JP2016160352A - Curable epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable epoxy resin composition used in a sealing material for an optical semiconductor capable of forming a cured product which has high heat resistance, moisture resistance and thermal shock resistance, and has improved conduction characteristics, thermal shock resistance and moisture absorption reflow resistance of an optical semiconductor device under high temperature and under high temperature and high humidity.SOLUTION: A curable epoxy composition contains an alicyclic epoxy compound (A), an epoxy compound (B) having an aromatic ring in the molecule, a curing agent (C), and a curing accelerator (D). The epoxy compound (B) includes at least one selected from a biphenyl type epoxy compound, a dicyclopentadiene type epoxy compound, a naphthalene type epoxy compound and a bisphenol F type epoxy compound. The curing agent (C) includes a compound represented by formula (1).SELECTED DRAWING: None

Description

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

  In recent years, the output of optical semiconductor devices has been increased, and high heat resistance and light resistance are required for a resin (encapsulant) that covers an optical semiconductor element in such an optical semiconductor device. Conventionally, as a sealing agent for forming a sealing material having high heat resistance, for example, a composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin is known (see Patent Document 1). However, when the composition is used as a sealant for a high-power blue / white light semiconductor, the coloring of the sealant proceeds by light or heat emitted from the optical semiconductor element and should be output originally. As a result, the light is absorbed, and as a result, the intensity of the light output from the optical semiconductor device is lowered with time.

  3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4 as a sealing agent that forms a cured product (sealing material) that has high heat resistance and light resistance and is not easily yellowed -Liquid alicyclic epoxy resins having an alicyclic skeleton such as an adduct of epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and ε-caprolactone, 1,2,8,9-diepoxylimonene, etc. are known. ing. However, the cured products of these alicyclic epoxy resins are susceptible to various stresses, and cracks are generated when a thermal shock such as a cooling cycle (repeating heating and cooling periodically) is applied. Etc. had occurred.

  In addition, an optical semiconductor device (for example, a surface-mount type optical semiconductor device) generally undergoes a reflow process for bonding an electrode of the optical semiconductor device to a 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 material is peeled off from the lead frame of the optical semiconductor device due to the heat treatment in the reflow process, or the sealing material is cracked. Has occurred.

  For this reason, the sealing material in the optical semiconductor device has high heat resistance and light resistance, and also has a characteristic that cracks are not easily generated when a thermal shock is applied (sometimes referred to as “thermal shock resistance”), and Further, there is a demand for characteristics in which cracks and peeling are unlikely to occur even when heat treatment is performed in the reflow process. In particular, in recent years, from the viewpoint of ensuring higher reliability of the sealing material, the optical semiconductor device is kept under high humidity conditions for a certain time (for example, 192 hours under conditions of 30 ° C. and 60% RH; 60 ° C., 60% RH). The above-mentioned cracks and peeling are not likely to occur even when heat treatment is performed in the reflow process after placing and absorbing moisture under the above conditions (for 52 hours, etc.) (this characteristic is sometimes referred to as “moisture absorption reflow resistance”). There is also a need.

JP 2000-344867 A

  When the above-mentioned cracks or peeling occurs in the sealing material in the optical semiconductor device, there arises a problem of quality deterioration such as a decrease in relative luminous intensity (decrease in luminous intensity) or non-lighting of the total light flux of the optical semiconductor device.

  Furthermore, the conventional optical semiconductor device has a problem that durability (that is, moisture resistance) under high humidity (particularly high temperature and high humidity) is insufficient. Specifically, for example, when the optical semiconductor device is energized at high temperature and high humidity, the relative luminous intensity of the total luminous flux is greatly reduced, or the encapsulant becomes white turbid due to hydrolysis or the like. There has been a problem that the quality is significantly reduced.

Accordingly, an object of the present invention is to form a cured product having high heat resistance, moisture resistance, and thermal shock resistance, and in particular, the current-carrying characteristics, thermal shock resistance, and resistance to resistance of an optical semiconductor device at high temperature and high temperature and high humidity. It is providing the curable epoxy resin composition which can form the hardened | cured material which improves moisture absorption reflow property.
Another object of the present invention is to have high heat resistance, moisture resistance, and thermal shock resistance. In particular, the current-carrying characteristics, thermal shock resistance, and moisture absorption reflow resistance of the optical semiconductor device at high temperature and high temperature and high humidity. It is in providing the hardened | cured material which can improve property.
In addition, another object of the present invention is excellent in energization characteristics at high temperature and high temperature and high humidity, and further suppressed deterioration such as a decrease in luminous intensity when heated in a reflow process after being stored under high humidity conditions. Another object of the present invention is to provide an optical semiconductor device with high durability and quality.

  As a result of intensive studies to solve the above problems, the present inventor has at least an alicyclic epoxy compound, an epoxy compound having an aromatic ring in the molecule, a curing agent, and a curing accelerator, and the aromatic ring in the molecule. A curable epoxy resin composition containing one or more of specific compounds as an epoxy compound and a specific compound as a curing agent as essential components, and having a controlled amount of succinic anhydride within a specific range, has a high heat resistance. Can form cured products that have heat resistance, moisture resistance, and thermal shock resistance, and in particular, forms cured products that improve the energization characteristics, thermal shock resistance, and moisture absorption reflow resistance of optical semiconductor devices at high temperatures and high temperatures and humidity. The present invention has been completed by finding out what can be done.

［式中、Ｒ¹〜Ｒ⁸は、同一又は異なって、水素原子又はメチル基を示す。］
で表される化合物を含み、
硬化剤（Ｃ）全量中のコハク酸無水物の含有量が０．４重量％以下である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 includes an alicyclic epoxy compound (A), an epoxy compound (B) having an aromatic ring in the molecule, a curing agent (C), and a curing accelerator (D),
The epoxy compound (B) includes at least one selected from the group consisting of a biphenyl type epoxy compound, a dicyclopentadiene type epoxy compound, a naphthalene type epoxy compound, and a bisphenol F type epoxy compound,
As a hardening | curing agent (C), following formula (1)

[Wherein, R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom or a methyl group. ]
Including a compound represented by
A curable epoxy resin composition characterized in that the content of succinic anhydride in the total amount of the curing agent (C) is 0.4% by weight or less.

  Further, the curable epoxy resin composition comprising, as the curing agent (C), at least one selected from the group consisting of methylnorbornane-2,3-dicarboxylic acid anhydride and norbornane-2,3-dicarboxylic acid anhydride. I will provide a.

  Furthermore, the said curable epoxy resin composition which further contains an alicyclic polyester resin (E) is provided.

  Furthermore, the curable epoxy resin composition is provided in which the alicyclic polyester resin (E) is an alicyclic polyester resin having an alicyclic ring in the main chain.

  Furthermore, the said curable epoxy resin composition which further contains the siloxane derivative (F) which has a 2 or more epoxy group in a molecule | numerator is provided.

  Furthermore, the curable epoxy resin composition is provided in which the alicyclic epoxy compound (A) is a compound having 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。 Furthermore, 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.

  The present invention also provides a cured product obtained by curing the curable epoxy resin composition.

  Furthermore, the said curable epoxy resin composition which is a resin composition for optical semiconductor sealing is provided.

  Moreover, this invention provides the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the said curable epoxy resin composition.

  Since the curable epoxy resin composition of the present invention has the above-described configuration, by curing the resin composition, it has high heat resistance, moisture resistance, and thermal shock resistance. A cured product that improves the current-carrying characteristics, thermal shock resistance, and moisture absorption reflow resistance under high temperature and high humidity can be formed. For this reason, in particular, when the curable epoxy resin composition of the present invention is used as a resin composition for optical semiconductor encapsulation, deterioration such as a decrease in luminous intensity is caused even under severe conditions such as high temperature and high temperature and humidity. In addition, it is possible to obtain an optical semiconductor device having high durability and high quality, which is less likely to be generated and is less likely to be deteriorated such as a decrease in luminous intensity even when heat-treated in a reflow process after being stored under high humidity conditions.

It is the schematic which shows one Embodiment of the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the curable epoxy resin composition of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. It is an example of the surface temperature profile (temperature profile in one heat processing among two heat processing) of the optical semiconductor device in the solder heat resistance test of an Example.

<Curable epoxy resin composition>
The curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A), an epoxy compound (B) having an aromatic ring in the molecule (sometimes referred to as “epoxy compound (B)”), and curing. An agent (C) and a curing accelerator (D) are included as essential components, and as an epoxy compound (B), from a biphenyl type epoxy compound, a dicyclopentadiene type epoxy compound, a naphthalene type epoxy compound, and a bisphenol F type epoxy compound It is a composition (curable composition) containing a compound represented by the formula (1) described later as the curing agent (C), including at least one selected from the group consisting of: In the curable epoxy resin composition of the present invention, the content of succinic anhydride in the total amount of the curing agent (C) is 0.4% by weight or less as described later.

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group (oxiranyl group) in the molecule (in one molecule). . As the alicyclic epoxy compound (A), specifically, (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, (Ii) A compound having an epoxy group that is directly bonded to the alicyclic ring with a single bond. The alicyclic epoxy compound (A) does not include the epoxy compound (B) and the siloxane derivative (F) having two or more epoxy groups in the molecule described later.

  The compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (i) is arbitrarily selected from known or commonly used compounds. Can be used. Especially, as said alicyclic epoxy group, a cyclohexene oxide group is preferable.

As the compound (i) having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, a compound having a cyclohexene oxide group from the viewpoint of transparency and heat resistance of the cured product In particular, a compound (alicyclic epoxy compound) represented by the following formula (I) is preferable.

  In the above 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, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (I).

  Examples of the compound in which X in the above formula (I) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane and the like.

  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-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

  The linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation. An alkenylene group; a group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include those exemplified above.

Representative examples of the compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10), bis (3,4-epoxycyclohexylmethyl) ether, 1 , 2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3 , 4-epoxycyclohexane-1-yl) propane and the like. In the following formulas (I-5) and (I-7), l and m each represent an integer of 1 to 30. R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene. And linear or branched alkylene groups such as a group, a heptylene group, and an octylene group. Among these, C1-C3 linear or branched alkylene groups, such as a methylene group, ethylene group, a propylene group, an isopropylene group, are preferable. N1 to n6 in the following formulas (I-9) and (I-10) each represent an integer of 1 to 30.

Examples of the compound (ii) having an epoxy group directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).

In the formula (II), R ′ is a group (p-valent organic group) obtained by removing p hydroxyl groups (—OH) from a p-valent alcohol in the structural formula, and p and n each represent a natural number. Examples of the p-valent alcohol [R ′ (OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each () (inside parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (II) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

  In the curable epoxy resin composition of the present invention, the alicyclic epoxy compound (A) can be used singly or in combination of two or more. In addition, as the alicyclic epoxy compound (A), for example, commercially available products such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) may be used.

  As the alicyclic epoxy compound (A), a compound represented by the above formula (I-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; for example, trade name “Celoxide 2021P” (Daicel Co., Ltd.) etc. are particularly preferred.

  The content (blending amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is 10 with respect to the total amount (100% by weight) of the curable epoxy resin composition. -60% by weight is preferable, more preferably 15-55% by weight, and still more preferably 15-50% by weight. By controlling the content of the alicyclic epoxy compound (A) within the above range, the curability of the curable epoxy resin composition tends to be further improved, and the heat resistance and mechanical strength of the cured product tend to be further improved. .

  The ratio of the alicyclic epoxy compound (A) to the total amount of the compounds having an epoxy group contained in the curable epoxy resin composition of the present invention (total epoxy compound; 100% by weight) is not particularly limited, but is 30 to 95% by weight. % Is preferable, more preferably 40 to 90% by weight, still more preferably 45 to 85% by weight. By setting the ratio of the alicyclic epoxy compound (A) to 30% by weight or more, the curability of the curable epoxy resin composition tends to be further improved, and the heat resistance of the cured product tends to be further improved. On the other hand, when the ratio of the alicyclic epoxy compound (A) is 95% by weight or less, the thermal shock resistance and moisture resistance of the cured product tend to be further improved.

[Epoxy compound having aromatic ring in molecule (B)]
The epoxy compound (B) in the curable epoxy resin composition of the present invention is an epoxy compound having at least one or more aromatic rings and at least one or more epoxy groups in the molecule.

  The aromatic ring that the epoxy compound (B) has in the molecule is not particularly limited, and for example, an aromatic monocyclic hydrocarbon ring [for example, a benzene ring], an aromatic condensed polycyclic hydrocarbon ring [for example, a naphthalene ring, Aromatic hydrocarbon rings such as anthracene ring, fluorene ring, pyrene ring]; aromatic heterocycles such as pyridine ring, furan ring, pyrrole ring, benzofuran ring, indole ring, carbazole ring, quinoline ring, benzimidazole ring, quinoxaline ring A ring etc. are mentioned. Among them, the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring, from the viewpoints of heat resistance and moisture resistance of the cured product.

In addition, the aromatic ring which an epoxy compound (B) has in a molecule | numerator also includes the aromatic ring which one or more substituents couple | bonded. Examples of the substituent include substituents having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms), and more specifically, aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group; alkenyloxy group such as allyloxy group The aromatic ring may have a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, a C _1-4 alkoxy group, such as a phenoxy group, a tolyloxy group, or a naphthyloxy group; Aryloxy group; aralkyloxy group such as benzyloxy group and phenethyloxy group; acetyloxy group, propionyloxy group, (meth) acrylo Aryloxy group, an acyloxy group such as a benzoyloxy group; a mercapto group; methylthio group, an alkylthio group such as an ethylthio group; alkenylthio groups such as allyl group; a phenylthio group, tolylthio group, such as a naphthylthio group, C _1-4 aromatic ring Arylthio group optionally having substituent such as alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group; aralkylthio group such as benzylthio group, phenethylthio group; carboxy group; methoxycarbonyl Groups, ethoxycarbonyl groups, propoxycarbonyl groups, butoxycarbonyl groups and the like; phenoxycarbonyl groups, tolyloxycarbonyl groups, naphthyloxycarbonyl groups and other aryloxycarbonyl groups; benzyloxycarbonyl groups and other aralkyloxycarbonyl groups; Mino group; mono- or dialkylamino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group; acylamino group such as acetylamino group, propionylamino group, benzoylamino group; oxetanyl group such as ethyloxetanyloxy group Group; acyl group such as acetyl group, propionyl group, benzoyl group; oxo group; a group in which two or more of these are bonded via a C _1-6 alkylene group, if necessary. The epoxy compound (B) may have only one type of aromatic ring in the molecule, or may have two or more types of aromatic rings.

  The number of aromatic rings in the molecule of the epoxy compound (B) may be one or more, and is not particularly limited, but is preferably 1 to 100, and more preferably 1 to 20.

  Although the number of the epoxy groups which an epoxy compound (B) has in a molecule | numerator is not specifically limited, 2-50 pieces are preferable, More preferably, it is 2-20 pieces. Moreover, the form and position of the epoxy group that the epoxy compound (B) has in the molecule are not particularly limited. For example, the aromatic ring described above can be used in various forms such as an epoxy group, a glycidyl group, a glycidyloxy group, and a methylglycidyloxy group. Or you may couple | bond with arbitrary positions in structures (for example, the substituent of the above-mentioned aromatic ring) other than an aromatic ring.

  The epoxy compound (B) may be a liquid epoxy compound at room temperature and normal pressure, or may be a solid epoxy compound.

  Specifically, as the epoxy compound (B), for example, a bisphenol A type epoxy compound [for example, bisphenol A or a derivative thereof (for example, an alkylene oxide adduct of bisphenol A, a polymer of bisphenol A and epichlorohydrin, Diglycidyl ethers of alkylene oxide adducts of the polymer, etc.], bisphenol F type epoxy compounds [for example, bisphenol F or derivatives thereof (for example, alkylene oxide adducts of bisphenol F, bisphenol F and epichlorohydrin Diglycidyl ethers of polymers, bisphenol A, bisphenol F and epichlorohydrin, alkylene oxide adducts of these polymers, etc.], biphenyl type epoxy compounds (epoxy compounds having a biphenyl structure) , Phenol novolac type epoxy compound, cresol novolac type epoxy compound, cresol type epoxy compound, cresol novolac type epoxy compound of bisphenol A, polyphenol type epoxy compound, brominated bisphenol A type epoxy compound, brominated bisphenol F type epoxy compound, hydroquinone di Glycidyl ether, resorcin diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, addition reaction product of terminal carboxylic acid polybutadiene and bisphenol A type epoxy compound, naphthalene type epoxy compound (epoxy compound having naphthalene structure), fluorene ring Epoxy compound having dicyclopentadiene type epoxy compound (having dicyclopentadiene structure and aromatic ring Epoxy compound), epoxy compounds obtained from trisphenolmethane the like.

  As described above, the curable epoxy resin composition of the present invention includes, among the epoxy compounds (B), biphenyl type epoxy compounds (biphenyl type epoxy resins), dicyclopentadiene type epoxy compounds (dicyclopentadiene type epoxy resins), At least one selected from the group consisting of naphthalene type epoxy compounds (naphthalene type epoxy resins) and bisphenol F type epoxy compounds (bisphenol F type epoxy resins) is included as an essential component. Thereby, the moisture resistance and thermal shock resistance of the cured product of the curable epoxy resin composition of the present invention are improved, and the moisture absorption reflow resistance of the optical semiconductor device is improved.

  The epoxy equivalents of the above-mentioned biphenyl type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, and bisphenol F type epoxy compound are not particularly limited, but are preferably 80 to 2000, more preferably 100 to 1500, More preferably, it is 100-1000. There exists a tendency for the toughness of hardened | cured material to improve more because the epoxy equivalent of the said epoxy compound is 80 or more. On the other hand, when the epoxy equivalent of the epoxy compound is 2000 or less, the transparency, heat resistance, moisture absorption reflow resistance, and thermal shock resistance of the cured product tend to be further improved. The epoxy equivalent is a value measured according to JIS K7236.

［式中、Ｒ^a〜Ｒ^dは、同一又は異なって、水素原子又はメチル基を示す。］ Examples of the biphenyl type epoxy compound include compounds represented by the following formula (III).

[Wherein, R ^{a to} R ^d are the same or different and each represents a hydrogen atom or a methyl group. ]

［式中、ｑは、１〜１００の整数を示す。］ As said dicyclopentadiene type epoxy compound, the compound etc. which are represented by following formula (IV) are mentioned, for example.

[Wherein q represents an integer of 1 to 100. ]

Examples of the naphthalene type epoxy compound include compounds represented by the following formula (V).

Examples of the bisphenol F-type epoxy compound include compounds represented by the following formula (VI).

  In addition, an epoxy compound (B) can be manufactured by a well-known thru | or usual method, and a commercial item can also be used for it. For example, as an epoxy compound (B), a brand name “YX-4000” (manufactured by Mitsubishi Chemical Corporation), a brand name “HP-7200” (manufactured by DIC Corporation), a brand name “HP-4032D” (DIC ( And commercial name such as “806” (manufactured by Mitsubishi Chemical Corporation) are available.

  Although content (blending amount) of the epoxy compound (B) in the curable epoxy resin composition of the present invention is not particularly limited, it is 2 to 150 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). The amount is preferably 5 to 140 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 10 to 110 parts by weight. By setting the content of the epoxy compound (B) to 2 parts by weight or more, the moisture resistance and thermal shock resistance of the cured product are further improved, and the thermal shock resistance and moisture absorption reflow resistance of the optical semiconductor device tend to be further improved. is there. On the other hand, by setting the content of the epoxy compound (B) to 150 parts by weight or less, the heat resistance and moisture resistance of the cured product are further improved, and the moisture absorption reflow resistance of the optical semiconductor device tends to be further improved.

  Biphenyl type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, and bisphenol F type epoxy compound with respect to the total amount (100% by weight) of epoxy compound (B) contained in the curable epoxy resin composition of the present invention The ratio (the ratio of the total amount of these epoxy compounds) is not particularly limited, but is preferably 60% by weight or more (for example, 60 to 100% by weight), more preferably 80% by weight or more, and still more preferably 90% by weight or more. Preferably it is 95 weight% or more. When the ratio is 60% by weight or more, the heat resistance, moisture resistance, and thermal shock resistance of the cured product tend to be improved in a well-balanced manner.

  The ratio of the total amount of the alicyclic epoxy compound (A) and the epoxy compound (B) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable epoxy resin composition of the present invention is not particularly limited. 60% by weight or more (for example, 60 to 100% by weight), more preferably 80% by weight or more (for example, 80 to 99% by weight), and still more preferably 90% by weight or more (for example, 90 to 98% by weight). It is. By setting the proportion to 60% by weight or more, the transparency, hue, heat resistance, moisture resistance, and thermal shock resistance of the cured product tend to be improved in a well-balanced manner.

[Curing agent (C)]
The curing agent (C) in the curable epoxy resin composition of the present invention includes an alicyclic epoxy compound (A), an epoxy compound (B), and a siloxane derivative (F) having two or more epoxy groups in the molecule described later. It is a compound which has the function which hardens a curable epoxy resin composition by reacting with the compound which has epoxy groups (oxirane ring), such as. As the curing agent (C), a known or conventional curing agent can be used as a curing agent for epoxy resin, and is not particularly limited. For example, acid anhydrides (acid anhydride curing agents), amines ( Amine curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, etc. Can be mentioned.

  As the acid anhydrides (acid anhydride-based curing agents) as the curing agent (C), known or conventional acid anhydride-based curing agents can be used, and are not particularly limited. For example, methyltetrahydrophthalic anhydride (4 -Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride), dodecenyl succinic anhydride, methyl Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydrous Nadic acid, anhydrous methyl nadic acid, methyl hydride Dic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride copolymer And alkyl styrene-maleic anhydride copolymer. Among these, acid anhydrides [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] that are liquid at 25 ° C. are preferable from the viewpoint of handleability. On the other hand, for a solid acid anhydride at 25 ° C., for example, by dissolving in a liquid acid anhydride at 25 ° C. to form a liquid mixture, the curing agent (C in the curable epoxy resin composition of the present invention (C ) Tends to be improved.

The curable epoxy resin composition of this invention contains the compound represented by following formula (1) as an essential component as a hardening | curing agent (C). Thereby, especially the moisture resistance of the hardened | cured material of the curable epoxy resin composition of this invention improves, and the moisture absorption reflow resistance of an optical semiconductor device improves.

In formula (1), R < ¹ > -R < ⁸ > is the same or different and shows a hydrogen atom or a methyl group. Among them, the compounds represented by formula (1), the moisture resistance of the cured product, with absorption resistance humidity reflow the viewpoint of the optical semiconductor device 0-4 of R ¹ to R ⁸ (especially 0-2) is A compound that is a methyl group is preferable, and methylnorbornane-2,3-dicarboxylic acid anhydride and norbornane-2,3-dicarboxylic acid anhydride are more preferable. In particular, the curable epoxy resin composition of the present invention preferably contains both methylnorbornane-2,3-dicarboxylic acid anhydride and norbornane-2,3-dicarboxylic acid anhydride.

  The compound represented by the formula (1) has an exo isomer and an endo isomer. When the ratio of the exo compound in the compound represented by formula (1) is increased, it tends to be liquid at room temperature, so that it tends to be easy to handle as the curing agent (C). Therefore, the compound represented by the formula (1) preferably contains the exo form as an essential component. More specifically, the abundance ratio [exo isomer / (exo isomer + endo isomer)] in the compound represented by formula (1) is preferably 40% by weight or more, more preferably 50% by weight or more. . When the abundance ratio of the exo form is less than 40% by weight, the compound represented by the formula (1) is likely to be a solid at room temperature, and it may be difficult to handle. The method for setting the exo-isomer content ratio to 40% by weight or more is not particularly limited, but as described in the following specific example, the isomerization to the exo-isomer proceeds in the precursor of the compound represented by the formula (1). The method of letting it be mentioned is mentioned.

  The “methylnorbornane-2,3-dicarboxylic anhydride” in the present specification is a general term for isomers having different methyl bond positions on the norbornane ring. Representative examples of methylnorbornane-2,3-dicarboxylic acid anhydride include 5-methylnorbornane-2,3-dicarboxylic acid anhydride.

  In the same manner as described for the compound represented by the formula (1), the methylnorbornane-2,3-dicarboxylic acid anhydride has exo and endo stereoisomers. When the exo form ratio of methylnorbornane-2,3-dicarboxylic acid anhydride is increased, it tends to be liquid at room temperature, so that it can be easily handled as the curing agent (C). Therefore, the methylnorbornane-2,3-dicarboxylic acid anhydride preferably contains an exo isomer as an essential component. More specifically, the abundance ratio of the exo isomer in the methylnorbornane-2,3-dicarboxylic anhydride [exo isomer / (exo isomer + endo isomer)] is preferably 40% by weight or more, more preferably 50% by weight or more. It is. If the abundance ratio of the exo isomer is less than 40% by weight, the methylnorbornane-2,3-dicarboxylic acid anhydride tends to be a solid at room temperature, which may make handling difficult.

  Methylnorbornane-2,3-dicarboxylic acid anhydride is obtained by hydrogenating methylnorbornene-2,3-dicarboxylic acid anhydride. In particular, from the viewpoint of increasing the abundance ratio of the exo isomer and making it liquid at room temperature, it is possible to isomerize at least a part of the endo isomer to the exo isomer in the process of producing methylnorbornane-2,3-dicarboxylic acid anhydride. preferable. More specifically, methylnorbornane-2,3-dicarboxylic acid anhydride is a part of methylnorbornene-2,3-dicarboxylic acid anhydride or methylenenorbornane-2,3-dicarboxylic acid anhydride in the presence of an acid catalyst. It is preferable to produce the product by isomerization to a product, followed by hydrogenation (see, for example, JP-A-6-25207).

  In the same manner as described for the compound represented by the formula (1), norbornane-2,3-dicarboxylic acid anhydride includes stereoisomers of exo and endo. When the ratio of the exo form of norbornane-2,3-dicarboxylic acid anhydride is increased, it tends to be liquid at room temperature, so that it can be easily handled as the curing agent (C). Therefore, it is preferable that norbornane-2,3-dicarboxylic acid anhydride has an exo isomer as an essential component. More specifically, the abundance ratio of the exo isomer in the norbornane-2,3-dicarboxylic anhydride [exo isomer / (exo isomer + endo isomer)] is preferably 30% by weight or more, more preferably 40% by weight or more. is there. When the abundance ratio of the exo isomer is less than 30% by weight, the norbornane-2,3-dicarboxylic acid anhydride tends to be a solid at room temperature and may be difficult to handle.

  Norbornane-2,3-dicarboxylic anhydride can be obtained by hydrogenating norbornene-2,3-dicarboxylic anhydride obtained by Diels-Alder reaction of cyclopentadiene and maleic anhydride. However, since norbornene-2,3-dicarboxylic acid anhydride obtained by Diels-Alder reaction of cyclopentadiene and maleic anhydride usually has an end-body ratio of 95% by weight or more, it is heated to 150 ° C. or higher. By carrying out a hydrogenation reaction after isomerization (thermal isomerization) of the exo isomer, norbornane-2,3-dicarboxylic acid anhydride (for example, the exo isomer abundance ratio is 30% by weight). The above norbornane-2,3-dicarboxylic acid anhydride) can be produced.

  When methylnorbornane-2,3-dicarboxylic anhydride and norbornane-2,3-dicarboxylic anhydride are used as the curing agent (C), methylnorbornane-2,3-dicarboxylic anhydride and norbornane-2 are used. , 3-dicarboxylic anhydride mixtures can be used. The above mixture can be prepared by mixing methylnorbornane-2,3-dicarboxylic acid anhydride and norbornane-2,3-dicarboxylic acid anhydride, or methylnorbornene-2,3-dicarboxylic acid anhydride. And norbornene-2,3-dicarboxylic anhydride can be produced by isomerization and hydrogenation.

  As described above, in the curable epoxy resin composition of the present invention, the content (ratio) of succinic anhydride in the total amount (100% by weight) of the curing agent (C) is 0.4% by weight or less (preferably 0.2% by weight or less). The content of succinic anhydride in the curing agent (C) is most preferably 0% by weight. When the content of succinic anhydride exceeds 0.4% by weight, succinic anhydride is precipitated in the curing agent (C) or the curable epoxy resin composition, and workability is reduced, or a curing accelerator (D ) May cause problems such as coloring of the cured product.

  The succinic anhydride in the curing agent (C) is, for example, isomerized and hydrogenated methyl norbornene-2,3-dicarboxylic anhydride, norbornene-2,3-dicarboxylic anhydride, or a mixture thereof. It is formed as a by-product when methylnorbornane-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, or a mixture thereof is produced. More specifically, in order to carry out the isomerization at a high temperature around 180 ° C. in the presence of an acid catalyst, dissociation of methylnorbornene-2,3-dicarboxylic acid anhydride into maleic anhydride and methylcyclopentadiene, norbornene- Dissociation of 2,3-dicarboxylic anhydride into maleic anhydride and cyclopentadiene proceeds, and the maleic anhydride thus produced is hydrogenated to produce succinic anhydride. Examples of a method for controlling the content of succinic anhydride in the total amount of the curing agent (C) to 0.4% by weight or less include, for example, methylnorbornane-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid Examples thereof include a method in which an acid anhydride or a mixture thereof is distilled under reduced pressure. More specifically, for example, a method of cutting 5% to 10% of the initial fraction under the conditions of 138 ° C. and 0.27 kPa, and further distilling the remainder under the conditions of 173 ° C. and 0.27 kPa, etc.

The curable epoxy resin composition of the present invention may further contain a compound represented by the following formula (2) as the curing agent (C). By including the compound represented by the following formula (2), the balance of the heat resistance, light resistance, and thermal shock resistance of the cured product tends to be better.

In formula (2), R < ⁹ > -R < ¹⁶ > is the same or different and shows a hydrogen atom or a methyl group. Among these, 0 to 4 (especially 0 to 2) of the compounds represented by the formula (2) are R ^{9 to} R ^{16 from} the viewpoint of moisture resistance of the cured product and moisture absorption reflow resistance of the optical semiconductor device. A compound having a methyl group is preferable, and methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.) and hexahydrophthalic anhydride are more preferable.

  As the amines (amine-based curing agent) as the curing agent (C), a known or conventional amine-based curing agent can be used, and is not particularly limited. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Aliphatic polyamines such as dipropylenediamine, diethylaminopropylamine, polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-amino Cycloaliphatic polyamines such as ethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; m-phenylenediamine, p-phenylenediamine, tri 2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6- Examples include mononuclear polyamines such as diamine, aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.

  As the phenols (phenolic curing agents) as the curing agent (C), known or conventional phenolic curing agents can be used, and are not particularly limited. For example, novolac type phenol resins, novolac type cresol resins, paraxylylene-modified phenols. Examples thereof include aralkyl resins such as resins, paraxylylene / metaxylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.

  Examples of the polyamide resin as the curing agent (C) include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.

  As the imidazole (imidazole curing agent) as the curing agent (C), a known or commonly used imidazole curing agent can be used, and is not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanate Nu 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)] -Ethyl-s-triazine and the like.

  Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (C) include liquid polymercaptan and polysulfide resin.

  Examples of polycarboxylic acids as the curing agent (C) include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxy group-containing polyester, and the like.

  In the curable epoxy resin composition of the present invention, the curing agent (C) can be used singly or in combination of two or more. Curing agents (C) are, for example, trade names “Likacid MH-700”, “Likacid MH-700F”, “Likacid HNA-100” (manufactured by Shin Nippon Rika Co., Ltd.); Commercial products such as “5500” (manufactured by Hitachi Chemical Co., Ltd.) are available.

  The content (blending amount) of the curing agent (C) in the curable epoxy resin composition of the present invention is not particularly limited, but is 100 parts by weight based on the total amount of the compounds having an epoxy group contained in the curable epoxy resin composition. The amount is preferably 50 to 200 parts by weight, more preferably 80 to 150 parts by weight. More specifically, the curing agent (C) is a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in the compound having all epoxy groups contained in the curable epoxy resin composition of the present invention. Is preferably used. By making content of a hardening | curing agent (C) into 50 weight part or more, hardening can fully be advanced and there exists a tendency which the toughness of hardened | cured material improves more. On the other hand, by setting the content of the curing agent (C) to 200 parts by weight or less, coloring tends to be suppressed and a cured product excellent in hue tends to be obtained.

  Although content (ratio) of the compound represented by Formula (1) with respect to the whole quantity (100 weight%) of the hardening | curing agent (C) contained in the curable epoxy resin composition of this invention is not specifically limited, 60 weight% The above is preferable (for example, 60 to 100% by weight), more preferably 70% by weight or more (for example, 70 to 98% by weight), and still more preferably 80% by weight or more (for example, 80 to 95% by weight). By setting the content of the compound represented by the formula (1) to 60% by weight or more, moisture resistance of the cured product, resistance in a heat and moisture resistance test of the optical semiconductor device, and moisture absorption reflow resistance tend to be further improved.

  When the curable epoxy resin composition of the present invention contains the compound represented by the formula (2) as the curing agent (C), it is represented by the formula (2) with respect to the total amount (100% by weight) of the curing agent (C). Although content (ratio) of a compound is not specifically limited, 1 to 30 weight% is preferable, More preferably, it is 2 to 20 weight%, More preferably, it is 3 to 15 weight%. By controlling the content of the compound represented by the formula (2) within the above range, the heat resistance, light resistance and thermal shock resistance of the cured product tend to be further improved.

  The content (ratio) of methylnorbornane-2,3-dicarboxylic acid anhydride in the total amount (100% by weight) of the curing agent (C) is not particularly limited, but is preferably 70 to 100% by weight, more preferably 75%. -100% by weight, more preferably 80% by weight or more (for example, 80-98% by weight). By setting the content of methylnorbornane-2,3-dicarboxylic anhydride to 70% by weight or more, moisture absorption reflow resistance of the optical semiconductor device tends to be further improved.

  The content (ratio) of norbornane-2,3-dicarboxylic acid anhydride in the total amount (100% by weight) of the curing agent (C) is not particularly limited, but is preferably 0 to 30% by weight, more preferably 0 to 0%. It is 25% by weight, more preferably 0 to 20% by weight (for example, 1 to 20% by weight). By setting the content of norbornane-2,3-dicarboxylic acid anhydride to 30% by weight or less, moisture absorption reflow resistance of the optical semiconductor device tends to be further improved. In particular, when methyl norbornane-2,3-dicarboxylic acid anhydride and norbornane-2,3-dicarboxylic acid anhydride are included as the curing agent (C), the total of these contents (total content) is not particularly limited. However, 80-100 weight% is preferable with respect to the whole quantity (100 weight%) of hardening | curing agent (C), More preferably, it is 90-100 weight% (for example, 90-99 weight%). By making the total content 80% by weight or more, the moisture absorption reflow resistance of the cured product may be remarkably improved.

[Curing accelerator (D)]
The curing accelerator (D) in the curable epoxy resin composition of the present invention is a compound having a function of accelerating the reaction rate when a compound having an epoxy group reacts with the curing agent (C). The curing accelerator (D) may be a known or conventional curing accelerator, and is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, , Phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (for example, phenol Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, etc. Tertiary amines; Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Acid esters; phosphines such as triphenylphosphine and tris (dimethoxy) phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organometallic salts such as zinc octylate, tin octylate and zinc stearate; Examples thereof include metal chelates such as aluminum acetylacetone complex.

  In addition, a hardening accelerator (D) can also be used individually by 1 type in a curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type. Further, as the curing accelerator (D), trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “U-CAT 12XD” ( (Developed product) (San Apro Co., Ltd.); trade names "TPP-K", "TPP-MK" (Hokuko Chemical Co., Ltd.); trade name "PX-4ET" (Nippon Chemical Industry ( It is also possible to use a commercial product such as a product manufactured by Co., Ltd.

  The content (blending amount) of the curing accelerator (D) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable epoxy resin composition is 100 parts by weight. On the other hand, 0.01-5 weight part is preferable, More preferably, it is 0.03-3 weight part, More preferably, it is 0.03-2 weight part. By setting the content of the curing accelerator (D) to 0.01 parts by weight or more, a more efficient curing promoting effect tends to be obtained. On the other hand, by setting the content of the curing accelerator (D) to 5 parts by weight or less, coloring tends to be suppressed and a cured product excellent in hue tends to be obtained.

  The curable epoxy resin composition of the present invention may contain other components (arbitrary components) other than the essential components described above.

[Alicyclic polyester resin (E)]
The curable epoxy resin composition of the present invention may further contain an alicyclic polyester resin (E). The alicyclic polyester resin (E) is a polyester resin having at least an alicyclic structure (aliphatic ring structure). When the curable epoxy resin composition of the present invention contains an alicyclic polyester resin (E), in particular, the heat resistance and light resistance of the cured product are improved, and the light intensity reduction of the optical semiconductor device is further suppressed. There is. Among these, from the viewpoint of improving the heat resistance and light resistance of the cured product, the alicyclic polyester resin (E) is preferably an alicyclic polyester resin having an alicyclic ring (alicyclic structure) in the main chain.

  Although it does not specifically limit as an alicyclic structure which an alicyclic polyester resin (E) has, For example, a monocyclic hydrocarbon structure, a bridged-ring hydrocarbon structure (for example, bicyclic hydrocarbon etc.), etc. are mentioned. Among these, a saturated monocyclic hydrocarbon structure or a saturated bridged ring hydrocarbon structure in which all of the alicyclic skeleton (carbon-carbon bond) is composed of carbon-carbon single bonds is particularly preferable. Moreover, the alicyclic structure which alicyclic polyester resin (E) has is introduce | transduced only in either one of the structural unit derived from the dicarboxylic acid which comprises alicyclic polyester resin (E), and the structural unit derived from diol. Alternatively, both may be introduced and are not particularly limited.

  The alicyclic polyester resin (E) has a structural unit derived from a monomer component having an alicyclic structure. Examples of the monomer having an alicyclic structure include diols and dicarboxylic acids having a known or conventional alicyclic structure, and are not particularly limited. Examples thereof include 1,2-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid. 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, highmic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydro Dicarboxylic acids having an alicyclic structure such as naphthalenedicarboxylic acid and 2,7-decahydronaphthalenedicarboxylic acid (including derivatives such as acid anhydrides) and the like; 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol 5-membered ring diol such as bis (hydroxymethyl) tricyclo [5.2.1.0] decane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedi Diols having an alicyclic structure such as 6-membered ring diols such as methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, and hydrogenated bisphenol A ( And derivatives thereof).

  The alicyclic polyester resin (E) may have a structural unit derived from a monomer component having no alicyclic structure. Examples of the monomer having no alicyclic structure include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides); adipic acid, sebacic acid and azelaic acid Aliphatic dicarboxylic acids such as succinic acid, fumaric acid, maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3- Butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 3-methyl-1,5-pentanediol, 2-methyl -1,3-propanediol, 2,2-diethyl-1,3-propanediol 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, ethylene oxide adduct of bisphenol A, etc. diols propylene oxide adduct of bisphenol A (including derivatives). A monomer having an appropriate alicyclic structure (for example, an alkyl group, an alkoxy group, a halogen atom, etc.) bonded to a dicarboxylic acid or diol having no alicyclic structure is also included in the monomer having no alicyclic structure.

  Although the ratio of the monomer unit which has an alicyclic ring with respect to all the monomer units (all monomer components) (100 mol%) which comprise an alicyclic polyester resin (E) is not specifically limited, 10 mol% or more (for example, 10-80) Mol%) is preferable, more preferably 25 to 70 mol%, and still more preferably 30 to 60 mol%. By setting the ratio of the monomer unit having an alicyclic ring to 10 mol% or more, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product and the optical semiconductor device may be further improved.

  The alicyclic polyester resin (E) is particularly preferably an alicyclic polyester resin containing at least one structural unit represented by the following formulas (3) to (5).

［式中、Ｒ¹⁷は直鎖、分岐鎖、又は環状の炭素数２〜１５のアルキレン基を示す。また、Ｒ¹⁸〜Ｒ²¹は、同一又は異なって、水素原子又は直鎖若しくは分岐鎖状の炭素数１〜４のアルキル基を示し、Ｒ¹⁸〜Ｒ²¹から選ばれる二つが結合して環を形成していてもよい。］

[Wherein, R ¹⁷ represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms. R ^{18 to} R ²¹ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two selected from R ^{18 to} R ²¹ are bonded to form a ring. It may be formed. ]

［式中、Ｒ¹⁷〜Ｒ²¹は、前記に同じ。］

[Wherein, R ^{17 to} R ²¹ are the same as defined above. ]

［式中、Ｒ¹⁷〜Ｒ²¹は、前記に同じ。］

[Wherein, R ^{17 to} R ²¹ are the same as defined above. ]

As a preferable specific example of the structural unit represented by the above formulas (3) to (5), for example, a configuration derived from 4-methyl-1,2-cyclohexanedicarboxylic acid and ethylene glycol represented by the following formula (6) Units are listed. The alicyclic polyester resin having the structural unit can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride and ethylene glycol.

Other preferred specific examples of the structural units represented by the above formulas (3) to (5) include, for example, those derived from 1,4-cyclohexanedicarboxylic acid and neopentyl glycol represented by the following formula (7). A structural unit is mentioned. The alicyclic polyester resin having the structural unit can be obtained, for example, by polycondensing 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.

  When the alicyclic polyester resin (E) has structural units represented by the above formulas (3) to (5), the total content of the structural units (total content; all monomers constituting the structural unit) The unit is not particularly limited, but 20 mol% or more (for example, with respect to the total structural unit (100 mol%; all monomer units constituting the alicyclic polyester resin (E)) of the alicyclic polyester resin (E) (for example, 20 to 100 mol%) is preferable, more preferably 50 to 100 mol%, and still more preferably 80 to 100 mol%. By setting the content of the structural unit represented by the above formulas (3) to (5) to 20 mol% or more, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product and the optical semiconductor device are improved. There is a tendency to improve.

  Although the number average molecular weight of alicyclic polyester resin (E) is not specifically limited, 300-100,000 are preferable, More preferably, it is 300-30000. By setting the number average molecular weight of the alicyclic polyester resin (E) to 300 or more, the toughness of the cured product is improved, and the thermal shock resistance and moisture absorption reflow resistance of the cured product and the optical semiconductor device tend to be further improved. . On the other hand, when the number average molecular weight of the alicyclic polyester resin (E) is 100000 or less, the compatibility with the curing agent (C) is increased, and the transparency of the cured product tends to be further improved. In addition, the said number average molecular weight of alicyclic polyester resin (E) is computed from the molecular weight of standard polystyrene conversion measured by GPC (gel permeation chromatography) method.

  In addition, alicyclic polyester resin (E) can also be used individually by 1 type in the curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type.

  The alicyclic polyester resin (E) can be produced by a known or conventional method. More specifically, for example, the alicyclic polyester resin (E) may be obtained by polycondensation of the above dicarboxylic acid and diol by a conventional method, or a derivative (acid anhydride, ester) of the above dicarboxylic acid. , Acid halides, and the like) and diols may be obtained by polycondensation by a conventional method. Moreover, a commercial item can also be obtained for alicyclic polyester resin (E).

  Although content (blending amount) of the alicyclic polyester resin (E) in the curable epoxy resin composition of the present invention is not particularly limited, the total amount of compounds having an epoxy group contained in the curable epoxy resin composition is 100 wt. The amount is preferably 1 to 50 parts by weight, more preferably 1 to 45 parts by weight, still more preferably 1 to 40 parts by weight with respect to parts. By setting the content of the alicyclic polyester resin (E) to 1 part by weight or more, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product and the optical semiconductor device tend to be further improved. On the other hand, when the content of the alicyclic polyester resin (E) is 50 parts by weight or less, the thermal shock resistance and moisture absorption reflow resistance of the cured product and the optical semiconductor device tend to be further improved.

[Siloxane derivative (F) having two or more epoxy groups in the molecule]
The curable epoxy resin composition of the present invention may further contain a siloxane derivative (F) having two or more epoxy groups in the molecule (sometimes referred to as “siloxane derivative (F)”). When the curable epoxy resin composition of the present invention contains a siloxane derivative (F), in particular, the heat resistance and light resistance of the cured product are further improved, and the light intensity of the optical semiconductor device tends to be further suppressed. .

  The siloxane skeleton (Si—O—Si skeleton) in the siloxane derivative (F) is not particularly limited, and examples thereof include a cyclic siloxane skeleton; a linear silicone, a cage-type or ladder-type polysilsesquioxane, and the like. Examples include a polysiloxane skeleton. Among these, as the siloxane skeleton, a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the light intensity of the optical semiconductor device. That is, the siloxane derivative (F) is preferably a cyclic siloxane having two or more epoxy groups in the molecule and a linear silicone having two or more epoxy groups in the molecule.

  When the siloxane derivative (F) is a cyclic siloxane having two or more epoxy groups in the molecule, the number of Si—O units forming the siloxane ring (equal to the number of silicon atoms forming the siloxane ring) is Although it does not specifically limit, 2-12 are preferable from a viewpoint of improving the heat resistance of a hardened | cured material, and light resistance, More preferably, it is 4-8.

  Although the weight average molecular weight of a siloxane derivative (F) is not specifically limited, From a viewpoint of improving the heat resistance of a hardened | cured material and light resistance, 100-3000 are preferable, More preferably, it is 180-2000. In addition, the said weight average molecular weight of a siloxane derivative (F) is computed from the molecular weight of standard polystyrene conversion measured by GPC method.

  The number of epoxy groups in the molecule of the siloxane derivative (F) is not particularly limited as long as it is 2 or more. However, from the viewpoint of improving the heat resistance and light resistance of the cured product, 2 to 4 (2) 3 or 4) is preferred.

  Although the epoxy equivalent of a siloxane derivative (F) is not specifically limited, From a viewpoint of improving the heat resistance and light resistance of hardened | cured material, 100-400 are preferable, More preferably, it is 140-400, More preferably, it is 180-350. . The epoxy equivalent is a value measured according to JIS K7236.

  The epoxy group in the siloxane derivative (F) is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. (Alicyclic epoxy group) is preferable, and among them, a cyclohexene oxide group is particularly preferable.

Specifically, as the siloxane derivative (F), for example, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6, 8,8-hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,2,4,6,6,8-hexamethyl -Cyclotetrasiloxane, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6,8-dipropyl-2,4,6,8-tetramethyl-cyclo Tetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane 2,4,8-tri [2- (3- {oxabicyclo [ .1.0] heptyl}) ethyl] -2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tri [2- (3- {oxabicyclo [4.1.0] Heptyl}) ethyl] -6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetra [2- (3- {oxabicyclo [4.1.0] Heptyl}) ethyl] -2,4,6,8-tetramethyl-cyclotetrasiloxane, silsesquioxane having two or more epoxy groups in the molecule, and the like. More specifically, for example, a cyclic siloxane having two or more epoxy groups in the molecule represented by the following formula.

  Examples of the siloxane derivative (F) include alicyclic epoxy group-containing silicone resins described in JP-A-2008-248169, and at least two epoxies in one molecule described in JP-A-2008-19422. An organopolysilsesquioxane resin having a functional group can also be used.

  In addition, in the curable epoxy resin composition of this invention, a siloxane derivative (F) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Examples of the siloxane derivative (F) include trade names “X-40-2678”, “X-40-2670”, and “X-40-2720” which are cyclic siloxanes having two or more epoxy groups in the molecule. Commercial products such as (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used. The siloxane derivative (F) can be produced by a known or conventional method.

  The content (blending amount) of the siloxane derivative (F) in the curable epoxy resin composition of the present invention is not particularly limited, but is the total amount (100% by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. The content is preferably 1 to 60% by weight, more preferably 3 to 40% by weight, and still more preferably 5 to 20% by weight. By setting the content of the siloxane derivative (F) to 1% by weight or more, the heat resistance and light resistance of the cured product tend to be further improved. On the other hand, when the content of the siloxane derivative (F) is 60% by weight or less, the thermal shock resistance and moisture absorption reflow resistance of the cured product tend to be further improved.

  The ratio of the siloxane derivative (F) to 100 parts by weight of the alicyclic epoxy compound (A) is not particularly limited, but is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 10 to 10 parts by weight. 30 parts by weight. By setting the ratio of the siloxane derivative (F) to 1 part by weight or more, the heat resistance and light resistance of the cured product tend to be further improved. On the other hand, when the ratio of the siloxane derivative (F) is 100 parts by weight or less, the thermal shock resistance and moisture absorption reflow resistance of the cured product tend to be further improved.

[Additive]
In addition to the above, the curable epoxy resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. For example, when a compound having a hydroxy group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained as the additive, the curing reaction can be allowed to proceed slowly. Other silane coupling agents such as silicone-based and fluorine-based antifoaming agents, leveling agents, and γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, as long as the viscosity and transparency are not impaired. , Surfactants, inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors (eg YAG phosphor fine particles, silicate phosphors) Conventional additives such as inorganic phosphor fine particles such as fine particles), release agents, rubber particles (for example, rubber particles having a core-shell structure), and the like can be used.

  Although the curable epoxy resin composition of this invention is not specifically limited, It can prepare by stirring and mixing each above-mentioned component in the state heated as needed. In addition, the curable epoxy resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more stored separately. These components can also be used as a multi-liquid composition (for example, a two-liquid system) that is used by mixing them at a predetermined ratio before use. The stirring / mixing method is not particularly limited, and for example, known or commonly used stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.

  Moreover, when the curable epoxy resin composition of this invention contains an alicyclic polyester resin (E), an alicyclic polyester resin (E) and a hardening | curing agent from a viewpoint of obtaining a more uniform curable epoxy resin composition. (C) is mixed in advance to obtain a mixture thereof (a mixture of alicyclic polyester resin (E) and curing agent (C)), and then a curing accelerator (D) and other additives are added to the mixture. It is preferable to prepare an epoxy curing agent by blending and subsequently mix the epoxy curing agent and a compound having an epoxy group. Although the temperature at the time of mixing an alicyclic polyester resin (E) and a hardening | curing agent (C) is not specifically limited, 60-130 degreeC is preferable, More preferably, it is 90-120 degreeC. The mixing time is not particularly limited, but is preferably 30 to 100 minutes, more preferably 45 to 80 minutes. Although mixing is not specifically limited, It is preferable to carry out in nitrogen atmosphere. Moreover, the above-mentioned well-known apparatus can be used for mixing.

  Although it does not specifically limit after mixing alicyclic polyester resin (E) and hardening | curing agent (C), Furthermore, appropriate chemical processing (For example, hydrogenation, terminal modification of alicyclic polyester resin (E), etc.), etc. May be applied. In the mixture of the alicyclic polyester resin (E) and the curing agent (C), a part of the curing agent (C) is an alicyclic polyester resin (E) (for example, an alicyclic polyester resin (E)). It may be reacted with a hydroxy group or the like.

  Examples of the mixture of the alicyclic polyester resin (E) and the curing agent (C) include commercial products such as trade names “HN-7200” and “HN-5700” (manufactured by Hitachi Chemical Co., Ltd.). It can also be used.

  Although the viscosity in 25 degreeC of the curable epoxy resin composition of this invention is not specifically limited, 60-6000 mPa * s is preferable, More preferably, it is 100-5500 mPa * s, More preferably, it is 150-5000 mPa * s. By setting the viscosity at 25 ° C. to 60 mPa · s or more, workability at the time of casting tends to be improved, and heat resistance of the cured product tends to be further improved. On the other hand, by setting the viscosity at 25 ° C. to 6000 mPa · s or less, the workability during casting is improved, and there is a tendency that defects resulting from casting defects are less likely to occur in the cured product. The viscosity of the curable epoxy resin composition of the present invention at 25 ° C. is measured using a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24, It is measured under the conditions of temperature: 25 ° C. and rotation speed: 0.5 to 10 rpm.

<Hardened product>
By curing the curable epoxy resin composition of the present invention, it has high heat resistance, moisture resistance, and thermal shock resistance, and in particular, current-carrying characteristics at high temperature and high temperature and high humidity of the optical semiconductor device, thermal shock resistance, In addition, a cured product that improves moisture absorption reflow resistance (a cured product obtained by curing the curable epoxy resin composition of the present invention may be referred to as a “cured product of the present invention”) may be obtained. As the curing means, known or conventional means such as heat treatment or light irradiation treatment can be used. Although the temperature (curing temperature) at the time of making it harden | cure by heating is not specifically limited, 45-200 degreeC is preferable, More preferably, it is 50-190 degreeC, More preferably, it is 55-180 degreeC. In addition, the heating time (curing time) for curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit value in the above range, curing is insufficient. On the contrary, when the curing temperature and the curing time are higher than the upper limit value in the above range, the resin component may be decomposed. Although the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased. Moreover, hardening can also be performed in one step and can also be performed in two or more steps.

<Resin composition for optical semiconductor encapsulation>
The curable epoxy resin composition of the present invention is a resin composition for sealing an optical semiconductor element in an optical semiconductor device, that is, an optical semiconductor sealing resin composition (an optical semiconductor element sealing agent in an optical semiconductor device). ) Can be preferably used. By using the curable epoxy resin composition of the present invention as a resin composition for optical semiconductor encapsulation, an optical semiconductor in which an optical semiconductor element is encapsulated with a cured product having high heat resistance, moisture resistance, and thermal shock resistance. A device is obtained. The above optical semiconductor device is resistant to a decrease in light intensity even when a thermal shock or high-temperature heat is applied, and has excellent current-carrying characteristics at high temperatures and moisture-absorbing reflow resistance, particularly excellent current-carrying characteristics at high temperatures and high humidity. Is expensive.

<Optical semiconductor device>
The optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition (resin composition for optical semiconductor sealing) of the present invention. The optical semiconductor element can be sealed, for example, by injecting the curable epoxy resin composition prepared by the above-described method into a predetermined mold and heat-curing under predetermined conditions. Thereby, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the curable epoxy resin composition is obtained. The curing temperature and the curing time can be appropriately set within the same range as when the cured product is prepared.

  The curable epoxy resin composition of the present invention is not limited to the above-mentioned optical semiconductor element sealing application, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, a resist, a composite material, Used for various applications such as 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, optical pickup sensors, etc. can do.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In Table 1, “-” means that the component was not blended. Moreover, the unit of the quantity (ratio) of the component shown in Table 1 is a weight part.

Production Example 1
(Manufacture of epoxy curing agent)
In each compounding ratio shown in Table 1, the product name “Rikacid MH-700” (manufactured by Shin Nippon Chemical Co., Ltd.), the product name “Rikacid HNA-100” (manufactured by Hitachi Chemical Co., Ltd.), and the product name “HN- 7200 "(manufactured by Hitachi Chemical Co., Ltd.), trade name" HN-5700 "(manufactured by Hitachi Chemical Co., Ltd.), trade name" U-CAT 18X "(manufactured by Sun Apro Co., Ltd.), ethylene glycol (Wako Pure) Yaku Kogyo Co., Ltd.) is uniformly mixed using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd., the same shall apply hereinafter), defoamed, Each epoxy curing agent (sometimes referred to as “K agent”) was obtained.

Example 1
First, with a blending ratio shown in Table 1, a trade name “Celoxide 2021P” (manufactured by Daicel Corporation) and a trade name “YX-4000” (manufactured by Mitsubishi Chemical Corporation) are mixed and stirred at 100 ° C. for 1 hour. Thus, YX-4000 was dissolved to obtain an epoxy resin (composition). Next, this epoxy resin and the epoxy curing agent obtained in Production Example 1 are uniformly mixed using a self-revolving stirrer so as to have the blending ratio shown in Table 1, defoamed, and cured. An epoxy resin composition was obtained.
Further, the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1, and then in an oven (resin curing oven) at 150 ° C. By heating for 5 hours, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the said curable epoxy resin composition was obtained. In FIG. 1, 100 is a reflector (light reflecting resin composition), 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a cured product (sealing material).

Examples 2-8, Comparative Examples 1-6
In Examples 2 to 8 and Comparative Examples 4 and 5, each curable epoxy resin composition was changed in the same manner as in Example 1 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 1. Prepared. In addition, X-40-2670 in Example 8 was used as a structural component of an epoxy resin.
On the other hand, in Comparative Examples 1 to 3 and 6, the stirring operation for 1 hour at 100 ° C. was not performed, and the epoxy resin and the epoxy curing agent obtained in Production Example 1 were mixed so that the mixing ratio shown in Table 1 was obtained. A curable epoxy resin composition was prepared by uniformly mixing and defoaming using a revolutionary stirrer.
Moreover, each optical semiconductor device was manufactured like Example 1 using the curable epoxy resin composition obtained above.

<Evaluation>
The following evaluation tests were carried out on the optical semiconductor devices obtained in the examples and comparative examples.

[Energization test]
The total luminous flux of the optical semiconductor device obtained in the example and the comparative example was measured with a total luminous flux measuring instrument, and this was defined as “0 hour total luminous flux”. Thereafter, for the optical semiconductor device after measuring the total luminous flux for 0 hour, a current of 10 mA was passed in a constant temperature bath at 85 ° C. for 100 hours, and then the total luminous flux was measured again. "Flux". And luminous intensity retention was computed from the following formula. The luminous intensity retention of two optical semiconductor devices was measured for each curable epoxy resin composition, and the average value of these was calculated (ie, N = 2). The results are shown in the column of “Luminance retention rate [%]” in Table 1.
{Luminance retention (%)}
= {Total luminous flux after 100 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

[Solder heat resistance test]
The optical semiconductor devices (two used for each curable epoxy resin composition) obtained in the examples and comparative examples were left to stand for 168 hours under the conditions of 85 ° C. and 85% RH to perform moisture absorption treatment. Subsequently, the said optical semiconductor device was put into the reflow furnace, and it heat-processed on the following heating conditions. Thereafter, the optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then again placed in a reflow furnace and heat-treated 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 a surface temperature profile (temperature profile in one of the two heat treatments) of the optical semiconductor device when heated by the reflow furnace.
Thereafter, the optical semiconductor device was observed using a digital microscope, and whether or not a crack having a length of 90 μm or more occurred in the cured product, and electrode peeling (peeling of the cured product from the electrode surface) occurred. Confirmed whether or not. Of the two optical semiconductor devices, the number of optical semiconductor devices having a crack of 90 μm or longer in the cured product is shown in the column of “Solder heat resistance test [number of cracks]” in Table 1, and electrode peeling occurred. The number of optical semiconductor devices is shown in the column of “Solder heat resistance test [number of electrode peelings]” in Table 1.

[Thermal shock test]
The optical semiconductor devices obtained in the examples and comparative examples (two were used for each curable epoxy resin composition) were exposed in an atmosphere of −40 ° C. for 30 minutes, and then in an atmosphere of 120 ° C. A thermal shock with one cycle of exposure to 30 minutes was applied for 200 cycles using a thermal shock tester. Then, the length of the crack which arose in the hardened | cured material in an optical semiconductor device was observed using a digital microscope, and the optical semiconductor device which the crack whose length was 90 micrometers or more generate | occur | produced in the hardened | cured material among two optical semiconductor devices. Was counted. The results are shown in the column of “Thermal shock test [number of cracks]” in Table 1.

[PCT test (pressure cooker test)]
First, the total luminous fluxes of the optical semiconductor devices (5 used for each curable epoxy resin composition) obtained in the examples and comparative examples were measured with a total luminous flux measuring instrument. It was. Thereafter, the optical semiconductor device after measuring the total luminous flux for 0 hour was stored for 24 hours in a constant temperature and humidity chamber (highly accelerated life test apparatus) at 120 ° C. and 100% RH. Next, after the optical semiconductor device was taken out of the constant temperature and humidity chamber, the total luminous flux was measured again, and this was designated as “total luminous flux after the PCT test”. And the luminous intensity retention after a PCT test was computed from following Formula. The average value of the luminous intensity retention of five optical semiconductor devices was calculated (ie, N = 5), and the results are shown in the column of “High temperature and high humidity resistance (PCT test) [%]” in Table 1.
{Luminance retention after PCT test (%)}
= {Total luminous flux after PCT test (lm)} / {0 hour total luminous flux (lm)} × 100

[Comprehensive judgment]
As a result of each test, the case where all of the following (1) to (5) were satisfied was determined to be “good”. On the other hand, when any of the following (1) to (5) was not satisfied, it was determined as x (defective).
(1) Current test: luminous intensity retention of 80% or more (2) Solder heat resistance test: No. of optical semiconductor devices having cracks of 90 μm or more in cured product (3) Solder heat resistance test: The number of optical semiconductor devices in which electrode peeling occurred was zero (4) Thermal shock test: the number of optical semiconductor devices in which cracks of 90 μm or more occurred in the cured product was zero (5) PCT test: luminous intensity retention 90% or more The results are shown in the “Comprehensive judgment” column of Table 1.

In addition, the component used by the Example and the comparative example is as follows.
(Epoxy resin)
Celoxide 2021P: Trade name “Celoxide 2021P” [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate], manufactured by Daicel Corporation X-40-2670: Trade name “X-40-2670” [ Siloxane derivatives having 4 epoxy groups in the molecule], YD-128 manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “YD-128” [bisphenol A type epoxy compound], YX- manufactured by Nippon Steel Chemical Co., Ltd. 4000: Trade name “YX-4000” [biphenyl type epoxy compound], manufactured by Mitsubishi Chemical Corporation HP-7200: Trade name “HP-7200” [dicyclopentadiene type epoxy compound], manufactured by DIC Corporation, HP-4032D : Brand name “HP-4032D” [Naphthalene type epoxy compound], Bis-F manufactured by DIC Corporation 806: Trade name “806” [bisphenol F type epoxy compound], manufactured by Mitsubishi Chemical Corporation (epoxy curing agent)
MH-700: trade name “Licacid MH-700” [4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30], manufactured by Shin Nippon Rika Co., Ltd. HNA-100: trade name “Licacid HNA-100” ] [Methylnorbornane-2,3-dicarboxylic anhydride and a mixture of norbornane-2,3-dicarboxylic anhydride (succinic anhydride content: 0.4 wt% or less)], manufactured by Shin Nippon Rika Co., Ltd. HN-7200: trade name "HN-7200" [mixture of curing agent and alicyclic polyester resin], manufactured by Hitachi Chemical Co., Ltd. HN-5700: trade name "HN-5700" [hardening agent and alicyclic polyester Resin mixture], Hitachi Chemical Co., Ltd. 18X: Trade name “U-CAT 18X” [curing accelerator], San Apro Co., Ltd. Ethylene glycol: Wako Pure Chemical Industries Ltd. The content of HN-7200, the succinic anhydride in each product HN-5700 are both 0.4 wt% or less.

Test equipment ・ Resin curing oven ESPH Co., Ltd. GPH-201
-Thermostatic chamber ESPEC Co., Ltd. Small high temperature chamber ST-120B1
・ Total luminous flux measuring machine Optronic Laboratories Multi-spectral Radiation Measurement System OL771
・ Thermal shock tester Espec Co., Ltd. Small thermal shock device TSE-11-A
-Reflow furnace UNI-5016F manufactured by Nippon Antom Co., Ltd.
・ Constant temperature and humidity chamber ESPEC Co., Ltd. Small environment tester SH-641
・ Highly accelerated life test equipment (for PCT test)
ESPEC Co., Ltd. Advanced Accelerated Life Tester EHS-411M
・ Digital microscope KEYENCE Co., Ltd., VHX-900

100: Reflector (resin composition for light reflection)
DESCRIPTION OF SYMBOLS 101: Metal wiring 102: Optical semiconductor element 103: Bonding wire 104: Hardened | cured material (sealing material)

Claims (10)

An alicyclic epoxy compound (A), an epoxy compound (B) having an aromatic ring in the molecule, a curing agent (C), and a curing accelerator (D),
The epoxy compound (B) includes at least one selected from the group consisting of a biphenyl type epoxy compound, a dicyclopentadiene type epoxy compound, a naphthalene type epoxy compound, and a bisphenol F type epoxy compound,
As a hardening | curing agent (C), following formula (1)

[Wherein, R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom or a methyl group. ]
Including a compound represented by
A curable epoxy resin composition, wherein the content of succinic anhydride in the total amount of the curing agent (C) is 0.4% by weight or less.   The curable epoxy resin according to claim 1, comprising at least one selected from the group consisting of methylnorbornane-2,3-dicarboxylic acid anhydride and norbornane-2,3-dicarboxylic acid anhydride as the curing agent (C). Composition.   Furthermore, the curable epoxy resin composition of Claim 1 or 2 containing an alicyclic polyester resin (E).   The curable epoxy resin composition according to claim 3, wherein the alicyclic polyester resin (E) is an alicyclic polyester resin having an alicyclic ring in the main chain.   Furthermore, the curable epoxy resin composition as described in any one of Claims 1-4 containing the siloxane derivative (F) which has a 2 or more epoxy group in a molecule | numerator.   6. The curable epoxy resin composition according to any one of claims 1 to 5, wherein the alicyclic epoxy compound (A) is a 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, wherein the curable epoxy resin composition is a compound represented by the formula:   Hardened | cured material obtained by hardening the curable epoxy resin composition as described in any one of Claims 1-7.   It is a resin composition for optical semiconductor sealing, The curable epoxy resin composition as described in any one of Claims 1-7.   An optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition according to claim 9.

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