JP7329320B2 - Curable epoxy resin composition - Google Patents

Description

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

In recent years, the output of optical semiconductor devices has been increasing, and in such optical semiconductor devices, the resin (encapsulant) that covers the optical semiconductor element is required to have high heat resistance and light resistance. Conventionally, a composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin is known as a sealant for forming a sealant with high heat resistance (see Patent Document 1). However, when the above composition is used as an encapsulant for high-output blue/white light semiconductors, the coloration of the encapsulant progresses due to the light and heat emitted from the optical semiconductor element, and the light that should originally be output Light is absorbed, and as a result, there has been a problem that the luminous intensity of light output from the optical semiconductor device decreases over time.

3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, 3,4 Adducts of -epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate and ε-caprolactone, and liquid alicyclic epoxy resins having an alicyclic skeleton such as 1,2,8,9-diepoxylimonene are known. ing. However, cured products of these alicyclic epoxy resins are vulnerable to various stresses, and cracks occur when subjected to thermal shocks such as thermal cycles (periodically repeating heating and cooling). etc. had occurred.

Further, an optical semiconductor device (for example, a surface-mount type optical semiconductor device) generally undergoes a reflow process for joining electrodes of the optical semiconductor device to a wiring board by soldering. In recent years, lead-free solder with a high melting point has been used as solder as a joining material, and the heat treatment in the reflow process has become higher (for example, the peak temperature is 240 to 260 ° C.). . Under these circumstances, conventional optical semiconductor devices suffer from deterioration problems such as peeling of the encapsulating material from the lead frame of the optical semiconductor device due to heat treatment in the reflow process, cracking of the encapsulating material, and the like. was occurring.

Therefore, in addition to high heat resistance and light resistance, the encapsulating material in the optical semiconductor device is resistant to cracking even when thermal shock is applied (sometimes referred to as "thermal shock resistance"), and Also, it is required to have characteristics that cracks and peeling do not easily occur even when heat-treated in a reflow process. In particular, in recent years, from the viewpoint of ensuring higher reliability of the sealing material, the optical semiconductor device is placed under high humidity conditions for a certain period of time (for example, 30 ° C., 60% RH for 192 hours; 60 ° C., 60% RH). (such as 52 hours under the conditions of ) to absorb moisture and then heat treatment in the reflow process, the above-mentioned cracks and peeling are unlikely to occur (such characteristics are sometimes referred to as "moisture absorption reflow resistance". Yes) are also required.

When the above-described cracks or peeling occurs in the encapsulating material in the optical semiconductor device, quality deterioration problems such as a decrease in the relative luminous intensity of the total luminous flux of the optical semiconductor device (decrease in luminous intensity) and non-lighting occur.

Furthermore, conventional optical semiconductor devices have a problem of insufficient durability (that is, moisture resistance) under high humidity (particularly under high temperature and high humidity). Specifically, for example, when the optical semiconductor device is energized under high temperature and high humidity, the relative luminous intensity of the total luminous flux is greatly reduced, and the encapsulating material becomes cloudy due to hydrolysis or the like, resulting in the deterioration of the optical semiconductor device. There was a problem that the quality was remarkably degraded.

Patent Document 2 discloses that a curable epoxy resin composition containing an alicyclic epoxy compound and a monoallyl diglycidyl isocyanurate compound forms a cured product having excellent heat resistance, light resistance, transparency and crack resistance. and is useful as an optical semiconductor encapsulant or the like. However, in optical semiconductor devices with high output, there have been problems such as insufficient heat resistance, moisture resistance, thermal shock resistance, moisture absorption reflow resistance, and the like.

In addition, the surface of the encapsulant in the optical semiconductor device is subjected to an antireflection treatment in order to prevent the deterioration of visibility due to the total reflection of incident light such as illumination light and sunlight from the outside. . Conventionally, as a method of imparting an antireflection function to the surface of a resin layer, a method of scattering incident light by dispersing an inorganic filler such as glass beads or silica in a resin is known (see, for example, Patent Document 3). ). However, there is a problem that the transparency, heat resistance, moisture resistance, etc. of the cured product deteriorate due to the addition of the inorganic filler.

JP-A-2000-344867 JP 2011-157462 A JP 2007-234767 A

Therefore, the object of the first aspect of the present invention is to be able to form a cured product having high heat resistance, moisture resistance, and thermal shock resistance. It is an object of the present invention to provide a curable epoxy resin composition capable of forming a cured product having improved properties and moisture absorption reflow resistance.
Another object of the first aspect of the present invention is to have high heat resistance, moisture resistance, and thermal shock resistance. Another object of the present invention is to provide a cured product capable of improving moisture absorption reflow resistance.
In addition, another object of the first aspect of the present invention is to provide excellent electrical properties under high temperature and high temperature and high humidity, and to deteriorate such as a decrease in luminous intensity when heat treated in a reflow process after being stored under high humidity conditions. To provide a highly durable and high-quality optical semiconductor device in which the is suppressed.
Further, the object of the second aspect of the present invention is to form a cured product having high heat resistance, moisture resistance, and thermal shock resistance. The object of the present invention is to provide a curable epoxy resin composition capable of forming a cured product having an excellent antireflection function while improving properties and moisture absorption reflow resistance.
Another object of the second aspect of the present invention is to have high heat resistance, moisture resistance, and thermal shock resistance. Another object of the present invention is to provide a cured product having an excellent antireflection function while improving moisture absorption reflow resistance.
Another object of the second aspect of the present invention is to provide excellent electrical properties under high temperature and high temperature and high humidity, and to prevent deterioration such as a decrease in luminous intensity when heat treated in a reflow process after being stored under high humidity conditions. To provide a highly durable and quality optical semiconductor device that is suppressed and has an excellent antireflection function.

As a result of intensive studies by the present inventors to solve the above problems, a curable epoxy resin composition containing an alicyclic epoxy compound, rubber particles, a silane coupling agent having a thiol group, and a triazine-based adhesive is A cured product that can form a cured product having high heat resistance, moisture resistance, and thermal shock resistance, and in particular, a cured product that improves electrical conduction characteristics, thermal shock resistance, and moisture absorption reflow resistance under high temperature and high temperature and high humidity conditions of optical semiconductor devices. and completed the first aspect of the present invention.
In addition, a hydrophobic porous inorganic filler and a nonporous filler are added to a curable epoxy resin composition containing an alicyclic epoxy compound, rubber particles, a silane coupling agent having a thiol group, and a triazine-based adhesion agent. It was found that by blending, it is possible to impart an excellent antireflection function to the cured product while maintaining high heat resistance, moisture resistance, thermal shock resistance, moisture absorption reflow resistance, etc., and the second aspect of the present invention. completed.
The first and second aspects of the present invention have been completed based on these findings.

That is, the first aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B), a silane coupling agent having a thiol group (C), and a triazine-based adhesion agent (D). Provided is a curable epoxy resin composition characterized by:

Further, the second aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B), a silane coupling agent having a thiol group (C), a triazine-based adhesion agent (D), and a hydrophobic Provided is a curable epoxy resin composition comprising a porous inorganic filler (E) and a nonporous filler (F).

The curable epoxy resin composition of the first aspect or second aspect of the present invention may further contain a curing agent (G) and a curing accelerator (H).

The curable epoxy resin composition of the first aspect or second aspect of the present invention may further contain a curing catalyst (I).

［式（１）中、Ｙは、単結合又は連結基を示す。Ｒ¹は、同一又は異なって、水素原子又は炭素数１～１２のアルキル基を示す。Ｒ²及びＲ³は、同一又は異なって、水素原子、炭素数１～４のアルキル基、ヒドロキシ基、又はメトキシ基を示す。Ｒ⁴は、水素原子、炭素数１～４のアルキル基、ヒドロキシ基、メトキシ基、又は－ＳｉＲ⁵ _s（ＯＲ⁶）_3-sで表される基を示す。Ｒ⁵及びＲ⁶は、同一又は異なって、水素原子、又は炭素数１～４のアルキル基を示す。ｒは、０～１６の整数を示す。ｓは、０～３の整数を示す。］
で表される化合物であってもよい。 In the curable epoxy resin composition of the first aspect or the second aspect of the present invention, the triazine-based adhesion agent (D) has the following formula (1)

[In formula (1), Y represents a single bond or a linking group. R ¹ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R ² and R ³ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a methoxy group. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, or a group represented by -SiR ⁵ _s (OR ⁶ ) _3-s . R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. r represents an integer from 0 to 16; s represents an integer from 0 to 3; ]
It may be a compound represented by.

In the curable epoxy resin composition of the first aspect or the second aspect of the present invention, the alicyclic epoxy compound (A) may be a compound having a cyclohexene oxide group.

で表される化合物であってもよい。 In the curable epoxy resin composition of the first aspect or the second aspect of the present invention, the alicyclic epoxy compound (A) has the following formula (I-1)

It may be a compound represented by.

The curable epoxy resin composition of the first aspect or second aspect of the present invention may further contain an isocyanuric acid derivative (J) having one or more oxirane rings in the molecule.

［式（２－１）中、Ｒ⁷及びＲ⁸は、同一又は異なって、水素原子又は炭素数１～８のアルキル基を示す。］
で表される化合物であってもよい。 In the curable epoxy resin composition of the first aspect or the second aspect of the present invention, the isocyanuric acid derivative (J) having one or more oxirane rings in the molecule has the following formula (2-1)

[In formula (2-1), R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
It may be a compound represented by.

The curable epoxy resin composition of the first aspect or second aspect of the present invention may further contain a siloxane derivative (K) having two or more epoxy groups in the molecule.

The present invention also provides a cured product of the curable epoxy resin composition of the first or second aspect of the present invention.

The curable epoxy resin composition of the first aspect or the second aspect of the present invention may be a resin composition for optical semiconductor encapsulation.

The present invention also provides 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 encapsulation) of the first or second aspect of the present invention. do.

Since the curable epoxy resin composition of the first aspect of the present invention has the above structure, by curing the resin composition, it has high heat resistance, moisture resistance, and thermal shock resistance, and is particularly suitable for optical semiconductor devices. It is possible to form a cured product that improves electrical conductivity, thermal shock resistance, and moisture absorption reflow resistance under high temperature and high temperature and high humidity. Therefore, in particular, when the curable epoxy resin composition of the first aspect of the present invention is used as a resin composition for optical semiconductor encapsulation, the luminous intensity is reduced even under severe conditions such as high temperature and high temperature and high humidity. It is possible to obtain an optical semiconductor device with high durability and quality, which is less likely to cause deterioration such as deterioration such as deterioration such as deterioration such as deterioration such as deterioration such as deterioration under high humidity conditions, and which is less likely to cause deterioration such as decrease in luminous intensity even when it is heat-treated in a reflow process after being stored under high humidity conditions.

Furthermore, since the curable epoxy resin composition of the second aspect of the present invention has the above configuration, by curing the resin composition, the cured product has high heat resistance, moisture resistance, thermal shock resistance, and moisture absorption reflow resistance. It is possible to impart an excellent antireflection function to the cured product while maintaining properties and the like. Therefore, in particular, when the curable epoxy resin composition of the second aspect of the present invention is used as a resin composition for optical semiconductor encapsulation, the luminous intensity is reduced even under severe conditions such as high temperature and high temperature and high humidity. Furthermore, even when heat treated in the reflow process after being stored under high humidity conditions, deterioration such as a decrease in luminosity does not easily occur, and it has excellent anti-reflection function, and has high durability and quality. A semiconductor device can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS 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 (the temperature profile in one of the two heat treatments) of the optical semiconductor device in the solder heat resistance test of the example.

<Curable epoxy resin composition>
The curable epoxy resin composition of the first aspect of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a silane coupling agent having a thiol group (C), and a triazine-based adhesion agent (D ) as essential components (curable composition).
Further, the curable epoxy resin composition of the second aspect of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a silane coupling agent having a thiol group (C), and a triazine-based adhesion agent. A composition (curable composition) containing (D), a hydrophobic porous inorganic filler (E), and a nonporous filler (F) as essential components.

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound ( A) is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group (oxiranyl group) in the molecule (in one molecule). Specific examples of the alicyclic epoxy compound (A) include (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms constituting an alicyclic ring and an oxygen atom; (ii) compounds having an epoxy group directly bonded to an alicyclic ring with a single bond;

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

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

In formula (I) above, X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and these and a group in which a plurality of is linked.

Compounds in which X in the above formula (I) is a single bond include (3,4,3′,4′-diepoxy)bicyclohexyl and the like.

Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, divalent alicyclic hydrocarbon groups, and the like. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group and 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- Divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, and the like are included.

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 vinylene group, propenylene group, and 1-butenylene group. , 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, and other linear or branched alkenylene groups 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 an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. It is an alkenylene group.

As the linking group X, a linking group containing an oxygen atom is particularly preferable, and specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-, epoxidized alkenylene groups; groups in which a plurality of these groups are linked; groups in which one or more of these groups are linked to one or more of divalent hydrocarbon groups; 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-epoxycyclohexan-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3 , 4-epoxycyclohexan-1-yl)propane and the like. Note that l and m in the following formulas (I-5) and (I-7) 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, and is a methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene. linear or branched alkylene groups such as radicals, heptylene groups, and octylene groups. Among these, straight-chain or branched-chain alkylene groups having 1 to 3 carbon atoms such as methylene, ethylene, propylene and isopropylene are preferred. n1 to n6 in the following formulas (I-9) and (I-10) each represent an integer of 1 to 30.

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

In formula (II), R′ is a group (p-valent organic group) obtained by removing p hydroxyl groups (—OH) from a p-valent alcohol, 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 1-6, and n is preferably 1-30. When p is 2 or more, n in each group in ( ) (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by formula (II) include a 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.] and the like.

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

As the alicyclic epoxy compound (A), the compound represented by the above formula (I-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate; for example, trade name "Celoxide 2021P" (manufactured by Daicel Corporation), etc.] is particularly preferable. A combination of the compound represented by the above formula (I-1) and the compound represented by the above formula (II) is also preferred.

The content (blending amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the first aspect of the present invention is not particularly limited. It is preferably 10 to 60% by weight, more preferably 20 to 55% by weight, still more preferably 20 to 50% by weight, based on the total amount (100% by weight) of the epoxy resin composition. On the other hand, when the curing catalyst (I) described below is included, the amount (content) of the alicyclic epoxy compound (A) used is 25 to 95% with respect to the curable epoxy resin composition (100% by weight). % by weight is preferred, more preferably 30 to 90% by weight, and even more preferably 35 to 90% 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 content (amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the second aspect of the present invention is not particularly limited, but when the curing agent (G) described below is included, curing It is preferably 5 to 50% by weight, more preferably 5 to 45% by weight, still more preferably 5 to 40% by weight, based on the total amount (100% by weight) of the epoxy resin composition. On the other hand, when the curing catalyst (I) described later is included, the amount (content) of the alicyclic epoxy compound (A) used is 5 to 50% with respect to the curable epoxy resin composition (100% by weight). % by weight is preferred, more preferably 10 to 40% by weight, and even more preferably 10 to 35% 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 compounds having epoxy groups contained in the curable epoxy resin composition of the present invention (total epoxy compounds; 100% by weight) is not particularly limited, but is 30% by weight or more. (eg, 30 to 100% by weight), more preferably 35% by weight or more (eg, 35 to 98% by weight), still more preferably 40% by weight or more (eg, 40 to 95% 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, for example, by setting the ratio of the alicyclic epoxy compound (A) to 98% by weight or less, the thermal shock resistance and moisture resistance of the cured product tend to be further improved.

[Rubber particles (B)]
The curable epoxy resin composition of the present invention contains rubber particles (B) as an essential component. Since the curable epoxy resin composition of the present invention contains the rubber particles (B), the cured product has excellent thermal shock resistance.

Examples of the rubber particles (B) include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxy group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). be done. As the rubber particles (B), rubber particles having a multi-layered structure (core-shell structure) comprising a core portion having rubber elasticity and at least one shell layer covering the core portion are preferred. The rubber particles (B) are particularly composed of a polymer (polymer) containing (meth)acrylic acid ester as an essential monomer component, and react with a compound having an epoxy group such as an alicyclic epoxy compound (A) on the surface. Rubber particles having hydroxy groups and/or carboxy groups (either or both of hydroxy groups and carboxy groups) as possible functional groups are preferred. If neither the hydroxy group nor the carboxy group is present on the surface of the rubber particles (B), the cured product tends to become cloudy due to thermal shock such as a thermal cycle and the transparency tends to decrease, which is not preferable.

The polymer constituting the core portion having rubber elasticity in the rubber particles (B) is not particularly limited, but (meth)acrylic (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate and butyl (meth)acrylate. A polymer containing an acid ester as an essential monomer component is preferred. Other polymers constituting the core portion having rubber elasticity include, for example, aromatic vinyls such as styrene and α-methylstyrene; nitriles such as acrylonitrile and methacrylonitrile; conjugated dienes such as butadiene and isoprene; α-Olefin such as isobutene may be included as a monomer component.

Among them, the polymer constituting the core portion having rubber elasticity is one selected from the group consisting of aromatic vinyls, nitriles, and conjugated dienes, or a combination of two or more of them, together with (meth)acrylic acid esters, as monomer components. preferably included. That is, as the polymer constituting the core portion, for example, binary copolymers such as (meth)acrylate/aromatic vinyl, (meth)acrylate/conjugated diene; (meth)acrylate/aromatic and terpolymers such as group vinyl/conjugated dienes. The polymer constituting the core portion may contain silicone such as polydimethylsiloxane or polyphenylmethylsiloxane, polyurethane, or the like.

The polymer constituting the core portion may contain, as other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, and the like. It may contain a reactive cross-linking monomer having two or more reactive functional groups in the molecule.

The core portion of the rubber particle (B) is, among others, a (meth)acrylic acid ester/aromatic vinyl binary copolymer (especially butyl acrylate/styrene) or a (meth)acrylic acid ester/aromatic vinyl It is preferable that the core portion is composed of a terpolymer of /reactive cross-linking monomers (especially, butyl acrylate/styrene/divinylbenzene) because the refractive index of the rubber particles (B) can be easily adjusted. .

The glass transition temperature of the polymer constituting the core portion of the rubber particle (B) is not particularly limited, but is preferably less than 60°C (for example, -150°C or higher and less than 60°C), more preferably -150 to 15°C. , more preferably -100 to 0°C. By setting the glass transition temperature of the polymer to be less than 60° C., the crack resistance of the cured product (the property of being resistant to cracks under various stresses) tends to be further improved. The glass transition temperature of the polymer constituting the core portion means a calculated value calculated by the following Fox formula (see Bull. Am. Phys. Soc., 1(3) 123 (1956)). In the following Fox formula, Tg indicates the glass transition temperature (unit: K) of the polymer constituting the core portion, and W _i is the weight of monomer i with respect to the total amount of monomers constituting the polymer constituting the core portion. rate. Tg _i indicates the glass transition temperature (unit: K) of a homopolymer of monomer i. The following Fox formula represents a formula when the polymer constituting the core is a copolymer of monomer 1, monomer 2, . . . and monomer n.
1/Tg= _W1 / _Tg1 + _W2 / _Tg2 +...+ _Wn / _Tgn
For the glass transition temperature of the homopolymer, values described in various documents can be adopted, for example, values described in "POLYMER HANDBOOK 3rd Edition" (published by John Wiley & Sons, Inc.) can be adopted. For those not described in the literature, the value of the glass transition temperature measured by the DSC method of a homopolymer obtained by polymerizing a monomer by a conventional method can be adopted.

The core portion of the rubber particles (B) can be produced by a commonly used method, for example, a method of polymerizing the above monomers by emulsion polymerization. In the emulsion polymerization method, the total amount of the above monomers may be charged at once and polymerized, or after a part of the above monomers is polymerized, the rest may be added continuously or intermittently for polymerization. However, polymerization methods using seed particles may also be used.

The polymer constituting the shell layer of the rubber particle (B) is preferably a different polymer (a polymer having a different monomer composition) from the polymer constituting the core portion. Moreover, as described above, the shell layer preferably has a hydroxy group and/or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as the alicyclic epoxy compound (A). As a result, the adhesion can be improved particularly at the interface with the alicyclic epoxy compound (A), and the cured product obtained by curing the curable epoxy resin composition containing the rubber particles (B) having the shell layer. It is possible to exhibit excellent crack resistance against. It is also possible to prevent the glass transition temperature of the cured product from lowering.

The polymer constituting the shell layer is preferably a polymer containing a (meth)acrylic ester such as methyl (meth)acrylate, ethyl (meth)acrylate, or butyl (meth)acrylate as an essential monomer component. . For example, when butyl acrylate is used as the (meth)acrylic acid ester in the core portion, the monomer component of the polymer constituting the shell layer may be, for example, a (meth)acrylic acid ester other than butyl acrylate (e.g., ( It is preferred to use methyl methacrylate, ethyl (meth)acrylate, butyl methacrylate, etc.). Examples of monomer components that may be contained in addition to the (meth)acrylic acid ester include aromatic vinyls such as styrene and α-methylstyrene; nitriles such as acrylonitrile and methacrylonitrile. In the rubber particles (B), it is preferable that the above-mentioned monomers are contained alone or in combination of two or more together with (meth)acrylic acid esters as monomer components constituting the shell layer, and in particular, at least aromatic vinyl is preferable in that the refractive index of the rubber particles (B) can be easily adjusted.

Furthermore, the polymer constituting the shell layer is used as a monomer component to form a hydroxyl group and/or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as the alicyclic epoxy compound (A). , hydroxy group-containing monomers (e.g., hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate) and carboxy group-containing monomers (e.g., α, β-unsaturated acids such as (meth) acrylic acid; α,β-unsaturated acid anhydrides such as maleic anhydride) are preferably contained.

The polymer constituting the shell layer in the rubber particles (B) preferably contains, as a monomer component, a (meth)acrylic acid ester and one or more selected from the above monomers in combination. That is, the shell layer is composed of, for example, (meth)acrylic acid ester/aromatic vinyl/hydroxyalkyl (meth)acrylate, (meth)acrylic acid ester/aromatic vinyl/α,β-unsaturated acid, (meth)acrylic The shell layer is preferably composed of a ternary copolymer such as acid ester/α,β-unsaturated acid/reactive cross-linking monomer (methyl methacrylate/acrylic acid/allyl methacrylate, etc.).

In addition to the above monomers, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, tri- It may contain a reactive cross-linking monomer having two or more reactive functional groups in the molecule such as allyl cyanurate, diallyl phthalate, butylene glycol diacrylate.

The glass transition temperature of the polymer constituting the shell layer of the rubber particles (B) is not particularly limited, but is preferably 60 to 120°C, more preferably 70 to 115°C. By setting the glass transition temperature of the polymer to 60° C. or higher, the heat resistance of the cured product tends to be further improved. On the other hand, by setting the glass transition temperature of the polymer to 120° C. or lower, the crack resistance of the cured product tends to be further improved. The glass transition temperature of the polymer constituting the shell layer means a calculated value calculated by the Fox formula, and can be measured, for example, in the same manner as the glass transition temperature of the polymer constituting the core.

The rubber particles (B) (rubber particles having a core-shell structure) are obtained by covering the core portion with a shell layer. The method of coating the core portion with the shell layer includes, for example, a method of coating the surface of the core portion having rubber elasticity obtained by the above method with a polymer that constitutes the shell layer; A method of graft-polymerizing the obtained core portion having rubber elasticity as a trunk component and each component constituting the shell layer as a branch component.

The average particle size of the rubber particles (B) is not particularly limited, but is preferably 10 to 500 nm, more preferably 20 to 400 nm. The maximum particle size of the rubber particles (B) is not particularly limited, but is preferably 50 to 1000 nm, more preferably 100 to 800 nm. By setting the average particle size to 500 nm or less (or the maximum particle size to 1000 nm or less), the dispersibility of the rubber particles (B) in the cured product tends to be improved and the crack resistance tends to be further improved. On the other hand, setting the average particle size to 10 nm or more (or the maximum particle size to 50 nm or more) tends to further improve the crack resistance of the cured product.

Although the refractive index of the rubber particles (B) is not particularly limited, it is preferably from 1.40 to 1.60, more preferably from 1.42 to 1.58. Further, the refractive index of the rubber particles (B) and the refractive index of the cured product obtained by curing the curable epoxy resin composition (the curable epoxy resin composition of the present invention) containing the rubber particles (B) The difference is preferably within ±0.03 (preferably within ±0.02). By setting the difference in refractive index to within ±0.03 (preferably within ±0.02), excellent transparency of the cured product is ensured, and the luminous intensity of the optical semiconductor device tends to be kept high.

The refractive index of the rubber particles (B) is determined, for example, by casting 1 g of rubber particles into a mold and compression molding at 210 ° C. and 4 MPa to obtain a flat plate with a thickness of 1 mm. A test piece is cut out, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) is measured in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate liquid. can be obtained by measuring the refractive index at 20° C. and the sodium D line.

The refractive index of the cured product of the curable epoxy resin composition of the present invention can be obtained, for example, from a cured product obtained by the heat-curing method described in the cured product section below. is cut out, and a prism and the test piece are brought into close contact using monobromonaphthalene as an intermediate liquid, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) is used, It can be determined by measuring the refractive index at 20° C. and the sodium D line.

The content (blended amount) of the rubber particles (B) in the curable epoxy resin composition of the present invention is not particularly limited. On the other hand, it is preferably 0.5 to 60 parts by weight, more preferably 1 to 50 parts by weight. By setting the content of the rubber particles (B) to 0.5 parts by weight or more, the crack resistance of the cured product tends to be further improved. On the other hand, setting the content of the rubber particles (B) to 60 parts by weight or less tends to further improve the heat resistance of the cured product.

[Silane coupling agent having a thiol group (C)]
The silane coupling agent (C) (hereinafter sometimes simply referred to as "silane coupling agent (C)"), which is one of the essential components of the curable epoxy resin composition of the present invention, has a thiol group in its molecule. It is a silane coupling agent that has a function of mainly improving the adhesion of the cured product obtained by curing the curable epoxy resin composition to an adherend such as a substrate of an optical semiconductor device.

The silane coupling agent (C) is not particularly limited, but the following formula:
(OR ^B ) _3-k (R ^C ) _k SiR ^A SH
A compound represented by is preferred. In the above formula, R ^A is a divalent organic group having 1 to 12 carbon atoms (preferably a linear or branched alkylene group having 1 to 12 carbon atoms, more preferably a linear alkylene group), and R ^B is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms (preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group), R ^C is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms (preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group ), and k is an integer of 0 to 3 (preferably 0). Substituents for R ^B and R ^C include, for example, monovalent aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups, etc.); monovalent aromatic hydrocarbon groups (e.g., aryl groups, etc.); monovalent organic group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group; and the like. In addition, the monovalent organic group may have a substituent (for example, a substituent such as a hydroxy group, a carboxyl group, and a halogen atom). When there are a plurality of R ^C or OR ^B , each R ^C or OR ^B may be the same or different.

Examples of the silane coupling agent (C) represented by the above formula include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and the like.

In the curable epoxy resin composition of the present invention, the silane coupling agent (C) can be used singly or in combination of two or more. A silane coupling agent (C) can be manufactured by a well-known method. Further, as the silane coupling agent (C), for example, trade names "KBM-802", "KBM-803" (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name "Z-6062" (Toray Dow A commercially available product such as one manufactured by Corning Co., Ltd. can also be used.

When adding the silane coupling agent (C) to the curable epoxy resin composition, the silane coupling agent (C) may be added alone, or the silane coupling agent (C) previously mixed with the epoxy compound (A) may be added. good too. Alternatively, the silane coupling agent (C) may be hydrolyzed in advance and mixed with the epoxy compound (A) to be added.

The content (blended amount) of the silane coupling agent (C) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the compound having an epoxy group contained in the curable epoxy resin composition is 100 parts by weight. 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight. By setting the content of the silane coupling agent (C) to 0.01 parts by weight or more, the adhesiveness of the cured product obtained by curing the curable epoxy resin composition to an adherend such as a substrate is further improved. , the moisture absorption reflow resistance of the cured product tends to be further improved. On the other hand, when the content of the silane coupling agent (C) is 5 parts by weight or less, coloring tends to be suppressed and a cured product with excellent hue can be obtained.

In the curable epoxy resin composition of the present invention, a silane coupling agent other than the silane coupling agent (C) (eg, γ-glycidoxypropyltrimethoxysilane, etc.) is added together with the silane coupling agent (C). may be used.

[Triazine-based adhesion agent (D)]
The triazine-based adhesion agent (D), which is one of the essential components of the curable epoxy resin composition of the present invention, is mainly used as a cured product obtained by curing the curable epoxy resin composition, such as a substrate of an optical semiconductor device. It has the function of improving adhesion (adhesion) to adherends. When the curable epoxy resin composition of the present invention contains the triazine-based adhesion agent (D) in addition to the silane coupling agent (C), the adhesion is further improved, and the moisture absorption reflow resistance and the like are improved.

The triazine-based adhesion agent (D) is not particularly limited, but a compound represented by the following formula (1) is preferable.

In formula (1) above, Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, a thioether group, an amino group, and groups in which a plurality of these are linked.

Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, divalent alicyclic hydrocarbon groups, and the like. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group and 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- Divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group, and the like are included.

Specifically, the linking group Y includes -CO-; -O-CO-O-; -COO-; -O-; -CONH-; -S-; -NH-; Linked groups; groups in which one or more of these groups and one or more of divalent hydrocarbon groups are linked. Examples of the divalent hydrocarbon group include those exemplified above. The linking group Y is preferably a group in which -S-; -NH-; -S- or -NH- is linked to a divalent hydrocarbon group, such as -S-; -NH-; or -CH ₂ CH ₂ -. S- is particularly preferred.

In the above formula (1), R ¹ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , a decyl group, an undecyl group, a dodecyl group, and other linear or branched alkyl groups. Among them, straight-chain or branched-chain alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group and isopropyl group are preferred. A hydrogen atom is particularly preferred as R ¹ .

In formula (1) above, R ² and R ³ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, or a methoxy group. Examples of alkyl groups having 1 to 4 carbon atoms include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and s-butyl group. Among them, alkyl groups having 1 or 2 carbon atoms such as methyl group and ethyl group are preferable.

When there are multiple R ² or R ³ in one molecule, the multiple R ² or R ³ may be independently the same or different. It is particularly preferred that R ² and R ³ in the above formula (1) are the same or different and represent a hydrogen atom or a hydroxy group.

In the above formula (1), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, or a group represented by --SiR ⁵ _s (OR ⁶ ) _3-s . R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s represents an integer from 0 to 3; Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ include the same groups as those described above for R ² and R ³ . R ⁴ is preferably a hydrogen atom, a hydroxy group, or a group represented by -SiR ⁵ _s (OR ⁶ ) _3-s , and is represented by a hydroxy group or -SiR ⁵ _s (OR ⁶ ) _3-s groups are particularly preferred. R ⁵ and R ⁶ are the same or different and are preferably alkyl groups having 1 or 2 carbon atoms such as methyl and ethyl. s is preferably 0 or 1;

In the above formula (1), r represents an integer of 0-16. r is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.

As the compound represented by the above formula (1), a group represented by the following formula (1-1) or (1-2) is particularly preferable. Each symbol in the following formula is the same as above.

As the compound represented by the above formula (1), a group represented by the following formula (1-1′) or (1-2′) is particularly preferable. Each symbol in the following formula is the same as above.

Specific examples of the triazine-based adhesion agent (D) include N-trihydroxysilanylmethyl-[1,3,5]triazine-2,4,6-triamine, N-(2-trihydroxysilanyl- ethyl)-[1,3,5]triazine-2,4,6-triamine, N-(3-trihydroxysilanyl-propyl)-[1,3,5]triazine-2,4,6-triamine, N-(4-trihydroxysilanyl-butyl)-[1,3,5]triazine-2,4,6-triamine, N-(6-trihydroxysilanyl-hexyl)-[1,3,5] triazine-2,4,6-triamine, N-(8-trihydroxysilanyl-octyl)-[1,3,5]triazine-2,4,6-triamine, N-(10-trihydroxysilanyl- decyl)-[1,3,5]triazine-2,4,6-triamine, N-(12-trihydroxysilanyl-dodecyl)-[1,3,5]triazine-2,4,6-triamine, N-trimethoxysilanylmethyl-[1,3,5]triazine-2,4,6-triamine, N-(2-trimethoxysilanyl-ethyl)-[1,3,5]triazine-2,4 ,6-triamine, N-(3-trimethoxysilanyl-propyl)-[1,3,5]triazine-2,4,6-triamine, N-(4-trimethoxysilanyl-butyl)-[1 ,3,5]triazine-2,4,6-triamine, N-(6-trimethoxysilanyl-hexyl)-[1,3,5]triazine-2,4,6-triamine, N-(8- trimethoxysilanyl-octyl)-[1,3,5]triazine-2,4,6-triamine, N-(10-trimethoxysilanyl-decyl)-[1,3,5]triazine-2,4 ,6-triamine, N-(12-trimethoxysilanyl-dodecyl)-[1,3,5]triazine-2,4,6-triamine, N-triethoxysilanylmethyl-[1,3,5] Triazine-2,4,6-triamine, N-(2-triethoxysilanyl-ethyl)-[1,3,5]triazine-2,4,6-triamine, N-(3-triethoxysilanyl- propyl)-[1,3,5]triazine-2,4,6-triamine, N-(4-triethoxysilanyl-butyl)-[1,3,5]triazine-2,4,6-triamine, N-(6-triethoxysilanyl-hexyl)-[1,3,5]triazine-2,4,6-triamine, N-(8-triethoxysilanyl-octyl)-[1,3,5] Triazine-2,4,6-triamine, N-(10-triethoxysilanyl-decyl)-[1,3,5]triazine-2,4,6-triamine, N-(12-triethoxysilanyl- dodecyl)-[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-trihydroxysilanylmethyl-[1,3,5]triazine-2,4,6 -triamine, N,N'-dimethyl-N"-(2-trihydroxysilanyl-ethyl)-[1,3,5]triazine-2,4,6-triamine, N,N'-dimethyl-N" -(3-trihydroxysilanyl-propyl)-[1,3,5]triazine-2,4,6-triamine, N,N'-dimethyl-N''-(4-trihydroxysilanyl-butyl)- [1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-(6-trihydroxysilanyl-hexyl)-[1,3,5]triazine-2,4 ,6-triamine, N,N′-dimethyl-N″-(8-trihydroxysilanyl-octyl)-[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl- N″-(10-trihydroxysilanyl-decyl)-[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-(12-trihydroxysilanyl-dodecyl )-[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-trimethoxysilanylmethyl-[1,3,5]triazine-2,4,6- triamine, N,N'-dimethyl-N''-(2-trimethoxysilanyl-ethyl)-[1,3,5]triazine-2,4,6-triamine, N,N'-dimethyl-N''- (3-trimethoxysilanyl-propyl)-[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-(4-trimethoxysilanyl-butyl)-[ 1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-(6-trimethoxysilanyl-hexyl)-[1,3,5]triazine-2,4, 6-triamine, N,N'-dimethyl-N''-(8-trimethoxysilanyl-octyl)-[1,3,5]triazine-2,4,6-triamine, N,N'-dimethyl-N ″-(10-trimethoxysilanyl-decyl)-[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-(12-trimethoxysilanyl-dodecyl) -[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-triethoxysilanylmethyl-[1,3,5]triazine-2,4,6-triamine , N,N′-dimethyl-N″-(2-triethoxysilanyl-ethyl)-[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-( 3-triethoxysilanyl-propyl)-[1,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-(4-triethoxysilanyl-butyl)-[1 ,3,5]triazine-2,4,6-triamine, N,N′-dimethyl-N″-(6-triethoxysilanyl-hexyl)-[1,3,5]triazine-2,4,6 -triamine, N,N'-dimethyl-N"-(8-triethoxysilanyl-octyl)-[1,3,5]triazine-2,4,6-triamine, N,N'-dimethyl-N" -(10-triethoxysilanyl-decyl)-[1,3,5]triazine-2,4,6-triamine, N,N'-dimethyl-N''-(12-triethoxysilanyl-dodecyl)- [1,3,5]triazine-2,4,6-triamine, 2,4-diamino-6-[2-(methylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6- [2-(ethylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(propylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6- [2-(isopropylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(butylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6 -[2-(isobutylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(pentylthio)ethyl]-1,3,5-triazine, 2,4-diamino- 6-[2-(hexylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(octylthio)ethyl]-1,3,5-triazine, 2,4-diamino- 6-[2-(decylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(dodecylthio)ethyl]-1,3,5-triazine, 2,4-diamino- 6-[2-(octadecylthio)ethyl]-1,3,5-triazine, 2,4-diamino-6-{2-[(2-hydroxyethyl)thio]ethyl}-1,3,5-triazine , 2,4-diamino-6-{2-[(3-hydroxypropyl)thio]ethyl}-1,3,5-triazine, 2,4-diamino-6-{2-[(2,3-dihydroxy propyl)thio]ethyl}-1,3,5-triazine and the like. Among others, N-(3-triethoxysilanyl-propyl)-[1,3,5]triazine-2,4,6-triamine, N-(4-triethoxysilanyl-butyl)-[1,3, 5] triazine-2,4,6-triamine, N-(6-triethoxysilanyl-hexyl)-[1,3,5]triazine-2,4,6-triamine, 2,4-diamino-6- {2-[(2-hydroxyethyl)thio]ethyl}-1,3,5-triazine, 2,4-diamino-6-{2-[(3-hydroxypropyl)thio]ethyl}-1,3, 5-triazine, 2,4-diamino-6-{2-[(2,3-dihydroxypropyl)thio]ethyl}-1,3,5-triazine and the like are preferred.

In the curable epoxy resin composition of the present invention, the triazine-based adhesion agent (D) can be used singly or in combination of two or more. The triazine-based adhesion agent (D) can be produced by a known method (for example, the method described in JP-A-2015-131772, JP-A-2017-2289, etc.). In addition, as the triazine-based adhesion agent (D), for example, commercially available products such as trade names "VD-3", "VD-4", and "VD-5" (manufactured by Shikoku Kasei Co., Ltd.) are used. You can also

The content (blended amount) of the triazine-based adhesion agent (D) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the compound having an epoxy group contained in the curable epoxy resin composition is 100 parts by weight. 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight. By setting the content of the triazine-based adhesion agent (D) to 0.01 parts by weight or more, the adhesiveness of the cured product obtained by curing the curable epoxy resin composition to an adherend such as a substrate is further improved. , the moisture absorption reflow resistance of the cured product tends to be further improved. On the other hand, when the content of the triazine-based adhesion agent (D) is 5 parts by weight or less, coloring tends to be suppressed and a cured product with excellent hue can be obtained.

The curable epoxy resin composition of the second aspect of the present invention comprises the above alicyclic epoxy compound (A), rubber particles (B), a silane coupling agent (C), and a triazine-based adhesion agent (D). In addition, it contains a hydrophobic porous inorganic filler (E) and a nonporous filler (F) as essential components. Since the curable epoxy resin composition of the second aspect of the present invention contains the hydrophobic porous inorganic filler (E) and the nonporous filler (F), the cured product has high heat resistance, moisture resistance, and thermal shock resistance. , and while maintaining moisture absorption reflow resistance and the like, it is possible to impart an excellent antireflection function to the cured product.

[Hydrophobic porous inorganic filler (E)]
The hydrophobic porous inorganic filler (E) in the curable epoxy resin composition of the second aspect of the present invention is uniformly dispersed throughout the curable epoxy resin composition or its cured product, and the dispersed state is As a result of the stabilization, the hydrophobic porous inorganic filler (E) present on the surface of the cured product functions to form irregularities for scattering incident light.

The hydrophobic porous inorganic filler (E) that can be used in the curable epoxy resin composition of the second aspect of the present invention is an inorganic filler having an apparent specific gravity smaller than the true specific gravity of the filler and having a porous structure inside. and the surface thereof is hydrophobically treated.

As the porous inorganic filler (the porous inorganic filler before the surface is hydrophobically treated) that constitutes the hydrophobic porous inorganic filler (E), a known or commonly used one can be used, and is not particularly limited. , inorganic glass [e.g., borosilicate glass, sodium borosilicate glass, sodium silicate glass, aluminum silicate glass, quartz, etc.], silica, alumina, iron zircon oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, oxide Porous powders of aluminum, forsterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nephelinsinite, cristobalite, wollastonite, diatomaceous earth, talc, etc., or moldings thereof bodies (eg, spherical beads, etc.), and the like.

The hydrophobic porous inorganic filler (E) is a known or commonly used hydrophobic surface treatment agent [e.g., metal oxide, silane coupling agent, titanium coupling agent, organic Hydrophobic surface treatment agent such as acid, polyol, organosilicon compound, etc.]. By applying such a hydrophobic surface treatment, the compatibility and dispersibility with the components of the curable epoxy resin composition can be improved, and the heat resistance of the cured product can be improved.
From the viewpoint of improving the compatibility and dispersibility with the components of the curable epoxy resin composition and improving the heat resistance of the cured product, organic silicon compounds (e.g., trimethylchlorosilane, hexa methyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, silicone oil, etc.) are preferred, and polydimethylsiloxane and the like are more preferred.
Among them, as the hydrophobic porous inorganic filler (E), the curable epoxy resin composition or its cured product can be uniformly dispersed to efficiently form unevenness on the surface of the cured product and is excellent. From the viewpoint of exhibiting heat resistance, hydrophobic porous inorganic glass or hydrophobic porous silica (hydrophobic porous silica filler) is preferred.

The hydrophobic porous silica is not particularly limited, and for example, known or commonly used porous silica such as fused silica, crystalline silica, high-purity synthetic silica, colloidal silica, etc., treated with the above hydrophobic surface treatment agent. can be used.

Further, the hydrophobic porous inorganic filler (E) includes an inorganic substance constituting the hydrophobic porous inorganic filler, a styrene resin, an acrylic resin, a silicone resin, an acrylic-styrene resin, a vinyl chloride resin, Composed of organic hybrid materials such as polymers such as vinylidene chloride resin, amide resin, urethane resin, phenol resin, styrene-conjugated diene resin, acrylic-conjugated diene resin, olefin resin, and cellulose resin. Hydrophobic porous inorganic-organic fillers and the like can also be used.

The hydrophobic porous inorganic filler (E) may be composed of a single material, or may be composed of two or more kinds of materials. Among them, the hydrophobic porous inorganic filler (E) can be uniformly dispersed throughout the curable epoxy resin composition or its cured product to efficiently form unevenness on the surface of the cured product, and has high heat resistance. Hydrophobic porous silica (hydrophobic porous silica filler) is more preferable from the viewpoint of having properties, availability and ease of production.

The shape of the hydrophobic porous inorganic filler (E) is not particularly limited, but examples thereof include powder, spherical, pulverized, fibrous, needle-like, scale-like and the like. Among them, the hydrophobic porous inorganic filler (E) spreads evenly throughout the curable epoxy resin composition or its cured product, making it easier to form a uniform and fine uneven shape on the surface of the cured product. From the point of view, spherical or crushed hydrophobic porous inorganic fillers are preferred.

The average particle size (median particle size) of the hydrophobic porous inorganic filler (E) is not particularly limited, but the hydrophobic porous inorganic filler (E) spreads throughout the curable epoxy resin composition or its cured product. It is preferably 1 to 20 μm, more preferably 2 to 15 μm, from the viewpoint of uniform dispersion and easy formation of uniform and fine irregularities on the surface of the cured product. The average particle diameter (median particle diameter) means the volume particle diameter (median volume diameter) at an integrated value of 50% in the particle size distribution measured by the laser diffraction/scattering method.

The porous structure of the hydrophobic porous inorganic filler (E) can be specified by various parameters such as specific surface area and oil absorption, and each parameter is suitable for the curable epoxy resin composition of the second aspect of the present invention. can be selected without particular limitation. Moreover, the above parameters can also be evaluated with the parameters of the porous inorganic filler before being subjected to the hydrophobic treatment.

The specific surface area of the porous inorganic filler (the porous inorganic filler before the surface is hydrophobically treated) constituting the hydrophobic porous inorganic filler (E) is not particularly limited, but the hydrophobic porous inorganic filler (E) is distributed uniformly throughout the curable epoxy resin composition or its cured product, making it easier to form a uniform and fine irregular shape on the surface of the cured product, and from the viewpoint of efficiently preventing reflection, It is preferably 200 m ² /g or more, more preferably 200 to 2000 m ² /g, even more preferably 200 to 1500 m ² /g, particularly preferably 200 to 1000 m ² /g. When the specific surface area is 200 m ² /g or more, the hydrophobic porous inorganic filler (E) spreads uniformly throughout the curable epoxy resin composition or the cured product thereof, thereby preventing reflection on the surface of the cured product. It tends to work better. On the other hand, when the specific surface area is 2000 m ² /g or less, the viscosity increase and thixotropy of the curable epoxy resin composition containing the hydrophobic porous inorganic filler (E) are suppressed, and when producing the encapsulant. liquidity tends to be secured. The specific surface area is the nitrogen adsorption isotherm at -196 ° C. based on the BET formula for the porous inorganic filler before the surface is hydrophobically treated, in accordance with JIS K6430 Annex E. It means adsorption specific surface area.

The oil absorption of the hydrophobic porous inorganic filler (E) is not particularly limited. It is preferably 10 to 2000 mL/100 g, more preferably 50 to 1000 mL/100 g, from the viewpoint of facilitating the formation of uniform and fine irregularities on the surface of the cured product and effectively preventing reflection. When the oil absorption is 10 mL/100 g or more, the hydrophobic porous inorganic filler (E) is dispersed evenly throughout the curable epoxy resin composition or its cured product, and the surface of the cured product becomes uneven. tends to form On the other hand, when the oil absorption is 2000 mL/100 g or less, the mechanical strength of the hydrophobic porous inorganic filler (E) tends to improve. The amount of oil supplied to the hydrophobic porous inorganic filler (E) is the amount of oil absorbed by 100 g of the filler, and can be measured according to JIS K5101.

In the curable epoxy resin composition of the second aspect of the present invention, the hydrophobic porous inorganic filler (E) can be used singly or in combination of two or more. The hydrophobic porous inorganic filler (E) can also be produced by a known or commonly used production method. ”, “Silohobic 100”, “Silohobic 200”, “Silohobic 704”, “Silohobic 507”, “Silohobic 603”, etc. (Fuji Silysia Chemical Co., Ltd. ), trade names “Aerosil RX200”, “Aerosil RX300” and other Aerosil series (manufactured by Evonik Degussa), trade names “Sunsphere H-121-ET”, “Sunsphere H-51-ET” Commercially available products such as Sunsphere ET series (manufactured by AGC Si Tech Co., Ltd.) can also be used.

The content (mixture amount) of the hydrophobic porous inorganic filler (E) in the curable epoxy resin composition of the second aspect of the present invention is not particularly limited, but the curable epoxy resin composition of the second aspect of the present invention is It is preferably 4 to 40% by weight, more preferably 4 to 35% by weight, still more preferably 4 to 30% by weight, relative to the total amount (100% by weight). Since the content of the hydrophobic porous inorganic filler (E) is 4% by weight or more, the hydrophobic porous inorganic filler (E) constitutes the curable epoxy resin composition or the antireflection material thereof. It spreads over the surface of the cured product and is evenly dispersed, making it easier to form a uniform irregular shape on the entire surface of the cured product. On the other hand, since the content of the hydrophobic porous inorganic filler (E) is 40% by weight or less, the curable epoxy resin composition of the second aspect of the present invention can be used, for example, as a sealing material for optical semiconductor devices. In some cases, there is a tendency to prevent a significant decrease in the total luminous flux and ensure sufficient illuminance.

The content (blended amount) of the hydrophobic porous inorganic filler (E) in the curable epoxy resin composition of the second aspect of the present invention is the resin component constituting the curable epoxy resin composition of the second aspect of the present invention. (Resin component excluding the hydrophobic porous inorganic filler (E) and the nonporous filler (F) from the curable epoxy resin composition of the second aspect of the present invention) (100 parts by weight), usually 5 ~80 parts by weight, preferably 5 to 70 parts by weight, more preferably 5 to 60 parts by weight. Since the content of the hydrophobic porous inorganic filler (E) is 5 parts by weight or more, the hydrophobic porous inorganic filler (E) is added to the curable epoxy resin composition of the second aspect of the present invention or its curing. It spreads over the entire product and is evenly dispersed, making it easier to form a uniform irregular shape on the entire surface of the cured product. On the other hand, since the content of the hydrophobic porous inorganic filler (E) is 80 parts by weight or less, the curable epoxy resin composition of the second aspect of the present invention can be used as a sealing material for optical semiconductor devices, for example. In some cases, there is a tendency to prevent a significant decrease in the total luminous flux and ensure sufficient illuminance.

[Nonporous filler (F)]
The curable epoxy resin composition of the second aspect of the present invention contains a nonporous filler (F) as an essential component. By including the nonporous filler (F) in the curable epoxy resin composition of the second aspect of the present invention, the thermal shock resistance of the cured product is further improved.

The nonporous filler (F) that can be used in the curable epoxy resin composition of the second aspect of the present invention is not particularly limited, but an inorganic ^or Examples include organic fillers. Hereinafter, they may be referred to as "inorganic nonporous filler (F1)" and "organic nonporous filler (F2)", respectively.

As the inorganic nonporous filler (F1) that can be used in the curable epoxy resin composition of the second aspect of the present invention, a known or commonly used inorganic nonporous filler can be used, and is not particularly limited. , inorganic glass [for example, borosilicate glass, sodium borosilicate glass, sodium silicate glass, aluminum silicate glass, quartz, etc.], silica, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, silicon nitride, Boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, forsterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline Powders of night, cristobalite, wollastonite, diatomaceous earth, talc, etc., or moldings thereof (eg, spherical beads, etc.) can be used. As the inorganic nonporous filler (F1), known or commonly used surface treatments for the above inorganic fillers [e.g., metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols, silicones, etc.] surface treatment with a surface treatment agent, etc.] may also be mentioned. By applying such a surface treatment, it may be possible to improve the compatibility and dispersibility with the components of the resin composition. Among them, as the inorganic nonporous filler (F1), inorganic nonporous glass or nonporous silica (nonporous silica filler) is preferable from the viewpoint that excellent thermal shock resistance can be imparted to the cured product.

The nonporous silica is not particularly limited, and for example, known or commonly used nonporous silica such as fused silica, crystalline silica, and high-purity synthetic silica can be used. The nonporous silica is subjected to a known or commonly used surface treatment [for example, surface treatment with a surface treatment agent such as metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyol, silicone, etc.]. can also be used.

Moreover, as the inorganic nonporous filler (F1), one having a hollow body structure may be used. Examples of the hollow inorganic nonporous filler include, but are not limited to, inorganic glass [for example, borosilicate glass, borosilicate soda glass, soda silicate glass, aluminum silicate glass, quartz, etc.], silica, alumina, zirconia, and the like. Inorganic hollow particles (including natural products such as shirasu balloons) composed of inorganic substances such as metal oxides, calcium carbonate, barium carbonate, nickel carbonate, calcium silicate, etc.; hybrid materials composed of inorganic and organic substances and inorganic-organic hollow particles. In addition, the hollow portion (internal space of the hollow particles) of the hollow inorganic nonporous filler may be in a vacuum state or may be filled with a medium. For this purpose, hollow particles filled with a medium having a low refractive index (for example, an inert gas such as nitrogen or argon, or air) are preferable.
When a hollow inorganic nonporous filler is used, its hollowness (ratio of void volume to the total volume of the inorganic filler) is not particularly limited, but is preferably 10 to 90% by volume, more preferably 30 to 90% by volume. .

As the organic nonporous filler (F2), known or commonly used fillers can be used without particular limitation, but examples include styrene-based resins, acrylic resins, silicone-based resins, acrylic-styrene-based resins, and vinyl chloride. resins, vinylidene chloride resins, amide resins, urethane resins, phenolic resins, styrene-conjugated diene resins, acrylic-conjugated diene resins, olefin resins, cellulose resins, etc. and organic nonporous fillers composed of organic substances such as
Inorganic-organic nonporous fillers composed of hybrid materials of the above inorganic and organic substances can also be used.

The nonporous filler (F) may be composed of a single material, or may be composed of two or more kinds of materials. Among them, as the nonporous filler (F), the inorganic nonporous filler (F1) is preferable from the viewpoint of imparting excellent thermal shock resistance to the cured product. Nonporous silica (nonporous silica filler) is more preferred.

The shape of the nonporous filler (F) is not particularly limited, but examples thereof include powder, spherical, pulverized, fibrous, needle-like, scale-like and the like. Among them, spherical or crushed nonporous fillers (F) are preferable from the viewpoint that the nonporous fillers (F) improve the thermal shock resistance of the cured product.

The median particle size of the nonporous filler (F) is not particularly limited, but from the viewpoint that the nonporous filler (F) improves the thermal shock resistance of the cured product, it is preferably 0.1 to 100 μm, more preferably 1 to 50 μm. The median particle size means a volume particle size (median volume diameter) at an integrated value of 50% in a particle size distribution measured by a laser diffraction/scattering method.

In the curable epoxy resin composition of the second aspect of the present invention, the nonporous filler (F) can be used singly or in combination of two or more. In addition, the nonporous filler (F) can be produced by a known or commonly used production method. 970FD" and other FB series (manufactured by Denki Kagaku Kogyo Co., Ltd.), trade names "MSR-2212" and "MSR-25" (manufactured by Tatsumori Co., Ltd.), trade names "HS-105", Commercially available products such as "HS-106" and "HS-107" (manufactured by Micron) can also be used.
In addition, the hollow inorganic nonporous filler can be produced by a known or commonly used production method. ) 34P30”, “Sphericel (trademark) 60P18”, “Q-CEL (trademark) 5020”, “Q-CEL (trademark) 7014”, “Q-CEL (trademark) 7040S” (above, Potters Barrottini Co., Ltd. ), trade names “Glass Microballoon”, “Fuji Balloon H-40”, “Fuji Balloon H-35” (manufactured by Fuji Silysia Chemical Co., Ltd.), trade names “Cellstar Z-20”, “Cellstar Z-27”, “Selstar CZ-31T”, “Selstar Z-36”, “Selstar Z-39”, “Selstar Z-39”, “Selstar T-36”, “Selstar PZ-6000” (Tokai Kogyo Co., Ltd.), trade name “Cyrax Fine Balloon” (manufactured by Fine Balloon Co., Ltd.), trade name “Super Balloon BA-15”, “Super Balloon 732C” (manufactured by Showa Chemical Industry Co., Ltd.) ) can be used.

The content (blended amount) of the nonporous filler (F) is not particularly limited, but the resin component constituting the curable epoxy resin composition of the second aspect of the present invention (the curable epoxy resin composition of the second aspect of the present invention It is preferably 10 to 200 parts by weight, more preferably 20 parts by weight, relative to the resin component (100 parts by weight) excluding the hydrophobic porous inorganic filler (E) and the nonporous filler (F) from the resin composition. ~150 parts by weight. When the content of the nonporous filler (F) is 10 parts by weight or more, the thermal shock resistance of the cured product of the curable epoxy resin composition of the second aspect of the present invention tends to be improved. On the other hand, when the content of the nonporous filler (F) is 200 parts by weight or less, the curable epoxy resin composition of the second aspect of the present invention is used as a sealing material for optical semiconductor devices, for example. There is a tendency to ensure sufficient illuminance by preventing a significant drop in total luminous flux.

The total content (total compounding amount) of the hydrophobic porous inorganic filler (E) and the nonporous filler (F) is not particularly limited, but the total amount of the curable epoxy resin composition of the second aspect of the present invention (100 % by weight), preferably 20 to 70% by weight. The total content of the hydrophobic porous inorganic filler (E) and the nonporous filler (F) is 20% by weight or more, so that the cured product of the curable epoxy resin composition of the second aspect of the present invention is subjected to thermal shock tend to improve. On the other hand, since the total content of the hydrophobic porous inorganic filler (E) and the nonporous filler (F) is 70% by weight or less, the curable epoxy resin composition of the second aspect of the present invention can be used as an optical semiconductor, for example. When used as a sealing material for devices, it tends to prevent a significant drop in total luminous flux and ensure sufficient illuminance.

[Curing agent (G)]
The curing agent (G) in the curable epoxy resin composition of the present invention is a compound having an epoxy group such as the alicyclic epoxy compound (A) described above, the isocyanuric acid derivative (J) described later, and the siloxane derivative (K). It is a compound that has the function of curing the curable epoxy resin composition by reacting with it. As the curing agent (G), known or commonly used curing agents can be used as curing agents for epoxy resins, and are not particularly limited, but examples include 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. mentioned.

As the acid anhydride (acid anhydride-based curing agent) as the curing agent (G), a known or commonly used acid anhydride-based curing agent can be used without particular limitation, but for example, methyltetrahydrophthalic anhydride (4 -methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenylsuccinic anhydride, methyl Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydride nadic acid, methyl nadic anhydride, hydrogenated methyl nadic anhydride, 4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methyl Examples include cyclohexenetetracarboxylic anhydride, vinyl ether-maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer and the like. Among them, acid anhydrides that are liquid at 25° C. [eg, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] are preferable from the viewpoint of handling. On the other hand, an acid anhydride that is solid at 25°C can be dissolved in an acid anhydride that is liquid at 25°C to form a liquid mixture, whereby the curing agent (G ) tends to be easier to handle. As the acid anhydride-based curing agent, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including an anhydride having a substituent such as an alkyl group bonded to the ring) is preferable from the viewpoint of heat resistance and transparency of the cured product.

As the amine (amine-based curing agent) as the curing agent (G), a known or commonly used amine-based curing agent can be used without particular limitation. Examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Aliphatic polyamines such as dipropylenediamine, diethylaminopropylamine, polypropylenetriamine; Menzenediamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-amino Alicyclic polyamines such as ethylpiperazine, 3,9-bis(3-aminopropyl)-3,4,8,10-tetraoxaspiro[5,5]undecane; m-phenylenediamine, p-phenylenediamine, tolylene -2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6-diamine and aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine and 2,6-naphthylenediamine.

Phenols (phenol-based curing agents) as the curing agent (G) can be known or commonly used phenol-based curing agents, and are not particularly limited. Examples include resins, aralkyl resins such as para-xylylene/meta-xylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.

Polyamide resins as the curing agent (G) include, for example, polyamide resins having either or both of a primary amino group and a secondary amino group in the molecule.

As the imidazole (imidazole-based curing agent) as the curing agent (G), a known or commonly used imidazole-based curing agent can be used, and is not particularly limited. Examples include 2-methylimidazole and 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 Nurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]- and ethyl-s-triazine.

Polymercaptans (polymercaptan-based curing agents) as the curing agent (G) include, for example, liquid polymercaptans and polysulfide resins.

Polycarboxylic acids as the curing agent (G) include, for example, adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxy group-containing polyesters.

Among them, as the curing agent (G), acid anhydrides (acid anhydride-based curing agents) are preferable from the viewpoint of the heat resistance and transparency of the cured product. In addition, in the curable epoxy resin composition of the present invention, the curing agent (G) can be used singly or in combination of two or more. Moreover, a commercial item can also be used as a hardening|curing agent (G). For example, commercial products of acid anhydrides include trade names "Rikashid MH-700" and "Rikashid MH-700F" (manufactured by Shin Nippon Rika Co., Ltd.); trade name "HN-5500" (Hitachi Chemical Industry Co., Ltd.) and the like.

The content (blended amount) of the curing agent (G) in the curable epoxy resin composition of the present invention is not particularly limited, but the compound having an epoxy group contained in the curable epoxy resin composition (for example, alicyclic epoxy It is preferably 40 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total amount of compound (A), isocyanuric acid derivative (J), and siloxane derivative (K)). More specifically, when acid anhydrides are used as the curing agent (G), 0.5 per equivalent of epoxy groups in all epoxy group-containing compounds contained in the curable epoxy resin composition of the present invention. It is preferable to use it at a ratio of up to 1.5 equivalents. By setting the content of the curing agent (G) to 40 parts by weight or more, curing can be sufficiently advanced, and the toughness of the cured product tends to be further improved. On the other hand, by setting the content of the curing agent (G) to 200 parts by weight or less, there is a tendency that coloring is further suppressed and a cured product with excellent hue is obtained.

[Curing accelerator (H)]
The curing accelerator (H) in the curable epoxy resin composition of the present invention is a compound having a function of accelerating the reaction rate when the compound having an epoxy group reacts with the curing agent (G). As the curing accelerator (H), a known or commonly used curing accelerator can be used, and is not particularly limited. , 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; phosphoric acid esters; phosphines such as triphenylphosphine and tris(dimethoxy)phosphine; tetraphenylphosphonium phosphonium compounds such as tetra(p-tolyl)borate; organic metal salts such as zinc octylate, tin octylate and zinc stearate; and metal chelates such as aluminum acetylacetone complexes.

In addition, in the curable epoxy resin composition of the present invention, the curing accelerator (H) can be used singly or in combination of two or more. In addition, as the curing accelerator (H), trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", "U-CAT 12XD" ( Developed product) (manufactured by San-Apro Co., Ltd.); trade names “TPP-K” and “TPP-MK” (manufactured by Hokko Chemical Industry Co., Ltd.); trade name “PX-4ET” (Nippon Chemical Industry ( (manufactured by Co., Ltd.) can also be used.

The content (blended amount) of the curing accelerator (H) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the compound having an epoxy group contained in the curable epoxy resin composition is On the other hand, it is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 4 parts by weight, still more preferably 0.03 to 3 parts by weight. By setting the content of the curing accelerator (H) to 0.01 parts by weight or more, there is a tendency to obtain a more efficient curing acceleration effect. On the other hand, by setting the content of the curing accelerator (H) to 5 parts by weight or less, there is a tendency that coloring is further suppressed and a cured product with excellent hue is obtained.

[Curing catalyst (I)]
The curing catalyst (I) in the curable epoxy resin composition of the present invention is the alicyclic epoxy compound (A) described above, the isocyanuric acid derivative (J) described later, the siloxane derivative (K), and other cationic polymerizable compounds. It is a compound that works to cure a curable epoxy resin composition by initiating and/or promoting a reaction (polymerization reaction). The curing catalyst (I) is not particularly limited, but for example, a cationic polymerization initiator (photocationic polymerization initiator, thermal cationic polymerization initiator) that generates cationic species by applying light irradiation or heat treatment and initiates polymerization. initiators, etc.), Lewis acid/amine complexes, Bronsted acid salts, imidazoles, and the like.

Examples of the photocationic polymerization initiator as the curing catalyst (I) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, etc. More specifically, , for example, triarylsulfonium hexafluorophosphate (e.g., p-phenylthiophenyldiphenylsulfonium hexafluorophosphate, etc.), sulfonium salts (especially triarylsulfonium salts) such as triarylsulfonium hexafluoroantimonate; , diaryliodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, iodonium salts such as iodonium [4-(4-methylphenyl-2-methylpropyl)phenyl]hexafluorophosphate; tetrafluorophosphonium phosphonium salts such as hexafluorophosphate; and pyridinium salts such as N-hexylpyridinium tetrafluoroborate. Further, as the photocationic polymerization initiator, for example, trade name "UVACURE 1590" (manufactured by Daicel Cytec Co., Ltd.); trade names "CD-1010", "CD-1011", "CD-1012" (manufactured by Sartomer); trade name "Irgacure 264" (manufactured by BASF); and trade name "CIT-1682" (manufactured by Nippon Soda Co., Ltd.).

Thermal cationic polymerization initiators as the curing catalyst (I) include, for example, aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., trade names "PP-33", "CP-66 ”, “CP-77” (manufactured by ADEKA Co., Ltd.); trade name “FC-509” (manufactured by 3M); trade name “UVE1014” (manufactured by GE); trade name “San-Aid SI-60L”, "San-Aid SI-80L", "San-Aid SI-100L", "San-Aid SI-110L", "San-Aid SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd.); trade name "CG-24-61" ( BASF) can be preferably used. Furthermore, as a thermal cationic polymerization initiator, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketones and a silanol such as triphenylsilanol, or a compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and compounds of phenols such as bisphenol S and the like.

As _the Lewis acid/amine complex as the curing catalyst (I), known or commonly used Lewis acid/amine complex-based curing catalysts can be used without particular limitation. ₃・monoethylamine, BF ₃・benzylamine, BF ₃・diethylamine, BF 3・piperidine, BF ₃・triethylamine _{, BF 3 ・}aniline, BF ₄・n-hexylamine, BF ₄・monoethylamine, BF ₄・benzylamine , _{BF4.diethylamine , BF4.piperidine , BF4.triethylamine} , _BF4.aniline , _{PF5.ethylamine ,} PF5.isopropylamine, PF5.butylamine, PF5.laurylamine, _{PF5.benzylamine} , AsF _5. Laurylamine and the like.

As the Bronsted acid salt as the curing catalyst (I), known or commonly used Bronsted acid salts can be used without particular limitation, but examples include aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphonium Salt etc. are mentioned.

As the imidazoles as the curing catalyst (I), known or commonly used imidazoles can be used without particular limitation, but examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-undecyl. imidazole, 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 isocyanurate, 2,4 -diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine etc.

In the curable epoxy resin composition of the present invention, the curing catalyst (I) can be used singly or in combination of two or more. In addition, as mentioned above, a commercial item can also be used as a curing catalyst (I).

The content (blending amount) of the curing catalyst (I) in the curable epoxy resin composition of the present invention is not particularly limited, but is , preferably 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0.05 to 8 parts by weight. By using the curing catalyst (I) within the above range, the curing speed of the curable epoxy resin composition tends to increase, and the heat resistance and transparency of the cured product tend to improve in a well-balanced manner.

[Isocyanuric acid derivative (J) having one or more oxirane rings in the molecule]
The curable epoxy resin composition of the present invention contains an isocyanuric acid derivative (J) having one or more oxirane rings in the molecule (hereinafter sometimes simply referred to as "isocyanuric acid derivative (J)"). good too. The isocyanuric acid derivative (J) is a derivative of isocyanuric acid and is a compound having at least one or more oxirane rings in the molecule. When the curable epoxy resin composition of the present invention contains the isocyanuric acid derivative (J), the toughness and thermal shock resistance of the cured product are further improved, and the moisture absorption reflow resistance of the optical semiconductor device tends to be further improved.

The number of oxirane rings that the isocyanuric acid derivative (J) has in the molecule is not particularly limited as long as it is 1 or more, but it is preferably 1 to 6, more preferably 1 to 3.

Examples of the isocyanuric acid derivative (J) include compounds represented by the following formula (2).

In formula (2), R ^X , R ^Y and R ^Z (R ^X to R ^Z ) are the same or different and represent a hydrogen atom or a monovalent organic group. However, at least one of R ^X to R ^Z is a monovalent organic group containing an oxirane ring. Examples of the monovalent organic groups include monovalent aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups, etc.); monovalent aromatic hydrocarbon groups (e.g., aryl groups, etc.); A cyclic group; a monovalent group formed by bonding two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group; Incidentally, the monovalent organic group may have a substituent (for example, a hydroxyl group, a carboxyl group, a halogen atom or the like). Examples of monovalent organic groups containing an oxirane ring include groups having an oxirane ring such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group and a cyclohexene oxide group.

More specifically, the isocyanuric acid derivative (J) includes a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-3). and the like.

wherein R ⁷ and R ⁸ are the same or different, It represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of alkyl groups having 1 to 8 carbon atoms include straight groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group and octyl group. A chain or branched alkyl group may be mentioned. Among them, straight-chain or branched-chain alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group and isopropyl group are preferable. R ⁷ and R ⁸ in the above formulas (2-1) to (2-3) are particularly preferably hydrogen atoms.

Representative examples of the compound represented by the above formula (2-1) include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis(2-methylepoxypropyl) isocyanurate, 1-(2 -methylpropenyl)-3,5-diglycidyl isocyanurate, 1-(2-methylpropenyl)-3,5-bis(2-methylepoxypropyl)isocyanurate and the like.

Representative examples of the compound represented by the above formula (2-2) include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5-(2-methylepoxypropyl) isocyanurate, 1,3-bis( 2-methylpropenyl)-5-glycidyl isocyanurate, 1,3-bis(2-methylpropenyl)-5-(2-methylepoxypropyl) isocyanurate and the like.

Typical examples of the compound represented by the above formula (2-3) include triglycidyl isocyanurate, tris(2-methylepoxypropyl) isocyanurate and the like.

The isocyanuric acid derivative (J) may be modified in advance by adding a compound that reacts with an oxirane ring, such as an alcohol or an acid anhydride.

Among them, the isocyanuric acid derivative (J) is preferably a compound represented by the above formulas (2-1) to (2-3), more preferably the above formula, from the viewpoint of the heat resistance and thermal shock resistance of the cured product. It is a compound represented by (2-1). In addition, in the curable epoxy resin composition of the present invention, the isocyanuric acid derivative (J) can be used alone or in combination of two or more. Examples of the isocyanuric acid derivative (J) include, for example, the trade name "TEPIC" (manufactured by Nissan Chemical Industries, Ltd.); (manufactured) can also be used.

When the curable epoxy resin composition of the present invention contains the isocyanuric acid derivative (J), its content (blended amount) is not particularly limited, but the total amount of compounds having epoxy groups contained in the curable epoxy resin composition. It is preferably 0 to 30% by weight (eg, 3 to 50% by weight), more preferably 5 to 25% by weight, still more preferably 5 to 20% by weight, relative to (total epoxy compounds: 100% by weight). By setting the content of the isocyanuric acid derivative (J) to 3% by weight or more, there is a tendency for the adhesion of the cured product to the electrode and the thermal shock resistance to be further improved. On the other hand, when the content of the isocyanuric acid derivative (J) exceeds 50% by weight, the solubility in the curable epoxy resin composition is lowered, which may adversely affect the physical properties of the cured product.

[Siloxane derivative (K) having two or more epoxy groups in the molecule]
The curable epoxy resin composition of the present invention further includes a siloxane derivative (K) having two or more epoxy groups in the molecule (in one molecule) (hereinafter sometimes simply referred to as "siloxane derivative (K)"). may contain By containing the siloxane derivative (K), the heat resistance and light resistance of the cured product can be particularly improved to a higher level.

The siloxane skeleton (Si—O—Si skeleton) in the siloxane derivative (K) is not particularly limited, but includes, for example, a cyclic siloxane skeleton; A polysiloxane skeleton and the like can be mentioned. Among them, the siloxane skeleton is preferably a cyclic siloxane skeleton or a linear silicone skeleton from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the decrease in luminous intensity. That is, the siloxane derivative (K) 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. In addition, a siloxane derivative (K) can be used individually by 1 type or in combination of 2 or more types.

When the siloxane derivative (K) is a cyclic siloxane having two or more epoxy groups, the number of Si—O units forming the siloxane ring (equal to the number of silicon atoms forming the siloxane ring) is not particularly limited. , preferably 2 to 12, more preferably 4 to 8, from the viewpoint of improving the heat resistance and light resistance of the cured product.

Although the weight average molecular weight of the siloxane derivative (K) is not particularly limited, it is preferably 100 to 3,000, more preferably 180 to 2,000 from the viewpoint of improving the heat resistance and light resistance of the cured product.

The number of epoxy groups in one molecule of the siloxane derivative (K) is not particularly limited as long as it is 2 or more. 3 or 4) are preferred.

The epoxy equivalent of the siloxane derivative (K) (according to JIS K7236) is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, it is preferably 180 to 400, more preferably 240 to 400, and further It is preferably 240-350.

The epoxy group in the siloxane derivative (K) 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 an oxygen atom that constitute an aliphatic ring A group (alicyclic epoxy group) is preferred, and a cyclohexene oxide group is particularly preferred.

Specific examples of the siloxane derivative (K) include 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[4.1.0]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, having two or more epoxy groups in the molecule silsesquioxane and the like. More specific examples include cyclic siloxanes having two or more epoxy groups in the molecule represented by the following formula.

Further, as the siloxane derivative (K), for example, an alicyclic epoxy group-containing silicone resin described in JP-A-2008-248169, or at least two epoxides per molecule described in JP-A-2008-19422 Organopolysilsesquioxane resins having functional groups can also be used.

As the siloxane derivative (K), for example, a cyclic siloxane having two or more epoxy groups in the molecule (trade name “X-40-2678” (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name “X-40- 2670” (manufactured by Shin-Etsu Chemical Co., Ltd.) and trade name “X-40-2720” (manufactured by Shin-Etsu Chemical Co., Ltd.).

When the curable epoxy resin composition of the present invention contains the siloxane derivative (K), its content (mixture amount) is not particularly limited, but the total amount of the compound having an epoxy group contained in the curable epoxy resin composition ( 100% by weight), preferably 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight, and particularly preferably 15 to 40% by weight. If the content of the siloxane derivative (K) is less than 5% by weight, the heat resistance and light resistance of the cured product may be insufficient. On the other hand, when the content of the siloxane derivative (K) exceeds 60% by weight, the thermal shock resistance and moisture absorption reflow resistance of the cured product may deteriorate.

Further, when the curable epoxy resin composition of the present invention contains the siloxane derivative (K), the content (blended amount) of the siloxane derivative (K) with respect to 100 parts by weight of the alicyclic epoxy compound (A) is particularly limited. However, it is preferably 1 to 200 parts by weight, more preferably 2 to 180 parts by weight, still more preferably 3 to 150 parts by weight, and particularly preferably 5 to 145 parts by weight. If the content of the siloxane derivative (K) is less than 1 part by weight, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be insufficient. On the other hand, when the content of the siloxane derivative (K) exceeds 200 parts by weight, the thermal shock resistance and moisture absorption reflow resistance of the cured product may deteriorate.

[Additive]
In addition to the above, the curable epoxy resin composition of the present invention may contain various additives as long as they do not impair the effects of the present invention. If a compound having a hydroxy group such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, etc., is included as the additive, the reaction can proceed slowly. In addition, silicone-based or fluorine-based defoaming agents, leveling agents, surfactants, flame retardants, coloring agents, antioxidants, ultraviolet absorbers, ion adsorbents, and pigments are used within the range that does not impair viscosity and transparency. , phosphors (for example, YAG-based phosphor fine particles, inorganic phosphor fine particles such as silicate-based phosphor fine particles, etc.), release agents, and other commonly used additives can be used.

Although the curable epoxy resin composition of the present invention is not particularly limited, it can be prepared by stirring and mixing each of the above components in a heated state if necessary. The curable epoxy resin composition of the present invention can be used as a one-liquid composition in which each component is premixed and used as it is. It can also be used as a multi-liquid system (for example, two-liquid system) composition in which the components are mixed in a predetermined ratio before use. The stirring/mixing method is not particularly limited, and known or commonly used stirring/mixing means such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and rotation-revolution stirrers can be used. Moreover, after stirring and mixing, defoaming may be performed under vacuum.

Although not particularly limited, the rubber particles (B) to be blended in the curable epoxy resin composition of the present invention may be a composition previously dispersed in the alicyclic epoxy compound (A) (this composition is referred to as "rubber particle dispersion (sometimes referred to as "epoxy compound"). That is, the curable epoxy resin composition of the first aspect of the present invention comprises the above rubber particle-dispersed epoxy compound, a silane coupling agent (C) having a thiol group, a triazine-based adhesion agent (D), and if necessary It can be prepared by mixing a curing agent (G), a curing accelerator (H) or a curing catalyst (I), an isocyanuric acid derivative (J), a siloxane derivative (K), and other components. preferable. Further, the curable epoxy resin composition of the second aspect of the present invention comprises the above-mentioned rubber particle-dispersed epoxy compound, a silane coupling agent (C) having a thiol group, a triazine-based adhesion agent (D), and a hydrophobic porous a porous inorganic filler (E), a nonporous filler (F), optionally a curing agent (G) and a curing accelerator (H) or a curing catalyst (I), an isocyanuric acid derivative (J), It is preferably prepared by mixing the siloxane derivative (K) with other components. Such a preparation method can particularly improve the dispersibility of the rubber particles (B) in the curable epoxy resin composition. However, the method of blending the rubber particles (B) is not limited to the above method, and a method of blending it alone may be used.

(Rubber particle-dispersed epoxy compound)
The rubber particle-dispersed epoxy compound is obtained by dispersing the rubber particles (B) in the alicyclic epoxy compound (A). The alicyclic epoxy compound (A) in the rubber particle-dispersed epoxy compound may be the total amount of the alicyclic epoxy compound (A) constituting the curable epoxy resin composition, or a partial amount. There may be. Similarly, the rubber particles (B) in the rubber particle-dispersed epoxy compound may be all or part of the rubber particles (B) constituting the curable epoxy resin composition.

The viscosity of the rubber particle-dispersed epoxy compound can be adjusted, for example, by using a reactive diluent (that is, the rubber particle-dispersed epoxy compound may further contain a reactive diluent). As the reactive diluent, for example, an aliphatic polyglycidyl ether having a viscosity of 200 mPa·s or less at room temperature (25° C.) can be preferably used. Examples of aliphatic polyglycidyl ethers having a viscosity (25° C.) of 200 mPa·s or less include cyclohexanedimethanol diglycidyl ether, cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. , trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, and the like. The amount of the reactive diluent used can be adjusted as appropriate and is not particularly limited.

The method for producing the rubber particle-dispersed epoxy compound is not particularly limited, and a well-known and commonly used method can be used. For example, after dehydrating and drying the rubber particles (B) into powder, it is mixed with the alicyclic epoxy compound (A) and dispersed, or an emulsion of the rubber particles (B) and the alicyclic epoxy compound (A ), followed by dehydration.

The viscosity of the curable epoxy resin composition of the present invention at 25° C. is not particularly limited, but is preferably 60 to 6000 mPa·s, more preferably 100 to 5500 mPa·s, still more preferably 150 to 5000 mPa·s. By setting the viscosity at 25° C. to 60 mPa·s or more, there is a tendency that the workability at the time of casting is improved and the heat resistance of the cured product is further improved. On the other hand, by setting the viscosity at 25° C. to 6000 mPa·s or less, there is a tendency that the workability at the time of casting is improved, and defects due to poor casting tend to be less likely to occur in the cured product. The viscosity of the curable epoxy resin composition of the present invention at 25° C. was measured using a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.) using a rotor: standard 1°34′×R24, Measured under conditions of temperature: 25° C., number of revolutions: 0.5 to 10 rpm.

<Cured product>
By curing the curable epoxy resin composition of the first aspect of the present invention, it has high heat resistance, moisture resistance, and thermal shock resistance, and especially the electrical characteristics of optical semiconductor devices under high temperature and high temperature and high humidity. A cured product that improves thermal shock resistance and moisture absorption reflow resistance (a cured product obtained by curing the curable epoxy resin composition of the first aspect of the present invention is referred to as a “cured product of the first aspect of the present invention” may be obtained).

As means for curing the curable epoxy resin composition of the first aspect of the present invention, known or commonly used means such as heat treatment and light irradiation treatment can be used. The temperature for curing by heating (curing temperature) is not particularly limited, but is preferably 45 to 200.degree. C., more preferably 50 to 190.degree. C., still more preferably 55 to 180.degree. The time for heating during curing (curing time) is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and even more preferably 60 to 480 minutes. When the curing temperature and curing time are lower than the lower limit of the above range, the curing becomes insufficient. The curing conditions depend on various conditions, but can be adjusted as appropriate by, for example, shortening the curing time when the curing temperature is raised and lengthening the curing time when the curing temperature is lowered. Moreover, curing can be carried out in one step or in multiple steps of two or more steps.

In addition, by curing the curable epoxy resin composition of the second aspect of the present invention, it has high heat resistance, moisture resistance, and thermal shock resistance. A cured product having an excellent antireflection function while improving properties, thermal shock resistance, and moisture absorption reflow resistance (a cured product obtained by curing the curable epoxy resin composition of the second aspect of the present invention is referred to as "this may be referred to as a "cured product of the second aspect of the invention") can be obtained.
In the cured product of the second aspect of the present invention, the hydrophobic porous inorganic filler (E) is uniformly dispersed throughout the entire cured product of the second aspect of the present invention, and as a result of stabilizing the dispersed state, curing The hydrophobic porous inorganic filler (E) present on the surface of the object forms irregularities and scatters incident light, thereby exerting an antireflection function. In addition, the porous structure on the surface of the hydrophobic porous inorganic filler (E) can also scatter incident light, further improving the antireflection function.

The method for uniformly spreading the hydrophobic porous inorganic filler (E) over the entire cured product of the second aspect of the present invention is not particularly limited. A method of preparing, uniformly dispersing the hydrophobic porous inorganic filler (E), and then curing. In order to efficiently produce the cured product of the second aspect of the present invention, a method of uniformly dispersing the hydrophobic porous inorganic filler (E) and then curing is preferred.
One aspect of the method for producing a cured product according to the second aspect of the present invention will be described below, but the present invention is not limited thereto.

The hydrophobic porous inorganic filler (E) and the nonporous filler (F) are added to the curable epoxy resin composition of the first aspect of the present invention, and the mixture can be uniformly dispersed by mixing and stirring. . The mixing/stirring method is not particularly limited, and known or commonly used stirring and mixing means such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and rotation-revolution stirrers can be used. Moreover, after stirring and mixing, defoaming may be performed under reduced pressure or vacuum.

Although the properties of the curable epoxy resin composition of the second aspect of the present invention before curing are not particularly limited, it is preferably liquid. The resin composition before curing that forms the cured product of the second aspect of the present invention can exhibit an antireflection function by adding a small amount by using the hydrophobic porous inorganic filler (E). It is preferable because it easily becomes liquid without using a solvent.

The cured product of the second aspect of the present invention can be obtained by curing the resin composition in which the hydrophobic porous inorganic filler (E) and the nonporous filler (F) are uniformly dispersed.
The amount of components volatilized during curing is not particularly limited to the total amount (100% by weight) of the resin composition before curing, but is preferably 10% by weight or less, more preferably 8% by weight or less, and further Preferably, it is 5% by weight or less. When the amount of components volatilized during curing is 10% by weight or less, the dimensional stability of the cured product is increased, which is preferable. The curable epoxy resin composition of the second aspect of the present invention before curing can exhibit an antireflection function by adding a small amount by using the hydrophobic porous inorganic filler (E). ) can be easily liquidized without using the volatile components, and the amount of components volatilized during curing can be reduced.

As curing means, known or commonly used means such as heat treatment and light irradiation treatment can be used. The temperature for curing by heating (curing temperature) is not particularly limited, but is preferably 45 to 200.degree. C., more preferably 50 to 190.degree. C., still more preferably 55 to 180.degree. The time for heating during curing (curing time) is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and even more preferably 60 to 480 minutes. When the curing temperature and curing time are lower than the lower limit of the above range, the curing becomes insufficient. The curing conditions depend on various conditions, but can be adjusted as appropriate by, for example, shortening the curing time when the curing temperature is raised and lengthening the curing time when the curing temperature is lowered. Moreover, curing can be carried out in one step or in multiple steps of two or more steps.
In the case of curing by light irradiation, for example, light (radiation) including i-line (365 nm), h-line (405 nm), g-line (436 nm), etc. is irradiated at an illuminance of 10 to 1200 mW/cm ² . The antireflection material of the present invention can be obtained by irradiation with a light amount of 20 to 2500 mJ/cm ² . From the viewpoint of suppressing deterioration of the cured product due to radiation and from the viewpoint of productivity, the irradiation light amount is preferably 20 to 600 mJ/cm ² , more preferably 20 to 300 mJ/cm ² . For irradiation, a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a laser beam, or the like can be used as an irradiation source.

<Resin composition for optical semiconductor encapsulation>
The curable epoxy resin composition of the first aspect of the present invention is a resin composition for encapsulating an optical semiconductor element in an optical semiconductor device, that is, an optical semiconductor encapsulating resin composition (an optical semiconductor element in an optical semiconductor device). can be preferably used as a sealant). By using the curable epoxy resin composition of the first aspect of the present invention as a resin composition for optical semiconductor encapsulation, an optical semiconductor element is sealed with a cured product having high heat resistance, moisture resistance, and excellent thermal shock resistance. An optical semiconductor device (sometimes referred to as "an optical semiconductor device according to the first aspect of the present invention") is obtained. Moreover, the curable epoxy resin composition of the second aspect of the present invention can be preferably used as a resin composition for encapsulating an optical semiconductor element in an optical semiconductor device, that is, as an optical semiconductor encapsulating resin composition. By using the curable epoxy resin composition of the second aspect of the present invention as a resin composition for encapsulating optical semiconductors, optical semiconductors can be obtained from cured products having high heat resistance, moisture resistance, thermal shock resistance, and excellent antireflection performance. An optical semiconductor device in which the element is encapsulated (sometimes referred to as "an optical semiconductor device according to the second aspect of the present invention") is obtained.
The optical semiconductor device of the first aspect of the present invention is excellent in electrical conduction characteristics and moisture absorption reflow resistance at high temperatures, such as less reduction in luminous intensity even when subjected to thermal shock or high temperature heat. Excellent properties and high durability. Moreover, the optical semiconductor device of the second aspect of the present invention further has an excellent antireflection function while maintaining the above durability.

<Optical semiconductor device>
The optical semiconductor device of the first aspect or the second aspect 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 encapsulating an optical semiconductor) of the present invention. is. The encapsulation of the optical semiconductor element can be performed, for example, by injecting the curable epoxy resin composition prepared by the method described above into a predetermined mold and heating and curing under predetermined conditions. As a result, an optical semiconductor device in which the optical semiconductor element is sealed with the cured product of the curable epoxy resin composition is obtained. The curing temperature and curing time can be appropriately set within the same ranges as in the preparation of the cured product.

The curable epoxy resin composition of the present invention is not limited to the sealing applications of the optical semiconductor elements described above. 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.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. "-" in Tables 1 and 2 means that the component was not blended. Moreover, the unit of the amount (proportion) of the components shown in Tables 1 and 2 is parts by weight. Examples 1 to 10 are described as reference examples.

Production example 1
(Production of rubber particles)
500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were placed in a 1 L polymerization vessel equipped with a reflux condenser, and the temperature was raised to 80° C. while stirring under a nitrogen stream. A monomer mixture consisting of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion of the rubber particles. was added all at once and emulsified by stirring for 20 minutes, then 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour to perform initial seed polymerization. Subsequently, 180.5 mg of potassium peroxodisulfate was added and stirred for 5 minutes. 0.95 g of sodium dioctyl sulfosuccinate to the remainder (about 95% by weight) required to form the core portion of 180.5 g of butyl acrylate, 48.89 g of styrene, and 7.33 g of divinylbenzene. was continuously added over 2 hours to carry out a second seed polymerization, followed by aging for 1 hour to obtain a core portion.
Then, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. A seed polymerization was carried out by continuously adding the polymer mixture over a period of 30 minutes. After that, it was aged for 1 hour to form a shell layer covering the core portion.
Then, the mixture was cooled to room temperature (25° C.) and filtered through a plastic mesh with an opening of 120 μm to obtain a latex containing rubber particles having a core-shell structure. The resulting latex was frozen at minus 30°C, dehydrated and washed with a suction filter, and then air-dried at 60°C for a whole day and night to obtain rubber particles. The obtained rubber particles had an average particle size of 254 nm and a maximum particle size of 486 nm.

The average particle diameter and the maximum particle diameter of the rubber particles were measured using a ^Nanotrac particle size distribution analyzer (trade name: UPA-EX150, Nikkiso Co., Ltd. ) is used to measure the sample, and in the obtained particle size distribution curve, the cumulative average diameter, which is the particle diameter at the time when the cumulative curve reaches 50%, is the average particle diameter, and the frequency (%) of the particle size distribution measurement results is 0 The maximum particle size at the time when the content exceeded 0.00% was defined as the maximum particle size. As the sample, 1 part by weight of the rubber particle-dispersed epoxy compound obtained in Production Example 10 below was dispersed in 20 parts by weight of tetrahydrofuran.

Production example 2
(Production of rubber particle-dispersed epoxy compound)
The rubber particles obtained in Production Example 1 were heated to 60° C. under a nitrogen stream at the respective compounding ratios shown in Tables 1 and 2, and then dissolved using a dissolver under the trade name of “Celoxide 2021P” (manufactured by Co., Ltd.). Daicel) (1000 rpm, 60 minutes) and vacuum defoamed to obtain a rubber particle-dispersed epoxy compound.

Production example 3
(Production of curing agent composition)
Curing agent (trade name “Rikashid MH-700”, manufactured by Shin Nippon Rika Co., Ltd.) 100 parts by weight, curing accelerator (trade name “U-CAT 18X”, manufactured by San-Apro Co., Ltd.) 0.5 parts by weight, ethylene 1 part by weight of glycol (manufactured by Wako Pure Chemical Industries, Ltd.) is uniformly mixed using a rotation-revolution stirring device (trade name "Awatori Mixer AR-250", manufactured by Thinky Co., Ltd., hereinafter the same). and defoamed to obtain a curing agent composition (sometimes referred to as "K agent").

Example 1
100 parts by weight of the rubber particle-dispersed epoxy compound obtained in Production Example 2 (containing 90 parts by weight of celoxide 2021P and 10 parts by weight of rubber particles), 101.5 parts by weight of the curing agent composition obtained in Production Example 3, A silane coupling agent having a thiol group (trade name “KBM-803”, 3-mercaptopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight, and a triazine-based adhesion agent (trade name “VD-3” , manufactured by Shikoku Kasei Kogyo Co., Ltd.) were uniformly mixed using a rotation-revolution stirrer and defoamed to obtain a curable epoxy resin composition.
Furthermore, after casting the curable epoxy resin composition obtained above into the optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. By heating for 5 hours, an optical semiconductor device in which an optical semiconductor element was sealed with a cured product of the 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 (sealant).

Examples 2-5; Comparative Examples 1-4
Each curable epoxy resin composition was prepared 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, and an optical semiconductor device was produced. In Example 5, a rubber particle-dispersed epoxy compound containing 70 parts by weight of celoxide 2021P and 30 parts by weight of rubber particles was used, and in Comparative Examples 2 and 3, celoxide 2021P was used instead of the rubber particle-dispersed epoxy compound. used.

Example 6
100 parts by weight of the rubber particle-dispersed epoxy compound (containing 90 parts by weight of Celoxide 2021P and 10 parts by weight of rubber particles) obtained in Production Example 2, and a curing catalyst (trade name "San-Aid SI-100L", Sanshin Chemical Industry ( Co., Ltd.) 0.5 parts by weight, a silane coupling agent having a thiol group (trade name “KBM-803”, 3-mercaptopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight, and triazine System adhesion agent (trade name “VD-3”, manufactured by Shikoku Kasei Co., Ltd.) 0.5 parts by weight is uniformly mixed using a rotation-revolution stirring device, defoamed, and a curable epoxy resin. A composition was obtained. Further, an optical semiconductor device was produced in the same manner as in Example 1.

Examples 7-10; Comparative Examples 5-8
Each curable epoxy resin composition was prepared in the same manner as in Example 6, except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 1, and an optical semiconductor device was produced. In Example 10, a rubber particle-dispersed epoxy compound containing 70 parts by weight of celoxide 2021P and 30 parts by weight of rubber particles was used, and in Comparative Examples 6 and 8, celoxide 2021P was used instead of the rubber particle-dispersed epoxy compound. used.

<Evaluation>
The optical semiconductor devices obtained in Examples 1 to 10 and Comparative Examples 1 to 8 were subjected to the following evaluation tests.

[Electricity test]
The total luminous flux of each optical semiconductor device obtained in Examples 1 to 10 and Comparative Examples 1 to 8 was measured with a total luminous flux measuring instrument, and this was defined as "the total luminous flux at time 0". After that, this optical semiconductor device was subjected to the following two types of tests: a heat resistance test and a heat and moisture resistance test.
・Heat resistance test For the optical semiconductor device after measuring the total luminous flux for 0 hours, a current of 30 mA was applied for 100 hours in a constant temperature chamber at 85 ° C., and then the total luminous flux was measured again. total luminous flux”. Then, the luminous intensity retention rate after the heat resistance test was calculated from the following equation. The luminous intensity retention rate of two optical semiconductor devices was measured for each curable epoxy resin composition, and the average value was calculated (that is, N=2). The results are shown in the column of "Luminous intensity retention after heat resistance test [%]" in Table 1.
{Brightness retention after heat resistance test (%)}
= {Total luminous flux after heat resistance test (lm)} / {Total luminous flux at 0 hour (lm)} x 100
・Heat and humidity resistance test For the optical semiconductor device after measuring the total luminous flux for 0 hours, a current of 20 mA is passed for 100 hours in a constant temperature and humidity chamber at 60 ° C. and 90% RH, and then the total luminous flux is measured again, This was taken as "the total luminous flux after the heat and humidity resistance test". Then, the luminous intensity retention after the heat and humidity resistance test was calculated from the following equation. The luminous intensity retention rate of two optical semiconductor devices was measured for each curable epoxy resin composition, and the average value was calculated (that is, N=2). The results are shown in the column of "Luminous intensity retention [%] after heat and humidity resistance test" in Table 1.
{Brightness retention after heat and humidity resistance test (%)}
= {Total luminous flux (lm) after heat and humidity resistance test} / {Total luminous flux (lm) at 0 hour} x 100

[Thermal shock test]
Each optical semiconductor device obtained in Examples 1 to 10 and Comparative Examples 1 to 8 (5 pieces were used for each curable epoxy resin composition) was exposed to an atmosphere of −40° C. for 30 minutes, followed by Then, 200 cycles of thermal shock were applied using a thermal shock tester, with one cycle of exposure to an atmosphere of 120° C. for 30 minutes. After that, the length of cracks generated in the cured product in the optical semiconductor device was observed using a digital microscope (trade name "VHX-900", manufactured by Keyence Corporation), and cured out of the five optical semiconductor devices. The number of optical semiconductor devices in which a crack having a length of 90 μm or longer was generated was counted. The results are shown in the column of "thermal shock test [number of cracks]" in Table 1.

[Solder heat resistance test]
Each optical semiconductor device obtained in Examples 1 to 10 and Comparative Examples 1 to 8 (5 pieces were used for each curable epoxy resin composition) was allowed to stand under the conditions of 30° C. and 60% RH for 192 hours. and moisture absorption treatment. Then, the optical semiconductor device was placed in a reflow furnace and heat-treated under the following heating conditions. After that, the above optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then placed in the reflow furnace again and heat-treated under the same conditions. That is, in the solder heat resistance test, the optical semiconductor device was subjected to two heat histories under the following heating conditions.
[Heating conditions (based on surface temperature of optical semiconductor device)]
(1) Preheating: 60 to 120 seconds at 150 to 190°C (2) Main heating after preheating: 60 to 150 seconds at 217°C or higher, maximum temperature 260°C
However, the rate of temperature increase during transition from preheating to main heating was controlled to 3° C./sec at maximum.
FIG. 2 shows an example of the surface temperature profile of the optical semiconductor device during heating by the reflow furnace (temperature profile in one of the two heat treatments).
After that, the optical semiconductor device was observed using a digital microscope (trade name "VHX-900", manufactured by Keyence Corporation) to determine whether cracks with a length of 90 μm or more occurred in the cured product, and It was evaluated whether or not electrode detachment (detachment of the cured product from the electrode surface) occurred. Of the five optical semiconductor devices, the number of optical semiconductor devices in which cracks with a length of 90 μm or more occurred 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.

[PCT test (pressure cooker test)]
Each optical semiconductor device obtained in Examples 1 to 10 and Comparative Examples 1 to 8 (5 pieces were used for each curable epoxy resin composition) was subjected to a constant temperature and humidity constant pressure of 121 ° C., 100% RH, and 2 atm. It was stored in a tank (highly accelerated life test equipment) for 2 hours. Next, after removing the optical semiconductor device from the constant temperature, humidity and constant pressure chamber, the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), and the cured product was provided with an electrode. It was evaluated whether or not peeling (peeling of the cured product from the electrode surface) occurred. The number of optical semiconductor devices in which electrode peeling occurred in the cured product among the five optical semiconductor devices is shown in the column of "PCT test [number of electrode peelings]" in Table 1.

[Comprehensive judgment]
As a result of each test, when all of the following (1) to (6) were satisfied, it was judged as ◯ (good). On the other hand, when any one of the following (1) to (6) was not satisfied, it was determined as x (defective).
(1) Electricity test: luminous intensity retention after heat resistance test is 80% or more (2) Electricity test: luminous intensity retention is 80% or more after heat and humidity resistance test (3) Thermal shock test: length of cured product is 90 μm or more The number of optical semiconductor devices with cracks is 0 (4) Soldering heat resistance test: The number of optical semiconductor devices with cracks of 90 μm or more in the cured product is 0 (5) Soldering heat resistance test: The number of optical semiconductor devices in which electrode peeling occurred was 0 (6) PCT test: The number of optical semiconductor devices in which electrode peeling occurred was 0 The results are shown in Table 1, "Comprehensive Judgment" column.

Example 11
100 parts by weight of the rubber particle-dispersed epoxy compound obtained in Production Example 2 (containing 90 parts by weight of celoxide 2021P and 10 parts by weight of rubber particles), 101.5 parts by weight of the curing agent composition obtained in Production Example 3, A silane coupling agent having a thiol group (trade name “KBM-803”, 3-mercaptopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight, and a triazine-based adhesion agent (trade name “VD-3” , manufactured by Shikoku Kasei Kogyo Co., Ltd.) were uniformly mixed using a rotation-revolution stirrer and defoamed to obtain a curable epoxy resin composition.
The total amount of the curable epoxy resin composition obtained above, 50 parts by weight of a hydrophobic porous inorganic filler (trade name “Silophobic 702”, manufactured by Fuji Silysia Chemical Co., Ltd.), and a nonporous filler (trade name FB-970FD (manufactured by Denki Kagaku Kogyo Co., Ltd.) was mixed with 200 parts by weight using a rotation-revolution stirrer and defoamed to obtain a curable epoxy resin composition. After casting into a semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm), by heating in a resin curing oven at 120 ° C. for 5 hours, the cured product of the above curable epoxy resin composition forms an optical semiconductor element. An optical semiconductor device was obtained in which the was sealed. In FIG. 1, the hydrophobic porous inorganic fillers are uniformly dispersed over the entire sealing material 104, and the hydrophobic porous inorganic fillers present on the upper surface thereof form a uniform and fine irregular shape. (The uneven shape is not shown).

Examples 12-17, Comparative Examples 9-15
Table 2 shows the compositions of the curable epoxy resin composition, the hydrophobic porous inorganic filler, the nonporous filler, and the non-hydrophobicized porous inorganic filler (trade name “Silysia 430”, manufactured by Fuji Silysia Chemical Co., Ltd.). Each curable epoxy resin composition was prepared and an optical semiconductor device was produced in the same manner as in Example 11, except that the composition was changed to that shown in . For Example 15, a rubber particle dispersed epoxy compound containing 45 parts by weight of celoxide 2021P and 10 parts by weight of rubber particles was used, and for Examples 16 and 17, 80 parts by weight of celoxide 2021P and 10 parts by weight of rubber were used. A rubber particle-dispersed epoxy compound containing particles was used, and in Comparative Examples 11, 12 and 14, Celoxide 2021P was used instead of the rubber particle-dispersed epoxy compound.

<Evaluation>
The optical semiconductor devices obtained in Examples 11 to 17 and Comparative Examples 9 to 15 were subjected to the following evaluation tests.

[Reflection of fluorescent light]
When the top surface of each optical semiconductor device obtained in Examples 11 to 17 and Comparative Examples 9 to 15 (the top surface of the sealing material 104 in FIG. 1) was illuminated with a fluorescent lamp and the reflection was observed, the antireflection material The vividness of the fluorescent lamp reflected in the image was visually evaluated on a two-grade scale. The results are shown in the column of "Fluorescent lamp reflection [visual observation]" in Table 2.
The case where the outline of the fluorescent lamp could not be recognized was evaluated as ◯, and the case where the outline could be recognized as ×.

[Electricity test]
The total luminous flux of each optical semiconductor device obtained in Examples 11 to 17 and Comparative Examples 9 to 15 was measured with a total luminous flux measuring instrument, and this was defined as "the total luminous flux at time 0". After that, this optical semiconductor device was subjected to the following two types of tests: a heat resistance test and a heat and moisture resistance test.
・Heat resistance test For the optical semiconductor device after measuring the total luminous flux for 0 hours, a current of 30 mA was applied for 100 hours in a constant temperature chamber at 85 ° C., and then the total luminous flux was measured again. total luminous flux”. Then, the luminous intensity retention rate after the heat resistance test was calculated from the following equation. The luminous intensity retention rate of two optical semiconductor devices was measured for each curable epoxy resin composition, and the average value was calculated (that is, N=2). The results are shown in the column of "Luminous intensity retention after heat resistance test [%]" in Table 2.
{Brightness retention after heat resistance test (%)}
= {Total luminous flux after heat resistance test (lm)} / {Total luminous flux at 0 hour (lm)} x 100
・Heat and humidity resistance test For the optical semiconductor device after measuring the total luminous flux for 0 hours, a current of 20 mA is passed for 100 hours in a constant temperature and humidity chamber at 60 ° C. and 90% RH, and then the total luminous flux is measured again, This was taken as "the total luminous flux after the heat and humidity resistance test". Then, the luminous intensity retention after the heat and humidity resistance test was calculated from the following equation. The luminous intensity retention rate of two optical semiconductor devices was measured for each curable epoxy resin composition, and the average value was calculated (that is, N=2). The results are shown in the column of "Luminous intensity retention [%] after heat and humidity resistance test" in Table 2.
{Brightness retention after heat and humidity resistance test (%)}
= {Total luminous flux (lm) after heat and humidity resistance test} / {Total luminous flux (lm) at 0 hour} x 100

[Thermal shock test]
Each optical semiconductor device obtained in Examples 11 to 17 and Comparative Examples 9 to 15 (5 pieces were used for each curable epoxy resin composition) was exposed to an atmosphere of −65° C. for 30 minutes, followed by Then, 200 cycles of thermal shock were applied using a thermal shock tester, with one cycle of exposure to an atmosphere of 150° C. for 30 minutes. After that, the length of cracks generated in the cured product in the optical semiconductor device was observed using a digital microscope (trade name "VHX-900", manufactured by Keyence Corporation), and cured out of the five optical semiconductor devices. The number of optical semiconductor devices in which a crack having a length of 90 μm or longer was generated was counted. The results are shown in the column of "thermal shock test [number of cracks]" in Table 2.

[Solder heat resistance test]
Each optical semiconductor device obtained in Examples 11 to 17 and Comparative Examples 9 to 15 (5 pieces were used for each curable epoxy resin composition) was allowed to stand under the conditions of 30° C. and 60% RH for 192 hours. and moisture absorption treatment. Then, the optical semiconductor device was placed in a reflow furnace and heat-treated under the following heating conditions. After that, the above optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then placed in the reflow furnace again and heat-treated under the same conditions. That is, in the solder heat resistance test, the optical semiconductor device was subjected to two heat histories under the following heating conditions.
[Heating conditions (based on surface temperature of optical semiconductor device)]
(1) Preheating: 60 to 120 seconds at 150 to 190°C (2) Main heating after preheating: 60 to 150 seconds at 217°C or higher, maximum temperature 260°C
However, the rate of temperature increase during transition from preheating to main heating was controlled to 3° C./sec at maximum.
FIG. 2 shows an example of the surface temperature profile of the optical semiconductor device during heating by the reflow furnace (temperature profile in one of the two heat treatments).
After that, the optical semiconductor device was observed using a digital microscope (trade name "VHX-900", manufactured by Keyence Corporation) to determine whether cracks with a length of 90 μm or more occurred in the cured product, and It was evaluated whether or not electrode detachment (detachment of the cured product from the electrode surface) occurred. Of the five optical semiconductor devices, the number of optical semiconductor devices in which cracks with a length of 90 μm or more occurred in the cured product is shown in the column of “solder heat resistance test [number of cracks]” in Table 2, and electrode peeling occurred. The number of optical semiconductor devices is shown in the column of "solder heat resistance test [number of electrode peeling]" in Table 2.

[PCT test (pressure cooker test)]
Each optical semiconductor device obtained in Examples 11 to 17 and Comparative Examples 9 to 15 (5 pieces were used for each curable epoxy resin composition) was subjected to constant temperature and humidity constant pressure of 121 ° C., 100% RH, and 2 atm. It was stored in a tank (highly accelerated life test equipment) for 40 hours. Next, after removing the optical semiconductor device from the constant temperature, humidity and constant pressure chamber, the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), and the cured product was provided with an electrode. It was evaluated whether or not peeling (peeling of the cured product from the electrode surface) occurred. The number of optical semiconductor devices in which electrode peeling occurred in the cured product among the five optical semiconductor devices is shown in the column of "PCT test [number of electrode peelings]" in Table 2.

[Comprehensive judgment]
As a result of each test, when all of the following (1) to (7) were satisfied, it was judged as ◯ (good). On the other hand, when any one of the following (1) to (7) was not satisfied, it was determined as x (defective).
(1) Reflection of fluorescent lamp: ◯ indicates reflection of fluorescent lamp.
(2) Current test: 90% or more luminous intensity retention after heat resistance test (3) Current test: 90% or more luminous intensity retention after heat and humidity resistance test (4) Thermal shock test: Cured product has a length of 90 μm or more The number of optical semiconductor devices with cracks is 0 (5) Soldering heat resistance test: The number of optical semiconductor devices with cracks having a length of 90 μm or more in the cured product is 0 (6) Soldering heat resistance test: 0 optical semiconductor devices with electrode peeling (7) PCT test: 0 optical semiconductor devices with electrode peeling

The components used in Examples and Comparative Examples are as follows.
[Alicyclic epoxy compound (A)]
Celoxide 2021P: trade name "Celoxide 2021P" [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate], manufactured by Daicel Corporation EHPE3150: trade name "EHPE3150" [2,2-bis(hydroxymethyl )-1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 1-butanol], manufactured by Daicel Corporation [siloxane derivative (K)]
X-40-2670: trade name “X-40-2670” [siloxane derivative having four epoxy groups in the molecule], manufactured by Shin-Etsu Chemical Co., Ltd. [isocyanuric acid derivative (J)]
MA-DGIC: trade name "MA-DGIC" [monoallyl diglycidyl isocyanurate], manufactured by Shikoku Chemical Industry Co., Ltd. [silane coupling agent having a thiol group (C)]
KBM-803: trade name "KBM-803" [3-mercaptopropyltrimethoxysilane], manufactured by Shin-Etsu Chemical Co., Ltd. [triazine-based adhesion agent (D)]
VD-3: trade name "VD-3", manufactured by Shikoku Chemical Industry Co., Ltd. VD-4: trade name "VD-4" manufactured by Shikoku Chemical Industry Co., Ltd. VD-5: trade name "VD-5", Made by Shikoku Kasei Co., Ltd. [Epoxy curing agent]
MH-700: Product name “Likacid MH-700” [curing agent (G): 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride = 70/30], manufactured by Shin Nippon Chemical Co., Ltd. 18X: Product name “ U-CAT 18X” [curing accelerator (H)], manufactured by San-Apro Co., Ltd. Ethylene glycol: manufactured by Wako Pure Chemical Industries, Ltd. [curing catalyst]
SI-100L: trade name “San-Aid SI-100L” [curing catalyst (I)], manufactured by Sanshin Chemical Industry Co., Ltd. [hydrophobic porous inorganic filler (E)]
Cyrophobic 702: trade name “Cylophobic 702” [Porous silica filler hydrophobically treated with polydimethylsiloxane, volume average particle size: 4.1 μm; Porous silica filler before hydrophobic surface treatment specific surface area: 350 m ² /g; oil absorption: 170 mL/100 g], manufactured by Fuji Silysia Chemical Ltd.,
[Porous inorganic filler]
Silysia 430: Trade name “Silysia 430” [porous silica filler not subjected to hydrophobic surface treatment, volume average particle size: 4.1 μm; specific surface area: 350 m ² /g; average pore size: 17 nm; pore volume: 1 .25 mL / g; oil absorption: 230 mL / 100 g], Fuji Silysia Chemical Co., Ltd. [nonporous filler (F)]
FB-970FD: Trade name “FB-970FD” [nonporous silica filler, volume average particle size: 16.7 μm; specific surface area: 2.0 m ² /g], manufactured by Denki Kagaku Kogyo Co., Ltd.

Test equipment ・Resin curing oven Espec Co., Ltd. GPHH-201
・Constant temperature bath Small high temperature chamber ST-120B1 manufactured by Espec Co., Ltd.
・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 oven UNI-5016F manufactured by Nippon Antom Co., Ltd.
・Constant temperature, humidity, and pressure chamber Small environmental tester SH-641 manufactured by ESPEC Co., Ltd.
・Highly accelerated life test equipment (for PCT test)
Highly accelerated life test device EHS-411M manufactured by Espec Co., Ltd.

100: Reflector (resin composition for light reflection)
101: Metal wiring 102: Optical semiconductor element 103: Bonding wire 104: Cured product (sealant)

Claims (12)

An alicyclic epoxy compound (A), rubber particles (B), a silane coupling agent having a thiol group (C), a triazine-based adhesion agent (D), a hydrophobic porous inorganic filler (E), and an inorganic nonporous filler (F1) ,
The inorganic nonporous filler (F1) includes inorganic glass, silica, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, silicon nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, From zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, forsterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nephelinesinite, cristobalite, wollastonite, diatomaceous earth, and talc A curable epoxy resin composition comprising at least one selected from the group consisting of : The curable epoxy resin composition according to claim 1 , further comprising a curing agent (G) and a curing accelerator (H). The curable epoxy resin composition according to Claim 1 , further comprising a curing catalyst (I). The triazine-based adhesion agent (D) is represented by the following formula (1)

[In formula (1), Y represents a single bond or a linking group. R ¹ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R ² and R ³ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a methoxy group. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, or a group represented by -SiR ⁵ _s (OR ⁶ ) _3-s . R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. r represents an integer from 0 to 16; s represents an integer from 0 to 3; ]
The curable epoxy resin composition according to any one of claims 1 to 3 , which is a compound represented by The curable epoxy resin composition according to any one of claims 1 to 4 , wherein the alicyclic epoxy compound (A) is a compound having a cyclohexene oxide group. The alicyclic epoxy compound (A) has the following formula (I-1)

The curable epoxy resin composition according to any one of claims 1 to 5 , which is a compound represented by The curable epoxy resin composition according to any one of claims 1 to 6 , further comprising an isocyanuric acid derivative (J) having one or more oxirane rings in the molecule. An isocyanuric acid derivative (J) having one or more oxirane rings in the molecule is represented by the following formula (2-1)

[In formula (2-1), R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
The curable epoxy resin composition according to claim 7 , which is a compound represented by: The curable epoxy resin composition according to any one of claims 1 to 8, further comprising a siloxane derivative (K) having two or more epoxy groups in the molecule. A cured product of the curable epoxy resin composition according to any one of claims 1 to 9 . The curable epoxy resin composition according to any one of claims 1 to 9 , which is a resin composition for optical semiconductor encapsulation. 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 11 .

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