JP5764419B2 - Curable epoxy resin composition - Google Patents

Description

  The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, a resin composition for optical semiconductor encapsulation comprising the curable epoxy resin composition, and the optical semiconductor encapsulation. The present invention relates to an optical semiconductor device in which an optical semiconductor element is sealed with a resin composition for use.

  Optical semiconductor devices using an optical semiconductor element (LED element) as a light source are currently used in various applications such as various indoor or outdoor display boards, image reading light sources, traffic signals, large display units, and the like. Such an optical semiconductor device generally has a structure in which an optical semiconductor element is sealed with a resin (sealing resin), and the sealing resin protects the optical semiconductor element from moisture, impact, and the like. Have a role.

  In recent years, higher output and shorter wavelengths of such optical semiconductor devices have been developed. For example, in blue and white optical semiconductor devices, yellowing of the sealing resin due to light and heat emitted from the optical semiconductor element is a problem. It has become. Since the yellowing sealing resin absorbs light emitted from the optical semiconductor element, the luminous intensity of the light output from the optical semiconductor device decreases with time.

  Conventionally, the hardened | cured material of the resin composition containing monoallyl diglycidyl isocyanurate and the bisphenol A type epoxy resin is known as sealing resin for optical semiconductors excellent in heat resistance (refer patent document 1). However, even when the cured product is used as a sealing resin for a high-output blue / white light semiconductor device, the coloration proceeds due to light and heat emitted from the optical semiconductor element, and is output originally. As a result, the problem is that the light intensity of the light output from the optical semiconductor device decreases with time.

JP 2000-344867 A

  3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl (3) as encapsulating resins having higher heat resistance and light resistance and less likely to be colored (yellowing) , 4-epoxy) cyclohexanecarboxylate and ε-caprolactone adducts, and liquid alicyclic epoxy resin cured products having an alicyclic skeleton such as 1,2,8,9-diepoxylimonene are known. However, the cured products of these alicyclic epoxy resins are vulnerable to various stresses, and cracks (cracks) are generated when a thermal shock such as a cold cycle (repeating heating and cooling) is applied. Had a problem.

  The optical semiconductor device usually undergoes a reflow process for joining the electrodes of the optical semiconductor device to the wiring board by soldering. In recent years, lead-free solder having a high melting point has been used as a solder as a bonding material, and heat treatment in a reflow process has become a higher temperature (for example, a peak temperature of 240 to 260 ° C.). . Under such circumstances, in the conventional optical semiconductor device, there is a problem of deterioration such that the sealing resin is peeled off from the lead frame of the optical semiconductor device or a crack is generated by the heat treatment in the reflow process. There was found.

  For this reason, as a sealing resin in an optical semiconductor device, a transparent material having both high heat resistance, light resistance, and crack resistance and excellent in reflow resistance is currently required. In the present specification, “crack resistance” refers to a characteristic in which cracking is hardly generated in the sealing resin even when a thermal shock is applied. In addition, “reflow resistance” means that the sealing resin is peeled off from the lead frame or cracked in the sealing resin even when heat treatment is performed in the reflow process performed when the optical semiconductor device is mounted on the substrate. It refers to characteristics that are unlikely to deteriorate.

Accordingly, an object of the present invention is to provide a curable epoxy resin composition that has a high transparency, heat resistance, light resistance, and crack resistance, and gives a cured product excellent in reflow resistance.
Another object of the present invention is a cured product obtained by curing the above curable epoxy resin composition, having high transparency, heat resistance, light resistance, and crack resistance, and having excellent reflow resistance. Is to provide.
Another object of the present invention is to provide an optical semiconductor encapsulation comprising the above-mentioned curable epoxy resin composition capable of producing an optical semiconductor device in which deterioration due to heat treatment in the reflow process and a decrease in light intensity over time are suppressed. Another object is to provide a resin composition.
Another object of the present invention is to suppress degradation due to heat treatment in the reflow process and decrease in light intensity over time, which are obtained by sealing an optical semiconductor element using the above resin composition for optical semiconductor sealing. Another object is to provide an optical semiconductor device.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors include, as an essential component, an alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, and a polyol other than a polycarbonate polyol, and further include a curing agent or a curing catalyst. An optical semiconductor device comprising a curable epoxy resin composition containing a cured product having high transparency, heat resistance, light resistance, crack resistance, and reflow resistance, and encapsulating an optical semiconductor element with the cured product Found that deterioration due to heat treatment in the reflow process and a decrease in light intensity over time hardly occur, and the present invention has been achieved.

［式中、Ｒ¹及びＲ²は水素原子または炭素数１〜８のアルキル基を示す］
で表されるモノアリルジグリシジルイソシアヌレート化合物（Ｂ）と、ポリカーボネートポリオールを除くポリオール（Ｃ）と、硬化剤（Ｄ）又は硬化触媒（Ｅ）とを含むことを特徴とする硬化性エポキシ樹脂組成物を提供する。 That is, the present invention relates to an alicyclic epoxy compound (A) and the following formula (1).

[Wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A curable epoxy resin composition comprising a monoallyl diglycidyl isocyanurate compound (B) represented by formula (I), a polyol (C) excluding polycarbonate polyol, and a curing agent (D) or a curing catalyst (E). Offer things.

  Furthermore, the said alicyclic epoxy compound (A) provides the said curable epoxy resin composition which is an alicyclic epoxy compound which has a cyclohexene oxide group.

で表される化合物である前記の硬化性エポキシ樹脂組成物を提供する。 Further, the alicyclic epoxy compound (A) is represented by the following formula (I-1)

The said curable epoxy resin composition which is a compound represented by these is provided.

  Furthermore, the said curable epoxy resin composition containing a hardening accelerator (F) is provided.

  Furthermore, the said curable epoxy resin composition containing an acrylic block copolymer is provided.

  Moreover, this invention provides the hardened | cured material formed by hardening | curing the said curable epoxy resin composition.

  Moreover, this invention provides the resin composition for optical semiconductor sealing which consists of said curable epoxy resin composition.

  Moreover, this invention provides the optical semiconductor device which sealed the optical semiconductor element with the said resin composition for optical semiconductor sealing.

  Since the curable epoxy resin composition of the present invention has the above-described configuration, it has high heat resistance, light resistance, transparency, and crack resistance by curing the resin composition, and also has reflow resistance. An excellent cured product can be obtained. In addition, an optical semiconductor device in which an optical semiconductor element is encapsulated using the curable epoxy resin composition (resin composition for encapsulating an optical semiconductor) of the present invention is not easily deteriorated by high-temperature treatment in a reflow process, and has a luminous intensity. Has excellent quality and durability.

FIG. 1 is a schematic view showing an embodiment of an optical semiconductor device in which an element (optical semiconductor element) is sealed with a curable epoxy resin composition of the present invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. FIG. 2 is an example of the surface temperature profile of the optical semiconductor device in the solder heat resistance test of the example (temperature profile in one of the two heating operations in the reflow furnace).

［式中、Ｒ¹及びＲ²は水素原子または炭素数１〜８のアルキル基を示す］
で表されるモノアリルジグリシジルイソシアヌレート化合物（Ｂ）と、ポリカーボネートポリオールを除くポリオール（Ｃ）と、硬化剤（Ｄ）又は硬化触媒（Ｅ）とを含む樹脂組成物である。 <Curable epoxy resin composition>
The curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A) and the following formula (1).

[Wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
The resin composition containing the monoallyl diglycidyl isocyanurate compound (B) represented by these, the polyol (C) except a polycarbonate polyol, and a hardening | curing agent (D) or a hardening catalyst (E).

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (A) constituting the curable epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in the molecule (in one molecule). More specifically, the alicyclic epoxy compound (A) includes, for example, (i) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (“alicyclic epoxy group”). And (ii) a compound in which an epoxy group is directly bonded to the alicyclic ring by a single bond.

  (I) A compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring is arbitrarily selected from known or commonly used compounds. be able to. Especially, it is preferable that the said compound has an epoxy group comprised by two adjacent carbon atoms and oxygen atoms which comprise a cyclohexane ring, ie, an alicyclic epoxy compound which has a cyclohexene oxide group.

式（Ｉ）中、Ｘは単結合又は連結基（１以上の原子を有する２価の基）を示す。上記連結基としては、例えば、２価の炭化水素基、カルボニル基、エーテル基（エーテル結合）、チオエーテル基（チオエーテル結合）、エステル基（エステル結合）、カーボネート基（カーボネート結合）、アミド基（アミド結合）、及びこれらが複数個連結した基等が挙げられる。 (I) As a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring, the following formula ( The alicyclic epoxy compound (alicyclic epoxy resin) represented by I) is preferable.

In formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include divalent hydrocarbon groups, carbonyl groups, ether groups (ether bonds), thioether groups (thioether bonds), ester groups (ester bonds), carbonate groups (carbonate bonds), amide groups (amides). Bond), and a group in which a plurality of these are linked.

Examples of the alicyclic epoxy compound in which X in the formula (I) is a single bond include compounds represented by the following formula. As such an alicyclic epoxy compound, for example, a commercial product such as a trade name “Celoxide 8000” (manufactured by Daicel Chemical Industries, Ltd.) can be used.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group. And divalent cycloalkylene groups (including cycloalkylidene groups) such as a silylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  As the linking group X, a linking group containing an oxygen atom is preferable, and specifically, —CO— (carbonyl group), —O—CO—O— (carbonate group), —COO— (ester group). ), -O- (ether group), -CONH- (amide group), a group in which a plurality of these groups are linked, one or more of these groups and one or more of divalent hydrocarbon groups Examples include linked groups. Examples of the divalent hydrocarbon group include those exemplified above.

  Typical examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-8). For example, commercially available products such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Chemical Industries, Ltd.) can also be used. In the following formulas (I-1) to (I-8), l and m each represent an integer of 1 to 30. R is an alkylene group having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene group, heptylene group, octylene group, etc. A linear or branched alkylene group is mentioned. Among these, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group is preferable.

式（ＩＩ）中、Ｒ’はｐ価のアルコールからｐ個の−ＯＨを除した基であり、ｐ、ｎは自然数を表す。ｐ価のアルコール［Ｒ’−（ＯＨ）_p］としては、２，２−ビス（ヒドロキシメチル）−１−ブタノール等の多価アルコールなど（炭素数１〜１５のアルコール等）が挙げられる。ｐは１〜６が好ましく、ｎは１〜３０が好ましい。ｐが２以上の場合、それぞれの（ ）内（丸括弧内）の基におけるｎは同一でもよく異なっていてもよい。上記化合物としては、具体的には、２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物、商品名「ＥＨＰＥ ３１５０」（ダイセル化学工業（株）製）などが挙げられる。 (Ii) Examples of the compound in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).

In formula (II), R ′ is a group obtained by removing p —OH from a p-valent alcohol, and p and n represent natural numbers. Examples of the p-valent alcohol [R ′-(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (such as alcohols having 1 to 15 carbon atoms). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each () (in parentheses) may be the same or different. Specific examples of the above compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, trade name “EHPE 3150” (Daicel Chemical). Kogyo Co., Ltd.).

  An alicyclic epoxy compound (A) can be used individually or in combination of 2 or more types. Among these, as the alicyclic epoxy compound (A), 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate represented by the above formula (I-1), trade name “Celoxide 2021P” Is particularly preferred.

  The amount of use (content) of the alicyclic epoxy compound (A) is not particularly limited, but when the curable epoxy resin composition of the present invention contains a curing agent (D) as an essential component, a curable epoxy resin. 10-90 weight% is preferable with respect to a composition (100 weight%), More preferably, it is 15-80 weight%, More preferably, it is 18-70 weight%. On the other hand, when the curable epoxy resin composition of the present invention contains the curing catalyst (E) as an essential component, the use amount (content) of the alicyclic epoxy compound (A) is the curable epoxy resin composition ( 100% by weight) is preferably 25 to 95% by weight, more preferably 30 to 90% by weight, and still more preferably 35 to 85% by weight.

  Moreover, the usage-amount (content) of an alicyclic epoxy compound (A) with respect to the total amount (100 weight%) of an alicyclic epoxy compound (A) and a monoallyl diglycidyl isocyanurate compound (B) is especially limited. However, it is preferably 50 to 90% by weight, more preferably 60 to 90% by weight, and still more preferably 70 to 90% by weight. When the amount of the alicyclic epoxy compound (A) used is less than 50% by weight, the solubility of the monoallyl diglycidyl isocyanurate compound (B) is not sufficient, and it may be easily precipitated when placed at room temperature. On the other hand, when the usage-amount of an alicyclic epoxy compound (A) exceeds 90 weight%, the crack resistance of hardened | cured material may fall.

上記式（１）中、Ｒ¹及びＲ²は、同一又は異なって、水素原子又は炭素数１〜８のアルキル基を示す。 [Monoallyl diglycidyl isocyanurate compound (B)]
The monoallyl diglycidyl isocyanurate compound (B) constituting the curable epoxy resin composition of the present invention is represented by the following general formula (1).

The formula (1), R ¹ and R ² are the same or different, represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and octyl groups. A chain or branched alkyl group is exemplified. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable. In particular, R ¹ and R ² in the above formula (1) are particularly preferably hydrogen atoms.

  Representative examples of the monoallyl diglycidyl isocyanurate compound (B) include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methyl And propenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, and the like. In addition, a monoallyl diglycidyl isocyanurate compound (B) can be used individually or in combination of 2 or more types.

  The monoallyl diglycidyl isocyanurate compound (B) can be arbitrarily mixed as long as it dissolves in the alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B). The ratio of alicyclic epoxy compound (A): monoallyl diglycidyl isocyanurate compound (B) is preferably 50:50 to 90:10 (weight ratio). Outside this range, the solubility of the monoallyl diglycidyl isocyanurate compound (B) may be difficult to obtain, or crack resistance may be reduced.

  The monoallyl diglycidyl isocyanurate compound (B) may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.

[Polyol (C) excluding polycarbonate polyol]
The polyol (C) excluding the polycarbonate polyol constituting the curable epoxy resin composition of the present invention (hereinafter sometimes simply referred to as “polyol (C)”) contains two or more in the molecule (in one molecule). It is a polymer (oligomer or polymer) having a hydroxyl group and a number average molecular weight of 200 or more. Polyol (C) does not include polycarbonate polyol (polycarbonate having two or more hydroxyl groups in the molecule) (that is, polyol (C) does not have a carbonate skeleton). A polyol (C) can be used individually or in combination of 2 or more types.

  The hydroxyl group (two or more hydroxyl groups) possessed by the polyol (C) may be an alcoholic hydroxyl group or a phenolic hydroxyl group. Further, the number of hydroxyl groups (number of hydroxyl groups in one molecule) of the polyol (C) is not particularly limited as long as it is 2 or more.

  The position of the hydroxyl group (two or more hydroxyl groups) of the polyol (C) is not particularly limited, but it is preferably present at least at the end of the polyol (end of the polymer main chain) from the viewpoint of reaction with the curing agent. It is particularly preferable that it is present at least at both ends of the polyol.

  The polyol (C) may be a solid or liquid as long as it can form a liquid curable epoxy resin composition after being blended with the component (A) and the component (B).

  Although the number average molecular weight of a polyol (C) should just be 200 or more, it is not specifically limited, 200-100000 are preferable, More preferably, it is 300-50000, More preferably, it is 400-40000. If the number average molecular weight is less than 200, peeling or cracking may occur when the solder reflow process is performed. On the other hand, when the number average molecular weight exceeds 100,000, the liquid curable epoxy resin composition may not be precipitated or dissolved. In addition, the number average molecular weight of a polyol (C) means the number average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC).

  Although the hydroxyl value of a polyol (C) is not specifically limited, 30-600 mgKOH / g is preferable, More preferably, it is 50-500 mgKOH / g. If the hydroxyl value is less than 30 mgKOH / g, the glass transition temperature (Tg) of the cured product may be excessively lowered. On the other hand, if the hydroxyl value exceeds 600 mgKOH / g, the crack resistance may decrease. In addition, the hydroxyl value of a polyol (C) can be measured by the method as described in JISK1557-1, for example.

  More specifically, as the polyol (C), for example, a polyester polyol (including a polyester polyol oligomer) having an ester skeleton (polyester skeleton) in the molecule, and a polyether having an ether skeleton (polyether skeleton) in the molecule. Examples include polyols (including polyether polyol oligomers). Examples of the polyol (C) other than the polyester polyol and the polyether polyol include a phenoxy resin and an epoxy equivalent of 1000 g / eq. Bisphenol-type polymer epoxy resin exceeding 1, polybutadienes having two or more hydroxyl groups in the molecule, acrylic polyol, and the like.

  Examples of the polyester polyol include polyester polyols obtained by condensation polymerization (for example, transesterification) of polyols, polycarboxylic acids (polybasic acids), and hydroxycarboxylic acids, and polyester polyols obtained by ring-opening polymerization of lactones. Etc.

  Examples of the polyol as a monomer component constituting the polyester polyol include ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, and 1,4- Butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,3, 5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,6-hexanediol 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,2-dimethylol Hexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1 , 3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, pentaerythritol and the like. Examples of the polycarboxylic acid as a monomer component constituting the polyester polyol include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, and 2,6-naphthalene. Dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, 1,10-decanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyroanhydride Examples include merit acid and trimellitic anhydride. Examples of the hydroxycarboxylic acid include lactic acid, malic acid, glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of the lactones include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

  The polyester polyol can be produced by a known or conventional production method, and is not particularly limited. For example, condensation polymerization of the polyol and polycarboxylic acid, condensation polymerization of the hydroxycarboxylic acid, and ring-opening polymerization of the lactones. Etc. can be manufactured. The conditions for the polymerization are not particularly limited, and can be appropriately selected from known or common reaction conditions. The polyol, polycarboxylic acid, and hydroxycarboxylic acid are known or commonly used derivatives (for example, a hydroxyl group is protected with an acyl group, an alkoxycarbonyl group, an organic silyl group, an alkoxyalkyl group, an oxacycloalkyl group, etc. Derivatives and derivatives in which the carboxyl group is derived from an alkyl ester, an acid anhydride, an oxide halide, or the like can also be used.

  Examples of the polyester polyol include, for example, trade names “Placcel 205U”, “Placcel L205AL”, “Placcel L208AL”, “Placcel L212AL”, “Placcel L220AL”, “Placcel L230AL”, “Placcel 220ED”, “Placcel 220EC”, “Placcel 220EB”, “Plaxel 303”, “Plaxel 305”, “Plaxel 308”, “Plaxel 312”, “Plaxel L312AL”, “Plaxel 320”, “Plaxel L320AL”, “Plaxel 410”, “Plaxel 410D” “Plaxel P3403”, “Plaxel E227”, “Plaxel DC2009”, “Plaxel DC2016”, “Plaxel DC2209” (Daicel Chemical Industries, Ltd.) ) Commercially available products, or the like can also be used.

  Examples of the polyether polyol include polyether polyols obtained by addition reaction of cyclic ether compounds to polyols, polyether polyols obtained by ring-opening polymerization of alkylene oxide, and the like.

  More specifically, examples of the polyether polyol include ethylene glycol, diethylene glycol, 1,2-propanediol (propylene glycol), 2-methyl-1,3-propanediol, 1,3-propanediol, , 4-butanediol (tetramethylene glycol), 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexane Diol, 2,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, dipropylene glycol, glycerin, trimethylolpropane, 1 , 3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, pentaerythritol and other multimers of polyols; the above polyols, ethylene oxide, propylene oxide, 1, Adducts with alkylene oxides such as 2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran and epichlorohydrin; tetrahydro Ring-opened polymer of a cyclic ether, such as orchids (e.g., polytetramethylene glycol) and the like.

  The polyether polyol can be produced by a known or conventional production method, and is not particularly limited. For example, addition reaction of a cyclic ether compound to a polyol (ring-opening addition polymerization), ring-opening polymerization of an alkylene oxide ( (Homopolymerization or copolymerization). The conditions for the polymerization are not particularly limited, and can be appropriately selected from known or common reaction conditions.

  Examples of the polyether polyol include trade name “PEP-101” (manufactured by Freund Sangyo Co., Ltd.), trade names “Adeka Pluronic L”, “Adeka Pluronic P”, “Adeka Pluronic F”, “Adeka Pluronic R”. , “Adeka Pluronic TR”, “Adeka PEG” (above, manufactured by ADEKA Corporation), trade names “PEG # 1000”, “PEG # 1500”, “PEG # 11000” (above, manufactured by NOF Corporation) , “New Pole PE-34”, “New Pole PE-61”, “New Pole PE-78”, “New Pole PE-108”, “PEG-200”, “PEG-600”, “PEG-” 2000 ”,“ PEG-6000 ”,“ PEG-10000 ”,“ PEG-20000 ”(manufactured by Sanyo Chemical Industries, Ltd.), trade name“ TMG1000 "," PTMG1800 "," PTMG2000 "(manufactured by Mitsubishi Chemical Co., Ltd.), can also be used commercially available products such as trade name" PTMG prepolymer "(manufactured by Mitsubishi Plastics Co., Ltd.).

  Examples of the polyol (C) other than the above polyester polyol and polyether polyol include, for example, trade names “YP-50”, “YP-50S”, “YP-55U”, “YP-70”, “ZX-1356-2. ”,“ YPB-43C ”,“ YPB-43M ”,“ FX-316 ”,“ FX-310T40 ”,“ FX-280S ”,“ FX-293 ”,“ YPS-007A30 ”,“ TX-1016 ”( As described above, phenoxy resins such as Nippon Steel Chemical Co., Ltd., trade names “jER1256”, “jER4250”, “jER4275” (manufactured by Mitsubishi Chemical Corporation); trade names “Epototo YD-014”, “ "Epototo YD-017", "Epototo YD-019", "Epototo YD-020G", "Epototo YD-904", "Epototo YD-907" "Epototo YD-6020" (manufactured by Nippon Steel Chemical Co., Ltd.), trade names "jER1007", "jER1009", "jER1010", "jER1005F", "jER1009F", "jER1006FS", "jER1007FS" ( Epoxy equivalent of 1000 g / eq. Bisphenol type polymer epoxy resin exceeding the product name: “Poly bd R-45HT”, “Poly bd R-15HT”, “Poly ip”, “Epol”, “KRASOL” (above, manufactured by Idemitsu Kosan Co., Ltd.), 2 in the molecule such as “α-ω polybutadiene glycol G-1000”, “α-ω polybutadiene glycol G-2000”, “α-ω polybutadiene glycol G-3000” (Nippon Soda Co., Ltd.). Polybutadienes having at least one hydroxyl group; trade names “Hitaroid 3903”, “Hitaroid 3904”, “Hitaroid 3905”, “Hitaroid 6500”, “Hitaroid 6500B”, “Hitaroid 3018X” (manufactured by Hitachi Chemical Co., Ltd.), Product name “Acridic DL-1537”, “Acridic BL-61” 6 ”,“ Acridic AL-1157 ”,“ Acridic A-322 ”,“ Acridic A-817 ”,“ Acridic ”,“ Acridic A-870 ”,“ Acridic A-859-B ”, “Acridic A-829”, “Acridic A-49-394-IM” (manufactured by DIC Corporation), trade names “Dianar SR-1346”, “Dianar SR-1237”, “Dianar AS-” 1139 "(manufactured by Mitsubishi Rayon Co., Ltd.) and the like, and acrylic polyol (acrylic resin having two or more hydroxyl groups in the molecule).

  Although the usage-amount (content) of a polyol (C) is not specifically limited, 1-50 weight part is with respect to the whole quantity (100 weight part) of the compound which has an epoxy group contained in a curable epoxy resin composition. The amount is more preferably 5 to 35 parts by weight, further preferably 10 to 30 parts by weight, and particularly preferably 15 to 25 parts by weight. When the amount of the polyol (C) used is less than 1 part by weight, the reflow resistance is lowered, and the heat treatment in the reflow process may cause peeling or cracking of the sealing resin from the lead frame in the optical semiconductor device. is there. On the other hand, when the amount of the polyol (C) used exceeds 50 parts by weight, the Tg of the cured product is excessively lowered, the volume change due to heating becomes large, and problems such as non-lighting of the optical semiconductor device may occur. Moreover, although bending strength improves, transparency may fall.

  Since the curable epoxy resin composition of the present invention contains polyol (C) (polyol other than polycarbonate polyol), the reflow resistance of the cured product, in particular, the solder reflow process, compared with the case of using polycarbonate polyol. In this case, cracks (for example, cracks around the optical semiconductor element) are prevented from occurring in the cured product. Moreover, the crack resistance of the hardened | cured material with respect to a thermal shock (cool temperature cycle etc.) improves. Furthermore, the decrease in luminous intensity when energized under high temperature and high humidity conditions is reduced, and the reliability of the optical semiconductor device is improved.

[Curing agent (D)]
The curing agent (D) constituting the curable epoxy resin composition of the present invention has a function of curing a compound having an epoxy group. As a hardening | curing agent (D), a well-known thru | or usual hardening | curing agent can be used as a hardening | curing agent for epoxy resins. Among them, the curing agent (D) is preferably an acid anhydride which is liquid at 25 ° C. More specifically, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylene Examples include tetrahydrophthalic anhydride. In addition, solid acid anhydrides at room temperature (about 25 ° C.) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride are also liquid at room temperature (about 25 ° C.). It can be used as a hardening | curing agent (D) by making it melt | dissolve in the acid anhydride of and making it a liquid mixture. As the curing agent (D), particularly from the viewpoint of heat resistance, light resistance and crack resistance, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those in which a substituent such as an alkyl group is bonded to the ring) are included. preferable. In addition, a hardening | curing agent (D) can be used individually or in combination of 2 or more types.

  Further, in the present invention, as the curing agent (D), a trade name “Rikacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.), a trade name “HN-5500” (manufactured by Hitachi Chemical Co., Ltd.), etc. Commercial products can also be used.

  Although the usage-amount (content) of a hardening | curing agent (D) is not specifically limited, 50-200 weight part with respect to the whole quantity (100 weight part) of the compound which has an epoxy group contained in a curable epoxy resin composition. Is more preferable, and 100 to 145 parts by weight is more preferable. More specifically, it is preferably used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy group in the compound having all epoxy groups contained in the curable epoxy resin composition of the present invention. . When the usage-amount of a hardening | curing agent (D) is less than 50 weight part, hardening will become inadequate and there exists a tendency for the toughness of hardened | cured material to fall. On the other hand, when the usage-amount of a hardening | curing agent (D) exceeds 200 weight part, hardened | cured material may color and a hue may deteriorate.

[Curing catalyst (E)]
The curable epoxy resin composition of the present invention may contain a curing catalyst (E) instead of the above-mentioned curing agent (D). By using the curing catalyst (E), the curing reaction of the compound having an epoxy group can proceed as in the case of using the curing agent (D) to obtain a cured product. The curing catalyst (E) is not particularly limited. For example, a cationic catalyst (cationic polymerization initiator) capable of generating a cationic species by starting ultraviolet irradiation or heat treatment to start polymerization is used. be able to. In addition, a curing catalyst (E) can be used individually or in combination of 2 or more types.

  Examples of the cation catalyst that generates cation species by ultraviolet irradiation include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and the like. Examples of the cationic catalyst include trade name “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.), trade names “CD-1010”, “CD-1011”, “CD-1012” (above, manufactured by Sartomer, USA). ), Trade name “Irgacure 264” (manufactured by Ciba Japan Co., Ltd.), trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) and the like can be preferably used.

  Examples of the cation catalyst that generates cation species by heat treatment include aryl diazonium salts, aryl iodonium salts, aryl sulfonium salts, and allene-ion complexes. Examples of the cationic catalyst include trade names “PP-33”, “CP-66”, “CP-77” (manufactured by ADEKA Corporation), trade names “FC-509” (manufactured by 3M), and commercial products. Name “UVE1014” (manufactured by GE), trade names “Sun-Aid SI-60L”, “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L” (Sanshin Chemical Industry Co., Ltd.) )), And a commercial name such as “CG-24-61” (manufactured by Ciba Japan Co., Ltd.) can be preferably used. As the cationic catalyst, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketones and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketones A compound of the above chelate compound and a phenol such as bisphenol S can also be used.

  Although the usage-amount (content) of a curing catalyst (E) is not specifically limited, 0.01-15 with respect to the whole quantity (100 weight part) of the compound which has an epoxy group contained in a curable epoxy resin composition. Part by weight is preferable, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight. By using the curing catalyst (E) within the above range, a cured product having excellent heat resistance, light resistance and transparency can be obtained.

[Curing accelerator (F)]
The curable epoxy resin composition of the present invention may further contain a curing accelerator (F). A hardening accelerator (F) is a compound which has a function which accelerates | stimulates a cure rate, when the compound which has an epoxy group hardens | cures. In particular, it is often used in combination with a curing agent (D). As the curing accelerator (F), known or conventional curing accelerators can be used, and are not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and Salts thereof (eg, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), and salts thereof (Eg, phosphonium salts, sulfonium salts, quaternary ammonium salts, iodonium salts); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; 2 -Imidazoles such as ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphorus Esters, phosphines such as triphenylphosphine; tetraphenylphosphonium tetra (p- tolyl) phosphonium compounds such as borate, tin octylate, organic metal salts such as zinc octylate; metal chelate and the like. In addition, a hardening accelerator (F) can be used individually or in combination of 2 or more types.

  In the present invention, as the curing accelerator (F), trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 410”, “U-CAT” are used. CAT 18X "," 12XD (development) "(above, manufactured by San Apro Co., Ltd.), trade names" TPP-K "," TPP-MK "(above, manufactured by Hokuko Chemical Co., Ltd.), trade names" PX " Commercially available products such as “-4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) can also be used.

  Although the usage-amount (content) of a hardening accelerator (F) is not specifically limited, 0.05-about with respect to the whole quantity (100 weight part) of the compound which has an epoxy group contained in a curable epoxy resin composition. 5 parts by weight is preferable, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight. When the usage-amount of a hardening accelerator (F) is less than 0.05 weight part, the hardening promotion effect may become inadequate. On the other hand, when the usage-amount of a hardening accelerator (F) exceeds 5 weight part, hardened | cured material may color and a hue may deteriorate.

[Acrylic block copolymer]
The curable epoxy resin composition of the present invention preferably further contains an acrylic block copolymer from the viewpoint of suppressing a decrease in luminous intensity with time of the optical semiconductor device. More specifically, when the curable epoxy resin composition of the present invention includes an acrylic block copolymer, an optical semiconductor device manufactured using the curable epoxy resin composition is particularly high in luminance and high output. Even if it exists, it exists in the tendency for a light intensity to fall easily. That is, by using the acrylic block copolymer, the cured product obtained by curing the curable epoxy resin composition of the present invention tends to exhibit higher levels of heat resistance, light resistance, and crack resistance. is there.

  The acrylic block copolymer is a block copolymer having an acrylic monomer as an essential monomer component. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylic acid. (Meth) acrylic acid alkyl esters such as t-butyl acid, 2-ethylhexyl methacrylate, lauryl methacrylate and stearyl methacrylate; (meth) acrylic acid esters having an alicyclic structure such as cyclohexyl acrylate and cyclohexyl methacrylate; methacryl (Meth) acrylic acid ester having an aromatic ring such as benzyl acid; (fluoro) alkyl ester of (meth) acrylic acid such as 2-trifluoroethyl methacrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, etc. Min A carboxyl group-containing acrylic monomer having a carboxyl group therein; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacryl Hydroxyl group-containing acrylic monomer having hydroxyl group in molecule such as 4-hydroxybutyl acid, mono (meth) acrylic acid ester of glycerin; molecule such as glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate An acrylic monomer having an epoxy group therein; an allyl group-containing acrylic monomer having an allyl group in a molecule such as allyl acrylate and allyl methacrylate; γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyl Silane group-containing acrylic monomer having hydrolyzable silyl group in the molecule such as oxypropyltriethoxysilane; benzotriazole such as 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole And UV-absorbing acrylic monomers having a UV-absorbing group.

  In the acrylic block copolymer, in addition to the acrylic monomer, a monomer other than the acrylic monomer may be used as a monomer component. Examples of the monomer other than the acrylic monomer include aromatic vinyl compounds such as styrene and α-methylstyrene, conjugated dienes such as butadiene and isoprene, and olefins such as ethylene, propylene and isobutene.

  Although it does not specifically limit as said acrylic block copolymer, For example, the diblock copolymer which consists of two polymer blocks, the triblock copolymer which consists of three polymer blocks, four or more polymer blocks And a multi-block copolymer composed of these.

  Among these, as the acrylic block copolymer, from the viewpoint of improving heat resistance, light resistance, and crack resistance, a polymer block (S) (soft block) having a low glass transition temperature (Tg) and a polymer block ( A block copolymer in which polymer blocks (H) (hard blocks) having a higher Tg than S) are alternately arranged is preferred, more preferably a polymer block (S) in the middle and a polymer at both ends thereof. A triblock copolymer having an HSH structure having a block (H) is preferred. In addition, although Tg of the polymer which comprises the polymer block (S) of the said acrylic block copolymer is not specifically limited, Less than 30 degreeC is preferable. Moreover, Tg of the polymer which comprises a polymer block (H) is although it does not specifically limit, 30 degreeC or more is preferable. When the acrylic block copolymer has a plurality of polymer blocks (H), the polymer blocks (H) may have the same composition or different compositions. . Similarly, when the acrylic block copolymer has a plurality of polymer blocks (S), the polymer blocks (S) may have the same composition or different compositions. Also good.

The monomer component constituting the polymer block (H) in the acrylic block copolymer (such as the triblock copolymer having the HSH structure) is not particularly limited. For example, the Tg of the homopolymer is Examples thereof include monomers having a temperature of 30 ° C. or higher, and more specifically, methyl methacrylate, styrene, acrylamide, acrylonitrile and the like. On the other hand, the monomer component constituting the polymer block (S) in the acrylic block copolymer is not particularly limited, and examples thereof include monomers having a Tg of a homopolymer of less than 30 ° C., and more specifically, _Examples thereof include C _2-10 alkyl esters of acrylic acid such as butyl acrylate and 2-ethylhexyl acrylate, butadiene (1,4-butadiene), and the like.

  As a preferable specific example of the acrylic block copolymer in the curable epoxy resin composition of the present invention, for example, the polymer block (S) is a polymer composed of butyl acrylate (BA) as a main monomer, Polymethyl methacrylate-block-polybutyl acrylate-block-polymethyl methacrylate terpolymer (PMMA-b-PBA-b-), wherein the polymer block (H) is a polymer composed mainly of methyl methacrylate (MMA). PMMA) and the like. The PMMA-b-PBA-b-PMMA is preferable in terms of improving heat resistance, light resistance, and crack resistance. The PMMA-b-PBA-b-PMMA is a hydrophilic group (for example, hydroxyl group, carboxyl group, amino group, etc.) for the purpose of improving compatibility with the component (A) and the component (B), if necessary. A monomer having a group, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, or the like, copolymerized with a PMMA block and / or a PBA block. Good. In addition, an acrylic block copolymer can be used individually or in combination of 2 or more types.

  Although the number average molecular weight of the said acrylic block copolymer is not specifically limited, 3000-500000 are preferable, More preferably, it is 30000-400000. If the number average molecular weight is less than 3000, the toughness of the cured product is not sufficient, and crack resistance may be reduced. On the other hand, when the number average molecular weight exceeds 500,000, the compatibility with the alicyclic epoxy compound (A) is lowered, and the transparency of the cured product may be lowered.

  The acrylic block copolymer can be produced by a known or commonly used method for producing a block copolymer. As the method for producing the acrylic block copolymer, in particular, living polymerization (living radical polymerization, living anion polymerization, living room polymerization, etc., from the viewpoint of easy control of the molecular weight, molecular weight distribution, terminal structure, etc. of the acrylic block copolymer. Cationic polymerization etc.) are preferred. The living polymerization can be carried out by a known or conventional method.

  Examples of the acrylic block copolymer include trade names “Nano Strength M52N”, “Nano Strength M22N”, “Nano Strength M51”, “Nano Strength M52”, “Nano Strength M53” (above, manufactured by Arkema, Inc. Commercially available products such as PMMA-b-PBA-b-PMMA), trade names “Nanostrength E21”, “Nanostrength E41” (above, manufactured by Arkema, PSt (polystyrene) -b-PBA-b-PMMA) You can also.

  The amount of the acrylic block copolymer used (content) is not particularly limited, but is preferably 1 to 30 parts by weight with respect to the total amount (100 parts by weight) of the component (A) and the component (B). More preferably, it is 3-15 weight part, More preferably, it is 5-10 weight part. When the usage-amount of an acrylic block copolymer is less than 1 weight part, the toughness of hardened | cured material may not be enough, and heat resistance and light resistance may fall. On the other hand, when the usage-amount of an acrylic block copolymer exceeds 30 weight part, compatibility with an alicyclic epoxy compound (A) may fall, and transparency of hardened | cured material may fall.

[Rubber particles]
The curable epoxy resin composition 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 the like. The rubber particles have a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion, and react with an alicyclic epoxy resin on the surface. A rubber particle having a hydroxyl group and / or a carboxyl group as a functional group to be obtained, an average particle diameter of 10 nm to 500 nm, and a maximum particle diameter of 50 nm to 1000 nm, the refractive index of the rubber particle and the curable epoxy resin Rubber particles having a difference from the refractive index of the cured product of the composition within ± 0.02 may be used. The blending amount of the rubber particles can be appropriately adjusted as necessary and is not particularly limited, but with respect to the total amount of the compound having an epoxy group contained in the curable epoxy resin composition (100 parts by weight), 1-50 weight part is preferable, More preferably, it is 3-40 weight part. When the amount of rubber particles used is less than 1 part by weight, the crack resistance tends to decrease. On the other hand, when the usage-amount of rubber particle exceeds 50 weight part, there exists a tendency for heat resistance and transparency to fall.

[Additive]
In addition to the above, the curable epoxy resin composition of the present invention can use various additives within a range that does not impair the effects of the present invention. For example, when a compound having a hydroxyl group (excluding polyol (C)) such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin is used as an additive, the reaction (curing reaction) can proceed slowly. In addition, silicone and fluorine antifoaming agents, leveling agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, surfactants, silica, alumina, as long as viscosity and transparency are not impaired. Conventional additives such as inorganic fillers, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, mold release agents and the like can be used.

<Hardened product>
By curing the curable epoxy resin composition of the present invention, it is possible to obtain a cured product having excellent physical properties such as transparency, heat resistance, light resistance, and crack resistance, and also excellent reflow resistance. it can. Although it does not specifically limit as heating temperature (curing temperature) in the case of hardening, 45-200 degreeC is preferable, More preferably, it is 100-190 degreeC, More preferably, it is 100-180 degreeC. Moreover, it does not specifically limit as time to cure in the case of hardening (curing time), However, 30 to 600 minutes are preferable, More preferably, it is 45 to 540 minutes, More preferably, it is 60 to 480 minutes. If the curing temperature is too low and / or if the curing time is too short, curing may be insufficient. On the other hand, when the curing temperature is too high and / or when the curing time is too long, decomposition of the resin component may occur. The curing conditions depend on various conditions, but can be appropriately adjusted by shortening the curing time when the curing temperature is increased, and increasing the curing time when the curing temperature is lowered.

<Resin composition for optical semiconductor encapsulation>
The resin composition for optical semiconductor encapsulation of the present invention comprises the curable epoxy resin composition of the present invention. By using the resin composition for encapsulating an optical semiconductor of the present invention, an optical semiconductor is obtained by a cured product having excellent physical properties such as transparency, heat resistance, light resistance, and crack resistance, and also excellent reflow resistance. An optical semiconductor device in which elements are sealed can be manufactured.

<Optical semiconductor device>
The optical semiconductor device of the present invention is obtained by sealing an optical semiconductor element with the curable epoxy resin composition (resin composition for optical semiconductor sealing) of the present invention. The optical semiconductor element is sealed by injecting the curable epoxy resin composition prepared by the above-described method into a predetermined mold and heating and curing under predetermined conditions. Thereby, an optical semiconductor device in which the optical semiconductor element is sealed with the curable epoxy resin composition is obtained. As the curing temperature and the curing time at the time of sealing, for example, the same conditions as in forming the cured product can be employed. The optical semiconductor device of the present invention is less likely to be deteriorated by heat treatment in the reflow process, and the light intensity is less likely to decrease with time. In particular, the optical semiconductor device of the present invention has an advantage that the luminous intensity is less likely to decrease with time even when a high-output, high-luminance optical semiconductor element is provided.

  FIG. 1 is a schematic view showing an embodiment of an optical semiconductor device in which an element (optical semiconductor element) is sealed with a curable epoxy resin composition of the present invention. As shown in FIG. 1, generally, in an optical semiconductor device, an optical semiconductor element 102 is fixed to a lead frame by a die bond material 105. The present inventors have found that the reflow resistance can also be improved by optimizing the die bond material in the optical semiconductor device. More specifically, when the optical semiconductor device is heat-treated in the reflow process, a die bond material (high adhesiveness / durability) that prevents the optical semiconductor element from being peeled off from the lead frame due to stress caused by the volume change of the sealing resin. It was found that selecting a die bonding material) is important from the viewpoint of improving reflow resistance. This is because when the optical semiconductor element is peeled from the lead frame, the sealing resin around the semiconductor element is easily peeled or cracked, and the optical semiconductor device is significantly deteriorated due to the heat treatment in the reflow process. Therefore, in order to improve the reflow resistance and prevent the deterioration of the optical semiconductor device due to the heat treatment in the reflow process, the curable epoxy resin composition of the present invention (resin composition for optical semiconductor sealing) is used as the sealing resin. It is effective to use the above-mentioned cured product with high adhesion and durability as a die bond material. Examples of the die bond material include a die bond material in which conductive particles or the like (eg, silver particles) are contained in a base polymer such as a polyimide resin, an epoxy resin, or a silicone resin. As such a die bond material, for example, trade names “KER-3000 M2”, “KER-3100 O2”, “KER-3100” (manufactured by Shin-Etsu Chemical Co., Ltd.), trade names “EH1600-G2”. (Inabata Sangyo Co., Ltd.), trade names “CT200”, “CT284”, “CT265” (manufactured by Kyocera Chemical Co., Ltd.) and the like.

  The curable epoxy resin composition of the present invention is not limited to the above-described optical semiconductor element sealing application (for optical semiconductor sealing). For example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, Applications such as sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc. Also preferably used.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Example 1
(Manufacture of curing agent composition)
100 parts by weight of an acid anhydride [manufactured by Shin Nippon Rika Co., Ltd., trade name “Licacid MH-700”], 0.5 part by weight of a curing accelerator [manufactured by San Apro Co., Ltd., trade name “U-CAT 18X”] And 1 part by weight of an additive [made by Wako Pure Chemical Industries, Ltd., trade name “ethylene glycol”], a self-revolving stirrer [made by Shinkey Co., Ltd., trade name “Awatori Nerita AR-250”] The resulting mixture was uniformly mixed and defoamed to obtain a curing agent composition.

Examples 1-4
(Manufacture of epoxy resin)
Monoallyl diglycidyl isocyanurate [Shikoku Kasei Kogyo Co., Ltd., trade name “MA-DGIC”], alicyclic epoxy compound [Daicel Chemical Industries, Ltd., trade name “Celoxide 2021P”], polyol excluding polycarbonate polyol [Polytetramethylene ether glycol (trade name “PTMG2000”, manufactured by Mitsubishi Chemical Corporation), polycaprolactone polyol (trade name “PCL308”, manufactured by Daicel Chemical Industries, Ltd.), phenoxy resin (trade name “YP-70”) , Nippon Steel Chemical Co., Ltd.), hydroxyl group-containing long-chain epoxy resin (trade name “YD-6020”, manufactured by Nippon Steel Chemical Co., Ltd.)] are shown in Table 1. : All by weight) and stirred at 80 ° C. for 1 hour to dissolve monoallyl diglycidyl isocyanurate. Alkoxy to obtain a resin (epoxy resin composition).

(Manufacture of curable epoxy resin composition and manufacture of optical semiconductor device)
The above-prepared epoxy resin and the curing agent composition obtained in Production Example 1 were subjected to a self-revolving stirrer [manufactured by Shinky Co., Ltd.] so as to have a formulation (unit: parts by weight) shown in Table 1. Using a trade name “Awatori Netaro AR-250”], the mixture was uniformly mixed and defoamed to obtain a curable epoxy resin composition. After this curable epoxy resin composition was cast into an optical semiconductor lead frame (AlInGaP element, 3.5 mm × 2.8 mm), the curing conditions shown in Table 1 (Condition-1: 120 ° C.) using a resin curing oven. For 5 hours) to obtain an optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured product).

Example 5
(Manufacture of epoxy resin)
Monoallyl diglycidyl isocyanurate [Shikoku Kasei Kogyo Co., Ltd., trade name “MA-DGIC”], alicyclic epoxy compound [manufactured by Daicel Chemical Industries, Ltd., trade name “Celoxide 2021P”], polytetramethylene polyol [ Mitsubishi Chemical Co., Ltd., trade name “PTMG2000”], acrylic block copolymer [manufactured by Arkema, trade name “Nanostrength M52N”], according to the formulation (mixing ratio) (unit: parts by weight) shown in Table 1. By mixing and stirring at 80 ° C. for 4 hours, the monoallyl diglycidyl isocyanurate and the acrylic block copolymer were dissolved to obtain an epoxy resin (epoxy resin composition).

(Manufacture of curable epoxy resin composition and manufacture of optical semiconductor device)
The above-prepared epoxy resin and the curing agent composition obtained in Production Example 1 were subjected to a self-revolving stirrer [manufactured by Shinky Co., Ltd.] so as to have a formulation (unit: parts by weight) shown in Table 1. Using a trade name “Awatori Netaro AR-250”], the mixture was uniformly mixed and defoamed to obtain a curable epoxy resin composition. After casting this curable epoxy resin composition on a lead frame (AlInGaP element, 3.5 mm × 2.8 mm) of an optical semiconductor, the curing conditions (condition-1) shown in Table 1 using a resin curing oven are used. By heating, an optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured product) was obtained.

Example 6
(Manufacture of curable epoxy resin composition)
Monoallyl diglycidyl isocyanurate [Shikoku Kasei Kogyo Co., Ltd., trade name “MA-DGIC”], alicyclic epoxy compound [manufactured by Daicel Chemical Industries, Ltd., trade name “Celoxide 2021P”], and polytetramethylene ether Glycol [Mitsubishi Chemical Co., Ltd., trade name “PTMG2000”] was mixed according to the formulation (mixing ratio) (unit: parts by weight) shown in Table 1 and stirred at 80 ° C. for 1 hour to monoallyldiglycidyl. The isocyanurate was dissolved, and a curing catalyst [manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Sun-Aid SI-100L”] was added according to the blending formulation (blending ratio) (unit: parts by weight) shown in Table 1. Uniform mixing using a revolving stirrer [trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.], defoaming, and curable epoxy resin It was obtained Narubutsu.
(Manufacture of optical semiconductor devices)
The curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (AlInGaP element, 3.5 mm × 2.8 mm), and then cured using the resin curing oven shown in Table 1 (Condition-2). : An optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured product) by heating at 110 ° C. for 3 hours and subsequently at 140 ° C. for 4 hours.

Comparative Example 1
(Manufacture of curable epoxy resin composition and manufacture of optical semiconductor device)
An alicyclic epoxy compound [manufactured by Daicel Chemical Industries, Ltd., trade name “Celoxide 2021P”] and the curing agent composition obtained in Production Example 1 are blended formulations (unit: parts by weight) shown in Table 1. Thus, using a self-revolving stirrer [manufactured by Shinky Co., Ltd., trade name “Awatori Netaro AR-250”], the mixture was uniformly mixed and defoamed to obtain a curable epoxy resin composition. After casting this curable epoxy resin composition on a lead frame (AlInGaP element, 3.5 mm × 2.8 mm) of an optical semiconductor, the curing conditions (condition-1) shown in Table 1 using a resin curing oven are used. By heating, an optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured product) was obtained.

<Evaluation>
About the optical semiconductor device obtained by the Example and the comparative example, the evaluation test was done with the following method.

[Solder heat resistance test]
The optical semiconductor devices (two used for each curable epoxy resin composition) obtained in Examples and Comparative Examples were allowed to stand for 168 hours under conditions of 30 ° C. and 70% RH to absorb moisture. Subsequently, the said optical semiconductor device was put into the reflow furnace, and it heated on the following heating conditions. Thereafter, the optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then placed in a reflow furnace again and heated under the same conditions. That is, in the solder heat resistance test, the thermal history under the following heating conditions was given twice to the optical semiconductor device.
[Heating conditions (based on surface temperature of optical semiconductor device)]
(1) Preheating: 150 to 190 ° C. for 60 to 120 seconds (2) Main heating after preheating: 217 ° C. or more for 60 to 150 seconds, maximum temperature 260 ° C.
However, the rate of temperature increase when shifting from preheating to main heating was controlled to 3 ° C./second at the maximum.
FIG. 2 shows an example of the surface temperature profile of the optical semiconductor device during heating in the reflow furnace (temperature profile in one of the two heating operations).
Thereafter, the optical semiconductor device was observed using a digital microscope (VHX-900, manufactured by Keyence Corporation). As a result, when one or both of the two optical semiconductor devices have resin peeling observed on the electrode surface, it is determined that the solder heat resistance is poor (with peeling), and both of the above-mentioned resin peeling When no solder was observed, it was determined that the solder heat resistance was good (no peeling), and the result is shown in the column of “Solder Heat Resistance Test / Peeling” in Table 1. Further, when cracks are observed around the optical semiconductor element in either one or both of the two optical semiconductor devices, it is determined that the solder heat resistance is poor (with cracks), and the cracks are observed in both cases. The case where there was no solder was judged as good solder heat resistance (no crack), and the result is shown in the column of “Solder Heat Resistance Test / Crack” in Table 1.

[Energization test]
The total luminous fluxes of the optical semiconductor devices obtained in the examples and comparative examples were measured using a total luminous flux measuring machine (referred to as “0 hour total luminous flux”).
Furthermore, the total luminous flux after a 50 mA current was continuously passed through the optical semiconductor device for 1000 hours in a constant temperature bath of 60 ° C. and 90% RH was measured (referred to as “total luminous flux after 1000 hours”). And luminous intensity retention was computed from the following formula. The results are shown in the column of “luminance retention” in Table 1.
{Luminance retention (%)}
= ({Total luminous flux after 1000 hours (lm)} / {total luminous flux after 0 hours (lm)}) × 100

[Thermal shock test]
The optical semiconductor devices obtained in the examples and comparative examples (two used for each curable epoxy resin composition) were exposed for 15 minutes in an atmosphere of −40 ° C., and then in an atmosphere of 120 ° C. A thermal shock in which exposure for 15 minutes was defined as one cycle was applied for 1000 cycles using a thermal shock tester. Thereafter, a current of 20 mA was applied to the optical semiconductor device to confirm lighting, and the number of optical semiconductor devices that did not light (the number of non-lighting occurrences) was measured. The results are shown in the “thermal shock test” column of Table 1.

[Comprehensive judgment]
In the solder heat resistance test, neither peeling nor cracking occurred, the luminous intensity retention was 85% or more, and the number of non-lighting occurrences in the thermal shock test was 0. ). In other cases (when peeling and / or cracking occurs in the solder heat resistance test, when the luminous intensity retention is less than 85%, or when the number of non-lighting occurrences in the thermal shock test is 1 or more) Was made into comprehensive judgment x (it was inferior). The results are shown in the column “Comprehensive judgment” in Table 1.

In addition, the component used by the Example and the comparative example is as follows.
[Epoxy resin]
CEL2021P (Celoxide 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd. MA-DGIC: monoallyl diglycidyl isocyanurate, manufactured by Shikoku Chemical Industry Co., Ltd. [ Polyol]
PTMG2000: polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation PCL308: polycaprolactone polyol, manufactured by Daicel Chemical Industries, Ltd. YP-70: phenoxy resin, manufactured by Nippon Steel Chemical Co., Ltd. YD-6020: hydroxyl group-containing long chain Epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd. [Acrylic block copolymer]
M52N (Nanostrength M52N): Acrylic block copolymer, manufactured by Arkema [Curing agent composition]
Rikacid MH-700: 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Rika Co., Ltd. U-CAT 18X: curing accelerator, manufactured by San Apro Co., Ltd. Ethylene glycol: Wako Pure Chemicals Industrial Co., Ltd. [Curing catalyst]
SI-100L (Sun-Aid SI-100L): Arylsulfonium salt, manufactured by Sanshin Chemical Industry Co., Ltd.

Test equipment ・ Resin curing oven Espec Co., Ltd. “GPHH-201”
・ Reflow furnace “UNI-5016F” manufactured by Nippon Antom Co., Ltd.
・ Constant temperature bath Espec Co., Ltd., “Small high temperature chamber ST-120B1”
・ Total luminous flux measuring machine "Optical Laboratories USA", "Multi-spectral Radiation Measurement System OL771"
・ Thermal shock tester Espec Co., Ltd., “Small Thermal Shock Device TSE-11-A”

100: Reflector (resin composition for light reflection)
101: Metal wiring 102: Optical semiconductor element (LED element)
103: Bonding wire 104: Transparent sealing resin 105: Die bond material

Claims (9)

Alicyclic epoxy compound (A) (excluding those containing an aromatic ring) and the following formula (1)

[Wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A curable epoxy resin composition comprising a monoallyl diglycidyl isocyanurate compound (B) represented by formula (I), a polyol (C) excluding polycarbonate polyol, and a curing agent (D) or a curing catalyst (E). object.   The curable epoxy resin composition according to claim 1, wherein the alicyclic epoxy compound (A) is an alicyclic epoxy compound having a cyclohexene oxide group. The alicyclic epoxy compound (A) is represented by the following formula (I-1)

The curable epoxy resin composition according to claim 1, which is a compound represented by the formula:   Furthermore, the curable epoxy resin composition of any one of Claims 1-3 containing a hardening accelerator (F).   Furthermore, the curable epoxy resin composition of any one of Claims 1-4 containing an acrylic block copolymer. The content of the alicyclic epoxy compound (A) is from 50 to 90% by weight based on the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B). The curable epoxy resin composition according to any one of 1 to 5. Hardened | cured material formed by hardening | curing the curable epoxy resin composition of any one of Claims 1-6 . The resin composition for optical semiconductor sealing which consists of a curable epoxy resin composition of any one of Claims 1-6 . The optical semiconductor device which sealed the optical semiconductor element with the resin composition for optical semiconductor sealing of Claim 8 .

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