. In addition, Mingzhi Shuojie ^ ^ ^ ^ 虱 虱 resin composition sealed optical semiconductor components to obtain semiconductor devices, # 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤Ii that the luminosity of the optical semiconductor device can be suppressed from decreasing with time by using each of the hardening epoxy resin compositions, that is, when the two "output, ten-luminance optical semiconductor element-based optical semiconductor sealing resin is used." [Mode for carrying out the invention] <curable epoxy resin composition> The hardenable epoxy resin composition of the month includes: an alicyclic epoxy ring "t) and a hetero-cyanide represented by the following formula (1) Acid monoallyldi:oxypropane: compound (B) and alicyclic resin (c), hardener (υ) and hardening accelerator (Ε);

1) Further, the composition of the sclerosing ring-coating tree of the present invention comprises: a fat/oxygen compound (Α), and the above formula - fly (1), which is different from the cyanuric monoolefin 201233726 Glycidyl ester compound (B), alicyclic polyester resin (c), and hardening catalyst (F). (alicyclic epoxy compound (A)> The alicyclic epoxy compound (A) used in the present invention contains (1) a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, And (11) a compound in which a bad oxy group is directly bonded to an alicyclic ring by a single bond. (i) A compound having an epoxy group (a ring-epoxy group) composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring, which may be arbitrarily selected from known or customary. The above alicyclic epoxy group is preferably an epoxyhexene group. (1) A compound having an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring, in particular, an alicyclic epoxy resin represented by the following formula (I) from the viewpoints of transparency and heat resistance ( An alicyclic epoxy compound is desirable.

In the formula (I), X represents a single bond or a linking group (a divalent group having more than one atom). The above-mentioned linking group' is, for example, a hydrocarbon such as a divalent hydrocarbon, a #, a jade blast, a scaly bond, a Sa bond, a succinic acid S group, a stilbene group, and a group having a plurality of such a scorpion. The alicyclic epoxy compound wherein X in the formula (I) is a single bond, for example, a compound represented by the following formula. As such an alicyclic epoxy compound, for example, a commercially available product such as CELLOXIDE 8000 (manufactured by Daicel Co., Ltd.) can also be used. • 9 - 201233726

The above-mentioned divalent stalk &base' is, for example, a linear or branched chain alkyl group having a carbon number of 8, an alkyl group of 2 僭 to nt, and a “ 焉 哀 哀 哀 哀 哀 哀. a linear chain having a carbon number of 1 to i 8 or, for example, a mercapto group, a methylmethylene group, a diindenyl branched alkyl group, a methylene group, an exoethyl group, a propyl group, a trimethylene group, etc. . A bivalent alicyclic hydrocarbon group, for example, 1,2-ring pumping 1. „ pentyl group, 1,3-anthracene pentyl group, cyclopentylene group, anthracene, 2_cyclohexylene group, 1,3 - net μ a two-valent ring-extension group (including a cycloalkylene group), such as a hexyl group, a 1,4-cyclohexylene group, or a cyclohexylene group. The above-mentioned hydrazine group is preferably a linking group containing an oxygen atom, specifically例士CO 〇_c〇〇_, _c〇〇, _〇·, c〇NH·; these bases are connected to the base; the bases or more than two and two-valent hydrocarbon groups 1 or more or more linked groups, etc. The hydrocarbon group of the divalent group is, for example, the above-mentioned exemplified. Representative examples of the alicyclic epoxy compound represented by the above formula (I), for example, the following formula (1-1) to (1) -8) A compound such as CELLOXIDE 2021P or CELLOXIDE 20 8 1 (made by Daicel Co., Ltd.) can be used. In the following formula, b represents an integer of 〇3〇. R represents a carbon number of 1 to 8. Alkyl, such as anthracenylene, ethyl, propyl, isopropyl, butyl, isobutyl, butyl, pentyl, hexyl, heptyl, a linear or branched chain alkyl group such as an octyl group. Among them, a linear or branched alkyl group having a carbon number of 1 to 3 such as a methylene group, an ethylidene group, a propyl group or an iso-propyl group is preferred. -10- 201233726

(ii) a compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond, for example, a compound represented by the following formula (II).

In the formula (II), R' is a group in which a p-valent alcohol removes P-OH, and ρ and η represent a natural number. a ρ-valent alcohol [R'-(OH)p], for example, a polyol such as 2,2-bis(hydroxyindole-11-201233726-based)-1-butanol or the like (an alcohol such as carbon number 15) ep is preferably i~6, η is preferably 1 30. When p is 2 or more, η of each of the bases (in the parentheses) may be the same or different. The above compounds, specifically, for example, 2,2-bis(hydroxymethyl)-indolyl butanol, 2_epoxy_4_(2-epoxyethyl)cyclohexane adduct, EHPE 3150 (Daicel ( Stock system) and so on. These alicyclic epoxy compounds (A) may be used singly or in combination of two or more. The alicyclic epoxy compound (A) is preferably a 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate represented by the above formula (1_1}, and CELLOXIDE 2021P. The amount (content) used in A) is not particularly limited to the total amount (100% by weight) of the alicyclic cyclic oxime compound (A) and the iso-negative oxime monoallyl diglycidyl ester compound (B), It is preferably from 5 to 9 % by weight, more preferably from 60 to 90% by weight, still more preferably from 7 to 9 % by weight. When the amount of the alicyclic epoxy compound (A) is less than 50% by weight, The isocyanuric acid monoallyl diglycidyl ester compound (B) has insufficient solubility, and may be easily precipitated if left at room temperature. Alternatively, the amount of the alicyclic epoxy compound (4) used may be More than 90% by weight 'When a photo-semiconductor device is produced, cracking may occur easily. < (4), component (B), and component (total amount of ruthenium (10)% by weight) in the 'alicyclic epoxy compound (4) The sum (total amount) of the content of the iso-cyanuric acid monoterpene=based diglycidyl compound (B) is not particularly limited to 70 to 90% by weight. Monoallyl diglycidyl ester compound (B)> The isocyanuric acid mono-propyl propylene oxide compound (B) ' used in the present invention can be represented by the following general formula (1).

之 alkyl. Alkyl group having 1 to 8 carbon atoms such as methyl, ethyl propyl propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl and the like Alkyl or branched alkyl. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a mercapto group, a g group, a propyl group or an isopropyl group is preferred. It is preferable that R1 and R2 in (1) are hydrogen atoms. An example of a monoisopropyl diglycidyl ester compound of the above formula, such as isoallyl cyanurethane diglycidyl ester, isomeric cyanuric acid 1-allyl-3 , 5-bis(2·decyl epoxypropyl) vinegar, iso-cyanuric acid η: methacryloyl)-3,5-diepoxypropyl, iso-cyanuric ι (2 fluorenyl) = alkenyl)-3,5,2 methylepoxypropyl) vinegar, and the like. Further, the isotrimeric gas oxime monoallyl diglycidyl ester compound (Β) may be used singly or in combination of two or more. Isocyanuric acid monoallyl diglycidyl ester compound (Β), which can be optionally mixed in the range of the above-mentioned ruthenium ring epoxy compound (Α), alicyclic epoxy compound (Α) and heterotrimerization The ratio of the monoallyl propylene glycol epoxide compound (Β) is not particularly limited, and the alicyclic epoxy compound (Α): isocyanuric monoallyl methoxy propyl ester compound (Β) is preferably Μ : ~: 1 〇 (by weight) When the car is preferably outside the range of 4, the solubility of the isomeric cyanuric monoallyl diglycidyl ester compound (Β) is not easily obtained. -13- 201233726 Isopropyl cyanide isocyanate is reacted with an epoxy group by adding an alcohol or an acid anhydride ()'. Alpha

The total amount of the alicyclic epoxy compound (Α) and the iso-cyanide X-propyl vinegar compound (Β) is the total amount of the cypress for the epoxy tree II: propyl dimer} (100 weight is not particularly limited to two, wide rolling The viewpoint of the base light property and the crack resistance is 80% by weight / heat resistance is 80% by weight or more. Preferably, the above is ' alicyclic polyester resin (C;)> The curable ring of the present invention The oxy-resin composition, t (C) serves as a task for improving the heat resistance of the cured product, the light resistance, and the reduction of the luminosity of the alicyclic ring. The alicyclic polystyrene light semi-conductive ring structure (aliphatic ring structure) Polyester resin, especially in the case of heat-resistant, light-resistant, and crack-resistant, from the hardened resin (6), the main chain has an alicyclic ring (aliphatic ring, the above-mentioned alicyclic ring.) The alicyclic polycyclic vinegar resin (C) has an alicyclic structure monocyclic hydrocarbon structure or bridge pile γ 疋 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例4) 4 bridged cyclic hydrocarbon structure. „^Structure or structure, can only be used for any of the constituents of the fat* and DD_ from the dicarboxylic acid in the bribe (C) and the constituents of the unit; Alternatively, the alicyclic polyester resin (c) may be introduced from both sides, and the monomer having the structure of p π &#> It can make the modified epoxy. The polyester vinegar with the fat-resistant resin body is better than the polyester vinegar with the fat content of the sulphate. The diol with the alicyclic structure is used. The dicarboxylic acid is not particularly limited, and examples thereof include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 4-methyl-1. , 2-cyclohexanedicarboxylic acid, cimic acid, 1,4-decahydronaphthalene dicarboxylic acid, 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid, 2, a dicarboxylic acid having an alicyclic structure such as 7-decahydronaphthalene dicarboxylic acid (including a derivative such as an acid anhydride) or the like; 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-ring Pentane dimethanol, 1,3-cyclopentane dinonanol, bis(hydroxymethyl) three [5.2.1.0] 5-membered cyclic diol such as decane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexane 6-membered cyclic diol such as alkyl decyl alcohol, 1,3-cyclohexane dimethyl alcohol, 1,4-cyclohexane decyl alcohol, 2,2-bis-(4-hydroxycyclohexyl) propane, hydrogenation double A diol having an alicyclic structure such as phenol A (including such a derivative), etc. The alicyclic polyester resin (C) may also have a constituent unit derived from a monomer component having no alicyclic structure. a monomer component of the structure, for example, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid or naphthalene dicarboxylic acid (including a derivative such as an acid anhydride); adipic acid and hydrazine; Aliphatic dicarboxylic acids such as diacids, sebacic acid, succinic acid, fumaric acid, maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol , 3-methyl-1,5-pentanediol, 2-mercapto-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2- a diol (also including such a derivative) such as ethyl-1,3-propanediol, stilbene diol, bis-A oxyethylene adduct, and bis-A oxypropylene adduct Further, in the above-mentioned dicarboxylic acid or diol having no alicyclic structure, a substituent having a suitable substituent (for example, an alkyl group, an alkoxy group, a halogen atom or the like) is also contained in a monomer component having no alicyclic structure. -15- 201233726 The ratio of the monomer unit of the known 辰辰 to the Λβ m 〇9 ___ early element (all monomer component) (100 ym%) constituting the alicyclic polyester resin (c) is not particularly limited.疋' is preferably 10 mol% or more (for example, 10 to 80 mol%), more preferably 25 to 70 mol%, and still more preferably 40 to 60 mol%. The monomer with an alicyclic ring D〇 has a less than 1% molar solution, and the heat, light resistance and crack resistance of the cured product may sometimes decrease. The ruthenium polyester resin (c) ' is particularly preferably an alicyclic polyester containing at least one of the units represented by the following formulas (2) to (4).

(2) Stretching base. Also, R4~R, from the independent carbon number or branch #状> μ & , , % of the original 'sub or straight word trend of the number of 1 to 4 alkyl, from r4 ~ Han 7 left to 4· ϋ..., the two 4 key knots and form a ring)

-16- 201233726 (wherein R3 represents a linear, branched, or cyclic alkyl group having 2 to 15 carbon atoms. Further, R4 to R7 each independently represent a hydrogen atom or a linear or branched chain. A chain of alkyl groups having 1 to 4 carbon atoms, and two selected from R4 to R7 may be bonded to a ring).

(wherein R3 represents a linear, branched, or cyclic alkyl group having 2 to 15 carbon atoms. Further, R4 to R7 each independently represent a hydrogen atom or a linear or branched carbon. The alkyl group of 1 to 4 may be bonded to the two selected from R4 to R7. Preferred specific examples of the constituent units represented by the above formulas (2) to (4) are, for example, 4-methyl-1,2-cyclohexanedicarboxylic acid represented by the following formula (5) and ethylene glycol. Form the unit. The alicyclic polyester resin (C) having this constituent unit can be obtained by polycondensing, for example, f-hexahydrophthalic anhydride with ethylene glycol. Ο Ο C—〇—CH2-CH2—0

-17- 201233726 Other specific examples of the constituent units represented by the two formulas (:) to (4), the configuration of the example (6) indicates that M_cyclohexanthene and neopentyl glycol < constitute early . With this structure For example: 1 4 production? The oxime resin (C) can be obtained by polycondensing % hexane dicarboxylic acid with neopentyl glycol. 0 〇 -c

CHa C—0—CH2-C-CH2 ICHa 0 (6) When the ring is made of polyester resin (C) and the right is + ±, the structure of β Κ is represented by the above formula (2) to (4). The unit is fixed, relative to the mouth of π. Ten miles (5 counts) are not particularly limited to all the constituent units of the polyester resin (C) (100 mol 0 is more than 〇 mol % (for example: 20 to 100 moles / Ui # ,

ςΛ , Λ ΐυυ Wu Dou /. ) 杈 better, better A shows: constitute Mo == Μ 0 mole %. The above formula (7), heat, light resistance, :::, = ear % ' Sometimes the hardness of the cured product: the number average molecular weight of the cyclic polyester resin (C) is not particularly limited, more than ~ (10) just, better than the side . Epoxy resin (〇: if the average molecular weight is less than 300', the toughness of the hardened material is not enough, on the other hand, the average molecular weight of the alicyclic polyester resin (C) exceeds 100,000, and the hardener ( D) The mutual solubility will decrease: the transparency of the cured product will be reduced. In addition, the alicyclic polycarbonate resin (C): the number average molecular weight can be determined by GPC (gel permeation chromatography) method as a standard. 201233726 Further, two or more types of alicyclic polyester resins (c) are used. One type or one type of alicyclic polyester resin (C) is not particularly limited, and it can be produced according to the method. In particular, for example, a alicyclic polyester resin (6) \ = by the method of polycondensation of the above dibasic acid and diol, or the above:: as a regular derivative (acid needle, ester, 醯 醯 等, etc.) and two The composition of the curable epoxy resin of the present invention, the blending amount (content) of the fat =::: (C) is not particularly limited to the total amount of the relative enthalpy and the hardener (9) (100 weight; 7 Polyacetate resin (9) More preferably Asm壬) is preferably 1 to 60% by weight, and = "heavy". If the amount of the alicyclic polyester resin (c) is less than If the weight of the hardened material (6) is more than 6% by weight, the penetration of the hardened material may be lowered. On the other hand, when the hardening epoxy resin composition of the present invention contains the curing catalyst (F) as an essential component, the blending amount (content) of the alicyclic polyester resin (d) is not particularly limited, and is relative to the alicyclic ring. The polyester resin (D) and the hardening catalyst ^ are measured (1% by weight), preferably 50 to 99% by weight, more preferably 65 to 99% by weight. Blending of the alicyclic polyester resin (D) If the amount is less than 5 〇. 4, the crack resistance of the cured product may be lowered. On the other hand, if the blending amount of the alicyclic polymer: resin (D) exceeds 99% by weight, the transparency of the cured product Or heat resistance = sometimes it is lowered. ... <hardener (D)> The hardener (D) has a function of hardening a compound having an epoxy group. In the present invention, the hardener (D) can be used as an epoxy resin. It is a known or customary hardener for the hardener. In the present invention, the hardener (D) is preferably 25 L as the liquid -19-.201233726 s-type anhydride, for example: methyl tetrahydrogen Phthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, fluorenyl intrinsic fluorenyltetrahydrophthalic anhydride, etc. Further, for example, phthalic anhydride or tetrahydrogen Normal temperature such as phthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, etc. (about 25. 〇 is a solid acid anhydride dissolved in normal temperature (about 25. 〇 is a liquid anhydride to become a liquid mixture Therefore, it can also be used as the hardener (D) of the present invention. In the curable epoxy resin composition of the present invention, the hardener (D) is heat-resistant, light-resistant, and crack-resistant from the cured product. The viewpoint is preferably a saturated monocyclic hydrocarbon dicarboxylic anhydride (which also includes a substituent in which a ring such as an alkyl group is bonded). Further, the curing agent (D) may be used singly or in combination of two or more. Further, in the present invention, a commercially available product such as Rikacid MH-700 (manufactured by Nippon Chemical and Chemical Co., Ltd.) or HN_55 (manufactured by Hitachi Chemical Co., Ltd.) can be used as the curing agent (D). The amount (content) of the hardener (D) is not particularly limited, and is 50 to 200 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention. Preferably, it is more preferably 100 to 145 parts by weight. More specifically, the epoxy group in the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention is preferably used in an amount of from 0.5 to 1.5 equivalents per equivalent of the epoxy group. When the amount of the curing agent (D) used is less than 50 parts by weight, the hardening is insufficient, and the strong character of the cured product tends to be lowered. On the other hand, when the amount of the curing agent used exceeds 200 parts by weight, the cured product may be colored, and the hue may be deteriorated. -20-201233726 <hardening accelerator (E)> The curable epoxy resin composition of the present invention further contains hardening (8). The hardening accelerator (8) is a compound having a function of promoting the curing speed when the epoxy compound is cured by hardening. As the hardening accelerator (E), a known or customary hardening accelerator may be used, for example, diazabicyclod...doukawa ten-sweet-grass and its salt (9), such as: phenate, octanoic acid, p-toluenesulfonic acid Salt, citrate, barium diphenylborate, diazabicyclo[4_3.0]nonene-5 (DBN), and salts thereof (for example, scales, strontium salts, grade 4 ammonium salts, barium salts); a dimethylamine, a 2,4,6-glycol (dimethylaminomercapto) phenol, a N-N-dimethylcyclohexylamine or the like, a tertiary amine; a 2-ethyl-4-methyl silane Base ethyl-2-ethyl-4-indenyl. Wait and wait. Rice bran: a phosphine such as a carboxylic acid ester or a diphenylphosphine; a scaly compound such as tetraphenyl scaly tetra(p-phenylene) borate; an organic metal salt such as tin octylate or zinc octoate; a metal chelate compound. These may be used singly or in combination of two or more. Further, in the present invention, the curing accelerator (Ε) may also be U CAT sa 506, U-CAT SA 102, U-CAT 5 003, U-CAT 18X, 12XD (developed product) (both San-apro) )), ΤΡΡ-Κ, TPP-MK (both from Beixing Chemical Industry Co., Ltd.), and PX-4ET (manufactured by Sakamoto Chemical Industry Co., Ltd.). The amount (content) of the hardening accelerator (E) is not particularly limited, and is 〇. 5 to 5 by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. The portion is preferably more preferably 0.1 to 3 parts by weight and more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 2.5% by weight. If the amount of the hardening accelerator (Ε) is less than 〇.〇5 parts by weight, the hardening promoting effect may sometimes be insufficient. On the other hand, when the amount of the curing accelerator (Ε) is more than 5 parts by weight, the cured product may be colored, and the hue may be deteriorated. -2 1-201233726 <Curing Catalyst (F)> In the curable epoxy resin composition of the present invention, a curing catalyst (F) may be used instead of the above curing agent (D) and a curing accelerator (E). . As in the case of using the hardener (D) and the hardening accelerator (E), by using the hardening catalyst (F), the hardening reaction of the epoxy group-containing compound can be carried out and a cured product can be obtained. The hardening catalyst (F) is not particularly limited, and a % ion catalyst (cationic polymerization initiator) which generates a cationic substance by polymerization by ultraviolet irradiation or heat treatment and starts polymerization can be used. Further, the curing catalyst (F) may be used singly or in combination of two or more. A cationic catalyst which generates a cationic substance due to ultraviolet irradiation, for example, hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, hexafluoroarsenate or the like. UVACURE1 590 (Daicel. Cytec), CD-1010, CD-1011 'CD-1012 (made by Sartomer, USA), Irgacure 264 (made by Ciba Japan), CIT_ 1682 (Japan #达达) Commercial products such as those are preferred. The heat treatment may produce a cationic catalyst of a cationic substance, for example, an aryl diazonium salt, an aryl sulfonium salt, an aryl sulfonium salt, an arene-ion complex, or the like, and preferably, for example, pp_33 may be used. CP_66, CP-77 (made by ADEKA), FC-509 (made by 3M), UVE1014 (made by GE), San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L,

San-Aid SI-110L (Sanshin Chemical Industry Co., Ltd.), CG_24 6 1

A commercial item such as Japan. Further, a compound of a metal such as aluminum or titanium and a chelating compound of acetonitrile acetic acid or a diketone, a sterol compound such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and a chelating compound of acetonitrile or a diketone. Compounds such as Shuangxi S can also be used. -22- 201233726 The amount (content) of the hardening catalyst (F) is not limited to the amount of the compound which is contained in the curable epoxy resin composition.曰0 parts by weight) is preferably from 0. 01 to 15 parts by weight, more preferably from 0.01 to 12 parts by weight, and even more preferably from 5 to 10 parts by weight, particularly preferably parts by weight. By using the hardened contact 褀u坰姝(h) in this range, a cured product excellent in heat resistance, light resistance, and transparency can be obtained. ... < rubber particles> The hardenable silicone resin composition of this month may further contain rubber particles. The rubber particles are, for example, rubber particles such as particles & NBR (acrylonitrile butadiene rubber), reactive terminal retarded NBR (CTBN), metal-free, and particulate SBR (styrene-butadiene rubber). The rubber particles ' are preferably rubber particles including a core portion having rubber elasticity and a multilayer structure (nuclear sheath structure) composed of at least one sheath layer covering the core portion. The above rubber particles are particularly preferably composed of a polymer (polymer) which is a necessary monomer component of (mercapto)acrylic acid and has a hydroxyl group and/or a carboxyl group (either one or both of a base group and a carboxyl group). It is preferred to use a rubber particle which can react with a functional group having an oxiranic group such as an alicyclic epoxy group (A). When the surface of the rubber particles does not have a hydroxyl group and/or a carboxyl group, the cured product becomes cloudy due to thermal shock such as % heat and the transparency is lowered, which is not preferable. Among the rubber particles, the polymer constituting the core portion having rubber elasticity is not particularly limited, and is preferably decyl acrylate, ethyl acrylate or butyl acrylate. Acrylate is used as an essential monomer component. The polymer constituting the rubber-elastic core portion may contain, for example, styrene, aryl-23-.201233726 fragrant vinyl compound such as X-nonyl styrene; acrylonitrile or mercapto propylene. A nitrile such as nitrile; a conjugated diene such as butadiene or isoprene; an olefin such as ethylene, propylene or isobutylene as a monomer component. § wherein 'the polymer constituting the above-mentioned rubber-elastic core portion is a monomer component It is preferable to contain (meth) acrylate, and a combination of 12 or more selected from the group consisting of an aromatic vinyl compound, a nitrile, and a conjugated diene, that is, constituting the above-mentioned core portion. a polymer such as a (fluorenyl) lactone/aromatic vinyl compound, a binary copolymer such as (methionate/conjugated diene; (meth) acrylate/aryl = private vinyl a ternary copolymer such as a compound/conjugated diene, etc. Further, the polymer of the core portion may also contain polyfluorene oxide such as polydidecyl fluorene oxide or polystyrylmethyl oxalate or Polyamine phthalate, etc. β = polymer into the above core portion, other monomers Terms of points, there may be 3 - ethylene benzene, (Yue-yl) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanuric _

A reactive crosslinking monomer having two reactive functional groups in a monomer such as benzophenone-, knee I--propylpropionate or butanediol diacrylate. ^ In the core portion of the above rubber particles, the core portion composed of a (meth) acrylate/aromatic 'organic 5 one-membered copolymer (especially butyl acrylate / stupid) can be easily adjusted from rubber particles. The viewpoint of the refractive index is preferred. The core portion of the above rubber particles can be produced by a commonly used method: for example, a method in which the above monomer is polymerized by an emulsion polymerization method can be used. In the emulsion polymerization method, the above monomers may be added in one portion at a time, and after a part of the precursors, the remaining portions are continuously or intermittently added and polymerized, and a polymerization method using the seed particles may also be used. -24- 201233726 The polymer constituting the core portion of the sheath of the above rubber particles is different. #马/, the above-mentioned layer should preferably have a base group and/or a thiol group as an alicyclic epoxy group (4). A functional group reactive with an epoxy group compound. Therefore, the adhesion of the interface with the alicyclic epoxy compound (A) and the % of the alicyclic epoxy compound (A) is improved, and the rubber particles of the sheath layer are hardened, so that the urethane resin is oxidized. The hardened material obtained by hardening the composition exhibits excellent crack resistance. Further, it is also possible to prevent the glass transition temperature of the hardened material from being lowered. It is possible to prevent the polymer constituting the above sheath layer, the ester, the ethyl (meth) acrylate, and the (methic acid) acrylic acid oxime. Example h in the core part (A:): dilute acid: when using butyl acrylate, the polymerization of the formation of the layer:) The composition should be butyl (meth) acrylic acid other than butyl acrylate. ... two () acrylic acid vinegar (for example: 箄...I: fine acid succinct, methacrylic butyl styrene:): methyl) acrylic acid S can also contain monomers ☆, for example: SI dimethyl An aromatic vinyl compound such as styrene, acrylonitrile, diacrylonitrile or the like. In the above rubber particles, a "single layer of a single layer is formed, and (meth)acrylic acid is used alone or in combination with the above monomers.

It is preferable that St is preferable, especially when at least the aromatic ethyl group-based compound is contained, and the refractive index of the rubber particles is easily adjusted. Further, 'the polymer constituting the sheath layer is formed as a base group capable of reacting with a functional group having an epoxy group such as an alicyclic epoxy compound (A) in terms of a monomer component. Or a carboxyl group, preferably containing a (meth)acrylic acid hydroxyalkyl anthracene such as (mercapto)propyl-hydroxyethyl ester, or an α,β-unsaturated acid, maleic anhydride or the like of (meth)acrylic acid: anthracene or the like, Beta-unsaturated anhydride temples. -25-201233726 The polymer constituting the sheath layer in the above rubber particles is preferably one or more selected from the above monomers in terms of a monomer component, and is preferably a m/amp; methyl acrylate. The combination. That is, the sheath layer is, for example, (mercapto) propylene 1 S 曰 / aromatic vinyl / hydroxyalkyl (fluorenyl) acrylate, (meth) olefin oxime from 曰 7 aromatic vinyl / α, β A sheath layer composed of a ternary copolymer such as an unsaturated acid or the like is preferred. Further, the polymer constituting the sheath layer is a second core in terms of other monomer components. Similarly, in addition to the above monomers, the file may also contain divinylbenzene/methyl)acrylic acid acrylonitrile, ethylene glycol bis(indenyl)acrylic acid vinegar, malathion sulphuric acid, cyanuric acid. Triisopropyl propyl ester, dipropylene propylene phthalate, butane diol diacrylate acrylate ... a reactive cross-linking monomer having two or more reaction-producing fluorenyl groups in a monomer (one molecule). The rubber particles (rubber particles having a core-sheath structure) can be obtained by coating the core portion with a sheath. a method of coating the above-mentioned core portion with a sheath layer, for example, on the surface of the rubber-elastic core portion obtained by the above method, coating a copolymer constituting the sheath layer to perform coating; and obtaining rubber elasticity obtained by the above method The core portion is used as a dry component, and each component constituting the sheath layer is used as a branch component, and a graft polymerization method or the like is carried out. The average particle diameter of the above rubber particles is not particularly limited to 10 to 500 nm, and more γ to ubiquino μα ^ ^ is 00 nm. Further, the maximum particle diameter of the above rubber particles is not particularly preferable, and is 50 to l 〇〇〇 nrn, more preferably 100 to 800 nm. Pingzhuo complement-丄 该 The rain The average grain size is more than 500nm, or the most lOOOnm, the initial work of the rubber Τ ^ Α ^ The dispersibility of the deer hardened material is reduced, and sometimes the cracking property is reduced. On the other hand, if the average particle diameter is less than 1 〇 nm or the maximum -26-201233726 particle size is less than 50 nm, the effect of improving the crack resistance of the cured product is sometimes difficult to obtain. The refractive index of the rubber particles is not particularly limited, and is preferably 404.60, more preferably, the refractive index of the rubber particles: and a curable epoxy resin composition containing the rubber particles (curable epoxy resin of the present invention) The difference between the refractive indices of the hardened materials obtained by the hardening of the composition is preferably within 0.03 (_〇·〇3 to 〇〇3) of the soil. When the difference in refractive index is greater than 0.03 Å of the soil, the transparency of the cured product may be lowered, and the opacity may be lowered. The illuminance of the optical semiconductor device tends to decrease, and the function of the optical semiconductor device may be lost. The rubber particles are folded, for example, by inserting the rubber particles into a forming mold at 21 (TC, 4 MPa for compression molding, and obtaining a flat plate of thickness imm, which is cut out from the obtained flat plate and called "the test piece," In the state in which the sputum and the test piece are intimate, a multi-wavelength Abbe refractometer (trade name "DR_M2", - (share)) is used to measure 2 (TC). The refractive index of the cured epoxy resin composition of the present invention is refracted from the hardening method described in the following optical semiconductor device, and is cut out. Longitudinal 2〇mmx horizontal 6mmx thickness 1mm s type test piece, and use i, self-installed from aa test piece tightly mixed with the liquid, so that the use of multi-wavelength Abbe refractometer ( "The product name is obtained.", Atag(R) (manufactured by Atag) (measured at 20 ° C, the refractive index % of the sodium D line • The oxygen resin composition is limited, and the hardenability content (mixing amount) with respect to the present invention不特中'The above rubber particle hardenable epoxy resin group-27- •201233726

The compound (I 〇 5 3 ) and the total amount of the compound (100 parts by weight) of the soil contained in the product are preferably 0.5 to 30 parts by weight, and θ ^ is preferably 1 to 2 parts by weight. The content of the rubber particles is less than 0.5 parts by weight, and the crack resistance of the mash is reduced. On the other hand, in the winter, the rubber particles have a tendency to lower the heat resistance of the cured product by more than 3 parts by weight. <Additive> The curable property of the present invention; in addition to the above, in the range of the g k oxynitrein composition, various additives may be used insofar as the effect of the present invention is not known. For example, if an additive is used, a compound such as ethylene glycol, diethylene glycol or propylene glycol 'glycerin is used, the reaction can be carried out gently. In addition, polysiloxane or fluoro 4U, leveling agent, γ-glycidoxypropyltrimethoxy group can be used without damaging viscosity or seizure, Jvt m ^ sub-monthly range.矽 等 etc. (4) coupling agent 'surfactant', surfactant, dioxo, oxidized, etc. Additives. <Preparation method of curable epoxy resin composition> The curative epoxy resin composition of the present invention contains the above-mentioned lipid oxime compound (Α), and iso-cyanuric acid monoallyl propylene oxide. The propyl ester compound (Β), the alicyclic polymer resin (c), the curing agent (D), the curing accelerator (Ε) or the curing catalyst (F) may be used, and the preparation method is not particularly limited. For example, an α-agent containing an epoxy group-containing compound such as an alicyclic epoxy compound (A), an isomeric cyanuric acid monopropyl propylene glycol compound (B), or the like as an essential component can be prepared, respectively. And a β agent containing a hardener (D) and a hardening accelerator (E), or a hardening catalyst (F) as an essential component, and the alpha agent and the β agent are mixed and mixed in a predetermined ratio and optionally under vacuum Defoaming to prepare. Further, -2 8-201233726 In this case, the alicyclic polyester resin (c) may be previously mixed as a constituent of the alpha agent and/or the beta agent, or may be mixed with the alpha agent and! In the case of three doses, the components other than the alpha agent and the beta agent were blended. In the preparation of the above α agent, the temperature at the time of stirring and mixing is not particularly limited, and is preferably from 3 0 to 150 ° C, more preferably from 3 5 to 130 ° C. Further, when the above-mentioned β agent (when two or more components are used) is prepared, the temperature at the time of stirring and mixing is not particularly limited, and is preferably from 3 to 10 ° C, more preferably from 3 5 to 80 ° C. For the stirring and mixing, a known device such as a self-rotating public-transition mixer, a planetary mixer, a kneader, a dissolver, or the like can be used. In particular, when the curable epoxy resin composition of the present invention contains the hardener (D) as an essential component, the viewpoint of obtaining a homogeneous composition is preferably by using an alicyclic polyester resin (C) and a hardener ( d) premixing to obtain a mixture of the above (a mixture of the alicyclic polyester resin (C) and the hardener (D)), then adding a hardening accelerator (E) or other additives to the mixture to prepare a beta agent, and then The β agent and the α agent are mixed to prepare. The temperature at which the alicyclic polyester resin (c) is mixed with the hardener (D) is not particularly limited, and is preferably from 60 to 130 ° C ', more preferably from 90 to 12 ° C. The mixing time is not particularly limited, and is preferably 3 0 to 1 〇 〇 minutes, more preferably 4 5 to 8 0 minutes. The mixing is not particularly limited and is preferably carried out under a nitrogen atmosphere. Further, the above-mentioned known device can be used for mixing. The alicyclic polyester resin (C) and the curing agent (D) are not particularly limited, and may be further subjected to an appropriate chemical treatment (for example, hydrogenation or terminal modification of an alicyclic polyester). Further, in the mixture of the alicyclic polyester resin (C) and the curing agent (D), a part of the curing agent (D) may be combined with the alicyclic polyester resin (C) (for example, a hydroxyl group of an alicyclic polyester, etc.) reaction. -29- 201233726 For the mixture of the above-mentioned alicyclic polyester resin (c) and hardener (D), for example, "HN-72" (made by Hitachi Chemical Co., Ltd.), "hn 57〇〇 (曰) can also be used. Commercial product such as Lihua Chemical Industry Co., Ltd. <Cured product> By curing the curable epoxy resin composition of the present invention, transparency, heat resistance, light resistance, and crack resistance can be obtained. The cured product having excellent physical properties is not particularly limited, and is preferably 45 to 200. (:, more preferably 1 to 19 〇. 〇, more preferably 1 〇〇 18 〇 ° C. Further, the heating time (hardening time) during hardening is not particularly limited, and is preferably 30 600 knives for 4 liters, more preferably 45 to 540 minutes, and even more preferably 6 〇 to 48 〇 minutes. If the hardening time is lower than the lower limit of the above range, the hardening does not fill the knife. On the other hand, if the upper limit of the above range is exceeded, the resin component may be decomposed and may be poor. The hardening condition depends on various conditions, by hardening. When the temperature is high, the hardening time is shortened, and when the hardening temperature is low, the hardening time is extended, etc. <Resin composition for optical semiconductor sealing> The resin composition for optical semiconductor sealing of the present invention comprises the curable epoxy resin composition of the present invention. The optical semiconductor sealing of the present invention is used. The resin composition can be sealed with an optical semiconductor device which is excellent in various physical properties such as transparency, heat resistance, light resistance, and crack resistance, and can be used in an optical semiconductor device. When a high-output, high-intensity optical semiconductor element is provided, the illuminance is not easily lowered with time. -30-.201233726 <Opto-Semiconductor Device> The optical semiconductor device epoxy resin composition of the present invention (light semiconductor device & Sealing and sealing the resin composition by the curable body member of the present invention)

The above method was prepared =:. The ring body is widely sealed and is U-mode' and heated under the established conditions: The material is incorporated into a predetermined form of the epoxy resin composition, and the photo-semiconductor device can be obtained by hardening the semiconductor. The hardening temperature and the hardening time may be the same as described above. The curable epoxy resin composition of the present invention, the conductor (the lane of the lane, the opening, the +-limit, the & _1, the light, the light, the semi-conductor, the cow) can be used for, for example, an adhesive, an electrical insulation. Materials, laminates, coatings, inks, coatings, sealants, anti-agents, composites, transparent substrates, transparent sheets, transparent films, optical components, optical lenses, optical components, light, % K-shaped, electronic paper, touch panel, solar cell substrate, optical waveguide, track body, etc. Light guide plate, holographic memory [Embodiment] However, the present invention is not limited to the following, and the present invention will be described in more detail based on the embodiments. - Production Example 1 (manufacture of rubber particles) Ion exchange was carried out under a nitrogen stream and stirred in a 1 L polymerization vessel equipped with a reflux condenser, water of 50 〇g, and dioctyl succinyl succinate, sodium sulphate ggg, and Warm up to m:. The monomer consisting of 9.5 g of butyl acrylate, 2.57 g of styrene, and 2.5% of styrene is added to the amount necessary for forming the core portion, which is equivalent to about 5% by weight. 201233726 The mixture was stirred for 20 minutes for emulsification, and then 9 5 mg of peroxydisulfate clock was added, and the mixture was stirred for an hour to carry out initial polymerization. Next, 0.5 mg of potassium peroxydisulfate 1 8 was added and stirred for 5 minutes. Among them, it took 2 hours to continuously add the remaining amount (about 9.5 wt% component) necessary for forming the core portion to butyl acrylate 1 8 〇 5 g, styrene 48.89 g, and diethyl benzene 7.33 g dissolved dioctane. A monomer mixture of 95 g of sodium sulfosuccinate was subjected to the second seed polymerization, followed by aging for 1 hour to obtain a core portion. Next, 60 mg of potassium peroxydisulfate was added, stirred for 5 minutes, and it was continuously added to methyl methacrylate 6 〇g, propylene 1 1.5 g, and methacrylic acid isopropyl sulfonate jg for 30 minutes. Dioctyl is a sodium succinate 〇. 3g monomer mixture 'is polymerized. Thereafter, it was aged for 1 hour to form a sheath of the coated core portion. : The person was cooled to room temperature (25 ° C) and filtered through a plastic mesh having a mesh size of 120 μm to obtain a latex containing rubber particles having a core-sheath structure. The obtained knees were frozen at -30 C and dehydrated and washed with a suction filter, and then dried at 6 (TC-day and night air-dried to obtain the rubber particles of the flat phase α Λ ^ pass the rubber hook melon to 254 nm The maximum particle size is 486 nm. Also, the average particle size of the rubber particles is the best, and the 'i* is used by you.

The first action of the heart is to measure the principle of "Nan〇tracT particle size distribution measurement Jin Jin # 0々" into the Nanotrac J疋 public (product name "UPA_EXl5〇 system" measurement sample, oblique material from _ 曰 machine installed ( Shares) For the particle size distribution curve of the service, the frequency of the measurement is 50%, the cumulative curve is the frequency of the measurement results, and the average length of the grain is divided into the maximum particle size. Further, the maximum particle diameter of h m ' was dispersed in 20 parts by weight of tetrahydrofuran by using 1 part by weight of the rubber particle-dispersed epoxy compound of -32 to 201233726 obtained in the following Production Example 2. Production Example 2 (Production of Rubber Particle-Dispersed Epoxy Compound) The weight fraction of the rubber particles obtained in Example 1 was prepared under a nitrogen flow: using a dissolver (i〇〇〇rpm, at 6 (TC state) 6 〇 minutes) 刀政于商〇〇名 "(^11〇又1(1620211)" (3,4_epoxycyclohexyl fluorenyl (3,4-% rolled) hexane carboxylate, Daicel ( 70 parts by weight of the product, the true de-foaming was carried out to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C: 624 mPa · s) ° Further, in Production Example 2, the rubber particles were dispersed in an epoxy compound (i weight) The viscosity of the rubber particles dispersed in 7 parts by weight (the viscosity at 25 ° C) was measured using a digital viscometer (trade name "DVU-EII type", manufactured by Tokimec Co., Ltd.). 3 (The ring-rolling resin is isomeric cyanuric acid monoallyl diepoxypropyl vinegar (trade name "MA_DGIC", manufactured by Shikoku Chemical Industries Co., Ltd.), and alicyclic epoxy compound (trade name "Cell〇xide2021P") , Daicel (share system 又 W)), the rubber particle dispersion epoxy resin obtained in Production Example 2, bisphenol A 创搭# u-type bismuth resin The name "YD-128" and Nippon Steel Chemical Co., Ltd. are mixed with 丄W not the volume of the 公西公方 (mixing ratio) (unit: parts by weight), stir at 8〇t, 曰' Isopropyl methacrylate dissolving m TM is obtained in % gas connection! (mixture) (corresponding to the above α agent). Further, the table i φ T t _" represents the component The same is shown in Table 2. • 33-201233726 Production Example 4 (Manufacture of at least a hardener composition containing a curing agent (hereinafter referred to as "kappa"): Examples 1 to 6 and Comparative Examples 1 to 3) A mixture of a curing agent (anhydride) (trade name: r Rikacid ΜΗ-700), a new Japan Physicochemical Co., Ltd., a curing agent (anhydride), and an alicyclic polyester resin (trade name "HN-7200", trade name" HN_5700", all manufactured by Hitachi Chemical Co., Ltd.), hardening accelerator (trade name "U-CAT 18X", San-apro (share)), additives (trade name "ethylene glycol", and Wako Pure Chemical Industries ( Co., Ltd.), according to the blending formula shown in Table 1 (unit: parts by weight), using a self-propelled scramble device (trade name "debubbing" Taro AR-250", manufactured by Thinky Co., Ltd.) uniformly mixed and defoamed to obtain K agent (corresponding to the above-mentioned β agent). Examples 1 to 6 and Comparative Examples 1 to 3 (Manufacture of curable % oxygen resin composition) The epoxy resin obtained in the production example 3 and the κ agent obtained in the production example* were uniformly mixed and defoamed using a self-propelled stirring device (trade name "defoaming Ryotaro AR 25", manufactured by Thinky Co., Ltd.). The blending ratio (unit: part by weight) shown in Table i was used to obtain a curable epoxy resin composition. In the case of the epoxy resin, the product name "Celloxide 2 〇 21P" (manufactured by Daicel Co., Ltd.) was used. (Manufacturing of Photo-Semiconductor Device) The curable epoxy resin composition obtained above was cast into a lead frame (InGaN element, 35 mrn×2_8 mm) of the optical semiconductor shown in Fig. i, and then baked at 1 2 〇C (resin). The hardening case is heated for $hour to obtain an optical semiconductor device in which the optical semiconductor element is sealed with a hardened resin (hardened material). In addition, the 'ith towel, 1 〇〇 indicates a reflection member (light reflection -34-201233726 resin composition), 1 〇1 indicates metal wiring, 丨〇2矣_ element, 103 indicates bonding wire, and 104 indicates penetration. Rent a resin (hardened). Production Example 5 (Production of epoxy resin: Examples 7 to 1 2, Comparative Example 5, isopropyl cyanuric acid monoallyl dioxime gas oxypropyl propyl ester (trade name "MA-DGIC", four countries Chemical Industry Co., Ltd.), a fine oxygen compound (trade name "Cell〇Xide2021P", manufactured by Daicel Co., Ltd.), a rubber particle-dispersed epoxy resin obtained in Production Example 2, and a double-aged A-cut g 1 5 Oxygenated resin (trade name "YD-128", manufactured by Nippon Steel Chemical Co., Ltd.) is mixed according to the blending formula (mixing ratio) (unit · · parts by weight) shown in Table 2, at 8 (rc) The mixture was mixed for a few hours to dissolve the mono-l-propyl diglycidyl isocyanate to obtain an epoxy resin (mixture) (corresponding to the above-mentioned α agent). Production Example 6 (alicyclic polyester resin) Production: Example 7 to 1 2) 172 parts by weight of 1,4-cyclohexanedicarboxylic acid (East, manufactured by Kyowa Chemical Industry Co., Ltd.) was added to a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser. 208 parts by weight of neopentyl glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.) 1 part by weight, heated to 160 ° C, and then heated from 160 ° C to 250 ° C for 4 hours. Secondly, it took 1 hour to reduce pressure to 5 mmHg, and then reduced to 0.3 mmHg or less and then reacted at 250 ° C. 1 hour, the alicyclic polyester resin was obtained. Examples 7 to 12, and Comparative Examples 4 to 6 (Production of Curable Epoxy Resin Composition) -35-201233726 The epoxy resin obtained in Production Example 5 and Production Example 6 were obtained. The alicyclic polyester resin and the hardening catalyst (trade name "San_aid si_i〇〇l" 'Sanshin Chemical Industry Co., Ltd.)' use a self-propelled stirring device (trade name "Degassing Ryotaro AR-250", Thinky (manufactured by the company) was uniformly mixed and defoamed to obtain a blending ratio (unit: parts by weight) shown in Table 2 to obtain a curable epoxy resin composition. Further, in the case of Comparative Example 4, the epoxy resin was used as a product. "Celloxide 2021P" (made by Daicel); (Manufacture of optical semiconductor device) The curable epoxy resin composition obtained above is cast into the lead frame of the optical semiconductor of the first embodiment (InGaN element, 3 5mmx2 8mm) After mold, 5 hours in an oven (resin hardened oven) at 120 °C Heat, an optical semiconductor device in which an optical semiconductor element is sealed with a hardened resin (cured material) is obtained. <Evaluation> The optical semiconductor device obtained in the examples and the comparative examples was subjected to an evaluation test by the following method. The total light flux of the optical semiconductor device obtained in the examples and the comparative examples was measured using a full beam measuring machine. Further, the total beam of the current of 60 mA was applied to the optical semiconductor device for 1 hour in the thermostat of 85. The photometric retention rate is calculated by the following formula. The results are shown in Tables 1 and 2. {Photometric retention rate (%) } = {full beam (100) after 100 hours } / (full beam (〇) of 〇 hours } χΙΟΟ -36- 201233726 [Thermal impact test] The light obtained in the examples and comparative examples The semiconductor device (two for each curable epoxy resin composition) was exposed to -4 (3 〇 minutes in a gas atmosphere of TC), followed by exposure for 3 〇 minutes in a gas atmosphere of KC for 1 cycle. The thermal shock was applied to the thermal shock tester for 2 cycles. After that, the sealing resin of the optical semiconductor device (hardened product of the curable epoxy resin composition) was observed using a digital microscope (VHX-900, manufactured by KEYENCE). The length of the crack generated was measured, and the number of optical semiconductor devices having cracks having a length of 90/zm or more in two optical semiconductor devices was measured. The results are not shown in Tables 1 and 2. [Comprehensive judgment] In the energization test The luminosity retention rate is 90% or more, and the number of cracked optical semiconductor devices having a length of 90 &quot;m or more in the thermal shock test is 0, and is evaluated as 〇 (good) in the comprehensive judgment. Is x (bad). The results are shown in Table 1, Table 2. -37- 201233726 Comparative Example 3 1 1 〇1 1 »~Η 0〇〇X Comparative Example 2 &lt; § 1 〇1 1 〇〇X Comparative Example 1 〇Η 1 1 1 100 1 1 irj Ο yn 00 CN X Example 6 〇1 1 1 沄1 00 OS 〇〇Example 5 Ο » 〇1 1 in ο »-Η 〇〇 Example 4 Ο 卜 1 1 i 1 Ό Ο τ — Η Ον α\ 〇〇Example 3 ο 1 1 t 1 130 Ο Ον ΟΝ 〇〇 Example 2 g 〇CS 1 1 1 沄1 Ο 〇〇 Example 1 〇1 1 1 沄1 00 Os 〇〇CEL2021P MA-DGIC YD-128 Rubber particles MH- 700 HN-7200 HN-5700 Glycol _ U-CAT 18Χ Thermal shock test [number] Comprehensive judgment of epoxy resin [parts by weight] Hard ^ (tantalum composition (K agent) [parts by weight] Photometric retention rate [ %: 1 Curable epoxy resin composition hardened material (optical semiconductor device) (Ν&lt;1 Comparative Example 6 1 1 1 1 〇〇X Comparative Example 5 j 1 1 1 ο 00 Ό 〇X Comparative Example 4 〇1 1 1 1 dm 00 CN X Example 12 1 1 d On OS 〇〇 Example 11 〇 1 〇Ο 〇〇 Example 10 〇 1 1 ο 00 Ο 〇〇 〇〇 Example 9 〇 1 1 ο Ον Ον 〇Example 8 g 1 1 ο ΟΟ 〇\ 〇〇 Example 7 〇1 1 Ό ο S; 〇〇CEL2021P MA-DGIC | YD-128 Rubber particle alicyclic polyester resin [parts by weight] San-aid SI-100L Thermal shock test [number] Comprehensive judgment of epoxy resin [parts by weight] Hardening catalyst [parts by weight] Photometric retention rate [%] 1 Cured epoxy resin composition cured product (optical semiconductor device) -8ε- .201233726 The components used in the examples and comparative examples are as follows. [Epoxy Resin] CEL2021P(CELLOXIDE2021P): 3,4_epoxycyclohexylmethyl (3,4_epoxy) cyclohexanyl citrate g, Daicel (MA) DGIC: Iso-cyanuric acid Monoallyl diglycidyl ester, Siguo Chemical Industry Co., Ltd. ° YD-128: bisphenol A type epoxy resin, neodymium iron chemical (share) system [K agent] MH-700 (Rikacid MH- 700) : 4-methylhexahydrophthalic anhydride / hexahydro-dodecanoic anhydride = 7 0/30, manufactured by Xinyi Physicochemical Co., Ltd. HN-7200: 4-mercaptohexahydrophthalic acid A mixture of an acid anhydride and an alicyclic polyester, HN-5 700 (formerly known as "DHZ-01") manufactured by Hitachi Chemical Co., Ltd.: 4-methylhexahydrophthalic anhydride/3-mercaptohexahydrophthalic acid Diphthalic anhydride ^ 7 〇 / 3 〇 and alicyclic polyester, a mixture, U-CA1T 1 8X made by 曰立化成工业 (股): hardening accelerator, SAN_ApR 〇 (stock) ethyl alcohol: Wako Pure Chemical Industries ( Co., Ltd. [hardening catalyst] SA&gt;J_AID SI-100L: aryl sulfonium salt, Sanxin Chemical Industry Co., Ltd. Test equipment • Resin hardening oven ESPEC (stock) g ρ η Η - 2 01 • Thermostatic bath ESPEC (version) small high temperature chamber ST-120B1 -39- 20123372 6 &lt;* Full Beam Measuring Machine Multi-spectral Radiation Setting System OL771 manufactured by Optronic Laborat〇ries, USA. Thermal Shock Tester ESPEC (small) thermal and thermal shock device tse-U-a [Industrial Applicability] The curable epoxy resin composition of the present invention can be preferably used for sealing applications of optical semiconductor elements. Moreover, the curable epoxy resin composition of the present invention can also be used for an adhesive, an electrical insulating material laminated board, a coating, an ink, a coating, a potting agent, an anti-rhying agent, a composite material, and a transparent meaning. Materials, transparent sheets, transparent films, optical components, optical lenses, optical components, optical shapes, electronic paper, touch panels, solar cell substrate waveguides, light guides, holographic memory, etc. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an embodiment of an optical semiconductor device obtained by sealing a curable epoxy resin composition (optical semiconductor element) of the present invention. The picture on the left side (a) is the 栌 ^ &lt; the circle is a perspective view, and the right side diagram (b) is a cross-sectional view. [Description of main component symbols] 100 reflectors (resin composition for light reflection) 1 0 1 Metal wiring 102 LED components 1〇3 Bonding wires 104 Transparent sealing resin -40-

Claims (1)

201233726 VII. Patent application scope: 1. A curable epoxy resin composition characterized by comprising an oxygen-producing compound (A) and a different isocyanuric acid represented by the following formula (1) a glycidyl ester compound (B), an alicyclic polyester resin (c), a hardened lanthanum (D), and a hardening accelerator (E); [wherein, R1 and R2 represent a hydrogen atom or an alkyl group having a carbon number]. 'Cure hardening epoxy resin composition characterized by: inclusion of 3 alicyclic ring medium (F); oxygen compound (A), and isomeric cyanuric acid monoolefin represented by the following formula (1) Epoxy propylene compound (B), and alicyclic polyester resin (c), and hard = [where, R The alicyclic epoxy compound (A) of the alicyclic epoxy compound demon 1 to 8 alkyl group of the hardening epoxy resin composition A) alicyclic epoxy group is epoxy-41-201233726 4. Patent application The hardenable epoxy resin composition of the third aspect, wherein the alicyclic epoxy compound (A) is represented by the following formula (11): :0 1-1) 5. If the patent application 笳 [fi 1st to 4th towel 4 not τ7- τ with the number π dry circumference brother 1 芏 * item A ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ The alicyclic polyester resin (c) is an alicyclic polyester having a protective chain in the main chain. u 曰% 6. The sclerosing lipid composition of any one of the items i to 5 of the patent application, which further comprises rubber particles. A hardened material obtained by hardening a curable epoxy resin composition according to any one of claims 6 to 6. 8. A resin composition for optical semiconductor sealing comprising a curable epoxy resin composition according to any one of claims 1 to 6 of the patent application. 9.: Seed light The semiconductor device is obtained by pre-sealing an optical semiconductor element with a resin composition for optical semiconductor sealing as in the eighth aspect of the patent application.