TW201330333A - Resin composition for sealing optical semiconductor and optical semiconductor device using the same - Google Patents

Abstract

The present invention provides a resin composition for sealing optical semiconductor. The resin composition can gain a curing product which has excellent transparency, heat resistance, light resistance and crack resistance. An optical semiconductor using the curing product as a sealing material can show excellent conductivity and thermal-shock resistance. The resin composition for sealing optical semiconductor of the present invention comprises an alicyclic epoxy compound (A), an alicyclic polyester resin (B), a curing agent (C) and a curing accelerator (D). The resin composition is characterized by: the alicyclic epoxy compound (A) is at least one compound selected from the group comprising (A1) a compound represented by following formula (I), (A2) a compound that the alicyclic group is directly bonded with epoxy group by single bond, and (A3) a compound having 3 or more epoxy groups formed by oxygen atom and 2 neighboring carbon atoms constituting the alicyclic group; the total content of the alicyclic epoxy compound (A) is 55 to 100 mass% relative to the whole quantity (100 mass%) of the compound having epoxy groups comprised in the resin composition for sealing optical semiconductor; the alicyclic polyester resin (B) is an alicyclic polyester having an alicyclic structure in the main chain; the curing agent (C) is an anhydride curing agent; and an organic zinc carboxylate is comprised as the curing accelerator (D).

Description

Resin composition for optical semiconductor encapsulation and optical semiconductor device using same

The present invention relates to a resin composition for optical semiconductor encapsulation, a cured product obtained by curing the resin composition for optical semiconductor encapsulation, and an optical semiconductor device using the same.

An optical semiconductor device in which an optical semiconductor element such as an LED is used as a light source is currently used in various applications such as various indoor or outdoor display panels, light sources for image reading, communication numbers, and units for large displays. Such an optical semiconductor device generally has a structure in which an optical semiconductor element is encapsulated (coated) with a transparent encapsulant (encapsulation resin). In recent years, the high output and short wavelength of such optical semiconductor elements are rapidly progressing. Under such circumstances, for example, in the case of an optical semiconductor device using an aromatic epoxy resin as a package material, light and heat emitted from the optical semiconductor element cause a problem of yellowing of the package material. The thus-yellowing package absorbs the light emitted from the optical semiconductor element, and the illuminance of the light output by the optical semiconductor device is lowered over time.

Therefore, in the package of an optical semiconductor device, excellent transparency, heat resistance, and light resistance are sought, and from the viewpoint of protecting the optical semiconductor element, those who are not susceptible to cracking (cracking) against various stresses are also sought (also such characteristics) It is called "crack resistance".

Further, in the optical semiconductor device, from the viewpoint of ensuring the reliability, the luminosity (brightness) of the light emitted at the time of energization is stabilized (this characteristic is also referred to as "photometric stability (brightness stability)"). That is, those having excellent electric conduction characteristics. In particular, in recent years, in order to further improve the reliability, it is also looking for Excellent electrical conduction characteristics in a high temperature and high humidity environment. Further, in the optical semiconductor device, in addition to the above-described energization characteristics, it is also sought to cause cracks (cracks) in the package material even if a thermal shock such as a heating/cooling cycle (repetition of heating and cooling periodically) is applied. Characteristics, that is, excellent thermal and thermal shock resistance.

As an encapsulant for forming a package for an optical semiconductor device, an epoxy resin composition containing an epoxy resin, a hardener, and a hardening accelerator is often reported. For example, an epoxy resin composition containing an epoxy resin having two or more epoxy groups in one molecule, an epoxy resin hardener of an epoxy modified ester compound, and a hardening accelerator is known (refer to a patent) Document 1); a resin composition comprising: a thermosetting epoxy resin composition, a hardener, and a hardening accelerator, wherein the thermosetting epoxy resin composition contains a cyclic aliphatic skeleton in a molecule; a solvent of an alicyclic epoxy compound having two or more epoxy groups, a (meth) acrylate monomer having an alicyclic epoxy group, and/or a polymer containing the monomer as a monomer component (refer to Patent Document 2); a resin composition comprising a hydrogenated epoxy resin, a curing agent, and a curing accelerator (see Patent Document 3). However, the optical semiconductor device obtained by using the resin composition as a sealing agent has a problem that the illuminance is easily changed during energization, and the electric conduction characteristics (especially, the electric conduction characteristics under high temperature and high humidity conditions) are inferior.

That is, as an encapsulant in an optical semiconductor device, excellent transparency, heat resistance, light resistance, and crack resistance have not been obtained so far, and in particular, electrical characteristics of an optical semiconductor device can be improved (especially in high temperature and high humidity conditions). Under the power-on characteristics) and materials resistant to thermal shock.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-217869

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-320974

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-126662

Therefore, an object of the present invention is to provide a resin composition for optical semiconductor encapsulation, which is capable of obtaining a cured product having excellent transparency, heat resistance, light resistance and crack resistance, and the cured product is used as a package material. The semiconductor device can exhibit excellent electrical conduction characteristics (especially, electrical conduction characteristics under high temperature and high humidity conditions) and resistance to thermal shock.

Further, another object of the present invention is to provide a cured product which has excellent transparency, heat resistance, light resistance, and crack resistance, and exhibits excellent electric conduction characteristics to an optical semiconductor device as an encapsulant (especially Those who are energized under high temperature and high humidity conditions) and those resistant to thermal shock.

Furthermore, another object of the present invention is to provide an optical semiconductor device which has excellent electric conduction characteristics (especially, electric conduction characteristics under high temperature and high humidity conditions) and resistance to thermal shock resistance.

The inventors of the present invention have found a resin composition comprising an alicyclic epoxy compound having a specific structure, an alicyclic polyester resin having a specific structure, a specific hardener, and a specific hardening accelerator in order to solve the above problems. A cured product having excellent transparency, heat resistance, light resistance, and crack resistance, and an optical semiconductor using the cured product Since the device has excellent electric conduction characteristics (especially, electric conduction characteristics under high temperature and high humidity conditions) and cold shock resistance, the present invention can be used as a resin composition for optical semiconductor encapsulation.

That is, the present invention provides a resin composition for optical semiconductor encapsulation, which comprises an alicyclic epoxy compound (A), an alicyclic polyester resin (B), a hardener (C), and a hardening accelerator (D). The resin composition for optical semiconductor encapsulation characterized in that the alicyclic epoxy compound (A) is at least one selected from the group consisting of (A1) a compound represented by the following formula (I) and an (A2) alicyclic ring. a compound which is directly bonded by an epoxy group and a compound of (A3) which is a group of compounds having three or more epoxy groups which constitute two adjacent carbon atoms and oxygen atoms of the alicyclic ring, The total amount (100% by weight) of the epoxy group-containing compound contained in the resin composition for optical semiconductor encapsulation, the total content of the above alicyclic epoxy compound (A) is 55 to 100% by weight, and the above alicyclic poly The ester resin (B) is an alicyclic polyester having an alicyclic structure in the main chain, the curing agent (C) is an acid anhydride curing agent, and the curing accelerator (D) contains an organic carboxylic acid zinc. In the formula (I), X represents a single bond or a linking group, and the linking group is a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine bond or a plurality of linked groups.

The present invention further provides a resin composition for optical semiconductor encapsulation, wherein the organic zinc carboxylate is zinc octoate.

Further, the present invention provides a resin composition for optical semiconductor encapsulation, wherein the curing accelerator (D) further contains a cerium ion represented by the following formula (6) and a halogen anion capable of forming an ion pair with the cerium ion. Ion combination, [R ⁶ , R ⁷ , R ⁸ and R ⁹ in the formula (6) represent a hydrocarbon group having 1 to 20 carbon atoms, respectively, which may be the same or different from each other].

The present invention further provides the resin composition for optical semiconductor encapsulation, wherein the halogen anion is a bromide ion or an iodide ion.

The present invention further provides a cured product obtained by curing the resin composition for optical semiconductor encapsulation.

Further, the present invention provides an optical semiconductor device in which an optical semiconductor element is packaged by the resin composition for optical semiconductor packaging.

Since the resin composition for optical semiconductor encapsulation of the present invention has the above-described configuration, a cured product having excellent transparency, heat resistance, light resistance, and crack resistance can be obtained by curing the resin composition. Therefore, the optical semiconductor device in which the optical semiconductor element is encapsulated by using the resin composition for optical semiconductor encapsulation of the present invention has small fluctuation in luminosity in various reliability tests, and electrification characteristics (especially in the case of high temperature and high humidity) Excellent) and excellent in thermal shock resistance and high quality.

[Formation of the Invention] <Resin composition for optical semiconductor encapsulation>

The resin composition for optical semiconductor encapsulation of the present invention contains at least a fat A resin composition for optical semiconductor encapsulation of a cyclic epoxy compound (A), an alicyclic polyester resin (B), a curing agent (C), and a curing accelerator (D).

[Cycloaliphatic epoxy compound (A)]

The alicyclic epoxy compound (A) which is an essential component of the resin composition for optical semiconductor encapsulation of the present invention is at least one selected from the group consisting of (A1) a compound represented by the following formula (I) and an (A2) alicyclic ring. a compound in which a compound directly bonded by an epoxy group and (A3) are a group of compounds having three or more epoxy groups constituting two adjacent carbon atoms and an oxygen atom of the alicyclic ring, In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms), and the linking group is a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, or a guanamine bond. Or the basis of a plurality of links]. When the resin composition for optical semiconductor encapsulation of the present invention contains the alicyclic epoxy compound (A), it is possible to impart high heat resistance and transparency to the cured product.

(A1) In the compound represented by the above formula (I), the divalent hydrocarbon group represented by the linking group X is preferably a linear or branched alkyl group having a carbon number of 1 to 18, and a divalent alicyclic ring. A hydrocarbon group (particularly a divalent cycloalkyl group) or the like. Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group, and a trimethylene group. Base. Examples of the divalent alicyclic hydrocarbon group include, for example, 1,2-cyclopentyl group, 1,3-cyclopentyl group, cyclopentylene group, 1,2-extended cyclohexyl group, and 1,3-extension ring. A divalent cycloalkyl group (including a cycloalkylene group) such as a hexyl group, a 1,4-cyclohexylene 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 (I-1) to (I-6). Examples of such alicyclic epoxy compounds include commercially available products such as Celloxide 2021P and Celloxide 2081 (manufactured by Daicel Co., Ltd.). Further, in the following formula (I-5), m represents an integer of from 1 to 30.

Further, (A1) the compound represented by the above formula (I) may be, for example, an alicyclic epoxy compound such as 3,4,3',4'-dicyclooxybicyclohexane.

(A2) Examples of the compound in which the epoxy group is directly bonded to the alicyclic ring are, for example, compounds represented by the following formulas (I-7) to (I-8). Further, (A3) is a compound having three or more epoxy groups which are composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and examples thereof include the following formulas (I-9) to (I-10). Compounds shown and the like.

In the above formula (I-7), R is a group obtained by removing q (q) of -OH from a q-valent alcohol, and for example, a hydrocarbon group having a carbon number of about 2 to 18, which may be a straight chain or a branched chain, and It may also contain a ring skeleton. Examples of R include a non-aromatic hydrocarbon group such as an alkyl group, an alkylene group, an alkane-triyl group, a cycloalkyl group or a cycloalkyl group. p and q represent natural numbers. The q-valent alcohol [R-(OH) _q ] may, for example, be a polyol such as 2,2-bis(hydroxymethyl)-1-butanol or the like (an alcohol having 1 to 15 carbon atoms). q is preferably from 1 to 6, and p is preferably from 1 to 30. When q is 2 or more, p in the base of each [ ] (with the parentheses in q) may be the same or different. The compound represented by the above formula (I-7) may specifically be exemplified by 1,2-epoxy-4-(2-epoxyethyl) of 2,2-bis(hydroxymethyl)-1-butanol. Base) cyclohexane adduct, EHPE 3150 (manufactured by Daicel), and the like. Further, a, b, c, d, e, and f in the above formulae (I-9) and (I-10) are each an integer of 0 to 30.

The compounds (A1) to (A3) used in the above alicyclic epoxy compound (A) may be used alone or in combination of two or more. Further, as the compounds (A1) to (A3), commercially available products such as Celloxide 2021P, Celloxide 2081, EHPE 3150, EHPE 3150CE (manufactured by Daicel) can also be used.

The total amount (all epoxy compound) (100% by weight) of the compound having an epoxy group contained in the resin composition for optical semiconductor encapsulation, and the content (usage amount) of the alicyclic epoxy compound (A) ( The total content of the alicyclic epoxy compound (A) is from 55 to 100% by weight, preferably from 70 to 100% by weight, more preferably from 80 to 100% by weight. When the content is less than 55% by weight, the transparency, heat resistance and light resistance of the cured product may be lowered.

The resin composition for optical semiconductor encapsulation of the present invention may contain an epoxy compound (epoxy resin) other than the alicyclic epoxy compound (A) (may also be referred to as "other epoxy compound"). Examples of the other epoxy compound include a glycidyl type epoxy compound (glycidyl type epoxy resin) represented by the following formula. Among them, the other epoxy compound described above is preferably an alicyclic epoxy compound other than the alicyclic epoxy compound (A).

Further, in the resin composition for optical semiconductor encapsulation of the present invention (100% by weight), the total amount of the epoxy group-containing compound (all epoxy compounds) is not particularly limited, but is 30 to 99.9% by weight. good.

[Cycloaliphatic Polyester Resin (B)]

The alicyclic polyester resin (B) which is an essential component of the curable epoxy resin composition of the present invention serves to improve the heat resistance, light resistance and crack resistance of the cured product, and to suppress the decrease in the illuminance of the optical semiconductor device and improve the luminosity. The task of luminosity stability and resistance to thermal shock. The alicyclic polyester resin (B) is a polyester resin (alicyclic polyester) having an alicyclic structure (aliphatic ring structure) in its main chain. Further, the alicyclic polyester resin (B) may be used singly or in combination of two or more.

The alicyclic structure in the alicyclic polyester resin (B) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure or a crosslinked cyclic hydrocarbon structure (for example, a bicyclic hydrocarbon). Among them, the above alicyclic structure is particularly preferably a saturated monocyclic hydrocarbon structure or a saturated crosslinked cyclic hydrocarbon structure in which an alicyclic ring (a carbon-carbon bond constituting an alicyclic ring) is entirely composed of a carbon-carbon single bond. Further, the alicyclic structure in the alicyclic polyester resin (B) may be introduced into only one of the constituent units derived from the dicarboxylic acid and the constituent unit derived from the diol, and may be introduced at the same time. Specially limited.

The alicyclic polyester resin (B) has a constituent unit derived from a monomer component containing an alicyclic structure. The monomer having an alicyclic structure may, for example, be a conventionally known diol having a alicyclic structure or a dicarboxylic acid, and is not particularly limited, and examples thereof include 1,2-cyclohexanedicarboxylic acid, and 1 , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, humic acid, 1,4-decahydronaphthalene dicarboxylate a dicarboxylic acid having an alicyclic structure such as acid, 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid or 2,7-decahydronaphthalene dicarboxylic acid (including derivatives derived from an acid anhydride or the like) 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentane dimethanol, 1,3-cyclopentane dimethanol, bis(hydroxymethyl) three 5-membered ring diol such as cyclo [5.2.1.0] decane; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexane a 6-membered cyclic diol such as dimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or 2,2-bis(4-hydroxycyclohexyl)propane; hydrogenated bisphenol A or the like An alicyclic structure diol (also including such derivatives) and the like.

The alicyclic polyester resin (B) may have a constituent unit derived from a monomer component of a non-lipid ring structure. Examples of the monomer component of the non-lipid ring structure include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid (including derivatives such as acid anhydrides); Aliphatic dicarboxylic acids such as acid, sebacic acid, sebacic acid, succinic acid (succinic acid), fumaric acid (fumaric acid), maleic acid (maleic acid) (including acid anhydride, etc.) Derivatives); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentane Alcohol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2 -Diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, decanediol, ethylene oxide adduct of bisphenol A, propylene oxide of bisphenol A A diol (including such a derivative) such as an adduct or the like. Further, the above-mentioned dicarboxylic acid-free diol or diol having a suitable substituent (for example, an alkyl group, an alkoxy group or a halogen atom) is also contained in the monomer component having no alicyclic structure.

The ratio of the monomer unit having an alicyclic ring is not particularly limited with respect to the total monomer unit (total monomer component) (100 mol%) constituting the alicyclic polyester resin (B), but is 10 mol%. The above (e.g., 10 to 80 mol%) is preferred, more preferably 25 to 70 mol%, still more preferably 40 to 60 mol%. When the proportion of monomer units having an alicyclic ring is less than 10 mol%, the heat resistance of the cured product is obtained. , light resistance, crack resistance is reduced.

The alicyclic polyester resin (B) is particularly preferably an alicyclic polyester containing one or more constituent units represented by the following formulas (1) to (3).

Wherein R ¹ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; and R ² to R ⁵ represent each independently hydrogen atom or a linear or branched chain. An alkyl group having 1 to 4 carbon atoms; two selected from the group consisting of R ² to R ⁵ may be bonded to form a ring].

Wherein R ¹ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; and R ² to R ⁵ represent each independently hydrogen atom or a linear or branched chain. An alkyl group having 1 to 4 carbon atoms; two selected from the group consisting of R ² to R ⁵ may be bonded to form a ring].

Wherein R ¹ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; and R ² to R ⁵ represent each independently hydrogen atom or a linear or branched chain. An alkyl group having 1 to 4 carbon atoms; two selected from the group consisting of R ² to R ⁵ may be bonded to form a ring].

Preferable specific examples of the constituent units represented by the above formulas (1) to (3) include 4-methyl-1,2-cyclohexanedicarboxylic acid derived from the following formula (4). The constituent unit of ethylene glycol. The alicyclic polyester resin (B) having such a structural unit is obtained, for example, by polycondensation of methylhexahydrophthalic anhydride and ethylene glycol.

Further, other preferable specific examples of the constituent units represented by the above formulas (1) to (3) include those derived from 1,4-cyclohexanedicarboxylic acid and neopentane represented by the following formula (5). a constituent unit of a diol. The alicyclic polyester resin (B) having such a structural unit is obtained, for example, by polycondensing 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.

Further, the terminal structure of the alicyclic polyester resin (B) is not particularly limited, and may be a hydroxyl group or a carboxyl group, or may be a structure in which the hydroxyl group or the carboxyl group is appropriately modified (for example, the terminal hydroxyl group is via a monocarboxylic acid or The structure in which the acid anhydride is esterified or the structure in which the carboxyl group at the terminal is esterified via an alcohol, etc.).

When the alicyclic polyester resin (B) has the constituent units represented by the above formulas (1) to (3), the total amount of the constituent units (the total content; the total monomer unit constituting the constituent unit) is not Particularly limited, only with respect to the total constituent unit of the alicyclic polyester resin (B) (100 mol%; constitutes an alicyclic polyester The total monomer unit of the resin (B) is preferably 20 mol% or more (e.g., 20 to 100 mol%), more preferably 50 to 100 mol%, still more preferably 80 to 100 mol%. When the content of the constituent unit represented by the above formulas (1) to (3) is less than 20 mol%, the heat resistance, light resistance, and crack resistance of the cured product may be lowered.

The number average molecular weight of the alicyclic polyester resin (B) is not particularly limited, but is preferably from 300 to 100,000, more preferably from 300 to 30,000. When the number average molecular weight of the alicyclic polyester resin (B) is less than 300, the toughness of the cured product is insufficient, and the cracking property may be lowered. When the number average molecular weight of the alicyclic polyester resin (B) exceeds 100,000, the compatibility with the curing agent (C) is lowered, and the transparency of the cured product may be lowered. Further, the number average molecular weight of the alicyclic polyester resin (B) can be measured, for example, by a GPC (gel permeation chromatography) method as a standard polystyrene equivalent value.

The alicyclic polyester resin (B) is not particularly limited and can be produced by a conventional method. More specifically, for example, the alicyclic polyester resin (B) can be obtained by polycondensing the above dicarboxylic acid and a diol by a usual method, or by using the above-mentioned dicarboxylic acid derivative (anhydride). , esters, acid halides, etc.) and diols are obtained by polycondensation according to the usual method.

In the resin composition for optical semiconductor encapsulation of the present invention, the content (usage amount) of the alicyclic polyester resin (B) is not particularly limited, and is relative to the alicyclic polyester resin (B) and the hardener (C). The total amount (100% by weight) is preferably from 1 to 60% by weight, more preferably from 1 to 30% by weight. When the content of the alicyclic polyester resin (B) is less than 1% by weight, the crack resistance of the cured product may be lowered. When the content of the alicyclic polyester resin (B) exceeds 60% by weight, the transparency and heat resistance of the cured product may be lowered.

[hardener (C)]

The curing agent (C) contained in the resin composition for optical semiconductor encapsulation of the present invention is an acid anhydride-based curing agent. The acid anhydride-based curing agent can be arbitrarily selected from those conventionally used as a curing agent for epoxy resins. Among them, those which are liquid at normal temperature are preferred, and specific examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, and methylene. Methyltetrahydrophthalic anhydride or the like. Further, even if it is an acid anhydride which is solid at normal temperature, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or methylcyclohexene dicarboxylic anhydride, it is dissolved at normal temperature. When a liquid acid anhydride is used as a liquid mixture, it can be used as a curing agent (C). Further, the curing agent (C) may be used singly or in combination of two or more.

In addition, the present invention can also be used as a curing agent (C), such as "Rikacid MH-700" (manufactured by Shin-Nippon Chemical Co., Ltd.) and "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.).

The content (amount of use) of the curing agent (C) is not particularly limited, and is preferably 50 to 200 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. More preferably, it is 80 to 145 parts by weight. More specifically, the content (usage amount) of the curing agent (C) is used per one equivalent of the epoxy group in all the epoxy group-containing compounds contained in the resin composition for semiconductor encapsulation. A ratio of 0.5 to 1.5 equivalents is preferred. When the amount of the curing agent (C) used is less than 50 parts by weight, the hardening is insufficient, and the toughness of the cured product tends to be lowered. When the amount of the hardener (C) used is more than 200 parts by weight, the cured product may be colored to deteriorate the hue.

[hardening accelerator (D)]

The resin composition for optical semiconductor encapsulation of the present invention contains an organic carboxylic acid zinc as a hardening accelerator (D) as an essential component. The organic zinc carboxylate exhibits a function as a curing accelerator in the reaction of a compound having an epoxy group with a curing agent (C) (an acid anhydride-based curing agent), and is imparted to a colorless and transparent cured product (hardened epoxy resin). good. Specifically, since the organic carboxylic acid component of the organic zinc carboxylate has excellent light resistance, it is particularly suitable for any one of a linear type, a branched type, and an ether group containing carbon 6 to 18. It is preferred that the fatty acid zinc is composed of one or two kinds of fatty acids. Specific examples thereof include zinc octoate, zinc laurate, and zinc stearate.

In the present invention, commercially available products such as zinc ethylhexanoate (manufactured by Nippon Chemical Industry Co., Ltd.) may be used as the organic zinc carboxylate.

The inventors of the present invention have found that the curing accelerator (D) in the resin composition for optical semiconductor encapsulation of the present invention can reduce the glass transition temperature of the cured product by containing the organic zinc carboxylate as an essential component. In the semiconductor device, the adhesion between the cured product and the lead frame tends to be lowered. Thus, it has been found that the optical stability of the optical semiconductor device (especially the photometric stability under high temperature and high humidity) is remarkably improved by lowering the adhesion to the lead frame of the cured product.

The resin composition for optical semiconductor encapsulation of the present invention may be used alone as the curing accelerator (D), or may be used in combination with a curing accelerator other than organic zinc carboxylate (also referred to as "other hardening promotion". The case of the agent.) The above-mentioned other hardening accelerator is preferably an ion-bonded body having a cerium ion represented by the following formula (6) and a halogen anion capable of forming an ion pair with the cerium ion, from the viewpoint of further enhancing the photostability. [R ⁶ , R ⁷ , R ⁸ and R ⁹ in the formula (6) represent a hydrocarbon group having 1 to 20 carbon atoms, respectively, which may be the same or different from each other]. In other words, the resin composition for optical semiconductor encapsulation of the present invention contains the organic carboxylic acid zinc as the curing accelerator (D), further contains cerium ions represented by the above formula (6), and forms ions with the cerium ions. It is preferred that the ionic combination of the halogen anion is used.

The ionic bond (quaternary organic phosphonium salt) of the cesium ion and the halogen anion represented by the above formula (6) forms at least one ion pair with the halogen anion. The ion-bonding body is rapidly dissociated when exposed to a high temperature and hardens, and the cerium ion system has an effect of promoting hardening. Therefore, in the manufacture of a semiconductor device, it is considered that the effect of improving the photometric stability is improved by lowering the adhesion between the halogen anion and the lead frame in the package.

The hydrocarbon group having 1 to 20 carbon atoms of R ⁶ , R ⁷ , R ⁸ and R ⁹ in the formula (6) may, for example, be an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or carbon. A number of 6 to 20 aryl groups and the like. 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, a second butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, and a cyclohexyl group. A linear, branched or cyclic alkyl group such as methylcyclohexyl, heptyl, octyl, isooctyl, decyl, isodecyl, decyl or isodecyl. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a methylbenzyl group, an ethylbenzyl group, a dimethylbenzyl group, a diethylbenzyl group, a phenethyl group, a methylphenethyl group, and an ethyl group. Phenylethyl, methylphenethyl, ethylphenethyl and the like. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group; a substituted phenyl group such as a methylphenyl group, a dimethylphenyl group or an ethylphenyl group; and a naphthyl group. Among these, an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group or a butyl group; a carbon number of 7 to 10 such as a benzyl group, an ethylbenzyl group, a phenethyl group or an ethylphenethyl group; An aralkyl group; an aryl group having 6 to 8 carbon atoms such as a phenyl group or a methylphenyl group; and preferably a phenyl group, a butyl group or an ethyl group.

Examples of the halogen anion which can form an ion pair with the cerium ion represented by the above formula (6) include a chloride ion, a bromide ion, an iodide ion, and the like. Among them, bromide ion and iodide ion are preferred.

Examples of the ionic combination of the phosphonium ion and the halogen anion (the fourth-order organic phosphonium salt) represented by the above formula (6) include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, and chlorinated tetrachloride. Benzoquinone, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, propyltriphenylphosphonium chloride, and propyl bromide Triphenyl hydrazine, iodide propyl triphenyl hydrazine, chlorobutyl triphenyl hydrazine, bromobutyl triphenyl hydrazine, butyl iodide, brominated methyl triphenyl hydrazine, methyl iodide Benzoquinone, tetramethylphosphonium iodide, tetraethylphosphonium bromide, and the like. Among them, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium iodide, etc. are preferred.

Further, the ionic combination of the cerium ion and the halogen anion (the quaternary organic sulfonium salt) represented by the above formula (6) may be a commercial product such as the product name "U-CAT 5003" (manufactured by Sanapro Co., Ltd.). .

In addition to the ionic combination of the cerium ion and the halogen anion represented by the above formula (6), the other curing accelerator may be a conventional to conventional curing accelerator. Examples of such a hardening accelerator include, for example, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and salts thereof (for example, phenate, octanoate, p-toluenesulfonate, Formate, tetraphenylborate); 1,5-diazabicyclo[4.3.0]-5-pinene (DBN) and its salts (eg; phenate, octyl) Acid salt, p-toluenesulfonate, formate, tetraphenyl borate); benzyldimethylamine, 2,4,6-glucos(dimethylaminomethyl)phenol, N,N-dimethyl a tertiary amine such as cyclohexylamine; an imidazole such as 2-ethyl-4-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole; a phosphine such as a phosphate or triphenylphosphine a compound such as tetraphenylphosphonium tetra(p-tolyl)borane; a metal chelating agent;

The amount (content) of the hardening accelerator (D) is preferably 0.05 to 7 parts by weight based on 100 parts by weight of the total of the epoxy group-containing compound contained in the resin composition for photo-semiconductor encapsulation. More preferably, it is 0.1 to 5 parts by weight, more preferably 0.2 to 5 parts by weight, still more preferably about 0.25 to 4 parts by weight. When the amount of the curing accelerator (D) used is less than 0.05 parts by weight, the curing acceleration effect may be insufficient. On the other hand, when the amount of the curing accelerator (D) is more than 7 parts by weight, the color of the cured product may be colored. The situation of poor phase change. In addition, the "amount of use of the hardening accelerator (D)" refers to the sum (total content) of these contents when two or more types of hardening accelerators are used.

Among the hardening accelerators (D), the content of the organic carboxylic acid salt (especially zinc octoate) is not particularly limited, but is the total amount of the epoxy group-containing compound contained in the resin composition for optical semiconductor encapsulation. The amount is preferably from 0.1 to 4 parts by weight, more preferably from 0.3 to 3.5 parts by weight, still more preferably from 0.5 to 3 parts by weight, per 100 parts by weight. When the content of the organic carboxylic acid zinc is less than 0.1 part by weight, it may be difficult to obtain an effect of improving the photosensitivity of the optical semiconductor device (especially the photometric stability under high temperature and high humidity conditions). Further, when the content exceeds 4 parts by weight, the crack resistance (cold heat shock resistance) of the optical semiconductor device may be lowered.

Further, the ion of the cerium ion and the halogen anion represented by the above formula (6) The conjugate (four-stage organic sulfonium salt) is not particularly limited, and is formulated to have a halogen (especially bromine or iodine) contained in the resin composition for optical semiconductor encapsulation to be 200 mg/kg or more (for example, 200 to 8000 mg/kg). The amount is preferably from 200 to 5000 mg/kg, more preferably from 300 to 4000 mg/kg. When the halogen content is less than 200 mg/kg, it may be difficult to obtain an effect of improving the photostability of the optical semiconductor device.

[Solvent]

The resin composition for optical semiconductor encapsulation of the present invention may contain a solvent. Examples of the solvent include diol (ethylene glycol; polyalkylene glycol; neopentyl glycol, etc.), ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl Ether, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1, a chain ether such as a 3-butanediol mono- or dialkyl ether, a 1,4-butanediol mono- or dialkyl ether, a glycol ether such as glycerol mono-, di- or trialkyl ether; tetrahydrofuran, two Dioxane, etc., ester (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Carboxylic acid esters such as 3-methoxybutyl acetate, C _5-6 cycloalkane mono or diacetate, C _5-6 cycloalkanediethanol mono or diacetate; Monoalkyl ether acetate, ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, Propylene glycol mono or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1,3-propanediol mono or diacetic acid Ester, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4- Butanediol mono or diacetate, glycerol mono, di or triacetate, glycerol mono or di C _1-4 alkyl ether di or monoacetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol a diol acetate such as a mono- or diacetate or a glycol ether acetate, etc.), a ketone (acetone, methyl ethyl ketone, methyl isoform) Butanone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc., decylamine (N,N-dimethylacetamide, N,N-dimethyl Myramine, etc.), anthracene (dimethylene, etc.), alcohol (methanol, ethanol, propanol, 3-methoxy-1-butanol, C _5-6 cycloalkanediol, C _5-6 ring) An alkane dimethanol or the like, a hydrocarbon (an aromatic hydrocarbon such as benzene, toluene or xylene, an aliphatic hydrocarbon such as hexane or the like, or an alicyclic hydrocarbon such as cyclohexane), or a mixed solvent thereof.

[Rubber particles]

The resin composition for optical semiconductor encapsulation of the present invention may contain rubber particles. Examples of the rubber particles include particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, particulate SBR (styrene-butadiene rubber), and SMB (benzene). Ethylene-butadiene-methyl methacrylate rubber, MAM (methyl methacrylate-butyl methacrylate-methyl methacrylate rubber), MAM imparting a functional group, and the like. A rubber particle system having a multilayer structure (core-shell structure) comprising a core portion having rubber elasticity and a shell layer covering at least one layer of the core portion, the surface having an epoxy group (for example, an alicyclic epoxy compound (A) The epoxy group and the carboxyl group of the functional group of the epoxy group, and having an average particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm, the refractive index of the rubber particle and the optical semiconductor package may be used. The rubber particles having a difference in refractive index of the cured product of the resin composition within ±0.02. The amount of the above-mentioned rubber particles can be appropriately adjusted as necessary, and is not particularly limited, but is 100% of the total amount of the compound having an epoxy group contained in the resin composition for optical semiconductor encapsulation. The parts by weight are preferably from 0.5 to 30 parts by weight, more preferably from 1 to 20 parts by weight. When the amount of the rubber particles used is less than 0.5 part by weight, the crack resistance tends to be lowered. On the other hand, when the amount of the rubber particles used is more than 30 parts by weight, heat resistance and transparency tend to be lowered.

[additive]

The resin composition for optical semiconductor encapsulation of the present invention may contain various additives in addition to the above, insofar as it does not impair the effects of the present invention. The above-mentioned additives are, for example, when a compound having a hydroxyl group of ethylene glycol, diethylene glycol, propylene glycol or glycerin is used, the reaction can be progressed slowly. Other decane coupling agents such as polyfluorene-based or fluorine-based antifoaming agents, leveling agents, and γ-methacryloxypropyltrimethoxydecane may be used in the range of non-destructiveness and viscosity or transparency. A conventional additive such as an inorganic filler such as a surfactant, cerium oxide or aluminum oxide, a flame retardant, a colorant, an antioxidant, an ultraviolet absorber, an ion adsorbent, a pigment, a phosphor, and a release agent.

<Modulation Method of Resin Composition for Optical Semiconductor Packaging>

The resin composition for optical semiconductor encapsulation of the present invention may contain at least the above-described alicyclic epoxy compound (A), alicyclic polyester resin (B), curing agent (C), and curing accelerator (D). The modulation method is not particularly limited. For example, an α agent containing an alicyclic epoxy compound (A) as an essential component and a β agent containing a hardener (C) and a hardening accelerator (D) as essential components are separately prepared, and the α agent and the β agent are prepared. Stir in a predetermined ratio. Mixing can be prepared by defoaming under vacuum as necessary. Further, in this case, the alicyclic polyester resin (B) may be previously mixed as a constituent component of the alpha agent and/or the beta agent (either or both of the alpha agent and the beta agent), and when the alpha agent is mixed with In the case of a beta agent, it may be formulated as a component other than the alpha agent or the beta agent. In particular, in view of obtaining a uniform resin composition, it is preferred to premix the alicyclic polyester resin (B) and the hardener (C) to obtain a mixture of the alicyclic polyester resin (B) and the hardener. After the mixture of (C), the hardening accelerator (D) or other additives are blended in the mixture to prepare a β agent, followed by mixing the β agent and the α agent.

The temperature at the time of stirring and mixing in preparing the above-mentioned α agent is not particularly limited, and is preferably from 30 to 150 ° C, more preferably from 35 to 130 ° C. Further, the temperature at the time of stirring and mixing in preparing the above-mentioned β agent is not particularly limited, and is preferably 30 to 100 ° C, more preferably 35 to 80 ° C. Conventional devices such as a self-rotating mixer, a planetary mixer, a kneader, a dissolver, and the like can be used for stirring and mixing.

Further, the temperature at the time of mixing the alicyclic polyester resin (B) and the curing agent (C) is not particularly limited, and is preferably 60 to 130 ° C, more preferably 90 to 120 ° C. The mixing time is not particularly limited, and is preferably from 30 to 100 minutes, more preferably from 45 to 80 minutes. The mixing is not particularly limited, and it is preferably carried out under a nitrogen atmosphere. Further, the above-mentioned conventional device can be used for mixing.

The mixed alicyclic polyester resin (B) and the curing agent (C) are not particularly limited, and may be further subjected to an appropriate chemical treatment (for example, hydrogenation or terminal modification of an alicyclic polyester resin). Further, in the mixture of the above alicyclic polyester resin (B) and the hardener (C), one part of the hardener (C) may be combined with the alicyclic polyester resin (B) (for example, the hydroxy group of the alicyclic polyester) Etc.) Reaction.

For the mixture of the above alicyclic polyester resin (B) and the hardener (C), for example, "HN-7200" (manufactured by Hitachi Chemical Co., Ltd.), "HN-5700" can also be used. (Marketing products manufactured by Hitachi Chemical Co., Ltd.).

<hardened matter>

The resin composition for optical semiconductor encapsulation of the present invention is not particularly limited, and may be, for example, at a temperature of 45 to 200 ° C (preferably 100 to 190 ° C, more preferably 100 to 180 ° C), and a hardening time of 30 to 600 minutes (45 It is preferably 540 minutes, and it is hardened by conditions of 60 to 480 minutes. When either or both of the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening becomes insufficient, and if either or both are higher than the upper limit of the above range, the resin component may be caused. The situation of decomposition, so neither is good. The hardening conditions depend on various conditions, but may be appropriately adjusted depending on whether the hardening time is high when the hardening temperature is high, and the hardening time is increased when the hardening temperature is low. By curing the resin composition for optical semiconductor encapsulation of the present invention, a cured product excellent in physical properties such as heat resistance, transparency, light resistance, and crack resistance can be obtained.

<Optical semiconductor device>

The optical semiconductor device of the present invention is obtained by encapsulating an optical semiconductor element in the resin composition for optical semiconductor encapsulation of the present invention. In the package of the optical semiconductor device, the resin composition for optical semiconductor encapsulation prepared by the above method is injected into a predetermined molding die, and heat-hardened under predetermined conditions. In this way, the optical semiconductor element is encapsulated by the cured product of the resin composition for optical semiconductor encapsulation, and electrical conduction characteristics (photometric stability) (especially, electric conduction characteristics (photometric stability) under high temperature and high humidity conditions) and resistance are obtained. An optical semiconductor device having excellent properties such as thermal shock resistance. The hardening temperature and the hardening time are the same as those obtained when the cured product is obtained.

[Examples]

In the following, the detailed description of the present invention is made by the examples, but the invention is not limited by the embodiments.

Example 1

As shown in Table 1, the alpha agent (hereinafter referred to simply as "alpha agent") which is an essential component of the alicyclic epoxy compound is used under the trade name "Ceroxide 2021P" (manufactured by Daicel Co., Ltd.): 55 parts by weight. Product name "EHPE 3150" (manufactured by Daicel Co., Ltd.): 15 parts by weight, trade name "jER YX8034" (manufactured by Mitsubishi Chemical Corporation): 20 parts by weight and trade name "Ceroxide 2081" (manufactured by Daicel Co., Ltd.) : 10 parts by weight of a mixture.

In addition, as shown in Table 1, the β agent (hereinafter referred to as "β agent") containing a curing agent and a curing accelerator as essential components is a product name "Rikacid MH-700" (manufactured by Shin-Nihon Chemical Co., Ltd.). : 90 parts by weight, the product name "HN-5700" (manufactured by Hitachi Chemical Co., Ltd.): 40 parts by weight, the trade name "zinc ethylhexanoate 15%" (zinc octoate; manufactured by Nippon Chemical Industry Co., Ltd.): 2.0 parts by weight and the product name "U-CAT 5003" (manufactured by Sanapro): a mixture of 0.7 parts by weight.

The above-mentioned α agent and β agent were uniformly mixed (2000 rpm; 5) in a mixing ratio (unit: parts by weight) shown in Table 1 using a self-revolving stirring device (trade name "Defoaming Rantaro"; Thinky). After the minute, defoaming was performed to obtain a resin composition for optical semiconductor encapsulation.

Example 2

As shown in Table 1, in addition to the alpha agent, the product name "Ceroxide 2021P" (manufactured by Daicel Co., Ltd.): 65 parts by weight, trade name "EHPE 3150" (manufactured by Daicel): 15 parts by weight, product name " jER YX8034 (manufactured by Mitsubishi Chemical Corporation): The same treatment as in Example 1 was carried out except that 10 parts by weight and a product name "Ceroxide 2081" (manufactured by Daicel Co., Ltd.): 10 parts by weight, to obtain an optical semiconductor package. Resin composition.

Example 3

As shown in Table 1, the product name "Ceroxide 2021P" (manufactured by Daicel Co., Ltd.) was used in an amount of 75 parts by weight, and the product name "EHPE 3150" (manufactured by Daicel): 15 parts by weight, and the product was used. The name "Ceroxide 2081" (manufactured by Daicel): 10 parts by weight and the trade name "Nanostrength M52N" (manufactured by Arkema): 5 parts by weight, stirred at 100 ° C for 2 hours and dissolved in Nanostrength M52N (mixture) The same treatment as in Example 1 was carried out, and a resin composition for optical semiconductor encapsulation was obtained.

Comparative example 1

As shown in Table 1, except for the beta agent, the product name "Rikacid MH-700" (manufactured by Shin-Nihon Chemical Co., Ltd.): 90 parts by weight, trade name "HN-5700" (manufactured by Hitachi Chemical Co., Ltd.): 40 parts by weight and a product of the product name "U-CAT 5003" (manufactured by Sanapro Co., Ltd.): 0.7 parts by weight, the same treatment as in Example 1 was carried out to obtain a resin composition for optical semiconductor encapsulation.

Comparative example 2

As shown in Table 1, except for the beta agent, the product name "Rikacid MH-700" (manufactured by Shin-Nihon Chemical Co., Ltd.): 90 parts by weight, trade name "HN-5700" (manufactured by Hitachi Chemical Co., Ltd.): 40 parts by weight and the product name "U-CAT 5003" (manufactured by Sanapro): 0.7 parts by weight The same treatment as in Example 2 was carried out, except for the mixture, to obtain a resin composition for optical semiconductor encapsulation.

Comparative example 3

As shown in Table 1, except for the beta agent, the product name "Rikacid MH-700" (manufactured by Shin-Nihon Chemical Co., Ltd.): 90 parts by weight, trade name "HN-5700" (manufactured by Hitachi Chemical Co., Ltd.): 40 parts by weight and the same product as the product of "U-CAT 5003" (manufactured by Sanapro Co., Ltd.): 0.7 parts by weight, the same treatment as in Example 3 was carried out to obtain a resin composition for optical semiconductor encapsulation.

[Evaluation]

The resin compositions for optical semiconductor encapsulation obtained in the examples and the comparative examples were evaluated by the following methods.

<Photometric stability (high temperature and high humidity energization characteristics)>

The resin composition for optical semiconductor encapsulation obtained in the examples and the comparative examples was injected into a lead frame with an optical semiconductor element (InGaN), and heated at 110 ° C for 2 hours, followed by heating at 140 ° C for 3 hours by using a resin curing furnace. It is hardened to form an optical semiconductor device.

The produced optical semiconductor device was subjected to high-temperature and high-humidity energization (85° C./85% RH/20 mA), and the photometric retention rate after 100 hours and the photometric retention rate after 500 hours were measured, thereby evaluating the high temperature over time. Wet energization characteristics. Further, the luminosity of the optical semiconductor device was measured using the following measuring device.

Measuring device: "OL771" manufactured by OPTRONIC LABORATORIES

The specific evaluation method is as follows.

First, the photo-semiconductor device produced was measured for luminosity (20 mA) before storage under high temperature and high humidity conditions (as "initial luminosity"). Subsequently, the mixture was placed in a high-temperature and high-humidity bath (85 ° C / 85% RH), and then energized (20 mA), and the luminosity after 100 hours and the luminosity after 500 hours were measured from the energization. Then, the luminosity retention rate after 100 hours and the luminosity retention rate after 500 hours were determined in the following formula.

. [Photos retention after 100 hours] (%) = 100 × [luminosity after 100 hours (1m)] / [initial luminosity (1m)]

. [Photos retention after 500 hours] (%) = 100 × [luminance after 500 hours (1m)] / [initial luminosity (1m)]

The results are shown in the columns of "The luminosity retention rate is 100 hours" and "The luminosity retention rate is 500 hours" in Table 1.

Next, the change rate of the luminosity retention rate after 100 hours (100 luminosity retention ratio after 100 hours) - 100 (%) was determined from the luminosity retention rate after 100 hours, and the luminosity stability was evaluated according to the following indexes. Sex (high temperature and high humidity energization characteristics).

The rate of change of the luminosity retention rate after 100 hours exceeded -3% and did not reach 3%, and when the luminosity retention rate after 500 hours was 80% or more, it was evaluated as ○ (good luminosity stability), and other cases were evaluated. It is × (photometric stability is poor). The results are shown in the column "Photometric stability (high temperature and high humidity energization characteristics)" in Table 1.

<Crack resistance (cold heat shock resistance)>

The resin composition for optical semiconductor encapsulation obtained in the examples and the comparative examples was injected into a lead frame with an optical semiconductor element (InGaN), and heated at 110 ° C for 2 hours and then at 140 ° C using a resin curing oven. It was hardened in 3 hours to prepare an optical semiconductor device.

For the fabricated optical semiconductor device, a thermal shock test was performed using a thermal shock tester [for 30 minutes at -40 ° C, followed by cooling and heating at 100 ° C for 30 minutes as a thermal shock test for one cycle], After 800 cycles, the crack length of the cured product in the optical semiconductor device was measured using the following measuring apparatus.

Measuring device: "Digital Microscope VHX-900" manufactured by Keyence

The crack resistance is based on the crack generated by the edge portion of the lead frame of the optical semiconductor device, and when the crack length after 800 cycles is 800 μm or more, it is evaluated as × (poor crack resistance), and is less than 800 μm. In the case of evaluation, it was evaluated as ○ (good crack resistance). The results are shown in the column of "crack resistance (cold heat shock resistance)" in Table 1.

<Comprehensive evaluation>

The result of the above test and the evaluation result of the photometric stability (high-temperature and high-humidity electric current) are ○ (good), and when the evaluation result of the crack resistance (cold heat shock resistance) is ○ (good), the overall evaluation is ○ (Excellent), in addition to this, the overall rating is × (poor). The results are presented in the column "Comprehensive Assessment" in Table 1.

The ingredients used in the examples are presented below.

[α agent]

Ceroxide 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate (manufactured by Daicel)

EHPE 3150: 1,2-epoxy-4-(2-epoxyethyl)cyclohexene adduct of 2,2-bis(hydroxymethyl)-1-butanol (manufactured by Daicel)

Ceroxide 2081: ε-caprolactone modified 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate (manufactured by Daicel)

jER YX8034: hydrogenated bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation)

Nanostrength M52N: Rubber particles (made by Arkema)

[β agent]

Rikacid MH-700: 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30 (manufactured by Nippon Chemical and Chemical Co., Ltd.)

HN-5700: 4-methylhexahydrophthalic anhydride/3-methylhexahydrophthalic anhydride=70/30 and alicyclic polyester resin mixture (manufactured by Hitachi Chemical Co., Ltd.)

Zinc octoate: zinc ethylhexanoate 15% (T) (manufactured by Japan Chemical Industry Co., Ltd.)

U-CAT 5003: Brominated quaternary phosphonium (manufactured by Sanapro)

Test machine . Resin hardening furnace

Espec (stock) manufacturing; GPHH-201

. High temperature and high pressure tank

Espec (stock) manufacturing; small environmental tester SH-641

. Thermal shock test machine

Espec (stock) manufacturing; small thermal shock device TSE-11-A

The optical semiconductor device (Example) using the resin composition for optical semiconductor encapsulation of the present invention is excellent in photometric stability (high temperature and high humidity electrification property) under high temperature and high humidity conditions, and crack resistance (cold heat shock resistance) is also Excellent.

On the other hand, the optical semiconductor device (comparative example) using a resin composition containing no zinc octoate was inferior in photometric stability and crack resistance.

Claims (6)

A resin composition for optical semiconductor encapsulation, which comprises an alicyclic epoxy compound (A), an alicyclic polyester resin (B), a curing agent (C), and a curing accelerator (D) for optical semiconductor encapsulating resin The composition is characterized in that the alicyclic epoxy compound (A) is at least one selected from the group consisting of: (A1) a compound represented by the following formula (I), and (A2) an alicyclic ring directly substituted with an epoxy group a compound of a single bond and (A3) a compound of a group of three or more epoxy groups constituting two carbon atoms and an oxygen atom adjacent to the alicyclic ring, and a resin for optical semiconductor encapsulation The total amount (100% by weight) of the compound having an epoxy group contained in the composition, the total content of the alicyclic epoxy compound (A) being 55 to 100% by weight, the alicyclic polyester resin (B) An alicyclic polyester having an alicyclic structure, the hardener (C) being an acid anhydride hardener, and the hardening accelerator (D) containing an organic zinc carboxylate, In the formula (I), X represents a single bond or a linking group, and the linking group is a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine bond or a plurality of linked groups. The resin composition for optical semiconductor encapsulation according to claim 1, wherein the organic zinc carboxylate is zinc octoate. The resin composition for optical semiconductor encapsulation according to claim 1 or 2, further comprising a cerium ion represented by the following formula (6) as the curing accelerator (D), and capable of forming an ion with the cerium ion An ionic combination of a halogen anion, [R ⁶ , R ⁷ , R ⁸ and R ⁹ in the formula (6) represent a hydrocarbon group having 1 to 20 carbon atoms, respectively, which may be the same or different from each other]. The resin composition for optical semiconductor encapsulation according to claim 3, wherein the halogen anion is a bromide ion or an iodide ion. A cured product obtained by curing a resin composition for optical semiconductor encapsulation according to any one of claims 1 to 4. An optical semiconductor device in which an optical semiconductor element is packaged by a resin composition for optical semiconductor encapsulation according to any one of claims 1 to 4.