TW201139493A - Optical semiconductor sealing resin composition and optical semiconductor device using the same - Google Patents

Abstract

Provided is an optical semiconductor sealing resin composition containing an epoxy resin composition, a hardener and a hardening accelerator, which contains 50 to 100 wt% of an alicyclic epoxy resin relative to a total amount of the epoxy resin; the alicyclic epoxy resin is at least one compound selected from of a group consisted of a compound represented by the following formula (I), an alicycli compound bonded an epoxy group by a directly single bond and a compound having 3 or more of epoxy groups which consists of 2 adjacent carbon atoms forming aliphatic cycle and 1 oxygen atom; the hardener is an anhydride-based hardener; and the hardening accelerator contains an ion complex of a phsophonium ion represented by following formula (1) and a halogen anion capable of forming an ion pair with the phsophonium ion.

Description

[Technical Field] The present invention relates to a resin composition for optical semiconductor encapsulation, a cured product obtained by curing the same, and a semiconductor device using the same. [Prior Art] As for the resin composition for optical semiconductor encapsulation, an epoxy resin composition composed of an epoxy resin, a hardener, and a hardening accelerator has been reported in many cases. For example, Patent Document 1 discloses that an epoxy-modified ester compound which is excellent in solubility in an organic solvent and which is easily mixed with an epoxy resin is used as an epoxy resin cured product, and has low hygroscopicity, low dielectric constant, and low dielectric property. An epoxy resin composition containing an epoxy resin (A) having two or more epoxy groups in one molecule, an epoxy resin curing agent (B), and a curing accelerator (C), which are excellent in electrical properties such as loss. Further, Patent Document 2 discloses a resin composition for the purpose of providing a resin composition for an optical semiconductor package having a low bending elastic modulus, high bending strength, excellent toughness, and high glass transition temperature and transparency. The resin composition contains a thermosetting epoxy resin composition (A), a curing agent (B), and a curing accelerator (C), wherein the thermosetting epoxy resin composition (A) contains a ring in the molecule. a solvent composed of an aliphatic skeleton and two or more epoxy group alicyclic epoxy compounds (a), and a (meth) acrylate monomer having an alicyclic epoxy group and/or using the monomer a monomer component (b). Further, the purpose of Patent Document 3 is to provide an epoxy resin composition which exhibits excellent light transmittance and resistance to ultraviolet light, and which does not discolor even when heated for a long period of time, and which has low hygroscopicity, and discloses a ring. An oxygen resin composition containing a hydrogenated epoxy resin, a hardener, and a hardening accelerator, wherein the active hydrogen equivalent of the hardener is 〇·7 to 13 times the epoxy equivalent of the epoxy resin component, and the hardening accelerator is in the epoxy The resin composition contains 0.01 to 5% by weight. On the one hand, the evaluation of the brightness stability of one of the reliability evaluations of LEDs indicates that the brightness of the package material can be seen to increase or decrease in the power-on test, and the brightness stability is poor. However, an epoxy resin composition which has little brightness variation and excellent brightness stability has not been obtained so far. [Prior Technical Literature] [Patent Literature].

[Patent Document 1] JP-A-2007-320974 [Patent Document 3] JP-A-2000-1.2 6 6 6 2

[Problem to be Solved by the Invention] An object of the present invention is to provide a resin composition for semiconductor encapsulation which can obtain a cured product having excellent brightness stability while maintaining high heat resistance and transparency. Further, another object of the present invention is to provide a cured product which is excellent in brightness stability while maintaining high heat resistance and transparency while curing the resin composition for optical semiconductor encapsulation. In addition, the other object of the present invention is to provide light semi-conducting for encapsulating an optical semiconductor element using the above-mentioned resin composition for mounting. [Means for Solving the Problems] The present inventors have eagerly reviewed the following matters in order to solve the above problems. The present invention has been completed: a resin composition having a specific structural oxygen resin and using a specific hardening accelerator has high heat resistance and transparency as a cured product thereof, and brightness variation is small in a reliability test using an optical semiconductor device. The resin composition for excellent optical semiconductor encapsulation has a causal relationship with the adhesion between the brightness resin and the frame. That is, the present invention provides a resin composition for semiconductor encapsulation which comprises an epoxy resin, a hardener (B), and a resin composition for curing a three-conductor encapsulation, wherein 55 to 10 〇 Wt% is contained with respect to the epoxy resin. The alicyclic epoxy resin (A), (A1) the following formula (I) optical semiconductor sealing device. As a result, the alicyclic ring was found to be used as the brightness stability and the seal of the cured product, and the full amount of the half of the special agent (C) was selected from

[In the formula (I), X represents a linking group, a single bond, a divalent hydrocarbon group bond, an ester bond, a carbonate group, a guanamine bond, and a compound thereof, and (3) a direct single bond to bond an epoxy group. The group is bonded to a lipid and (A 3 ) is a group consisting of two adjacent carbon atoms constituting the alicyclic ring and a compound having three or more epoxy groups of oxygen, a carbonyl group, and an ether group. At least one of the compounds of the compound of the formula 201139493, the hardener (B) is an acid anhydride-based hardener, and the hardening accelerator (C) contains the following formula (1)

R- p IR I 1R

3 R

[R, R2, R3 and R4 in the formula (1) respectively represent a scaly ion represented by a hydrocarbon group having a carbon number of 1 to 2 Å, which may be the same or different, and may form an ion pair with the scale ion. An ionic combination of halogen anions. The halogen anion is preferably a bromide ion or an iodide ion. Further, the present invention provides a cured product obtained by hardening the resin composition for optical semiconductor encapsulation described above. Further, the present invention provides an optical semiconductor device in which an optical semiconductor element is encapsulated via the above-described resin composition for optical semiconductor encapsulation. [Effects of the Invention] According to the present invention, it is possible to provide the cured product with high heat resistance and transparency, and in the reliability test of the optical semiconductor device using the cured product, light having small luminance variation and excellent brightness stability can be obtained. A resin composition for optical semiconductor encapsulation of a half body device. Moreover, the cured product obtained by curing the resin composition for optical semiconductor encapsulation of the present invention has high heat resistance and transparency, and in the reliability test of the optical semiconductor device using the cured product, the brightness variation is small and the brightness is stable. Excellent sex. Further, according to the present invention, a 201139493 optical semiconductor device having high heat resistance and transparency, small variation in luminance, and excellent brightness stability can be obtained. [Embodiment] [Form of the invention for carrying out the invention] <Resin composition for optical semiconductor encapsulation> The resin composition for optical semiconductor encapsulation of the present invention is characterized in that it contains an epoxy resin, a curing agent (B), and A resin composition for semiconductor encapsulation of a hardening accelerator (C), wherein the alicyclic epoxy resin (A) is contained in an amount of from 55 to 100% by weight based on the total amount of the epoxy resin, which is selected from the group consisting of (A1) (I)

In the formula (I), X represents a compound represented by a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine bond, and a repeating group thereof, (A2) a compound having a direct single bond to bond an epoxy group to an alicyclic ring and (A3) a compound having three or more epoxy groups formed by two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. At least one of the compounds in the group, the hardener (B) is an acid anhydride hardener and the hardening accelerator (C) contains the following formula (1)

R 4 - 2 R - p IR I 1R 201139493 [R1, R2, R3 and R4 in the formula (1) respectively represent a lanthanum having a carbon number of 1 to 20, which may be the same or different) A scaly ion and an ionic combination of a halogen anion capable of forming an ion pair with the cerium ion. Since the resin composition for optical semiconductor encapsulation of the present invention has an epoxy resin, it has high heat resistance and transparency. <Epoxy Resin> The epoxy resin contained in the resin composition for optical semiconductor encapsulation of the present invention contains 55 to 100% by weight of an alicyclic ring with respect to the total amount of the epoxy resin. The oxygen resin (A) is selected from the following formula (I1) (I)

In the formula (I), X represents a compound represented by a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine bond, and a plurality of these groups. (A2) A compound having three or more epoxy groups by a compound in which an epoxy group is bonded to an alicyclic ring by a direct single bond and (A3) is an adjacent two carbon atoms and an oxygen atom which constitute an alicyclic ring. At least one compound in the group formed. <Alipocyclic Epoxy Resin (A)&gt; The resin composition for optical semiconductor encapsulation of the present invention contains an alicyclic epoxy resin (A)' selected from (Ai) the following formula (I) 201139493 [Formula In (I), X represents a compound represented by a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine bond, and a repeating group thereof, and (A2) a group consisting of a compound having an epoxy group bonded to an alicyclic ring and a compound having three or more epoxy groups which are composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring. At least one compound in the group. (A1) In the compound represented by the above formula (I), as the divalent hydrocarbon group represented by the linking group, a linear or branched extension of 1 to 18 carbon atoms is preferred. An alkyl group, a divalent alicyclic hydrocarbon group (especially a divalent cycloalkyl group), and the like. Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylidene group, a propyl group, and a triphenyl group. Methyl and the like. The divalent alicyclic hydrocarbon group may, for example, be a 1.2-cyclopentylene group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2·cyclohexylene group, a 1.3-cyclohexylene group, or a 1,4-extension group. A divalent cycloalkyl group (including a cycloalkylene group) such as a cyclohexyl group or a cyclohexylene group. Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (1-1) to (1-7). For example, a commercially available product such as CELLOXIDE 2021 P' CELLOXIDE 2081 (manufactured by DAICEL Chemical Industry Co., Ltd.) can be used. Further, in the following formula, m represents an integer of 1 to 30. -10 - 201139493 ο

(1-1)

(1-3)

Ο 〇&lt;X'〇JWT, (1-5)

(1-7) (Α2) A compound in which an epoxy group is bonded to an alicyclic ring by a direct single bond can be exemplified by a compound represented by the following formulas (1-8) and (1-9). In addition, (3), a compound having three or more epoxy groups constituting two adjacent carbon atoms and an oxygen atom of the alicyclic ring, for example, is represented by the following formula (I-1 〇), (I) -1 1) The compound shown. -11- 201139493

(Il 1) In the following formula (1-8), R represents a group having a carbon number of from 2 to 18 in which q-OH groups are removed from the q-ary alcohol, and may be a straight chain or a branched chain. It may also contain a cyclic skeleton. q and η are expressed as natural numbers. The q-valent alcohol [R-(〇H)q] may, for example, be a polyol such as 2,2-bis(hydroxymethyl)-indolylbutanol or the like (an alcohol having 1 to 15 carbon atoms or the like is preferred. In the case of 丨6, p is preferably 1 to 30. When q is 2 or more, p may be the same or different in the group in each (). Specifically, the above compound (1-8) may be 2, I,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2-bis(hydroxymethyl)-1-butanol, EHPE3 150 (manufactured by DAICEL Chemical Industry Co., Ltd.) )Wait. Further, in the above formulae (1-10) and (1-11), a, b, c, d, e, and f -12 to 201139493 are integers of 〇30. In the above-mentioned alicyclic epoxy resin, the compounds (Α1) to (A3) to be used may be used alone or in combination of two or more. For example, CELLOXIDE202 1 P, CELLOXIDE 2081, ΕΗΡΕ3150, EHPE3150CE (DA ICEL) may be used. Commercial products such as Chemical Industry Co., Ltd.). The epoxy resin contained in the resin composition for optical semiconductor encapsulation of the present invention may contain an epoxy resin other than the above alicyclic epoxy resin (A). Examples of the other epoxy resin include a glycidyl type epoxy resin such as a bisphenol A type or a F type which is liquid and have an aromatic ring, or a glycidyl type epoxy resin represented by the following formula.

The content of the above alicyclic epoxy resin (A) relative to the total amount of the epoxy resin in the composition for photo-semiconductor encapsulation (all of the compounds having an epoxy group) may be 55 to 100% by weight, preferably 60 to 1% by weight 'more preferably 70 to 100% by weight. When the content of the alicyclic epoxy resin (A) is less than 55% with respect to the total amount of the epoxy resin, the effect of the present invention cannot be obtained. In particular, if the amount of the glycidyl type epoxy resin having an aromatic ring exceeds 30% by weight of the total epoxy group-containing compound, the desired properties cannot be obtained. -13-201139493 The content of the epoxy resin in the resin composition for optical semiconductor encapsulation of the present invention is preferably from 30 to 99.9 wt%. <Curing Agent (B) &gt; The hardener (B) contained in the resin composition for optical semiconductor encapsulation of the present invention is an acid anhydride-based curing agent. As the acid anhydride-based curing agent, a generalizing agent for a general epoxy resin which is optional from the conventional one can be used. In particular, it is preferably liquid at normal temperature, and specific examples thereof include methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, and methyl bridge methylene tetrahydrogen. Anthracene anhydride and the like. Further, for example, an acid anhydride which is solid at normal temperature, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or methylcyclohexene dicarboxylic anhydride, can be used as a liquid mixture which dissolves in a liquid acid anhydride at normal temperature. It is used as a hardener for the present invention. Further, in the present invention, a commercially available product such as RIKACID MH-700 (manufactured by Shin-Nippon Chemical Co., Ltd.) or HN-5500 (manufactured by Hitachi Chemical Co., Ltd.) may be used as the curing agent (B). The curing agent (B) is used in an amount of 50 to 200 parts by weight, preferably 100 to 145 parts by weight, based on 100 parts by weight of the compound having an epoxy resin group in the resin composition for optical semiconductor encapsulation. More specifically, it is preferable to use a ratio of 0.5 to 1.5 equivalents per one equivalent of all the compounds having an epoxy group contained in the resin composition for optical semiconductor encapsulation. When the amount of the curing agent (B) is less than 50 parts by weight, the effect is not complete, and there is a tendency to lower the toughness of the cured product (B). On the other hand, the amount of the curing agent (B) is more than 200 parts by weight. When the 'hardener' is -14 - 201139493 color and there is a situation of deteriorated hue. &lt;Corrosion-promoting 剤(C)&gt; The curing accelerator (C) contained in the resin composition for optical semiconductor encapsulation of the present invention contains the following formula (1) _ R4 Ί +

I R1 - P- R3 ( ί )

I R2 [R1, R2, R3 and R4 in the formula (1) are respectively represented by a scaly ion represented by a hydrocarbon group having 1 to 20 carbon atoms which may be the same or different) and may form an ion pair with the scale ion. An ionic combination of halogen anions. The ionic complex (the fourth-order organic scale salt) of the scaly ion and the halogen anion represented by the above formula (1) forms an ion pair of at least one of a scaly ion and a halogen anion. When the hardening accelerator is further hardened at a high temperature, the ion bonding system rapidly dissociates, and the scale ions have a function of promoting hardening. Therefore, when manufacturing an optical semiconductor device, it is conceivable that the halogen anion in the package material has a function of improving the brightness stability by lowering the adhesion to the lead frame. In the R1, R2, R3 and R4 represented by the hydrocarbon group having 1 to 20 carbon atoms in the formula (1), examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and a carbon number. 7 to 20 aralkyl groups, 6 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, and a cyclohexyl group. A linear, branched chain or cyclic alkyl group such as methylcyclohexyl, heptyl, octyl, isooctyl, fluorene-15-201139493, isodecyl, fluorenyl or isodecyl. For aralkyl groups having 7 to 20 carbon atoms, benzyl, methylbenzyl, ethylbenzyl, dimethylbenzyl, diethylbenzyl, phenethyl, methylbenzene Ethyl, ethylphenethyl, methylphenethyl, ethylphenethyl, and examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a methylphenyl group, and a dimethylphenyl group. A phenyl group, a naphthyl group or the like substituted with an ethylphenyl group or the like. Wherein, an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group or a butyl group; an aralkyl group having 7 to 10 carbon atoms such as a benzyl group, an ethylbenzyl group, a phenethyl group or an ethylphenethyl group; A phenyl group having 6 to 8 carbon atoms such as a phenyl group or a methylphenyl group is preferred, and a phenyl group, a butyl group or an ethyl group is particularly preferred. The halogen anion which forms an ion pair with the scale ions represented by the above formula (1) may, for example, be a chloride ion, a bromide ion or an iodide ion. Among them, bromide ion and iodide ion are preferred. Specific examples of the ruthenium compound of the ionic combination of the money ion represented by the above formula (1) and the halogen anion capable of forming an ion pair with the scaly ion may, for example, be tetrabutyl sulphate or brominated tetrachloride. Butyl hydrazine, tetrabutyl sulfonium iodide, tetraphenyl sulphate chloride, tetraphenyl sulfonium bromide, tetraphenyl sulphate iodide, ethyl triphenyl sulphate chloride, ethyl triphenyl iron bromide, Iodine ethyl triphenyl scale, propyl triphenyl iron, bromopropyl triphenyl money, iodide propyl triphenyl scale, chlorobutyl triphenyl scale, bromobutyl three Phenyl iron, butyl iodide triphenyl scale, methyl triphenyl bromide, methyl triphenyl sulfonium iodide, tetramethyl sulfonium iodide, tetraethyl bromide scale. Among them, preferred are tetraphenylferric bromide, tetrabutylammonium bromide, tetraphenylphosphonium iodide, and ethyltriphenylphosphonium iodide. In the present invention, a commercially available product such as U-CAT 5〇03 (manufactured by Sanapro Co., Ltd.) can be used as the hardening accelerator (C). The blending amount of the scaly compound is preferably such that the bromine or iodine content contained in the resin composition for photo-semiconductor encapsulation is 200 mg/kg or more (for example, 200 to 8000 mg/kg), preferably 200 to 5000 mg. /kg, more preferably 300 to 4000 mg/kg. When the bromine or iodine content is less than 200 mg/kg, brightness stability is not easily obtained. The hardening accelerator may be a scaly compound alone or a mixture of a conventional amine-based hardening accelerator or a phosphorus-based hardening accelerator. Examples of the amine-based hardening accelerator include tertiary grades such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol 'N,N-dimethylcyclohexylamine. amine. Further, examples of the phosphorus-based curing accelerator include phosphines such as phosphates and triphenylphosphine. For example, the curing accelerator (C) is used in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total of the epoxy group-containing compound contained in the resin composition for optical semiconductor encapsulation. It is preferably from 2 to 3 parts by weight, preferably from about 0.25 to 2.5 parts by weight. When the amount of the curing accelerator (C) is less than 0.05 parts by weight, the effect of the curing accelerator may be incomplete. On the other hand, when the amount of the curing accelerator (C) is more than 5 parts by weight, the cured product is cured. Coloring and deterioration of the hue. &lt;Solvent&gt; The resin composition for optical semiconductor encapsulation of the present invention may contain a solvent. The solvent may, for example, be an alcohol (ethylene glycol, polyalkylene glycol, neopentyl glycol, etc.), an ether (diethyl ether, ethylene glycol mono or dialkyl ether, diethylene glycol mono or dioxane-17). - 201139493 ether, diethylene glycol mono or dialkyl ether, propylene glycol mono or dialkyl ether alcohol mono or diaryl ether, dipropylene glycol mono or dialkyl ether, tripropylene or dialkyl ether, 1, a chain of glycol ethers such as 3-propanediol mono- or dialkyl ether, 1,3-butanedialkyl ether, 1,4-butanediol mono- or dialkyl ether, glycerol mono- or di-diethyl ether Ether, tetrahydrofuran, dioxane ether, etc., ester (methyl acetate, ethyl acetate, butyl acetate, acetic acid, ethyl lactate, methyl 3-methoxypropionate, 3-ethoxypropionic acid acetic acid 3-methoxybutyl ester, C5_6 cycloalkanediol mono or diacetate, C: dicarboxylic acid monoester or diacetate carboxylate, ethylene glycol monoalkyl ester, ethylene glycol mono or diacetic acid Ester, diethylene glycol monoalkyl ether acetate ethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propane or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol acetate, 1, 3-propanediol Monoalkyl ether acetate, 1,3-propanediol acetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol acetate, 1,4-butanediol monoalkyl ether Ethylene glycol such as acetate, 1,4-butanediol acetate, glycerol mono-, di- or triacetate, glycerol mono- or di-Cm or mono-acetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol acetate Acetate or glycol ether acetate, etc.) ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3, 5: yl-2-cyclohexen-1-one, etc.) Amine (N,N-dimethylacetamide, methylformamide, etc.), hydrazine (dimethyl hydrazine, etc.), alcohol (methanol, propanol, 3-methoxy-1-butanol, C5.6 cycloalkanediol, C5.6 cycloalcohol, etc.), hydrocarbyl group (aromatic hydrocarbon such as benzene, toluene, xylene, etc., hexamethylene glycol monool mono- or tri-yard cyclic isoamyl ester) , Ethyl-6-cycloalkane acetate, didiol mono- or di- or di- or di- or di-dialkyl ether mono or di-ketone (propane 5-trimethyl N, N-diethanol, alkane dimethane, etc. -18- 201139493 Aliphatic hydrocarbons, alicyclic hydrocarbons, etc., etc.) In addition to the above, the resin composition for optical semiconductor encapsulation of the present invention can use various additives within a range that does not impair the effects of the present invention. For example, ethylene glycol or diethylene glycol can be used as the additive. When a compound having a hydroxyl group such as propylene glycol 'glycerin is used, the reaction can be delayed. Further, a polyoxyalkylene-based or fluorine-based antifoaming agent, a leveling agent, and r- can be used without breaking the viscosity and transparency. a decane coupling agent such as a glycidoxypropyltrimethoxydecane, a surfactant, an inorganic filler such as cerium oxide or aluminum oxide, an organic rubber particle, a flame retardant, a coloring agent, an antioxidant, A conventional additive such as an ultraviolet absorber, an ion adsorbent, a pigment, a phosphor, a release agent, or the like. &lt;Cured product&gt; The resin composition for optical semiconductor encapsulation of the present invention may be at a temperature of 45 to 200 ° C, preferably 100 to 190 ° C, further preferably 1 to 180 ° C, and hardening time thereof. It is hardened for 30 to 600 minutes, preferably 45 to 540 minutes, and further preferably 60 to 480 minutes. When the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening may be incomplete. Conversely, when the upper limit is higher than the upper limit of the above range, the decomposition of the resin component may occur, so that neither of them is good. The hardening conditions are related to various conditions. When the hardening temperature is high, the hardening time is short, and when the hardening temperature is low, the hardening time is long and can be appropriately adjusted. By curing the resin composition for a light semiconductive package of the present invention, various physical properties such as brightness stability, heat resistance, and transparency can be obtained. -19·201139493. &lt;Optical semiconductor device&gt; The optical semiconductor device of the present invention is obtained by encapsulating a photo-semiconductor element with the resin composition for optical semiconductor encapsulation of the present invention. In the encapsulation of the optical semiconductor, the resin composition for optical semiconductor encapsulation prepared by the above-described method is injected into a specific molding die to perform heat curing under specific conditions. Therefore, the optical semiconductor device can be encapsulated by the resin composition for optical semiconductor encapsulation, and an optical semiconductor device excellent in various physical properties such as brightness stability, heat resistance, and transparency can be obtained. The hardening temperature and the hardening time can be the same as those described above. [Examples] Hereinafter, the present invention will be described in more detail based on examples, but these examples are not intended to limit the present invention. Example 1 50 parts by weight of an alicyclic epoxy resin manufactured by DAICEL Chemical Co., Ltd., trade name "CELLOXIDE 202 1 Pj, 50 parts by weight of DAICEL Chemical Industry Co., Ltd., trade name "EHPE 3150CE" was used. The hardener is used in an amount of 100 parts by weight of methyl hexahydrophthalic anhydride (trade name "RIKACID MH-700" manufactured by Shin Nippon Chemical Co., Ltd.), and the hardener accelerator is used in an amount of 1 part by weight of tetraphenyl bromide. (made by Wako Pure Chemical Co., Ltd.). Further, 1.5 parts by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was used. • 20-201139493 The optical semiconductor encapsulating resin composition was obtained by using "THINKY MIXER" uniform mixing (2〇〇OrPm, 5 minutes) manufactured by THINKY Co., Ltd. Example 2 except that 0.5 part by weight of ethyl iodide was used. A resin composition for optical semiconductor encapsulation was obtained in the same manner as in Example 1 except that 0.5 parts by weight of triphenylphosphine (manufactured by Kishida Chemical Co., Ltd.) was used as a curing accelerator. Example 3 The same as Example 1, except that 70 parts by weight of the trade name "EHPE3150CE" manufactured by DAICEL Chemical Industry Co., Ltd. and 30 parts by weight of the trade name "YD-128" manufactured by Toki Chemical Co., Ltd. were used as the epoxy resin. The resin composition for optical semiconductor encapsulation was obtained. Comparative Example 1 In addition to the hard accelerator of the trade name "Hishicolin PX-4ET" of tetrabutylphosphonium diethylphosphonium disulfide (manufactured by Nippon Chemical Industry Co., Ltd.), In the same manner as in Example 1, a fat composition for optical semiconductor encapsulation was obtained. Comparative Example 2 The same as Example 1, except that 50 parts by weight of the trade name "EHPE 3150CE" manufactured by DAICEL Chemical Industry Co., Ltd. and 50 parts by weight of the product name "YD-128" manufactured by Tohto Kasei Co., Ltd. were used as the epoxy resin. A resin composition for optical semiconductor encapsulation was obtained. In the case of the company, the company is the same as in the first embodiment, except that the product name "YD-1 28" manufactured by Tohto Kasei Co., Ltd. is used as the epoxy resin. A resin composition for optical semiconductor encapsulation was obtained. The blending system is shown in Table 1 (the number of parts is part by weight). The resin composition for optical semiconductor encapsulation obtained by the examples and the comparative examples was heated at 1 〇 ° C for 2 hours, and then heated at 130 ° C for 3 hours to obtain a cured product. The obtained resin composition for optical semiconductor encapsulation was evaluated by the following method. In the following evaluation test, the resin composition for optical semiconductor encapsulation was cured under the same conditions as above. [Brightness stability] On the lead frame having an optical semiconductor element (InGaN), the obtained resin composition for optical semiconductor encapsulation was injection-molded and heat-cured to fabricate a photo-semiconductor device. For the produced optical semiconductor device, low-temperature energization (-40 °C / 20 mA) and normal-temperature energization (23 °C / 60 mA) were performed, and the energization brightness stability in each condition was measured using the following measuring device. Measurement J: Device manufactured by OPTRONIC LABORATORIES OL771 was energized at a low temperature, and the brightness after 150, 300, 500, and 1,000 hours was measured, and the brightness retention rate from the initial stage (100%) was calculated. The rate of change of the brightness retention ratio is expressed by the initial maximum width. Further, the current was applied at room temperature, and the brightness after 300 hours was measured to calculate the brightness retention rate from the initial stage (100%). -22-201139493 The results are shown in Table 2. The low-temperature energization characteristic was evaluated as X when the rate of change of the brightness retention ratio was ±3% or more, and was evaluated as 〇 when it was less than 3%. Further, the normal temperature energization characteristic is evaluated as χ when the deterioration rate of luminance (from the initial luminance reduction rate) is 20% or more, and 平 is less than 20%. When both the low-temperature energization characteristic and the normal-temperature energization characteristic are 〇, the overall judgment is 〇, and the rest is X. The results are shown in Table 1. [Adhesive strength] A resin composition for optical semiconductor encapsulation obtained on a silver-plated copper plate was used to harden and bond a sand wafer of 1.25 mm x 1.5 mm x 1 mm. The cement was supplied to a die shear teater, and the bond strength was measured when the sand wafer was peeled off from the silver-silver copper plate. The results are shown in Table 1. Measurement conditions: test speed 3 00 pm / s, test height 500 μιη Measuring device: Dage Co., Ltd. Dage 4000 Table 1

EXAMPLES Comparative Example 1 2 3 1 2 3 Epoxy CELLOXIDE 2021P 50 50 50 Resin EHPE 3150CE 50 50 70 50 50 YD-128 30 50 100 Hardener RIKACIDMH-700 100 100 100 100 100 100 Hardening accelerator Brominated tetraphenyl scale 1 1 1 1 Iodinated ethyl diphenyl scale 0.5 Hishicolin PX-4ET 1 Diphenylphosphine 0.5 Additive ethylene glycol 1.5 1.5 1.5 1.5 1.5 1.5 Adhesive strength (N/r nm2) 6.7 6.5 6.5 21 7.8 12 Brightness stability low temperature Power-on characteristics (-40〇C/20mA) 0 〇〇XXX Normal-temperature energization characteristics (23 °C/60mA) 〇〇〇〇XX Comprehensive evaluation* 〇〇〇XXX-23-201139493 The compounds used in this case are shown below. Epoxy resin CELLOXIDE202 1 P : 3,4-epoxycyclohexenylmethyl_3,,4,_epoxy cyclohexene carboxylate, manufactured by DAICEL Chemical Industry Co., Ltd. EHPE3150CE : 2,2·double ( Hydroxymethyl)-1-butanol 1,2.epoxy-4-(2-oxiranyl)cyclohexane adduct and 3,4-epoxycyclohexenylmethyl-3' , 4'-Epoxycyclohexene carboxylate, manufactured by DAICEL Chemical Industry Co., Ltd. YD-1 28: bisphenol A epoxy resin, Dongdu Chemical Co., Ltd. Hardener (B) RIKACIDMH-700 : 4 -Methylhexahydrophthalic anhydride/hexahydrophthalic anhydride = 7 0/3 0, New Japan Physicochemical Co., Ltd. manufactures hardening accelerator (C) Tetraphenylphosphonium bromide: Wako Pure Chemical Industries Co., Ltd. manufactures iodide B Triphenylbenzene scale: Hishicolin PX-4ET manufactured by Wako Pure Chemical Industries Co., Ltd.: tetrabutylselenium diethylphosphonium disulfide, manufactured by Nippon Chemical Industry Co., Ltd.: triphenylphosphine: manufactured by Kishida Chemical Co., Ltd. Glycol: Wako Pure Chemical Industries Co., Ltd. Manufacturing Table 2 Example Comparative Example 1 2 3 1 2 3 Brightness Stability Low Lion Electric Characteristics (-40〇C /20 mA) 〇oo XXX 150hr 99% 99% 98% 98% 97% 106% 300hr 99% 98% 99% 97% 97% 105% 500hr 99% 98% 98% 99% 97% 104% lOOOhr 99% 99 % 98% 97% 96% 103% Rate of change (±) 1% 2% 2% 3% 4% 6% Normally charged characteristics (23〇C/60mA) 0 ooo XX 300hr 81% 81% 81% 82% 74% 65% -24-201139493 From the viewpoint of brightness stability, it is preferred that the cured product of the resin composition for optical semiconductor encapsulation of the present invention has low adhesion to the lead frame, and more preferably has a bonding strength of 18 N/mm 2 or less (for example, 〇~ 1 8 N / m m2), in particular, more preferably 15 N/mm 2 or less (e.g., 〇 1 to 15 N/m 2 ), still more preferably 7 N/mm 2 or less (for example, 〇 7 7 N/mm 2 ). Furthermore, there is no problem even if the bonding strength is zero. [Industrial Applicability] According to the present invention, in the reliability test of the optical semiconductor device using the cured product, which has high heat resistance and transparency, it is possible to obtain excellent brightness stability which is small in luminance variation. A resin composition for semiconductor encapsulation of an optical semiconductor device. Moreover, according to the present invention, it is possible to provide a cured product having high heat resistance and transparency and having a small variation in luminance and excellent brightness stability in the reliability test of the photo-semiconductor. Further, according to the present invention, it is possible to provide an optical semiconductor device having high heat resistance and transparency, small variation in luminance, and excellent brightness stability. [Simple description of the diagram] te 〇 [Description of main component symbols] Μ . -25-

Claims (1)

201139493 VII. Patent application scope: 1. A resin composition for optical semiconductor encapsulation characterized by comprising a resin composition for optical semiconductor encapsulation comprising an epoxy resin, a curing agent (B), and a curing accelerator (C), The alicyclic epoxy resin (A) containing 55 to 100% by weight, based on the total amount of the epoxy resin, is selected from the group consisting of the compound represented by the following formula (1) (A1) In the formula (I), X represents a linking group, and is a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine bond, and a plurality of groups thereof. (A2) a compound in which an epoxy group is bonded to a cycloester by a direct single bond, and (A3) has three or more epoxy groups which constitute two adjacent carbon atoms and an oxygen atom of the alicyclic ring. At least one of the compounds 'the hardener (B) is an acid anhydride hardener, and the 'hardening accelerator (C) contains the following formula (1) Γ R4 VI R1 — p - R3 ( 1 ) I .R2" [R1 in formula (1)! ^2! ^3 and R4 have an ionic combination of a scaly ion represented by a hydrocarbon group having a carbon number of 1 to 20, which may be the same or different from each other, and a halogen anion capable of forming an ion pair with the cerium ion. . The resin composition for optical semiconductor encapsulation according to claim 1, wherein the dentate anion is bromide ion or iodide ion. A hardened material obtained by curing a resin composition for optical semiconductor encapsulation according to claim 1 or 2. An optical semiconductor device which is obtained by encapsulating an optical semiconductor element by a resin composition for optical semiconductor encapsulation according to claim 1 or 2. -27- 201139493 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: