WO2019124476A1

WO2019124476A1 - Curable epoxy resin composition, cured product thereof, and optical semiconductor device

Info

Publication number: WO2019124476A1
Application number: PCT/JP2018/046899
Authority: WO
Inventors: 鈴木弘世
Original assignee: 株式会社ダイセル
Priority date: 2017-12-21
Filing date: 2018-12-20
Publication date: 2019-06-27
Also published as: TW201930390A

Abstract

The purpose of the present invention is to provide a curable epoxy resin composition capable of producing a cured product which is suitable for compression molding and has high light reflectivity, excellent heat resistance and light resistance, and excellent toughness and crack resistance, and in which the light reflectivity does not significantly decrease over time. The present invention provides: a curable epoxy resin composition containing an alicyclic epoxy compound (A) represented by formula (I) [in the formula, R^1a-R^18a are identical or different and represent hydrogen atoms, halogen atoms, hydrocarbon groups that may have oxygen atoms or halogen atoms, or alkoxy groups that may have substituents], a monoallyl diglycidyl isocyanurate compound (B) represented by formula (1) [in the formula, R¹-R² represent hydrogen atoms or C1-C8 alkyl groups], a white pigment (C), a curing agent (D), and a curing accelerator (F); a cured product of the curable epoxy resin composition; and an optical semiconductor device including a reflector made of the cured product.

Description

Curable epoxy resin composition, cured product thereof, and optical semiconductor device

The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, a curable resin composition for light reflection comprising the curable epoxy resin composition, and an optical semiconductor element The present invention relates to an optical semiconductor device including at least a reflector made of the cured product. Priority is claimed on Japanese Patent Application No. 2017-245102, filed Dec. 21, 2017, the content of which is incorporated herein by reference.

In recent years, in various indoor or outdoor display boards, light sources for image reading, traffic signals, units for large displays, etc., adoption of light emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources is in progress . Such a light emitting device generally includes an optical semiconductor device and a transparent resin for protecting the periphery of the optical semiconductor device, and further, to enhance the extraction efficiency of light emitted from the optical semiconductor device, light A light emitting device having a reflector (reflecting material) for reflecting light is widely used.

The reflector is required to have high light reflectivity, and to continuously exert such high light reflectivity. Conventionally, as a constituent material of the above-mentioned reflector, a resin composition etc. which made an inorganic filler etc. disperse in a polyamide resin (polyphthalamide resin) which makes a terephthalic acid unit an essential constitutional unit are known (patent document 1 to 3).

In addition, as a component of the above-mentioned reflector, a thermosetting resin composition for light reflection, which further contains a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0 in a specific ratio A thing is known (refer to patent documents 4). Furthermore, it contains a thermosetting resin component and one or more filler components, and the difference between the refractive index of the entire thermosetting resin component and the refractive index of each filler component, and the volume ratio of each filler component There is known a thermosetting resin composition for light reflection in which the calculated parameter is controlled within a specific range (see Patent Document 5). In addition, a curable resin composition for light reflection in which a monoallyl diglycidyl isocyanurate compound and a white pigment are mixed with an alicyclic epoxy compound is known (see Patent Document 6).

Japanese Patent Laid-Open No. 2000-204244 Unexamined-Japanese-Patent No. 2004-75994 JP, 2006-257314, A Unexamined-Japanese-Patent No. 2010-235753 JP, 2010-235756, A International Publication WO 2013/008680 Brochure

However, the reflectors made of the above polyamide resins described in Patent Documents 1 to 3 are particularly light emitting devices using high-power blue light semiconductors and white light semiconductors as light sources, and are aged over time by light and heat emitted from the light semiconductor elements. It has been deteriorated by yellowing and has a problem that sufficient light reflectivity can not be maintained. Furthermore, while the heating temperature in the reflow process (solder reflow process) at the time of manufacturing the light emitting device tends to be higher along with the adoption of lead-free solder, the reflector is aged over time by the heat applied in such a manufacturing process. And the light reflectivity is reduced.

Moreover, in the reflector which consists of a hardened | cured material of the thermosetting resin composition for light reflections of the patent documents 4 and 5, tris glycidyl isocyanurate is used as a main component of the said thermosetting resin, and heat resistance is This is not sufficient, and the problem arises that the light reflectivity decreases with time due to the heat generated from the optical semiconductor element and the heat in the reflow process. In the reflector formed of a cured product of the curable resin composition for light reflection described in Patent Document 6, although the heat resistance is improved more than Patent Documents 1 to 5, with the increase in output of the optical semiconductor device, There has been a problem that the light reflectivity is lowered by the use for a long time at high temperature.

In addition, the reflector is generally manufactured by subjecting a material (resin composition) for forming the reflector to transfer molding or compression molding. However, since many resin compositions for forming a conventional reflector are suitable for transfer molding, the reflector formed from the resin composition is excellent in heat resistance, but the reflector formed by compression molding has heat resistance. Many were relatively inferior.

Furthermore, when stress is applied to the above-mentioned reflector due to cutting or temperature change (for example, heating at a very high temperature such as a reflow process, cooling cycle, etc.) in addition to the above heat resistance and light resistance. In addition, it is required to be tough, such as being hard to cause cracks (such characteristics may be referred to as “crack resistance”). When the reflector is cracked, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), which makes it difficult to secure the reliability of the light emitting device. In the reflector which consists of hardened | cured material of the curable resin composition for light reflections of patent document 6, there existed a problem of being easy to produce a crack by a cold temperature cycle etc.

Therefore, it is possible to form a reflector suitable for compression molding without causing problems such as deterioration or cracking even with high output, short wavelength light, high temperature, cold temperature cycle, etc., and light reflectivity is unlikely to decrease with time. At present, there is a demand for a material which is excellent in heat resistance and light resistance, and is also tough and excellent in crack resistance.

Therefore, an object of the present invention is that it is suitable for compression molding, has high light reflectivity, is excellent in heat resistance and light resistance, is also tough and excellent in crack resistance, and is hard to be deteriorated in light reflectivity over time It is providing the curable epoxy resin composition which gives a thing.
In addition, another object of the present invention is to have high light reflectivity obtained by curing the above curable epoxy resin composition, to be excellent in heat resistance and light resistance, and also to be tough and excellent in crack resistance, to reflect light. It is an object of the present invention to provide a cured product which is less likely to deteriorate with time.
Another object of the present invention is to provide a curable resin composition for light reflection which can provide an optical semiconductor device in which the decrease in luminance of light with time is suppressed.
Another object of the present invention is to provide a highly reliable optical semiconductor device in which the luminance of light is unlikely to decrease with time.

As a result of intensive studies to solve the above problems, the present inventor contains a specific alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, and a white pigment as essential components, and further a curing agent and a curing accelerator, or A curable epoxy resin composition containing a curing catalyst has high light reflectivity, is excellent in heat resistance and light resistance, and is also tough and excellent in crack resistance, and it is found that light reflectivity is unlikely to decrease with time. The Furthermore, the present inventor includes, as an essential component, a specific alicyclic epoxy compound, monoallyl diglycidyl isocyanurate compound, a siloxane derivative having two or more epoxy groups in the molecule, an alicyclic polyester resin, and a white pigment. Further, a curable epoxy resin composition containing a curing agent and a curing accelerator or a curing catalyst particularly has high light reflectivity, is excellent in heat resistance and light resistance, and is also tough and excellent in crack resistance, It has been found that it gives a cured product which is less likely to decrease in light reflectivity over time. The present invention has been completed based on these findings.

That is, the present invention has the following formula (I)

[Wherein, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , R ^13a , R ^14a , R ^15a , R ^16a , R ^17a and R ^18a are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent . ]
And a cycloaliphatic epoxy compound (A) represented by the following formula (1)

[Wherein, R ¹ and R ^{2 each} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
Curable epoxy resin composition comprising: monoallyl diglycidyl isocyanurate compound (B), white pigment (C), curing agent (D), and curing accelerator (F) Provide the goods.

Further, the present invention provides the following formula (I)

[Wherein, R ¹ and R ^{2 each} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A curable epoxy resin composition comprising the monoallyl diglycidyl isocyanurate compound (B), a white pigment (C), and a curing catalyst (E).

Furthermore, the alicyclic epoxy compound (A) is represented by the following formula (I-1)

The above-mentioned curable epoxy resin composition which is a compound represented by

The curable epoxy resin composition is preferably liquid at 25 ° C.

Furthermore, the curable epoxy resin composition as described above is provided, which comprises a siloxane derivative (G) having two or more epoxy groups in the molecule.

Furthermore, the above-mentioned curable epoxy resin composition containing an alicyclic polyester resin (H) is provided.

Furthermore, the said curable epoxy resin composition whose said alicyclic polyester resin (H) is an alicyclic polyester resin which has an alicyclic ring in a principal chain is provided.

Furthermore, the above-mentioned curable epoxy resin composition containing rubber particles other than silicone rubber particles is provided.

Furthermore, the above-mentioned curable epoxy resin composition is provided, which comprises at least one leveling agent selected from the group consisting of a silicone-based leveling agent and a fluorine-based leveling agent.

Furthermore, the above-mentioned curable epoxy resin composition containing a polyol compound is provided.

Furthermore, the above-mentioned curable epoxy resin composition containing an acrylic block copolymer is provided.

Furthermore, the above-mentioned curable epoxy resin composition containing stress relaxation agent (I) is provided.

The stress relaxation agent (I) may be at least one selected from the group consisting of silicone rubber particles (I1) and silicone oil (I2).

The silicone rubber particles (I1) may be crosslinked polydimethylsiloxane having a silicone resin on the surface.

The silicone oil (I2) may be a polyalkylene ether modified silicone compound having a structure represented by the following formula (10) having an epoxy equivalent of 3000 to 15000.

[Wherein, xa is an integer of 80 to 140, ya is an integer of 1 to 5 and za is an integer of 5 to 20] R ²⁶ is a C 2 or C 3 alkylene group. A is a polyalkylene ether group having a structure represented by the following formula (10a).

(Wherein, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group.)

Furthermore, the above-mentioned curable epoxy resin composition containing an inorganic filler (J) is provided.

The present invention also provides a cured product of the curable epoxy resin composition described above.

The present invention also provides a curable resin composition for light reflection comprising the above-mentioned curable epoxy resin composition.

Further, the present invention provides an optical semiconductor device comprising at least an optical semiconductor element and a reflector comprising a cured product of the above-described curable resin composition for light reflection.

Since the curable epoxy resin composition of the present invention has the above-mentioned constitution, the curable epoxy resin composition is suitable for compression molding, and a cured product obtained by curing has high light reflectivity, and further, It is excellent in heat resistance and light resistance, and is tough and hardly causes cracks, so that the light reflectivity does not easily decrease with time. Therefore, the curable epoxy resin composition of the present invention can be preferably used as a curable resin composition for light reflection for various applications related to an optical semiconductor device, in particular, an LED package. Furthermore, a reflector (reflecting material) formed of a cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention can continuously exhibit high light reflectivity for a long time, so that an optical semiconductor An optical semiconductor device (light emitting device) including at least an element and the reflector can exhibit high reliability as a long-life optical semiconductor device.

It is the schematic which shows an example of the optical semiconductor element mounting substrate of this invention. The left figure (a) is a perspective view, and the right figure (b) is a cross-sectional view. It is the schematic (cross-sectional view) which shows an example of the optical semiconductor device of this invention. FIG. 5 is a schematic view (sectional view; in the case of having a heat sink) showing another example of the optical semiconductor device of the present invention. It is the schematic (when it has a heat sink (heat dissipation fin)) which shows another example of the optical semiconductor device of this invention. The left figure (a) is a top view, and the right figure (b) is an AA 'cross section in (a).

<Curable epoxy resin composition>
The curable epoxy resin composition of the present invention has the following formula (I)

[Wherein, R ¹ and R ^{2 each} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A resin composition comprising, as essential components, the monoallyl diglycidyl isocyanurate compound (B), the white pigment (C), the curing agent (D), and the curing accelerator (F), or Alicyclic epoxy compound (A) represented by formula (I), monoallyl diglycidyl isocyanurate compound (B) represented by the above formula (1), white pigment (C), curing catalyst (E) And the like as an essential component. In addition, the curable epoxy resin composition of this invention may contain the other component as needed other than the said essential component. The curable epoxy resin composition of the present invention can be used as a thermosetting composition (thermosetting epoxy resin composition) which can be cured by heating and converted to a cured product.

In the present specification, the term "curable resin composition for light reflection" refers to a curable resin composition capable of forming a cured product having light reflectivity. Specifically, for example, a curable resin composition capable of forming a cured product having a reflectance of 50% or more (particularly 90% or more) to light with a wavelength of 450 nm is preferable.

The curable epoxy resin composition of the present invention is preferably liquid at 25 ° C. When it is a liquid at 25 ° C., it tends to be suitable for compression molding, and its cured product (reflector) tends to be excellent in light reflectivity, and also excellent in heat resistance and light resistance. In the present specification, “liquid at 25 ° C.” means that the viscosity measured at 25 ° C. under normal pressure is 1,000,000 mPa · s or less (preferably, 800,000 mPa · s or less). The viscosity is measured using, for example, a digital viscometer (model number “DVU-EII type” manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24, temperature: 25 ° C., rotation speed: 0. It can be measured under the condition of 5 to 10 rpm.

The curable epoxy resin composition of the present invention which is liquid at 25 ° C. is, for example, a component (eg, alicyclic epoxy compound (A), liquid stress relaxation agent (I), curing agent (E), curing accelerator) It becomes easy to obtain by using the component of a liquid at 25 degreeC as (F) and a curing catalyst (G) etc.). In addition, although a component solid at 25 ° C. may be used as the above component, the content is adjusted so that the curable epoxy resin composition of the present invention becomes liquid at 25 ° C. In addition, the content of components which are solid at 25 ° C., such as rubber particles, white pigment (C), inorganic filler (J), solid stress relaxation agent (I), etc. is within the range which does not impair the effects of the present invention. It will be easier to obtain by making adjustments.

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (A) which comprises the curable epoxy resin composition of this invention is a compound represented by following formula (I).

When the curable epoxy resin composition of the present invention contains the above-mentioned alicyclic epoxy compound (A), the cured product has high light reflectivity, is excellent in heat resistance and light resistance, and is tough and crack resistant. Excellent, in particular, tend to improve the crack resistance to cold cycles.

In the formula (1), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , R ^13a , R ^14a , R ^15a R ^16a , R ^17a and R ^18a are the same or different and each is a hydrogen atom, a halogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent Indicates

In the formula (1), halogen atoms in R ^1a to R ^18a include fluorine, chlorine, bromine and iodine atoms. The hydrocarbon group in the “hydrocarbon group which may have an oxygen atom or a halogen atom” includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded. Can be mentioned. The aliphatic hydrocarbon group is, for example, a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl or decyl group (for example, carbon number 1-10, preferably an alkyl group having about 1 to 5 carbon atoms); alkenyl groups such as vinyl and allyl (eg, an alkenyl group having about 2 to 10 carbon atoms, preferably about 2 to 5 carbon atoms); ethynyl group and the like And the like (for example, an alkynyl group having about 2 to 10 carbon atoms, preferably about 2 to 5 carbon atoms). As an alicyclic hydrocarbon group, cycloalkyl groups, such as a cyclopentyl and a cyclohexyl group; cycloalkenyl group; bridged cyclic group etc. are mentioned, for example. Examples of the aromatic hydrocarbon group include phenyl and naphthyl groups. As a hydrocarbon group which has an oxygen atom, the group (For example, alkoxyalkyl groups, such as a methoxymethyl group and an ethoxymethyl group etc., etc.) etc. are mentioned, for example, in the carbon chain of the above-mentioned hydrocarbon group. . As a hydrocarbon group which has a halogen atom, 1 or 2 or more of hydrogen atoms which the said hydrocarbon groups, such as a chloromethyl group, a trifluoromethyl group, a chlorophenyl group, have, for example, have a halogen atom (a fluorine, chlorine, a bromine or an iodine atom And the like. The alkoxy group in the “optionally substituted alkoxy group” is an alkoxy group having about 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as methoxy, ethoxy, propyloxy, isopropyloxy and butyloxy groups Groups and the like. As a substituent of an alkoxy group, the said halogen atom etc. are mentioned, for example.

Among the alicyclic epoxy compounds (A) represented by the formula (I), compounds represented by the following formula (I-1) in which all of R ^1a to R ^18a are hydrogen atoms are preferable.

The alicyclic epoxy compounds (A) can be used alone or in combination of two or more. Among the above, (3,4,3 ′, 4′-diepoxy) bicyclohexyl represented by the above formula (I-1) is particularly preferable as the alicyclic epoxy compound (A).

The use amount (content) of the alicyclic epoxy compound (A) is not particularly limited, but when the curable epoxy resin composition of the present invention contains a curing agent (D) as an essential component, a white pigment (C 5 to 90% by weight is preferable, more preferably 5 to 80% by weight, still more preferably 5 to 70% by weight based on the total amount (100% by weight) of the curable epoxy resin composition excluding the inorganic filler (J). %. On the other hand, when the curable epoxy resin composition of the present invention contains the curing catalyst (E) as an essential component, the amount (content) of the alicyclic epoxy compound (A) used is the white pigment (C) and the inorganic The content is preferably 25 to 95% by weight, more preferably 30 to 92% by weight, still more preferably 30 to 90% by weight based on the total amount (100% by weight) of the curable epoxy resin composition excluding the filler (J). .

In particular, when the curable epoxy resin composition of the present invention contains one or both of a siloxane derivative (G) having two or more epoxy groups in the molecule and an alicyclic polyester resin (H) (especially, both) The amount (content) of the cycloaliphatic epoxy compound (A) used is not particularly limited, but when the curable epoxy resin composition of the present invention contains a curing agent (D) as an essential component, It is preferably 5 to 90% by weight, more preferably 8 to 80% by weight, still more preferably 8% by weight, based on the total amount (100% by weight) of the curable epoxy resin composition excluding the white pigment (C) and the inorganic filler (J). It is ̃75% by weight. On the other hand, when the curable epoxy resin composition of the present invention contains either one or both of the component (G) and the component (H) (especially when it contains both), the curing catalyst (E) is an essential component. In the case where it is contained, the used amount (content) of the alicyclic epoxy compound (A) is the total amount (100% by weight) of the curable epoxy resin composition excluding the white pigment (C) and the inorganic filler (J) The amount is preferably 10 to 95% by weight, more preferably 15 to 85% by weight, and still more preferably 20 to 75% by weight.

In addition, the use amount (content) of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) is particularly limited. Although not preferred, it is preferably 30 to 95% by weight, more preferably 35 to 95% by weight, still more preferably 40 to 95% by weight. If the amount of the alicyclic epoxy compound (A) used is less than 30% by weight, the solubility of the monoallyl diglycidyl isocyanurate compound (B) may not be sufficient, and precipitation at room temperature may be facilitated. On the other hand, when the use amount of the alicyclic epoxy compound (A) exceeds 95% by weight, the toughness of the cured product may be reduced, and a crack may easily occur.

In the curable epoxy resin composition of the present invention, an alicyclic epoxy compound other than the alicyclic epoxy compound (A) (hereinafter sometimes referred to as "other alicyclic epoxy compound"), the effect of the present invention May be included in the range which does not impair.

Another alicyclic epoxy compound is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in the molecule (in one molecule), and is a compound other than the alicyclic epoxy compound (A). More specifically, other alicyclic epoxy compounds include, for example, (i) an epoxy group ("alicyclic epoxy group") composed of two adjacent carbon atoms constituting an alicyclic ring and an oxygen atom; And compounds having an epoxy group directly bonded to the alicyclic ring by a single bond, and the like. However, the siloxane derivative (G) which has two or more epoxy groups in the below-mentioned molecule shall not be contained in other alicyclic epoxy compounds.

(I) As a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms constituting an alicyclic ring and an oxygen atom, any compound selected from known or common ones may be used. be able to. Among them, the above-mentioned compound has an epoxy group constituted of two adjacent carbon atoms constituting a cyclohexane ring and an oxygen atom, that is, a compound having a cyclohexene oxide group (alicyclic epoxy compound) preferable.

(I) As a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms constituting an alicyclic ring and an oxygen atom, particularly in terms of heat resistance and light resistance, The alicyclic epoxy compound (alicyclic epoxy resin) represented by II) is preferable.

In formula (II), X represents a linking group (a divalent group having one or more atoms). Examples of the linking group include divalent hydrocarbon groups, carbonyl groups, ether groups (ether bonds), thioether groups (thioether bonds), ester groups (ester bonds), carbonate groups (carbonate bonds), amide groups (amides (amides) A bond, and a group in which a plurality of these are linked, and the like. In addition, substituents, such as an alkyl group, may be couple | bonded with one or more of the carbon atom which comprises alicyclic (alicyclic epoxy group) in Formula (II).

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene group, methyl methylene group, dimethyl methylene group, ethylene group, propylene group, trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, and a 1,3-cyclohexene group. And bivalent cycloalkylene groups (including cycloalkylidene groups) such as silene group, 1,4-cyclohexylene group, and cyclohexylidene group.

Among them, a linking group containing an oxygen atom is preferable as the linking group X, and specifically, for example, -CO- (carbonyl group), -O-CO-O- (carbonate group), -COO- ( Ester group), -O- (ether group), -CONH- (amide group), a group in which a plurality of these groups are linked, one or two or more of these groups and one or more of divalent hydrocarbon groups And the like. As a bivalent hydrocarbon group, what was illustrated above is mentioned, for example.

Representative examples of the alicyclic epoxy compound represented by the above formula (II) include compounds represented by the following formulas (II-1) to (II-10). As these compounds, for example, commercially available products such as trade names “Ceroxide 2021 P” and “Ceroxide 2081” (manufactured by Daicel Co., Ltd.) can also be used. In the following formulas (II-5) and (II-7), l and m each represent an integer of 1 to 30. R in the following formula (II-5) is an alkylene group having 1 to 8 carbon atoms, and is methylene, ethylene, propylene, isopropylene, butylene, isobutylene, s-butylene, pentylene, hexylene And linear or branched alkylene groups such as heptylene group and octylene group. Among these, linear or branched alkylene groups having 1 to 3 carbon atoms, such as methylene, ethylene, propylene and isopropylene are preferable. In the following formulas (II-9) and (II-10), n1 to n6 each represent an integer of 1 to 30.

(Ii) Examples of the compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond include a compound represented by the following formula (III).

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

The other alicyclic epoxy compounds can be used alone or in combination of two or more. Among the above, as another alicyclic epoxy compound, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate represented by the above formula (II-1), trade name “Ceroxide 2021 P” Particularly preferred.

When the curable epoxy resin composition of the present invention contains another alicyclic epoxy compound, the other relative to the total amount (100% by weight) of the other alicyclic epoxy compound and the alicyclic epoxy compound (A) The use amount (content) of the alicyclic epoxy compound is not particularly limited, but is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, still more preferably 5 to 30% by weight, particularly preferably 5 to 5 It is 20% by weight. When the amount of the other alicyclic epoxy compound used exceeds 50% by weight, the heat resistance, light resistance and toughness of the cured product deteriorate, and cracks easily occur due to the decrease in light reflectivity over time or the cold cycle. There is.

[Monoallyl diglycidyl isocyanurate compound (B)]
The monoallyl diglycidyl isocyanurate compound (B) which comprises the curable epoxy resin composition of this invention is represented by following General formula (1).

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

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

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

The monoallyl diglycidyl isocyanurate compound (B) can be optionally mixed in the range which dissolves in the above-mentioned alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) The proportion of the alicyclic epoxy compound (A): monoallyl diglycidyl isocyanurate compound (B) is preferably 50:50 to 95: 5 (by weight), and more preferably 50:50. It is 50 to 90:10 (weight ratio). Outside this range, the solubility of the monoallyl diglycidyl isocyanurate compound (B) becomes difficult to obtain.

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

[White pigment (C)]
The white pigment (C), which is an essential component of the curable epoxy resin composition of the present invention, plays a role of exerting high light reflectivity to a cured product obtained by curing the curable epoxy resin composition. As the white pigment (C), known or commonly used white pigments can be used, and it is not particularly limited. For example, glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acid clay, active Inorganic white pigments such as white earth, boehmite, pseudo-boehmite, inorganic oxides, metal salts such as alkaline earth metal salts; styrenic resins, benzoguanamine resins, urea-formalin resins, melamine-formalin resins, amide resins, etc. And organic white pigments such as plastic pigments (plastic pigments); hollow particles having a hollow structure (balloon structure); These white pigments can be used alone or in combination of two or more.

As the white pigment (C), it is preferable to use a white pigment having a high refractive index in order to increase the reflectance of the reflector. For example, a white pigment having a refractive index of 1.5 or more is preferable. However, since the white pigment having a hollow particle structure contains a gas of low refractive index inside (core) and the surface reflectance is very large, the shell portion may be made of a material having a refractive index of less than 1.5 . Among those exemplified as the white pigment (C), those having a refractive index of 1.5 or more are regarded as the white pigment (C) and those having a refractive index of 1.5 are also applicable to the inorganic filler (J). The smaller one is the inorganic filler (J).

Examples of the inorganic oxide include aluminum oxide (alumina), magnesium oxide, antimony oxide, titanium oxide (rutile type titanium oxide, anatase type titanium oxide, brookite type titanium oxide), zirconium oxide, zinc oxide and the like. Also, as the alkaline earth metal salt, for example, magnesium carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, sulfuric acid Barium etc. are mentioned. Moreover, as metal salts other than alkaline-earth metal salt, aluminum silicate, aluminum hydroxide, a zinc sulfide etc. are mentioned, for example.

The hollow particles are not particularly limited, and examples thereof include inorganic glass (for example, sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, quartz and the like), metal oxides such as silica and alumina, calcium carbonate, barium carbonate, Inorganic hollow particles (including natural products such as Shirasu balloon) composed of inorganic substances such as nickel carbonate, calcium silicate etc. metal salts; styrenic resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride Polymers such as vinyl-based resins, vinylidene chloride-based resins, amide-based resins, urethane-based resins, phenol-based resins, styrene-conjugated diene resins, acrylic-conjugated diene resins, olefin resins (including crosslinked products of these polymers), etc. Hollow particles composed of organic matter of organic matter; hybrid of inorganic matter and organic matter Inorganic constructed of a material - such as an organic hollow particles. In addition, the said hollow particle may be comprised from a single material, and may be comprised from 2 or more types of materials. The hollow portion of the hollow particle (the space inside the hollow particle) may be in a vacuum state or may be filled with a medium, but in particular, the refractive index is low from the viewpoint of improving the reflectance. Hollow particles filled with a medium (for example, an inert gas such as nitrogen or argon, air or the like) are preferred.

The white pigment (C) is subjected to known or conventional 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.) It may be done. By performing such surface treatment, compatibility or dispersibility with other components of the white pigment (C) in the curable epoxy resin composition may be able to be improved.

Among them, inorganic pigments and inorganic hollow particles are preferable as the white pigment (C) from the viewpoints of availability, heat resistance and light resistance, and more preferably aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, Silicon oxide and at least one white pigment selected from the group consisting of inorganic hollow particles. In particular, titanium oxide is preferable as the white pigment (C) in that it has a higher refractive index.

The shape of the white pigment (C) is not particularly limited, and examples thereof include spherical, crushed, fibrous, needle, scaly, and whiskers. Among them, spherical white pigments are preferable, and spherical white pigments (for example, spherical white pigments having an aspect ratio of 1.2 or less) are particularly preferable from the viewpoint of dispersibility of the white pigment (C).

The central particle size of the white pigment (C) is not particularly limited, but is preferably 0.1 to 50 μm from the viewpoint of improving light reflectivity. In particular, when using an inorganic oxide as the white pigment (C), the central particle size of the inorganic oxide is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, and still more preferably It is 0.1 to 20 μm, particularly preferably 0.1 to 10 μm, and most preferably 0.1 to 5 μm. On the other hand, when hollow particles (in particular, inorganic hollow particles) are used as the white pigment (C), the central particle diameter of the hollow particles is not particularly limited, but preferably 0.1 to 50 μm, more preferably 0.1 to 50 It is 30 μm. In addition, the said center particle diameter means the particle size (median diameter) in 50% of the integration value in the particle size distribution measured by the laser diffraction and the scattering method.

The use amount (blending amount) of the white pigment (C) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of epoxy group-containing compounds contained in the curable epoxy resin composition (all epoxy groups The content is preferably 80 to 500 parts by weight, more preferably 90 to 400 parts by weight, and still more preferably 100 to 380 parts by weight with respect to 100 parts by weight of the contained compound. If the amount used is less than 80 parts by weight, the light reflectivity of the cured product tends to decrease. On the other hand, when the amount used exceeds 500 parts by weight, the toughness of the cured product tends to decrease.

The white pigment (C) can be produced by a known or conventional production method. Moreover, as a white pigment (C), a commercial item can also be used, For example, brand name "SR-1", "R-42", "R-45M", "R-650", "R-32" “R-5N”, “GTR-100”, “R-62N”, “R-7E”, “R-44”, “R-3L”, “R-11P”, “R-21”, "R-25", "TCR-52", "R-310", "D-918", "FTR-700" (above, made by Suga Chemical Industry Co., Ltd.), trade name "Typek CR-50", "CR-50-2", "CR-60", "CR-60-2", "CR-63", "CR-80", "CR-90", "CR-90-2", "CR -93 "," CR-95 "," CR-97 "(above, made by Ishihara Sangyo Co., Ltd.), brand name" JR-301 "," JR-403 "," JR-405 " "JR-600A", "JR-605", "JR-600E", "JR-603", "JR-805", "JR-806", "JR-701", "JRNC", "JR-800" "JR" (above, made by Tayca Co., Ltd.), trade name "TR-600", "TR-700", "TR-750", "TR-840", "TR-900" (above, Fuji Titanium Industry Co., Ltd., trade name "KR-310", "KR-380", "KR-380N" (above, titanium industry Co., Ltd.) trade name "ST-410WB", "ST-455" , “ST-455 WB”, “ST-457 SA”, “ST-457 EC”, “ST-485 SA15”, “ST-486 SA”, “ST-495 M” (all manufactured by Titan Kogyo Co., Ltd.), etc. -Type titanium oxide; trade name "A-110 , “TCA-123E”, “A-190”, “A-197”, “SA-1”, “SA-1L”, “SSP series”, “CSB series” (all, Sakai Chemical Industry Co., Ltd.) ), Brand names “JA-1”, “JA-C”, “JA-3” (all manufactured by Tayka Co., Ltd.), brand names “KA-10”, “KA-15”, “KA-20” , “STT-65C-S”, “STT-30EHJ” (all, manufactured by Titan Kogyo Co., Ltd.), trade names “DCF-T-17007”, “DCF-T-17008”, “DCF-T-17050” Anatase-type titanium oxide such as that of Reshino Color Industrial Co., Ltd. can be used.

[Hardener (D)]
The curing agent (D) constituting the curable epoxy resin composition of the present invention plays a role of curing a compound having an epoxy group. As the curing agent (D), known or commonly used curing agents can be used as curing agents for epoxy resins. Among them, as the curing agent (D), acid anhydride liquid at 25 ° C. is preferable, and more specifically, for example, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl endo methylene Tetrahydrophthalic anhydride and the like can be mentioned. Also, for example, acid anhydrides which are solid at normal temperature (about 25 ° C.) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, etc. are liquid at normal temperature (about 25 ° C.) It can be preferably used as a curing agent (D) by dissolving it in an acid anhydride of the above to form a liquid mixture. In addition, a hardening agent (D) can be used individually or in combination of 2 or more types. As the curing agent (D), particularly from the viewpoint of heat resistance, light resistance and crack resistance, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those in which a substituent such as an alkyl group is bonded to the ring) are used. preferable.

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

The amount (content) of the curing agent (D) used is not particularly limited, but it is 50 to 200 parts by weight based on the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. Is preferred, and more preferably 80 to 145 parts by weight. More specifically, it is preferable to use at a ratio of 0.5 to 1.5 equivalents per equivalent of epoxy groups in all the epoxy-containing compounds contained in the curable epoxy resin composition of the present invention. . When the amount of the curing agent (D) used is less than 50 parts by weight, curing tends to be insufficient, and the toughness of the cured product tends to decrease. On the other hand, when the amount of the curing agent (D) used exceeds 200 parts by weight, the cured product may be colored to deteriorate the hue.

[Hardening accelerator (F)]
In the curable epoxy resin composition of the present invention, the curing accelerator (F) is a compound having a function of accelerating the curing rate when the compound having an epoxy group is cured by the curing agent (D). As the curing accelerator (F), known or commonly used curing accelerators can be used, and it is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and The salt thereof (eg, phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and the salt thereof (Eg, phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexyl Tertiary amines such as amines; 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole etc. Imidazole compounds; phosphoric acid esters, phosphines such as triphenylphosphine; tetraphenylphosphonium tetra (p- tolyl) phosphonium compounds such as borate, tin octylate, organic metal salts such as zinc octylate; metal chelate and the like. In addition, a hardening accelerator (F) can be used individually or in combination of 2 or more types.

In the present invention, as the curing accelerator (F), trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “12XD ( "Development products" (above, San-Apro Co., Ltd.), trade names "TPP-K", "TPP-MK" (Hokuko Chemical Co., Ltd.), trade name "PX-4ET" (Nippon Chemical Industries, Ltd.) It is also possible to use commercially available products such as manufactured by Co., Ltd.).

The amount (content) of the curing accelerator (F) is not particularly limited, but it is preferably 0.05 to 0.05 parts by weight based on the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. The amount is preferably 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight. When the amount of the curing accelerator (F) used is less than 0.05 parts by weight, the curing acceleration effect may be insufficient. On the other hand, when the use amount of the curing accelerator (F) exceeds 5 parts by weight, the cured product may be colored to deteriorate the hue.

[Curing catalyst (E)]
The curable epoxy resin composition of the present invention may contain a curing catalyst (E) instead of the above-mentioned curing agent (D). As in the case of using the curing agent (D), by using the curing catalyst (E), the curing reaction of the compound having an epoxy group can be advanced to obtain a cured product. The curing catalyst (E) is not particularly limited. For example, a cationic catalyst (cationic polymerization initiator) capable of initiating polymerization by generating cationic species by ultraviolet irradiation or heat treatment can be used. .

As a cation catalyst which generate | occur | produces a cationic species by ultraviolet irradiation, a hexafluoroantimonate salt, a pentafluoro hydroxyantimonate salt, a hexafluorophosphate salt, a hexafluoroarsenate salt etc. are mentioned, for example. These cationic catalysts can be used alone or in combination of two or more. As said cation catalyst, the brand name "UVACURE1590" (made by Daicel ・ Cytec Co., Ltd. product), the brand name "CD-1010", "CD-1011", "CD-1012" (above, the United States Sartomer make), Commercial products such as trade name “IRGACURE 264” (manufactured by Ciba Japan Ltd.) and trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can also be preferably used.

Examples of the cation catalyst that generates a cation species by heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, and allene-ion complexes. These cationic catalysts can be used alone or in combination of two or more. Examples of the cationic catalyst include, for example, trade names “PP-33”, “CP-66”, “CP-77” (all manufactured by ADEKA Co., Ltd.), trade name “FC-509” (manufactured by 3M), and trade names Name "UVE 1014" (manufactured by G. E.), trade name "San Aid SI-60L", "San Aid SI-80 L", "San Aid SI-100 L", "San Aid SI-110 L", "San Aid SI-150 L" Commercial products such as Sanshin Chemical Industry Co., Ltd., trade name "CG-24-61" (Ciba Japan Co., Ltd.), etc. can be preferably used. Further, as the above-mentioned cation catalyst, a compound of a chelate compound of metal such as aluminum or titanium with acetoacetic acid or diketones and silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketones It is also possible to use a compound of the chelate compound of the above and a phenol such as bisphenol S.

The use amount (content) of the curing catalyst (E) is not particularly limited, but it is 0.01 to 15 with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. It is preferable to use parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, particularly preferably 0.1 to 10 parts by weight. By using the curing catalyst (E) within the above range, a cured product excellent in heat resistance and light resistance can be obtained.

The curable epoxy resin composition of the present invention may contain a siloxane derivative (G) having two or more epoxy groups in the molecule and / or an alicyclic polyester resin (H). In particular, the curable epoxy resin composition of the present invention preferably contains a siloxane derivative (G) having two or more epoxy groups in the molecule and an alicyclic polyester resin (H). That is, the curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A) represented by the above formula (I) and a monoallyl diglycidyl isocyanurate compound (B) represented by the above formula (1) ), A siloxane derivative (G) having two or more epoxy groups in the molecule, an alicyclic polyester resin (H), a white pigment (E), a curing agent (F), and a curing accelerator (H) And a cycloaliphatic epoxy compound (A) represented by the above formula (I) and a monoallyl diglycidyl isocyanurate compound (B) represented by the above formula (1); A resin composition comprising at least a siloxane derivative (G) having two or more epoxy groups in the molecule, an alicyclic polyester resin (H), a white pigment (E), and a curing catalyst (G) preferable.

[Siloxane derivative (G) having two or more epoxy groups in the molecule]
As described above, the curable epoxy resin composition of the present invention may contain a siloxane derivative (G) having two or more epoxy groups in the molecule (in one molecule). The siloxane derivative (G) having two or more epoxy groups in the molecule is a compound having a siloxane skeleton and having two or more epoxy groups in the molecule. The siloxane derivative (G) having two or more epoxy groups in the molecule plays a role of improving the heat resistance, light resistance and crack resistance of the cured product and suppressing the decrease in light intensity of the optical semiconductor device.

The siloxane skeleton of the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited. For example, cyclic siloxane skeleton; linear silicone, cage-type or ladder-type polysilsesquioxane And the like. Among them, as the above-mentioned siloxane skeleton, a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the heat resistance and light resistance of the cured product to suppress the decrease in light intensity. That is, as the siloxane derivative (G) having two or more epoxy groups in the molecule, 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 are preferable. In addition, the siloxane derivative (G) which has a 2 or more epoxy group in a molecule | numerator can be used individually or in combination of 2 or more types.

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

The weight average molecular weight of the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but it is preferably 100 to 3000, more preferably 180, from the viewpoint of improving the heat resistance and light resistance of the cured product. It is -2000. The weight average molecular weight of the siloxane derivative (G) having two or more epoxy groups in the molecule can be measured, for example, by GPC (gel permeation chromatography) as a value in terms of standard polystyrene.

The number of epoxy groups (number of epoxy groups in one molecule) possessed by the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited as long as it is two or more, but the heat resistance of the cured product From the viewpoint of improving the light resistance, two to four are preferable.

The epoxy equivalent (based on JIS K 7236) of the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but it is preferably 180 to 400 from the viewpoint of improving the heat resistance and light resistance of the cured product. More preferably, it is 240 to 400, and more preferably 240 to 350.

The epoxy group in the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, adjacent two carbons constituting an aliphatic ring It is preferable that it is an epoxy group (alicyclic epoxy group) comprised by an atom and an oxygen atom, and it is especially preferable that it is a cyclohexene oxide group especially.

Specific examples of the siloxane derivative (G) having two or more epoxy groups in the molecule 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-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,6-dipropyl-2,4, 6,8-Tetramethyl-cyclotetrasiloxane, 2,4,8- [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- (2 3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,8-tetramethyl-cyclotetrasiloxane, silsesquioxane having an epoxy group, and the like. More specifically, for example, cyclic siloxanes having two or more epoxy groups in one molecule represented by the following formulas (S-1) to (S-7) can be mentioned.

Moreover, as a siloxane derivative (G) having two or more epoxy groups in the molecule, for example, an alicyclic epoxy group-containing silicone resin described in JP-A-2008-248169, or JP-A-2008-19422 It is also possible to use an organopolysilsesquioxane resin or the like having at least two epoxy functional groups in one molecule.

As a siloxane derivative (G) having two or more epoxy groups in the molecule, for example, cyclic siloxane having two or more epoxy groups in the molecule, trade name “X-40-2678” (Shin-Etsu Chemical Co., Ltd. (Trade name) “X-40-2670” (Shin-Etsu Chemical Co., Ltd.), trade name “X-40-2720” (Shin-Etsu Chemical Co., Ltd.), etc. may be used. .

Although the usage-amount (content) of the siloxane derivative (G) which has a 2 or more epoxy group in a molecule | numerator is not specifically limited, The total amount (100 weight) of component (A), component (B), and component (G) % Is preferably 5 to 90% by weight, more preferably 5 to 85% by weight, still more preferably 5 to 80% by weight, and particularly preferably 8 to 75% by weight. When the amount of the siloxane derivative (G) having two or more epoxy groups in the molecule is less than 5% by weight, the heat resistance and light resistance of the cured product may be reduced. On the other hand, when the amount of the siloxane derivative (G) having two or more epoxy groups in the molecule exceeds 90% by weight, the crack resistance of the cured product may be reduced.

Alicyclic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), and siloxane having two or more epoxy groups in the molecule with respect to the total amount (100% by weight) of the compound having epoxy group (epoxy resin) Although the total amount of the derivative (G) is not particularly limited, it is preferably 30% by weight or more (for example, 30 to 100% by weight) and particularly preferably 40% by weight or more from the viewpoint of improving heat resistance, light resistance and crack resistance. preferable.

[Alicyclic polyester resin (H)]
The said alicyclic polyester resin (H) is a polyester resin which has an alicyclic structure (aliphatic ring structure) at least. The alicyclic polyester resin (H) improves the heat resistance, light resistance and crack resistance of the cured product and plays a role in suppressing the decrease in light intensity of the optical semiconductor device. In particular, from the viewpoint of improving the heat resistance, light resistance and crack resistance of the cured product, the alicyclic polyester resin (H) is preferably an alicyclic polyester having an alicyclic (alicyclic structure) in its main chain. . That is, the alicyclic polyester resin (H) is preferably a polyester resin in which a polymer main chain is constituted by a part or all of carbon atoms constituting an alicyclic ring. In addition, an alicyclic polyester resin (H) can be used individually or in combination of 2 or more types.

The alicyclic structure in the alicyclic polyester resin (H) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure and a bridged ring hydrocarbon structure (eg, bicyclic hydrocarbon etc.) And a saturated single ring hydrocarbon structure or a saturated bridged ring hydrocarbon structure in which an alicyclic ring (a carbon-carbon bond constituting an alicyclic ring) is entirely constituted by a carbon-carbon single bond. In addition, the alicyclic structure in the above-mentioned alicyclic polyester resin (H) may be introduced into either one of the structural unit derived from dicarboxylic acid and the structural unit derived from diol, or both may be introduced. Well, not particularly limited.

The alicyclic polyester resin (H) has a structural unit derived from a monomer component having an alicyclic structure. Examples of the monomer having an alicyclic structure include diols and dicarboxylic acids having a known or common alicyclic structure, and are not particularly limited. For example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, hymic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalene Dicarboxylic acids (including derivatives such as acid anhydrides) having an alicyclic structure such as dicarboxylic acids and 2,7-decahydronaphthalenedicarboxylic acid, etc .; 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1 , 2-cyclopentadimethanol, 1,3-cyclopentadimethanol 5-membered ring diols such as bis (hydroxymethyl) tricyclo [5.2.1.0] decane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediol 6-membered ring diols such as methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis- (4-hydroxycyclohexyl) propane, and diols having an alicyclic structure such as hydrogenated bisphenol A (Including their derivatives) and the like.

The alicyclic polyester resin (H) may have a structural unit derived from a monomer component having no alicyclic structure. The monomer component not having an alicyclic structure is not particularly limited, and examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalene dicarboxylic acid (including derivatives such as acid anhydrides); adipic acid Aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, succinic acid, fumaric acid and maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propane Diol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 3-methyl-1,5- Pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl- , 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A (including their derivatives) Etc. In addition, those in which an appropriate substituent (for example, an alkyl group, an alkoxy group, a halogen atom, etc.) is bonded to the dicarboxylic acid or diol having no alicyclic structure are also included in the monomer component having no alicyclic structure.

Although the ratio of the monomer unit having an alicyclic group to the total monomer units (all monomer components) (100 mol%) constituting the alicyclic polyester resin (H) is not particularly limited, it is 10 mol% or more (for example, 10 to 80) It is preferably mol%), more preferably 25 to 70 mol%, still more preferably 40 to 60 mol%. When the proportion of monomer units having an alicyclic group is less than 10 mol%, the heat resistance, light resistance and crack resistance of the cured product may be reduced.

As the alicyclic polyester resin (H), an alicyclic polyester resin containing at least one or more structural units represented by the following formulas (2) to (4) is particularly preferable.

(Wherein, R ³ represents a linear, branched or cyclic alkylene group having 2 to 15 carbon atoms. R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched chain And the two selected from R ⁴ to R ⁷ may combine to form a ring).

(Wherein, R ³ represents a linear, branched or cyclic alkylene group having 2 to 15 carbon atoms. R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched chain Or an alkyl group having 1 to 4 carbon atoms, and two selected from R ⁴ to R ⁷ may form a combined ring).

As a preferable specific example of the structural unit represented by said Formula (2)-(4), the structure derived from 4-methyl- 1, 2- cyclohexane dicarboxylic acid and ethylene glycol represented by following formula (5) is mentioned, for example Unit is mentioned. The alicyclic polyester resin (H) having the structural unit can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride and ethylene glycol.

Moreover, as another preferable specific example of the structural unit represented by said Formula (2)-(4), it is derived from the 1, 4- cyclohexane dicarboxylic acid represented by following formula (6), and neopentyl glycol, for example A structural unit is mentioned. The alicyclic polyester resin (H) having the structural unit can be obtained, for example, by polycondensation of 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.

The terminal structure of the alicyclic polyester resin (H) is not particularly limited, and may be a hydroxyl group or a carboxyl group, or a structure in which these hydroxyl groups or carboxyl groups are appropriately modified (for example, the terminal hydroxyl group is mono It may be a structure esterified with a carboxylic acid or an acid anhydride, a structure in which a terminal carboxyl group is esterified with an alcohol, and the like.

When the alicyclic polyester resin (H) has a constituent unit represented by the above formulas (2) to (4), the total content of the constituent units (total content; all monomers constituting the constituent unit The unit) is not particularly limited, but is 20 mol% or more (eg, 100 mol%; all monomer units constituting the alicyclic polyester resin (H)) of the alicyclic polyester resin (H) 20 to 100 mol%) is preferable, more preferably 50 to 100 mol%, and still more preferably 80 to 100 mol%. When the content of the structural unit represented by the above formulas (2) to (4) is less than 20 mol%, the heat resistance, light resistance and crack resistance of the cured product may be lowered.

The number average molecular weight of the alicyclic polyester resin (H) is not particularly limited, but is preferably 300 to 100,000, and more preferably 300 to 30,000. If the number average molecular weight of the alicyclic polyester resin (H) is less than 300, the toughness of the cured product may not be sufficient, and the crack resistance may be reduced. On the other hand, when the number average molecular weight of the alicyclic polyester resin (H) exceeds 100,000, the compatibility with other components (for example, the curing agent (D)) decreases, which adversely affects the mechanical properties of the cured product, Crack resistance may be reduced. In addition, the number average molecular weight of alicyclic polyester resin (H) can be measured as a value of standard polystyrene conversion, for example by GPC (gel permeation chromatography) method.

In addition, an alicyclic polyester resin (H) can be used individually by 1 type or in combination of 2 or more types.

The alicyclic polyester resin (H) is not particularly limited, and can be produced by a known or conventional method. More specifically, for example, the alicyclic polyester resin (H) may be obtained by polycondensation of the above-mentioned dicarboxylic acid and diol according to a conventional method, or a derivative of the above-mentioned dicarboxylic acid (acid anhydride, ester The acid halide may be obtained by polycondensation of an acid halide and the like with a diol according to a conventional method.

In the curable epoxy resin composition of the present invention, the compounding amount (content) of the alicyclic polyester resin (H) is not particularly limited, but when the curing agent (D) is an essential component, the alicyclic polyester resin The amount is preferably 1 to 60% by weight, more preferably 5 to 30% by weight, based on the total amount (100% by weight) of (H) and the curing agent (D). The crack resistance of a hardened | cured material may fall that the compounding quantity of alicyclic polyester resin (H) is less than 1 weight%. On the other hand, when the compounding quantity of alicyclic polyester resin (H) exceeds 60 weight%, the heat resistance of hardened | cured material may fall.

On the other hand, when the curable epoxy resin composition of the present invention contains the curing catalyst (E) as an essential component, the compounding amount (content) of the alicyclic polyester resin (H) is not particularly limited, but the alicyclic polyester The amount is preferably 50 to 99% by weight, more preferably 65 to 99% by weight, based on the total amount (100% by weight) of the resin (H) and the curing catalyst (E). The crack resistance of a hardened | cured material may fall that the compounding quantity of alicyclic polyester resin (H) is less than 50 weight%. On the other hand, when the compounding quantity of alicyclic polyester resin (H) exceeds 99 weight%, the heat resistance of hardened | cured material may fall.

[Leveling agent]
The curable epoxy resin composition of the present invention preferably further contains at least one leveling agent selected from the group consisting of a silicone-based leveling agent (polysiloxane-based leveling agent) and a fluorine-based leveling agent. The curable epoxy resin composition of the present invention can form a cured product exhibiting higher heat resistance, light resistance, and crack resistance by containing the above-mentioned leveling agent, and an optical semiconductor produced using the cured product The device is even less prone to loss of light intensity over time.

(Silicone-based leveling agent)
The silicone-based leveling agent is a leveling agent containing a compound having a polysiloxane skeleton. As the silicone-based leveling agent, known or commonly used silicone-based leveling agents can be used and are not particularly limited. For example, trade names “BYK-300”, “BYK-301 / 302”, “BYK-306”, “ BYK-307 "," BYK-310 "," BYK-315 "," BYK-313 "," BYK-320 "," BYK-322 "," BYK-323 "," BYK-325 "," BYK-325 " 330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-341 "," BYK-344 "," BYK-345 / 346 "," BYK-347 "," BYK-345 " 348 "," BYK-349 "," BYK-370 "," BYK-375 "," BYK-377 "," BYK-378 "," BYK-UV3500 "," YK-UV 3510 "," BYK-UV 3570 "," BYK-3550 "," BYK-SILCLEAN 3700 "," BYK-SILCLEAN 3720 "(above, made by Big Chemie Japan KK), trade name" AC FS 180 "," AC FS 360 "," AC S 20 "(all manufactured by Algin Chemie), trade names" Polyflow KL-400X "," Polyflow KL-400HF "," Polyflow KL-401 "," Polyflow KL-402 "," Polyflow KL -403 "," Polyflow KL-404 "(all manufactured by Kyoeisha Chemical Co., Ltd.), trade names" KP-323 "," KP-326 "," KP-341 "," KP-104 "," KP- 110 "," KP-112 "(hereinafter, Shin-Etsu Chemical Co., Ltd. product), trade name" LP-7001 ", LP-7002, "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", "56 Commercially available products such as "ADDITIVE" (hereinafter, Toray Dow Corning Co., Ltd.) can be used.

Especially as a compound which has the said polysiloxane skeleton, the silicone type polymer (However, component (C) is remove | excluded) which has a structural unit (repeating structural unit) represented by following formula (7) at least is preferable. That is, the silicone-based leveling agent is preferably a leveling agent containing at least the silicone-based polymer.

R ⁸ in the above formula (7) represents a linear or branched alkyl group which may have a substituent. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), an isobutyl group, an s-butyl group, a t-butyl group, and pentyl. And C 1 -C 30 linear or branched alkyl groups such as groups.

The substituent that the linear or branched alkyl group may have in R ⁸ is not particularly limited, and examples thereof include a hydroxyl group which may be protected by a protecting group [eg, a hydroxyl group, A substituted oxy group (for example, an alkoxy group having a carbon number of 1 to 4 such as methoxy group, ethoxy group and propoxy group) and the like, a carboxyl group which may be protected by a protecting group [for example, -COOR ^a group and the like: ^Ra Represents a hydrogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group and a hexyl group C1-C6 linear or branched alkyl group is mentioned], acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl , Propenyl group, an epoxy group, such as glycidyl groups.

R ⁹ in the above formula (7) is a linear or branched alkyl group which may have a substituent, an aralkyl group which may have a substituent, an organic group containing a polyether chain, Or an organic group containing a polyester chain. The linear or branched alkyl group for R ⁹ is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), an isobutyl group and an s-butyl group. Examples thereof include linear or branched alkyl groups having 1 to 30 carbon atoms such as a group, t-butyl group and pentyl group. The aralkyl group is not particularly limited, and examples thereof include a benzyl group, a methylbenzyl group, a phenethyl group, a methylphenethyl group, a phenylpropyl group and a naphthylmethyl group.

The substituent that the linear or branched alkyl group may have in R ^{9 and the} substituent that the aralkyl group may have is not particularly limited, and for example, in R ⁸ described above The exemplified substituents and the like can be mentioned.

The organic group containing a polyether chain in R ⁹ is a monovalent organic group containing at least a polyether structure. The polyether structure in the organic group containing a polyether chain is not particularly limited as long as it has a structure having a plurality of ether bonds, and examples thereof include polyethylene glycol structure (polyethylene oxide structure) and polypropylene glycol structure (polypropylene oxide structure) And polyoxyalkylene structures such as a polybutylene glycol (polytetramethylene glycol) structure, a polyether structure derived from a plurality of alkylene glycols (or alkylene oxides) (eg, a poly (propylene glycol / ethylene glycol) structure, etc.) Be The addition form of each alkylene glycol in the polyether structure derived from plural kinds of alkylene glycols may be block type (block copolymer type) or random type (random copolymer type), It is also good.

The organic group containing the above polyether chain may be an organic group consisting only of the above polyether structure, or one or more of the above polyether structure, and one or more of the linking groups (one or more atoms It may be an organic group having a structure in which it is connected to a divalent group having one). The linking group in the organic group containing the polyether chain is, for example, a divalent hydrocarbon group (in particular, a linear or branched alkylene group), a thioether group (-S-), an ester group (-COO- And an amide group (-CONH-), a carbonyl group (-CO-), a carbonate group (-OCOO-), and a group in which two or more of these are bonded.

Note that the organic group containing a polyether chain, exemplified substituent in R ⁸ above (e.g., hydroxyl group, carboxyl group, an acryloyl group, a methacryloyl group, acryloyloxy group, methacryloyloxy group, a vinyl group, such as propenyl For example, as the organic group containing such a polyether structure, an organic group having the above-mentioned substituent at the end (end opposite to the silicon atom in the formula (7)) may be mentioned. Be

The organic group containing a polyester chain in R ⁹ is a monovalent organic group containing at least a polyester structure. The polyester structure in the organic group containing the polyester chain may be any structure having a plurality of ester bonds, and is not particularly limited. Aromatic polyester structures, aliphatic / alicyclic polyester structures, alicyclic / aromatic polyester structures and the like can be mentioned.

More specifically, examples of the polyester structure include a polyester structure formed by polymerization of a polycarboxylic acid (in particular, a dicarboxylic acid) and a polyol (in particular, a diol). The above polycarboxylic acid is not particularly limited, and examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalene dicarboxylic acid (including derivatives of acid anhydride and ester); adipic acid and sebacic acid Aliphatic dicarboxylic acids such as azelaic acid, succinic acid, fumaric acid and maleic acid (including derivatives such as acid anhydrides and esters); 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 Cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, hymic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, Having an alicyclic structure such as 2,7-decahydronaphthalene dicarboxylic acid A carboxylic acid (including derivatives such as acid anhydrides and esters). The above-mentioned polyol is not particularly limited, but, for example, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4- Butanediol (tetramethylene glycol), neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4- Trimethyl-1,6-hexanediol, 3-methylpentanediol, diethylene glycol, dipropylene glycol, hexylene glycol (2-methylpentane-2,4-diol), 3-methyl-1,5-pentanediol, 2- Methyl-1,5-pentanediol, 2,3,5-trime 1, 5-pentanediol, 2-methyl-1,3-propanediol, 2, 2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, Diols such as 8-octanediol, 1,12-dodecanediol, xylylene glycol, 1,3-dihydroxyacetone, polybutadienediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A (including their derivatives 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentadimethanol, 1,3-cyclopentadimethanol, bis (hydroxymethyl) tricyclo [5.2.1.0) 5-membered ring diol such as decane, 1,2-cyclohexanediol 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol (1,2-dimethylolcyclohexane), 1,3-cyclohexanedimethanol (1,3-dimethylolcyclohexane), 1, 6-membered ring diols such as 4-cyclohexanedimethanol (1,4-dimethylol cyclohexane), 2,2-bis- (4-hydroxycyclohexyl) propane, and diols having an alicyclic structure such as hydrogenated bisphenol A (these compounds Derivatives), glycerin, trimethylolpropane, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, polyols having three or more hydroxyl groups such as pentaerythritol (including derivatives thereof), and the like. . The polyester structure may be formed of a single polyol or polycarboxylic acid, or may be formed of two or more polyols or polycarboxylic acid.

Moreover, as said polyester structure, the polyester structure formed by superposition | polymerization of hydroxycarboxylic acid, the polyester structure formed by superposition | polymerization (ring-opening polymerization) of the lactone which is cyclic ester of this hydroxycarboxylic acid, etc. are mentioned, for example. The hydroxycarboxylic acid is not particularly limited, and examples thereof include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid (salicylic acid), 3-methoxy-4-hydroxybenzoic acid (vanillic acid), 4 -Methoxy-3-hydroxybenzoic acid (isovanillic acid), 3,5-dimethoxy-4-hydroxybenzoic acid (silingic acid), 2,6-dimethoxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid 4-methyl-3-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 4-phenyl-3-hydroxybenzoic acid, 2-phenyl-4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3,4-Dihydroxycinnamic acid (caffeic acid), (E) -3- (4-hydroxy-3-methoxy-fu) Hydroxy aromatic carboxylic acids such as propane-2-enolic acid (ferulic acid) and 3- (4-hydroxyphenyl) -2-propenonic acid (coumaric acid); hydroxy acids such as glycolic acid, lactic acid, tartaric acid, and citric acid Aliphatic carboxylic acids and the like can be mentioned. The lactone is not particularly limited, and examples thereof include γ-butyrolactone, δ-valerolactone, ε-caprolactone, ξ-enantholactone, η-caprylolactone and the like. The polyester structure may be formed of a single hydroxycarboxylic acid or lactone, or may be formed of two or more hydroxycarboxylic acids or lactones.

The above-mentioned polyester structure is not limited to the above-exemplified structures, and, for example, a polyester structure formed by polymerization of the above-mentioned polycarboxylic acid and polyol, a polyester structure formed by polymerization of hydroxycarboxylic acid, polymerization of lactone It may be a structure in which two or more of the polyester structures to be formed are combined.

The organic group containing the above polyester chain may be an organic group consisting only of the above polyester structure, or an organic group having a structure in which one or more of the above polyester structures are linked to one or more of the linking groups. It may be Examples of the linking group in the organic group containing the polyester chain include a divalent hydrocarbon group (in particular, a linear or branched alkylene group), a thioether group (-S-), an ester group (-COO-) And an amide group (-CONH-), a carbonyl group (-CO-), a carbonate group (-OCOO-), and a group in which two or more of these are bonded.

In addition, the organic group containing the said polyester chain is a substituent (for example, a hydroxyl group, a carboxyl group, an acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, a vinyl group, propenyl group etc.) illustrated in the above-mentioned R ⁸ For example, as the organic group containing such a polyester structure, an organic group having the above-described substituent at the end (the end on the side opposite to the silicon atom in Formula (7)) may be mentioned.

The silicone polymer may be a polymer having only the structural unit represented by Formula (7) as the repeating structural unit, or has a structural unit other than the structural unit represented by Formula (7) It may be a polymer. The structural unit other than the structural unit represented by the formula (7) in the silicone polymer is not particularly limited, and examples thereof include a structural unit having a hydrosilyl group (Si-H). The silicone polymer may be a polymer having only one type of structural unit represented by formula (7), or a polymer having two or more types of structural units represented by formula (7) It may be Moreover, the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (7) may be sufficient.

Specific examples of the silicone-based polymer include, for example, polymers (polydimethylsiloxane or modified polydimethylsiloxane) represented by the following formulas (7a) to (7e).

The silicone polymer represented by the above formula (7a) is polydimethylsiloxane. The number x1 (the repeating number of the dimethylsilyloxy structural unit [-Si (CH ₃ ) ₂ -O-]) in the formula (7a) is not particularly limited, but is preferably 2 to 3,000, and more preferably 3 to 1,500.

The silicone polymer represented by the above formula (7b) is a polyether modified product of polydimethylsiloxane in which a polyether structure is introduced to the side chain of polydimethylsiloxane. R ¹⁰ in the formula (7b) represents a hydrogen atom or a methyl group. Further, R ¹¹ represents a hydrogen atom or a linear or branched alkyl group which may have a substituent. As the substituent in R ^11, include the substituents exemplified in R ⁸ above. Although m1 (the number of repeating of the methylene structural unit) in the formula (7b) is not particularly limited, it can be appropriately selected, for example, from the range of 1 to 30. Further, n1 (the number of repeating of the oxyethylene structural unit or the oxypropylene structural unit) is not particularly limited, but can be appropriately selected, for example, from the range of 2 to 3,000. Further, y1 (the repeating number of the structural unit containing a polyether structure (polyether side chain)) in the formula (7b) is not particularly limited, but is preferably 1 to 3000, more preferably 3 to 1,500. Furthermore, x 2 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 2 to 3,000, and more preferably 3 to 1,500. The addition form of the structural unit having a polyether structure and the dimethylsilyloxy structural unit in the silicone polymer represented by the formula (7b) may be a block type or a random type. . Further, when y1 is an integer of 2 or more, structural units having a polyether structure enclosed by parentheses with y1 may be identical to or different from each other.

The silicone polymer represented by the above formula (7c) is a long-chain alkyl-modified polydimethylsiloxane (polymethylalkylsiloxane) in which an alkyl group having a longer chain than a methyl group is introduced into the side chain of polydimethylsiloxane. It is. R ¹² in the formula (7c) represents a linear or branched alkyl group having 2 or more carbon atoms. Although y 2 (the number of repeating units of the methylalkylsilyloxy structural unit) in the formula (7c) is not particularly limited, it is preferably 2 to 3,000, and more preferably 3 to 1,500. Further, x3 (the number of repeating of the dimethylsilyloxy structural unit) is not particularly limited, but is preferably 0 to 3,000, and more preferably 2 to 1,500. The addition form of the methylalkylsilyloxy structural unit and the dimethylsilyloxy structural unit in the silicone polymer represented by the formula (7c) may be a block type or a random type. In addition, the methylalkylsilyloxy structural units enclosed in parentheses with y2 may be identical to or different from each other.

The silicone polymer represented by the above formula (7d) is an aralkyl modified product of polydimethylsiloxane in which an aralkyl group is introduced into the side chain of polydimethylsiloxane. The m 2 (the number of repeating of the methylene structural unit) in the formula (7d) is not particularly limited, but can be appropriately selected, for example, from the range of 1 to 30. Further, y 3 (the number of repeating units of the methylaralkylsilyloxy structural unit) is not particularly limited, but is preferably 2 to 3,000, and more preferably 3 to 1,500. Further, x 4 (the number of repeating of the dimethylsilyloxy structural unit) is not particularly limited, but is preferably 0 to 3,000, and more preferably 2 to 1,500. The addition form of the methylaralkylsilyloxy structural unit and the dimethylsilyloxy structural unit in the silicone polymer represented by the formula (7d) may be a block type or a random type. In addition, the methylaralkylsilyloxy structural units enclosed in parentheses with y3 may be identical to or different from each other.

The silicone polymer represented by the above formula (7e) is a polyester modified product of polydimethylsiloxane in which a polyester structure is introduced into the side chain of polydimethylsiloxane. R ¹³ and R ¹⁴ in the formula (7e) are the same or different and each represents a divalent organic group (eg, a divalent hydrocarbon group or the like). Further, R ¹⁵ represents a hydrogen atom or a linear or branched alkyl group which may have a substituent. As the substituent in R ^15, include the substituents exemplified in R ⁸ above. The m 3 (the number of repeating methylene structural units) in the formula (7e) is not particularly limited, but can be appropriately selected, for example, from the range of 1 to 30. Further, n2 (the number of repeating of the condensation structure of the polyol and the polycarboxylic acid) is not particularly limited, but can be appropriately selected, for example, from the range of 2 to 3,000. Further, y 4 (the number of repeating of the structural unit containing a polyester structure (polyester side chain)) in the formula (7e) is not particularly limited, but is preferably 1 to 3000, more preferably 3 to 1,500. Further, x5 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 2 to 3,000, and more preferably 3 to 1,500. The addition form of the structural unit having a polyester structure and the dimethylsilyloxy structural unit in the silicone polymer represented by the formula (7e) may be a block type or a random type. Moreover, when y4 is an integer greater than or equal to 2, the structural unit containing the polyester structure enclosed by the parenthesis which y4 was attached | subjected may be respectively the same, and may differ.

The silicone polymer can be obtained by a known or commonly used production method, and the production method is not particularly limited. For example, a polymer having a structure corresponding to the structural unit represented by the formula (7) is polymerized A compound having a predetermined structure (eg, polyether structure) with respect to the reactive group of a silicone polymer having a reactive group in the side chain (polydimethylsiloxane having a reactive group in the side chain, etc.) Or a compound having a polyester structure) by reaction and bonding. Moreover, a commercial item can also be used as said silicone type polymer.

(Fluorine-based leveling agent)
The fluorine-based leveling agent is a leveling agent including a compound having a fluorinated alkyl group in which part or all of the hydrogen atoms of the alkyl group are substituted with a fluorine atom. As the fluorine-based leveling agent, any known or commonly used fluorine-based leveling agent can be used, and it is not particularly limited. For example, trade name "BYK-340" (manufactured by Bick Chemie Japan Co., Ltd.), trade name "AC 110a" , "AC 100a" (or more, made by Algin Chemie), trade name "Megafuck F-114", "Megafuck F-410", "Megafuck F-444", "Megafuck EXP TP-2066", "Megafuck "Fuck F-430", "Megafuck F-472SF", "Megafuck F-477", "Megafuck F-552", "Megafuck F-553", "Megafuck F-554", "Megafuck F" -555 "," Megafuck R-94 "," Megafuck RS-72-K "," Megafuck RS-75 "," Megafuck Fuck F-556 "," Megafuck EXP TF-1367 "," Megafuck EXP TF-1437 "," Megafuck F-558 "," Megafuck EXP TF-1537 "(all manufactured by DIC Corporation), Brand name "FC-4430", "FC-4432" (above, Sumitomo 3M Co., Ltd. product), brand name "Futagent 100", "Futagent 100C", "Futagent 110", "Futagent 150", "Ftargent 150 CH", "Furgent AG", "Furgent 501", "Furgent 250", "Furgent 251", "Furgent 222F", "Furgent 208G", "Furgent 300", "Ftargent 310", "Faturgent 400SW" (or more Made by Neos Co., Ltd., trade names "PF-136A", "PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520" Alternatively, commercially available products such as “PF-651” and “PF-652” (manufactured by Kitamura Chemical Industrial Co., Ltd.) may be used.

As the compound having a fluorinated alkyl group, in particular, a fluorine-containing acrylic polymer having at least a structural unit (repeating structural unit) represented by the following formula (8), a structural unit represented by the following formula (9) The fluorine-containing polyether polymer which has at least (repeating structural unit) is preferable. That is, the fluorine-based leveling agent is preferably a leveling agent containing at least the fluorine-containing acrylic polymer or a leveling agent containing at least the fluorine-containing polyether polymer.

R ¹⁶ in the above formula (8) is a hydrogen atom, a fluorine atom, or a linear or branched alkyl having 1 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a fluorine atom Indicates a group. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group and a t-butyl group.

R ¹⁷ in the above formula (8) represents a fluorinated alkyl group (an alkyl group in which a part or all of hydrogen atoms are substituted with a fluorine atom). The fluorinated alkyl group is not particularly limited. For example, difluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group , Perfluoroethyl methyl group, 2,2,3,3,4,4-hexafluorobutyl group, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl group, 1,1-dimethyl-2 2,2,3,3,3-pentafluoropropyl group, 2- (perfluoropropyl) ethyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 1,1-dimethyl -2,2,3,3,4,4-hexafluorobutyl group, 1,1-dimethyl-2,2,3,3,4,4,4-heptafluorobutyl group, 2- (perfluorobutyl) Ethyl group 2,2,3,3 4,4,5,5,6,6-decafluorohexyl group, perfluoropentylmethyl group, 1,1-dimethyl-2,2,3,3,4,4,5,5-octafluoropentyl group, 1,1-dimethyl-2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2- (perfluoropentyl) ethyl group, 2,2,3,3,4,4 , 5, 5, 6, 6, 7, 7-dodecafluoroheptyl group, perfluorohexylmethyl group, 2- (perfluorohexyl) ethyl group, 2,2,3,3,4,4,5,5, 6,6,7,7,8,8-tetradecafluorooctyl group, perfluoroheptylmethyl group, 2- (perfluoroheptyl) ethyl group, 2,2,3,3,4,4,5,5, 6,6,7,7,8,8,9,9-hexadecafluorononyl group, puff Orooctylmethyl group, 2- (perfluorooctyl) ethyl group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10 -Octadecafluorodecyl group, perfluorononylmethyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3 3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridodeca A linear or branched alkyl group having 1 to 30 carbon atoms in which a part of hydrogen atoms such as fluorooctyl group is substituted with a fluorine atom; trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group , Heptafluoroisopropyl group, nonafluoro-n-butyl group, nonaflu Carbons such as oroisobutyl group, nonafluoro-s-butyl group, nonafluoro-t-butyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, etc. Examples include linear or branched perfluoroalkyl groups of 1 to 30 and the like. Among them, a perfluoroalkyl group is preferable as R ¹⁷ above.

The above-mentioned fluorine-containing acrylic polymer may be a polymer having only the structural unit represented by the formula (8) as a repeating structural unit, and it may be other than the structural unit represented by the formula (8) It may be a polymer having a structural unit. The fluorine-containing acrylic polymer may be a polymer having only one type of structural unit represented by formula (8) or may have two or more types of structural units represented by formula (8) It may be a polymer. Moreover, the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (8) may be sufficient.

The structural unit other than the structural unit represented by the formula (8), which the above-mentioned fluorine-containing acrylic polymer may have, is not particularly limited, and a monomer component (monomer component) of the acrylic polymer And structural units derived from known or commonly used monomers. Examples of the above monomers include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate and the like (including those having a functional group such as a hydroxyl group and a carboxyl group); methacrylic acid Methacrylates such as methyl, ethyl methacrylate, propyl methacrylate and butyl methacrylate (including those having functional groups such as hydroxyl and carboxyl); acrylamides such as acrylamide and N-methyl acrylamide; methacrylamide and the like Methacrylamides; allyl compounds; vinyl compounds such as aromatic vinyl compounds, vinyl ethers, vinyl esters and the like. Further, esters of polyalkylene glycol ethers with acrylic acid or methacrylic acid can also be used as the above-mentioned monomer.

As a specific example of the said fluorine-containing acrylic polymer, the fluorine-containing acrylic polymer etc. which are represented by following formula (8a) etc. are mentioned, for example.

R ¹⁸ in the formula (8a) represents a hydrogen atom or a methyl group. Also, R ¹⁹ represents a linear or branched alkyl group. The linear or branched alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), an isobutyl group, an s-butyl group, and a t group. And —C1-C30 linear or branched alkyl groups such as butyl group and pentyl group.

R ²⁰ in Formula (8a) represents a hydrogen atom or a methyl group. Also, R ²¹ represents a perfluoroalkyl group. Examples of the perfluoroalkyl group is not particularly limited, for example, perfluoroalkyl groups such as exemplified as R ¹⁷ in the formula (8) below.

R ²² in the formula (8a) represents a hydrogen atom or a methyl group. Further, R ²³ represents an organic group containing a polyether chain. The organic group comprising the polyether chain is not particularly limited, for example, such as those exemplified as R ⁹ in the formula (7) below.

R, s and t in the formula (8a) each represent an integer of 1 to 3000.

The fluorine-containing acrylic polymer can be obtained by a known or commonly used production method, and the production method is not particularly limited. For example, a monomer giving a structural unit represented by the formula (8) by polymerization For example, it can be produced by a method of polymerizing perfluoroalkyl acrylate, perfluoroalkyl methacrylate or the like. Moreover, a commercial item can also be used as said fluorine-containing acrylic polymer.

R ²⁴ in the above formula (9) represents a trivalent linear or branched hydrocarbon group. Examples of the trivalent linear or branched hydrocarbon group include methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, heptane And groups in which three hydrogen atoms have been removed from linear or branched alkanes such as 2-methylheptane, 3-methylheptane, octane, nonane and decane (alkane-triyl group) and the like. Among them, a group in which 3 hydrogen atoms have been removed from a linear or branched alkane having 1 to 10 carbon atoms is preferable.

R ²⁵ in the above formula (9) represents a fluorinated alkyl group. The fluorinated alkyl group is not particularly limited as long as it is an alkyl group in which a part or all of hydrogen atoms are substituted with a fluorine atom, for example, those exemplified as R ¹⁷ in the above formula (8) It can be mentioned. Among them, as R ²⁵ above, an alkyl group in which a part of hydrogen atoms are substituted by fluorine atoms is preferable.

Z (the repeating number of methylene structural units) in the above formula (9) represents an integer of 1 to 30. Among them, the integer of 1 to 10 is preferable.

The above-mentioned fluorine-containing polyether polymer may be a polymer having only the structural unit represented by the formula (9) as a repeating structural unit, and may be other than the structural unit represented by the formula (9) It may be a polymer having a structural unit of The fluorine-containing polyether polymer may be a polymer having only one structural unit represented by the formula (9), or two or more structural units represented by the formula (9). It may be a polymer having one. Moreover, the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (9) may be sufficient.

The structural unit other than the structural unit represented by the formula (9), which may be possessed by the fluorine-containing polyether polymer, is not particularly limited. For example, an oxyethylene unit [-OCH ₂ CH _2- And oxyalkylene structural units such as oxypropylene unit [—OCH (CH ₃ ) CH ₂ —].

As a specific example of the structural unit represented by said Formula (9), the structural unit etc. which are represented by a following formula are mentioned, for example. R ²⁶ in the following formula represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, n-butyl group, etc.). R ²⁵ and z in the following formulas are as defined above.

As a specific example of the said fluorine-containing polyether polymer, the fluorine-containing polyether polymer etc. which are represented by following formula (9a) etc. are mentioned, for example.

U, v and w in the formula (9a) each represent an integer of 1 to 50. Among them, the sum of u and w is preferably an integer of 2 to 80, more preferably an integer of 4 to 30, and still more preferably an integer of 6 to 14. Further, v is preferably an integer of 2 to 50, more preferably an integer of 5 to 20.

The above-mentioned fluorine-containing polyether polymer can be obtained by a known or commonly used production method, and the production method is not particularly limited. For example, a monomer giving a structural unit represented by formula (9) by polymerization (For example, cyclic ether compounds such as epoxy compounds and oxetane compounds, etc.) can be produced by polymerization (for example, ring-opening polymerization). Moreover, a commercial item can also be used as said fluorine-containing polyether type polymer.

The content (compounding amount) of the nonvolatile component of the leveling agent in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount (100 parts by weight of the compound having an epoxy group) contained in the curable epoxy resin composition Is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.1 to 4 parts by weight. The crack resistance of a hardened | cured material may fall that content (Level of non volatile matter conversion) of a leveling agent is less than 0.1 weight part. On the other hand, when the content of the leveling agent (in terms of nonvolatile content) exceeds 10 parts by weight, the heat resistance of the cured product may be lowered.

In particular, the content (blending amount) of the silicone polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer in the curable epoxy resin composition of the present invention is not particularly limited. The amount is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.1 to 10 parts by weight, based on the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. 0.1 to 4 parts by weight. When the content of the silicone polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer is less than 0.1 parts by weight, the crack resistance of the cured product may be reduced. On the other hand, when the content exceeds 10 parts by weight, the heat resistance of the cured product may be lowered. In addition, "the content (compounding amount) of the above-mentioned silicone polymer, the above-mentioned fluorine-containing acrylic polymer, and the above-mentioned fluorine-containing polyether polymer" means the above-mentioned silicone polymer, the above-mentioned fluorine-containing acrylic polymer And when it contains 2 or more types among the said fluorine-containing polyether type polymers, the sum total (total content) of these content is meant.

When the curable epoxy resin composition of the present invention contains the above-mentioned specific leveling agent, a reflector made of a cured product of the above resin composition can exhibit even higher levels of heat resistance and crack resistance. A decrease in luminous intensity over time of the optical semiconductor device provided with the reflector (in particular, a decrease in luminous intensity of the optical semiconductor device that emits high-intensity light) is suppressed. Such an effect is obtained by improving the adhesion of the curable epoxy resin composition (or the cured product thereof) of the present invention to the sealing material (the sealing resin for an optical semiconductor element) or the like by the blending of the leveling agent. It is presumed that

[Polyol compound]
The curable epoxy resin composition of the present invention preferably further contains a polyol compound. The curable epoxy resin composition of the present invention can form a cured product exhibiting higher heat resistance and crack resistance by containing the above-mentioned polyol compound, and an optical semiconductor device produced using the cured product will be aged over time. Less likely to occur at The above-mentioned polyol compound is a polymer (oligomer or polymer) having a number average molecular weight of 200 or more having two or more hydroxyl groups in one molecule (in one molecule), for example, polyether polyol, polyester polyol, polycarbonate polyol, etc. Is included. In addition, the said polyol compound can be used individually or in combination of 2 or more types.

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

The position of the hydroxyl group (two or more hydroxyl groups) possessed by the polyol compound is not particularly limited, but may be present at least at the end of the polyol (end of the polymer main chain) from the viewpoint of reactivity with the curing agent. It is particularly preferable to be present at least at both ends of the polyol.

The polyol compound may be solid or liquid as long as it can form a liquid curable epoxy resin composition after compounding with other components.

The number average molecular weight of the polyol compound may be 200 or more, and is not particularly limited, but is preferably 200 to 100,000, more preferably 300 to 50,000, and still more preferably 400 to 40,000. If the number average molecular weight is less than 200, peeling of the cured product or cracks may occur in the cured product when the solder reflow process is performed. On the other hand, when the number average molecular weight exceeds 100,000, it may be precipitated from the liquid curable epoxy resin composition or may not be dissolved. In addition, the number average molecular weight of the said polyol compound means the number average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC).

Examples of the polyol compound include a polyester polyol (including a polyester polyol oligomer) having an ester skeleton (polyester skeleton) in the molecule, and a polyether polyol (polyether polyol oligomer) having an ether skeleton (polyether skeleton) in the molecule. And polycarbonate polyols (including polycarbonate polyol oligomers) having a carbonate skeleton (polycarbonate skeleton) in the molecule. Other than the above, for example, phenoxy resin, epoxy equivalent is 1000 g / eq. Also included are bisphenol-type high molecular weight epoxy resins, polybutadienes having hydroxyl groups, acrylic polyols and the like.

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

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

The polyester polyol can be produced by a known or commonly used production method, and is not particularly limited. For example, condensation polymerization (polycondensation) of the above polyol and polycarboxylic acid, condensation polymerization of the above hydroxycarboxylic acid, the above lactones It can be produced by ring-opening polymerization of The conditions for polymerization are also not particularly limited, and can be appropriately selected from known or commonly used reaction conditions. In addition, as the above-mentioned polyol, polycarboxylic acid and hydroxycarboxylic acid, known or commonly used derivatives (for example, a hydroxyl group is protected by an acyl group, an alkoxycarbonyl group, an organic silyl group, an alkoxyalkyl group, an oxacycloalkyl group etc.) It is also possible to use derivatives, derivatives in which a carboxyl group is derived from an alkyl ester, an acid anhydride, an oxidized halide, and the like.

Examples of the polyester polyol include “Placcel 205”, “Placcel 205H”, “Placcel 205U”, “Placcel 205BA”, “Placcel 208”, “Placcel 210”, “Placcel 210CP”, and “Placcel 210BA”, for example. “Placcel 212”, “Placcel 212 CP”, “Placcel 220”, “Placcel 220 CPB”, “Placcel 220 NP1”, “Placcel 220 BA”, “Placcel 220 ED”, “Placcel 220 EB”, “Placcel 220 EC”, “Placcel 230”, “Placcel 230CP”, “Placcel 240”, “Placcel 240CP”, “Placcel 210N”, “Placcel 220N”, “Placcel L205AL”, “Placcel L208 L "," Placcel L212AL "," Placcel L220AL "," Placcel L230AL "," Placcel 305 "," Placcel 308 "," Placcel 312 "," Placcel L312AL "," Placcel 320 "," Placcel L320AL "," Placcel Commercially available products such as L330AL "," Placcel 410 "," Placcel 410D "," Placcel 610 "," Placcel P3403 "," Placcel CDE9P "(all manufactured by Daicel Co., Ltd.) can be used.

As said polyether polyol, the polyether polyol obtained by the addition reaction of the cyclic ether compound to polyols, the polyether polyol obtained by the ring-opening polymerization of an alkylene oxide, etc. are mentioned, for example.

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

The polyether polyol can be produced by a known or commonly used production method, and is not particularly limited. For example, addition reaction (ring-opening addition polymerization) of cyclic ether compound to polyols, ring-opening polymerization of alkylene oxide ( It can manufacture by homopolymerization or copolymerization). The conditions for polymerization are also not particularly limited, and can be appropriately selected from known or commonly used reaction conditions.

As said polyether polyol, for example, trade name "PEP-101" (made by Freund Sangyo Co., Ltd.), trade name "Adecaplulonic L", "Adecaplulonic P", "Adecaplulonic F", "Adecaplulonic R" , “Adecaplulonic TR”, “Adeca PEG” (all, manufactured by Adeka Co., Ltd.), trade names “PEG # 1000”, “PEG # 1500”, “PEG # 1 1000” (all, manufactured by NOF Corporation) , Brand name "New pole PE-34", "New pole PE-61", "New pole PE-78", "New pole PE-108", "PEG-200", "PEG-600", "PEG- 2000, “PEG-6000”, “PEG-10000”, “PEG-20000” (all manufactured by Sanyo Chemical Industries, Ltd.), trade name “P MG1000 "," PTMG1800 "," PTMG2000 "(or, Mitsubishi Chemical Co., Ltd.), can be used" PTMG prepolymer "(manufactured by Mitsubishi Plastics Inc.), and commercial products.

The polycarbonate polyol is a polycarbonate having two or more hydroxyl groups in the molecule. Among them, as the polycarbonate polyol, polycarbonate diol having two terminal hydroxyl groups in the molecule is preferable.

The polycarbonate polyol is a phosphation method or a carbonate exchange reaction using a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate or diphenyl carbonate as in the method for producing a conventional polycarbonate polyol (JP-A-62-187725, JP-A-62-187725). No. 2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420, etc.) and the like. Since the carbonate bond in the polycarbonate polyol is not susceptible to thermal decomposition, the resin cured product containing the polycarbonate polyol exhibits excellent stability even under high temperature and high humidity.

Examples of polyols used in a carbonate exchange reaction with the above dialkyl carbonate or diphenyl carbonate include, for example, 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butane Diol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,8-octanediol, 1,9-nonanediol, 1 , 12-dodecanediol, butadiene diol, neopentyl glycol, tetramethylene glycol, propylene glycol, dipropylene glycol and the like.

As the polycarbonate polyol, for example, trade names “Placcel CD 205 PL”, “Placcel CD 205 HL”, “Placcel CD 210 PL”, “Placcel CD 210 HL”, “Placcel CD 220 PL”, “Placcel CD 220 HL” (manufactured by Daicel Co., Ltd.), products Names "UH-CARB50", "UH-CARB100", "UH-CARB300", "UH-CARB90 (1/3)", "UH-CARB90 (1/1)", "UC-CARB100" (all above, Ube Use commercial products such as Kosan Co., Ltd., trade names “PCDL T4671”, “PCDL T4672”, “PCDL T5650J”, “PCDL T5651”, “PCDL T5652” (all manufactured by Asahi Kasei Chemicals Corporation) be able to

As polyol compounds other than the said polyether polyol, polyester polyol, and polycarbonate polyol, the brand names "YP-50", "YP-50S", "YP-55U", "YP-70", "ZX-1356-" are mentioned, for example. 2 "," YPB-43C "," YPB-43M "," FX-316 "," FX-310T40 "," FX-280S "," FX-293 "," YPS-007A30 "," TX-1016 " Phenoxy resin such as “JER1256”, “jER4250”, “jER4275” (Mitsubishi Chemical Co., Ltd.), trade names “Epototh YD-014”, "Epotote YD-017", "Epotote YD-019", "Epotote YD-020G", "Epotote YD-90 "," Epotote YD-907 "," Epotote YD-6020 "(all, made by Nippon Steel Chemical Co., Ltd.), brand name" jER1007 "," jER1009 "," jER1010 "," jER1005F "," jER1009F ", The epoxy equivalent of “jER1006FS”, “jER1007FS” (all, manufactured by Mitsubishi Chemical Corporation), etc. is 1000 g / eq. Bisphenol type polymer epoxy resin exceeding the brand name; “Poly bd R-45HT”, “Poly bd R-15HT”, “Poly ip”, “KRASOL” (all manufactured by Idemitsu Kosan Co., Ltd.), trade name “α Polybutadienes having a hydroxyl group such as -ω polybutadiene glycol G-1000, "α-ω polybutadiene glycol G-2000", "α-ω polybutadiene glycol G-3000" (all manufactured by Nippon Soda Co., Ltd.); "Hitaloid 3903", "Hitaloid 3904", "Hitaloid 3905", "Hitaloid 6500", "Hitaloid 6500B", "Hitaloid 3018X" (all manufactured by Hitachi Chemical Co., Ltd.), trade name "Acridic DL-1537" , "Acrydic BL-616", "Acrydi "AL-1157", "Acrydic A-322", "Acrydic A-817", "Acrydic A-870", "Acrydic A-859-B", "Acrydic A-829", "Acrydic A-49-394-IM "(all, DIC Corporation), trade names" DIALAN SR-1346 "," DIALAN SR-1237 "," DIALAN AS-1139 " Commercial products, such as acrylic polyols, such as (made) can be used.

The use amount (content amount) of the polyol compound is not particularly limited, but it is preferably 1 to 50 parts by weight, and more preferably, the total amount (100 parts by weight) of the component (A) and the component (B). The amount is 1.5 to 40 parts by weight, more preferably 5 to 30 parts by weight. When the content of the polyol compound exceeds 50 parts by weight, the Tg of the cured product is too low, and the volume change due to heating becomes large, which may cause a failure such as failure of the optical semiconductor device. When the content of the polyol compound is less than 1 part by weight, the light reflectivity may easily decrease with time.

When the curable epoxy resin composition of the present invention contains a siloxane derivative (G) having two or more epoxy groups in the molecule, the amount (content) of the above-mentioned polyol compound is not particularly limited. 1 to 50 parts by weight is preferable, more preferably 1.5 to 40 parts by weight, still more preferably 5 to 30 parts by weight, based on 100 parts by weight of the total amount of component (B) and component (G). It is a department. When the content of the polyol compound exceeds 50 parts by weight, the Tg of the cured product is too low, and the volume change due to heating becomes large, which may cause a failure such as failure of the optical semiconductor device. When the content of the polyol compound is less than 1 part by weight, the light reflectivity may easily decrease with time.

[Acrylic block copolymer]
The curable epoxy resin composition of the present invention preferably further contains an acrylic block copolymer. More specifically, when the curable epoxy resin composition of the present invention contains an acrylic block copolymer, an optical semiconductor device produced using the curable epoxy resin composition has a particularly high luminance and high output. Even if there is a tendency, the light intensity does not easily decrease. That is, by using the acrylic block copolymer, the cured product obtained by curing the curable epoxy resin composition of the present invention can exhibit higher levels of heat resistance, light resistance and crack resistance.

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

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

The above-mentioned acrylic block copolymer is not particularly limited. For example, a diblock copolymer consisting of two polymer blocks, a triblock copolymer consisting of three polymer blocks, and four or more polymer blocks The multiblock copolymer etc. which are comprised are comprised.

Among them, as the above-mentioned acrylic block copolymer, a polymer block [S] (soft block) having a low glass transition temperature (Tg) and a polymer block [a] from the viewpoint of heat resistance, light resistance and crack resistance improvement. Block copolymer in which polymer blocks [H] (hard blocks) having a higher Tg than S] are alternately arranged, more preferably polymer block [S] in the middle, and polymers at both ends thereof Preferred is a triblock copolymer of HSH structure having a block [H]. In addition, although Tg of the polymer which comprises polymer block [S] of the said acryl block copolymer is not specifically limited, Less than 30 degreeC is preferable. Moreover, Tg of the polymer which comprises polymer block [H] is although it does not specifically limit, 30 degreeC or more is preferable. When the said acryl block copolymer has several polymer block [H], each polymer block [H] may have the same composition, and may differ. Similarly, also when the said acryl block copolymer has several polymer block [S], each polymer block [S] may have the same composition, and may differ.

The monomer component constituting the polymer block [H] in the above acrylic block copolymer (the triblock copolymer of the above HSH structure and the like) is not particularly limited. The monomer which is 30 degreeC or more is mentioned, More specifically, methyl methacrylate, styrene, acrylamide, an acrylonitrile etc. are mentioned. On the other hand, the monomer component constituting the polymer block [S] in the above acrylic block copolymer is not particularly limited, but for example, a monomer having a homopolymer Tg of less than 30 ° C. can be mentioned, more specifically, Acrylic acid C _2-10 alkyl esters such as butyl acrylate and 2-ethylhexyl acrylate, butadiene (1,4-butadiene) and the like can be mentioned.

As a preferable specific example of the acryl block copolymer in the curable epoxy resin composition of this invention, the said polymer block [S] is a polymer comprised as a main monomer, for example with a butyl acrylate (BA), and said Polymethyl methacrylate-block-polybutyl acrylate-block-polymethyl methacrylate terpolymer (PMMA-b-PBA-b-) which is a polymer in which the polymer block [H] is composed mainly of methyl methacrylate (MMA) PMMA) and the like. The above-mentioned PMMA-b-PBA-b-PMMA is preferable in view of heat resistance, light resistance and improvement of crack resistance. Incidentally, the above-mentioned PMMA-b-PBA-b-PMMA is a hydrophilic group (for example, a hydroxyl group, a carboxyl group, an amino acid, etc.) for the purpose of improving the compatibility with the component (A) and the component (B) etc., if necessary. And / or (meth) acrylic acid such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid and the like are copolymerized with a PMMA block and / or PBA block. Good.

The number average molecular weight of the acrylic block copolymer is not particularly limited, but is preferably 3,000 to 500,000, and more preferably 30,000 to 400,000. If the number average molecular weight is less than 3000, the toughness of the cured product may not be sufficient, and the crack resistance may be reduced. On the other hand, when the number average molecular weight exceeds 500000, the compatibility with the alicyclic epoxy compound (A) may be reduced, and the mechanical properties of the cured product may be adversely affected and the crack resistance may be reduced.

The above acrylic block copolymer can be produced by a known or commonly used method for producing a block copolymer. Among the methods for producing the above acrylic block copolymer, living polymerization (living radical polymerization, living anionic polymerization, living), among others, from the viewpoint of ease of control of molecular weight, molecular weight distribution and terminal structure of acrylic block copolymer. Cationic polymerization etc.) is preferred. The above living polymerization can be carried out by known or conventional methods.

Moreover, as said acrylic block copolymer, the brand name "nano strength M52N", "nano strength M22 N", "nano strength M51", "nano strength M52", "nano strength M53" (made by Arkema, PMMA-) is mentioned, for example. Commercially available products such as b-PBA-b-PMMA), "NanoStrength E21" and "NanoStrength E41" (manufactured by Arkema, PSt (polystyrene) -b-PBA-b-PMMA) can be used.

The amount of use (content) of the acrylic block copolymer is not particularly limited, but preferably 1 to 30 parts by weight with respect to the total amount (100 parts by weight) of the component (A) and the component (B). More preferably, it is 3 to 15 parts by weight, still more preferably 3 to 10 parts by weight. If the amount of the acrylic block copolymer used is less than 1 part by weight, the toughness of the cured product may not be sufficient, and heat resistance and light resistance may be reduced. On the other hand, when the use amount of the acrylic block copolymer exceeds 30 parts by weight, the compatibility with the alicyclic epoxy compound (A) may be reduced, and the crack resistance of the cured product may be reduced.

When the curable epoxy resin composition of the present invention contains a siloxane derivative (G) having two or more epoxy groups in the molecule, the amount (content) of the above acrylic block copolymer is not particularly limited, The amount is preferably 1 to 30 parts by weight, more preferably 3 to 15 parts by weight, still more preferably 3 to 15 parts by weight based on the total amount (100 parts by weight) of the components (A), (B) and (G). It is 10 parts by weight. If the amount of the acrylic block copolymer used is less than 1 part by weight, the toughness of the cured product may not be sufficient, and heat resistance and light resistance may be reduced. On the other hand, when the use amount of the acrylic block copolymer exceeds 30 parts by weight, the compatibility with the alicyclic epoxy compound (A) may be reduced, and the crack resistance of the cured product may be reduced.

[Rubber particles other than silicone rubber particles]
The curable epoxy resin composition of the present invention may further contain rubber particles other than silicone rubber particles (hereinafter sometimes simply referred to as "rubber particles"). Examples of the rubber particles include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal free NBR, particulate SBR (styrene-butadiene rubber) and the like. The rubber particle is preferably a rubber particle having a multilayer structure (core-shell structure) comprising a core portion having rubber elasticity and at least one shell layer covering the core portion. The rubber particles 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 a hydroxyl group and / or a carboxyl group (any one or both of a hydroxyl group and a carboxyl group) as a functional group to be obtained are preferable. When hydroxyl groups and / or carboxyl groups are not present on the surface of the rubber particles, the cured product may be susceptible to cracking.

The polymer constituting the core portion having rubber elasticity in the rubber particles is not particularly limited, but (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like It is preferable to use an essential monomer component. The polymer constituting the core portion having the rubber elasticity is, for example, other, for example, conjugated vinyl such as styrene, aromatic vinyl (aromatic vinyl compound) such as α-methylstyrene, nitrile such as acrylonitrile and methacrylonitrile, butadiene, isoprene and the like Diene, ethylene, propylene, isobutene or the like may be contained as a monomer component.

Among them, the polymer constituting the core portion having rubber elasticity is, as a monomer component, together with a (meth) acrylic acid ester, one or more selected from the group consisting of aromatic vinyl, nitrile, and conjugated diene. It is preferable to include in combination. That is, as a polymer which comprises the said core part, binary copolymers, such as (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene, for example; (meth) acrylic acid ester / aroma And terpolymers such as vinyl group / conjugated diene. The polymer constituting the core portion may contain silicone such as polydimethyl siloxane and polyphenyl methyl siloxane, polyurethane and the like.

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

The core portion of the rubber particles is, among others, from the viewpoint of heat resistance, a binary copolymer of (meth) acrylic ester / aromatic vinyl (especially butyl acrylate / styrene) or (meth) acrylic ester / The core portion is preferably composed of a vinyl aromatic / reactive cross-linking monomer terpolymer (in particular, butyl acrylate / styrene / divinyl benzene).

The core portion of the rubber particles can be produced by a commonly used method, and can be produced, for example, by a method of polymerizing the above-mentioned monomers by an emulsion polymerization method. In the emulsion polymerization method, the entire amount of the above monomers may be charged at once and then polymerized, or after polymerization of a part of the above monomers, the remainder may be continuously or intermittently added and polymerized. Furthermore, polymerization methods using seed particles may be used.

It is preferable that the polymer which comprises the shell layer of the said rubber particle is a polymer different from the polymer which comprises the said core part. Further, as described above, the shell layer preferably has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A). Thereby, in particular, the adhesiveness can be improved at the interface with the alicyclic epoxy compound (A), and a cured product obtained by curing a curable epoxy resin composition containing a rubber particle having the shell layer is obtained. And can exhibit excellent crack resistance. Moreover, the fall of the glass transition temperature of hardened | cured material can also be prevented.

It is preferable that the polymer which comprises the said shell layer contains (meth) acrylic acid esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, 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, (meth) acrylic acid esters other than butyl acrylate (eg, (meth) acrylic acid) as monomer components of the polymer constituting the shell layer It is preferred to use methyl acid, ethyl (meth) acrylate, butyl methacrylate etc.). As a monomer component which may be contained other than (meth) acrylic acid ester, for example, aromatic vinyl such as styrene and α-methylstyrene, and nitrile such as acrylonitrile and methacrylonitrile can be mentioned. The rubber particles preferably contain the above monomers alone or in combination of two or more as a monomer component constituting the shell layer, together with the (meth) acrylic acid ester, and in particular, at least from the viewpoint of heat resistance. It is preferable to contain aromatic vinyl.

Furthermore, in order to form a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component, a polymer constituting the above-mentioned shell layer Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, α, β-unsaturated acids such as (meth) acrylic acid, α, β-unsaturated acid anhydrides such as maleic anhydride It is preferable to contain the following monomers.

It is preferable that the polymer which comprises the shell layer in the said rubber particle contains the (meth) acrylic acid ester as a monomer component in combination of 1 type, or 2 or more types selected from the said monomer. That is, the shell layer is, for example, (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / α, β-unsaturated acid, (meth) acrylic acid It is preferable that the shell layer is composed of a ternary copolymer such as an acid ester / α, β-unsaturated acid / reactive crosslinking monomer (methyl methacrylate / acrylic acid / allyl methacrylate etc.).

The polymer constituting the shell layer may contain, as the other monomer components, divinyl benzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triaryl in addition to the above-mentioned monomers as the core portion. You may contain the reactive crosslinking monomer which has a 2 or more reactive functional group in 1 monomer (1 molecule), such as allyl cyanurate, a diallyl phthalate, a butylene glycol diacrylate.

The rubber particles (rubber particles having a core-shell structure) can be obtained by coating the core portion with a shell layer. As a method of coating the core portion with a shell layer, for example, a method of coating the surface of the core portion having rubber elasticity obtained by the above method by applying a copolymer constituting the shell layer, the above method The core part which has the rubber elasticity obtained by these is used as a trunk component, and the method of graft-polymerizing each component which comprises a shell layer as a branch component etc. can be mentioned.

The average particle size of the rubber particles is not particularly limited, but is preferably 10 to 500 nm, and more preferably 20 to 400 nm. The maximum particle size of the rubber particles is not particularly limited, but is preferably 50 to 1000 nm, and more preferably 100 to 800 nm. When the average particle size exceeds 500 nm, or when the maximum particle size exceeds 1000 nm, the dispersibility of the rubber particles in the cured product may be reduced, and the crack resistance may be reduced. On the other hand, when the average particle size is less than 10 nm or the maximum particle size is less than 50 nm, it may be difficult to obtain the effect of improving the crack resistance of the cured product.

The content (blending amount) of the rubber particles in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition On the other hand, 0.5 to 30 parts by weight is preferable, and more preferably 1 to 20 parts by weight. When the content of the rubber particles is less than 0.5 parts by weight, the crack resistance of the cured product tends to decrease. On the other hand, when the content of the rubber particles exceeds 30 parts by weight, the heat resistance of the cured product tends to decrease.

[Stress Reliever (I)]
The curable epoxy resin composition of the present invention preferably contains a stress relaxation agent (I). The stress relaxation agent (I) is a compound capable of relieving internal stress in the cured product. The curable epoxy resin composition of the present invention uses the stress relaxation agent (I) in combination with the alicyclic epoxy compound (A), the monoallyl diglycidyl isocyanurate compound (B), and the white pigment (C). , Compression molding is possible even if the filling amount of the white pigment (C) and the inorganic filler (J) described later is increased, and the light reflectivity, heat resistance, and light resistance of a cured product formed by compression molding It tends to be excellent in The stress relaxation agent (I) can also relieve the internal stress of the cured product, thereby reducing the warpage of the molded product by compression molding.

The stress relaxation agent (I) is not particularly limited, and examples thereof include silicone rubber particles (I1), silicone oil (I2), liquid rubber component (I3), thermoplastic resin (I4) and the like.

The silicone rubber particles (I1) are not particularly limited, and examples thereof include those composed of polysiloxanes such as polymethylsiloxane and polymethylphenylsiloxane.
Moreover, it is preferable that the polysiloxane which comprises silicone rubber particle (I1) is bridge | crosslinked. The crosslinked polysiloxane is not particularly limited, and is crosslinked, for example, by condensation reaction such as silanol group, radical reaction of mercaptosilyl group and vinylsilyl group, addition reaction of vinylsilyl group and hydrosilyl group (SiH group), etc. And the like, but from the viewpoint of reactivity and reaction process, a polysiloxane obtained by addition reaction of a vinyl group-containing organopolysiloxane and an organohydrogenpolysiloxane in the presence of a platinum-based catalyst. Is preferred.

The silicone rubber particles (I1) may be surface-treated from the viewpoint of compatibility with the resin composition, improvement of dispersibility, and adjustment of viscosity of the resin composition after dispersion. The aspect of the surface treatment is not particularly limited, and examples thereof include silicone rubber particles coated with methyl methacrylate, silicone rubber particles coated with a silicone resin, and the like.

The average particle size (d ₅₀ ) of the silicone rubber particles (I1) is not particularly limited, but is preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm. The maximum particle diameter of the silicone rubber particles (I1) is not particularly limited, but is preferably 0.1 to 250 μm, and more preferably 0.1 to 150 μm. By setting the average particle size to 100 μm or less (or the maximum particle size to 250 μm or less), the crack resistance of the cured product tends to be further improved. On the other hand, when the average particle size is 0.1 μm or more (or the maximum particle size is 0.1 μm or more), the dispersibility of the silicone rubber particles (I1) tends to be further improved.
Further, the shape of the silicone rubber particles (I1) is also not particularly limited, but is preferably spherical from the viewpoint of improving the workability.

From the viewpoint of being able to form a cured product excellent in light reflectivity, heat resistance and light resistance by compression molding, the silicone rubber particles (I1) are made of crosslinked polysiloxane or The surface is preferably coated with a silicone resin, and from the viewpoint of the compatibility of the resin component and the silicone rubber particles (I1), the surface of the crosslinked polydimethylsiloxane is preferably coated with a silicone resin.

In the curable epoxy resin composition of the present invention, the silicone rubber particles (I1) can be used alone or in combination of two or more. Further, the silicone rubber particles (I1) can be produced by a known or commonly used method, and the production method thereof is, for example, silicone rubber particles produced by the method described in JP-A-7-196815. Or the brand names "KMP-600", "KMP-601", "KMP-602", "KMP-605", "X-52-7030", "KMP-597", " It is also possible to use commercially available products such as KMP-598 "," KMP-594 "," X-52-875 "," KMP-590 "," KMP-701 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). it can.

The silicone oil (I2) is not particularly limited, and examples thereof include non-modified silicone oil and modified silicone oil.

The non-modified silicone oil is not particularly limited, and examples thereof include polydimethylsiloxane type, polymethyl hydrogen siloxane type, and polymethyl phenyl siloxane type.

The modified silicone oil is not particularly limited. For example, any of reactive silicone oil having reactivity with epoxy resin and non-reactive silicone oil having no reactivity with epoxy resin may be used. Examples of the reactive silicone oil include amino-modified type, epoxy-modified type, carboxyl-modified type, carbinol-modified type, methacryl-modified type, mercapto-modified type, and phenol-modified type. Examples of non-reactive silicone oils include polyalkylene ether modified type, methylstyryl modified type, alkyl modified type, fatty acid ester modified type, alkoxy modified type, fluorine modified type and the like. In addition, the reactive silicone oil may have a non-reactive modifying group, and examples thereof include polyalkylene ether-amino-modified silicone oil, polyalkylene ether-epoxy-modified silicone oil, etc. Alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B), a polyalkylene derivative having reactivity with a compound having an epoxy group such as a siloxane derivative (G), and capable of controlling flowability and viscosity, and epoxy modified Silicone oil is preferred.

As the silicone oil (I2), a polyalkylene ether-epoxy-modified silicone oil is preferable from the viewpoint of being able to form a cured product excellent in light reflectivity, heat resistance and light resistance by compression molding, and epoxy is particularly preferable. A polyalkylene ether-modified silicone compound having a structure represented by the following formula (10) having an equivalent weight of 3000 to 15,000 (hereinafter, may be referred to as “polyalkylene ether-modified silicone compound (10)”) is preferable.

In the above formula (10), R ²⁶ is a C 2 or C 3 alkylene group. Examples of the alkylene group having 2 or 3 carbon atoms include a methyl methylene group, a dimethyl methylene group, an ethylene group, a propylene group, a trimethylene group and the like, and a trimethylene group is preferable.

In the above formula (10), xa represents an integer of 80 to 140.
In the above formula (10), ya represents an integer of 1 to 5. When ya is an integer of 2 or more, the structures in parentheses with ya may be identical to or different from each other.
In the above formula (10), za represents an integer of 5 to 20. The structures in the brackets with za may be identical to or different from each other.

In said formula (10), A is a polyalkylene ether group which has a structure represented by following formula (10a).

In the above formula (10a), a and b are each independently an integer of 0 to 40. When a is 40 or less, the water resistance of the cured product tends to be improved.
On the other hand, when b is 40 or less, the flowability of the curable epoxy resin composition tends to be improved.

Although the sum of a and b is not particularly limited, it is preferably an integer of 1 to 80. When the sum of a and b is in the above range, the water resistance of the cured product and the flowability of the curable epoxy resin composition can be easily controlled.

In the above formula (10a), B is a hydrogen atom or a methyl group. From the viewpoint of water resistance of the cured product, B is preferably a methyl group.

The addition form of each structural unit in the above formula (10) may be random or block as long as the two trimethylsilyl groups in formula (10) are present at both ends. In addition, the addition form of each structural unit in the above formula (10a) may also be random or block as long as B is present at the end. Moreover, the order of arrangement of each structural unit in the above formulas (10) and (10a) is not particularly limited.

The epoxy equivalent of the polyalkylene ether-modified silicone compound (10) is, as described above, 3,000 to 15,000, preferably 4,000 to 15,000, and more preferably 5,000 to 13,000. When the epoxy equivalent is 3000 or more, the stress relaxation inside the cured product tends to be further improved. On the other hand, when the epoxy equivalent is 15,000 or less, the compatibility with the resin tends to be further improved.
In addition, the epoxy equivalent of a polyalkylene ether modified silicone compound (10) can be measured based on JISK7236: 2001.

In the curable epoxy resin composition of the present invention, silicone oil (I2) may be used alone or in combination of two or more. Moreover, as said silicone oil (I2), it can manufacture by a well-known thru | or a usual method, For example, using silicone oil (I2) manufactured by the method described in Unexamined-Japanese-Patent No. 2008-201904 Use commercially available products such as “SF8421” (made by Toray Dow Corning Co., Ltd.) and “Y-19268” (made by Momentive Performance Materials Japan (made)). You can also.

The liquid rubber component (I3) is not particularly limited. For example, polybutadiene, maleated polybutadiene, acrylated polybutadiene, methacrylated polybutadiene, epoxidized polybutadiene, acrylonitrile butadiene rubber, carboxy terminal acrylonitrile butadiene rubber, amino terminal acrylonitrile butadiene rubber And vinyl-terminated acrylonitrile butadiene rubber, styrene butadiene rubber and the like.
The liquid rubber component (I3) may be used alone or in combination of two or more.

The thermoplastic resin (I4) is not particularly limited, and examples thereof include polyimide resin, polyamide resin, polyetherimide resin, polyester resin, polyesterimide resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, Polyether ketone resin etc. are mentioned. Among these, phenoxy resin and polyimide resin are preferable from the viewpoint of heat resistance. These thermoplastic resins can be used alone or in combination of two or more.

Although the glass transition temperature (Tg) of the said thermoplastic resin (I4) is not specifically limited, It is preferable that it is 200 degrees C or less.

The stress relaxation agents (I) may be used alone or in combination of two or more.
From the viewpoint that a cured product excellent in light reflectivity, heat resistance, and light resistance can be formed as the stress relaxation agent (I) by compression molding, silicone rubber particles (I1) and silicone oil (I2) can be used. Preferably, at least one selected from the group consisting of: a crosslinked polydimethylsiloxane having a silicone resin on its surface as the silicone rubber particles (I1); and a polyalkylene ether modified as the silicone oil (I2) The silicone compound (10) is preferred.

The content (blending amount) of the stress relaxation agent (I) of the present invention is not particularly limited, but it is preferably 1 to 250 parts by weight, more preferably 5 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). The amount is about 230 parts by weight, more preferably 10 to 200 parts by weight. By setting the content of the stress relaxation agent (I) to 1 part by weight or more, compression molding is possible even when the loading amount of the white pigment (C) and the inorganic filler (J) described later is increased, and molding The light reflectivity, heat resistance and light resistance of the cured product tend to be further improved. In addition, the warpage of the molded article is alleviated, and dimensional stability tends to be improved. On the other hand, when the content of the stress relaxation agent (I) is 250 parts by weight or less, the curability of the curable epoxy resin composition tends to be further improved.

The content (compounding amount) of the stress relaxation agent (I) of the present invention is not particularly limited, but it is 1 to 200 parts by weight with respect to 100 parts by weight of the compound having an epoxy group contained in the curable epoxy resin composition. It is preferably part, more preferably 5 to 150 parts by weight, still more preferably 8 to 120 parts by weight. By setting the content of the stress relaxation agent (I) to 1 part by weight or more, compression molding is possible even if the loading amount of the white pigment (C) and the inorganic filler (J) described later is increased, and molding The light reflectivity, heat resistance, and light resistance of the cured product tend to be further improved. In addition, the warpage of the molded article is alleviated, and dimensional stability tends to be improved. On the other hand, when the content of the stress relaxation agent (I) is 200 parts by weight or less, the curability of the curable epoxy resin composition tends to be further improved.

[Inorganic filler (J)]
The curable epoxy resin composition of the present invention preferably contains an inorganic filler (J) separately from the white pigment (C). The inorganic filler (J) mainly imparts excellent heat resistance and light resistance (particularly, excellent heat resistance) to the cured product formed when the curable epoxy resin composition is formed by compression molding. . It also has the function of reducing the coefficient of linear expansion of the cured product (reflector). Moreover, depending on the type of the inorganic filler (J), it may be possible to impart excellent light reflectivity to the cured product (reflector).

As the inorganic filler (J), known or commonly used inorganic fillers can be used, and it is not particularly limited. For example, silica, zircon, calcium silicate, calcium phosphate, silicon carbide, silicon nitride, silicon nitride, aluminum nitride, boron nitride Powders such as iron oxide, aluminum oxide, forsterite, steatite, spinel, clay, dolomite, hydroxyapatite, nepheline sainite, cristobalite, wollastonite, diatomaceous earth, etc., or molded products thereof (eg, spherical beads) Etc.). Further, examples of the inorganic filler (J) include those obtained by subjecting the above-mentioned inorganic filler to known or customary surface treatment. Among them, as the inorganic filler (J), silica, silicon nitride, aluminum nitride and boron nitride are preferable from the viewpoints of heat resistance (especially yellowing resistance), light resistance and fluidity of a cured product (reflector), More preferably, it is silica (silica filler).

The silica is not particularly limited, and for example, known or commonly used silicas such as fused silica, crystalline silica, high purity synthetic silica and the like can be used. In addition, as the silica, those to which a known or commonly used surface treatment [for example, a surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, a silicone, etc.] Can also be used.

The shape of the silica is not particularly limited, and examples thereof include powder, sphere, crushed, fibrous, needle, and scaly. Among them, spherical silica is preferable from the viewpoint of dispersibility, and spherical silica (for example, spherical silica having an aspect ratio of 1.2 or less) is particularly preferable.

The central particle size of the silica is not particularly limited, but is preferably 0.1 to 50 μm, and more preferably 0.1 to 30 μm from the viewpoint of improving the light reflectivity of the cured product (reflector). In addition, the said center particle diameter means the particle size (median diameter) in 50% of the integration value in the particle size distribution measured by the laser diffraction and the scattering method.

In addition, in the curable epoxy resin composition of this invention, an inorganic filler (J) can also be used individually by 1 type, and can also be used in combination of 2 or more types. The inorganic filler (J) can also be produced by a known or commonly used production method, for example, under the trade names "FB-910", "FB-940", "FB-950", "FB-105". , "FB-105FD", "FB-5D", "FB-8S", "FB-7SDC", "FB-5SDC", "FB-3SDC", "FB-9FDC", "FB-7FDC", FB series such as "FB-5FDC", "FB-970FD", "FB-975FD", "FB-950FD", "FB-40RFD", brand name "DAW-03DC", "DAW-0525", "DAW -1025 "and other DAW series, trade name" SGP "(above, made by Denka Co., Ltd.), trade name" HF-05 "(made by Tokuyama), trade name" 10 μm SE-CC5 "(made by Admatech Product names “MSR-2212” and “MSR-25” (all, manufactured by Ryumori Co., Ltd.), and product names “HS-105”, “HS-106” and “HS-107” (all and more, Micron) Commercial products, such as company-made) can also be used.

The content (blending amount) of the inorganic filler (J) in the curable epoxy resin composition of the present invention is not particularly limited, but it is 10 to 90% by weight with respect to the curable epoxy resin composition (100% by weight) Is more preferably 13 to 75% by weight, still more preferably 15 to 70% by weight, and still more preferably 20 to 70% by weight. When the content of the inorganic filler (J) is 10% by weight or more, the heat resistance and light resistance of the formed cured product (particularly, excellent when forming the curable epoxy resin composition by compression molding) Heat resistance tends to be further improved. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and defects such as warpage of a lead frame in a substrate for mounting an optical semiconductor element using the reflector tend not to occur easily. On the other hand, when the content of the inorganic filler (J) is 90% by weight or less, the moldability of the cured product (reflector) is improved, and the mass tends to be more suitable.

The content (blending amount) of the inorganic filler (J) in the curable epoxy resin composition of the present invention is not particularly limited, but 100 parts by weight in total of the compound having an epoxy group contained in the curable epoxy resin composition The amount is preferably 10 to 1500 parts by weight, more preferably 50 to 1200 parts by weight, and still more preferably 100 to 1000 parts by weight. When the content of the inorganic filler (J) is 10 parts by weight or more, the heat resistance and light resistance of the formed cured product (particularly, excellent when forming the curable epoxy resin composition by compression molding) Heat resistance tends to be further improved. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and defects such as warpage of a lead frame in a substrate for mounting an optical semiconductor element using the reflector tend not to occur easily. On the other hand, when the content of the inorganic filler (J) is 1,500 parts by weight or less, the moldability of the cured product (reflector) is improved, and the mass tends to be more suitable.

The maximum particle diameter of the white pigment (C) and the inorganic filler (J) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 200 μm or less, more preferably 185 μm or less, still more preferably 175 μm or less Particularly preferably, it is 150 μm or less. The heat resistance of the formed cured product formed by compression molding of the curable epoxy resin composition that the maximum particle diameter is 200 μm or less than when the white pigment or the inorganic filler having a maximum particle diameter exceeding 200 μm is used Properties, light resistance, and crack resistance (particularly, excellent heat resistance) tend to be further excellent. Moreover, it becomes possible to increase these content by using the white pigment (C) and the inorganic filler (J) with a small largest particle diameter, and the light reflectivity of a hardened material, heat resistance, and light resistance become more There is a tendency to improve further. The lower limit of the maximum particle diameter is, for example, 0.01 μm or more. The maximum particle size is the total maximum particle size of the white pigment (C) and the inorganic filler (J) contained in the curable epoxy resin composition of the present invention. The said largest particle diameter means the largest particle size in the particle size distribution measured by the laser diffraction and scattering method.

When titanium oxide is contained in the curable epoxy resin composition of the present invention, the ratio of titanium oxide to the total amount (100% by weight) of the white pigment (C) and the inorganic filler (J) is not particularly limited. From the viewpoint of the balance between heat resistance (yellowing resistance) and light reflectivity of the (reflector), it is preferably 5 to 70% by weight, more preferably 5 to 60% by weight. By setting the ratio of titanium oxide to 5% by weight or more, the light reflectivity of the cured product (reflector) tends to be further improved. In addition, heat resistance (in particular, yellowing resistance) and light resistance (in particular, ultraviolet resistance) tend to be further improved. On the other hand, by setting the ratio of titanium oxide to 70% by weight or less, the moldability of the cured product (reflector) is improved, and there is a tendency that mass production is more suitable.

[Release agent]
The curable epoxy resin composition of the present invention may further contain a release agent. By including the release agent, continuous molding by a molding method using a mold such as transfer molding becomes easy, and it becomes possible to manufacture a cured product (reflector) with high productivity. As the releasing agent, known or commonly used releasing agents can be used, and it is not particularly limited. For example, fluorine-based releasing agents (fluorine-containing compounds; for example, fluorine oil, polytetrafluoroethylene etc.), Silicone-based release agent (silicone compound; for example, silicone oil, silicone wax, silicone resin, polyorganosiloxane having a polyoxyalkylene unit, etc.), wax-based release agent (waxes; for example, vegetable wax such as carnauba wax Animal waxes such as wool wax, paraffins such as paraffin wax, polyethylene wax, oxidized polyethylene wax etc., higher fatty acids or their salts (eg, metal salts etc.), higher fatty acid esters, higher fatty acid amides, mineral oil etc. .

In addition, in the curable epoxy resin composition of this invention, a mold release agent can also be used individually by 1 type, and can also be used in combination of 2 or more types. Further, the release agent can be produced by a known or conventional method, or a commercially available product can be used.

When the curable epoxy resin composition of the present invention contains a release agent, the content (blending amount) of the release agent is not particularly limited, but the compound having an epoxy group contained in the curable epoxy resin composition The amount is preferably 1 to 12 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total amount. By setting the content of the release agent to 1 part by weight or more, the releasability of the cured product (reflector) tends to be further improved, and the productivity of the reflector tends to be further improved. On the other hand, by setting the content of the release agent to 12 parts by weight or less, good adhesion to the lead frame of the reflector in the optical semiconductor element mounting substrate tends to be able to be secured.

[Antioxidant]
The curable epoxy resin composition of the present invention may contain an antioxidant. By including the antioxidant, it is possible to produce a cured product (reflector) that is further excellent in heat resistance (particularly, yellowing resistance). As the antioxidant, known or commonly used antioxidants can be used and are not particularly limited. For example, phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), phosphorus And antioxidants (phosphorus compounds) and sulfur antioxidants (sulfur compounds).

Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 Monophenols such as 2, 5-di-t-butyl-4-hydroxyphenyl) propionate; 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl- 6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspi [5.5] Bisphenols such as undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3'-Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5'-di-t-butyl-4 Polymeric phenols such as' -hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like can be mentioned.

Examples of hindered amine antioxidants include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl Butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine etc. may be mentioned.

Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, and tris (2,4-di-t-). Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2 Phospha such as 2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite Fights; 9, 10- Hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene And oxaphosphaphenanthrene oxides such as -10-oxide.

Examples of sulfur-based antioxidants include dodecanethiol, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. Can be mentioned.

In the curable epoxy resin composition of the present invention, the antioxidant may be used singly or in combination of two or more. The antioxidant can also be produced by a known or conventional method, for example, under the trade name “Irganox 1010” (manufactured by BASF, a phenolic antioxidant), under the trade name “AO-60”, “AO-80 (Made by ADEKA Corporation, phenolic antioxidant), trade name “Irgafos 168” (manufactured by BASF, phosphorus antioxidant), trade name “Adekastab HP-10”, “Adekastab PEP-36” (traded) It is also possible to use commercially available products such as ADEKA, phosphorus-based antioxidants, and trade name "HCA" (manufactured by Sanko Co., Ltd., phosphorus-based antioxidants).

When the curable epoxy resin composition of the present invention contains an antioxidant, the content (blending amount) of the antioxidant is not particularly limited, but the compound having an epoxy group contained in the curable epoxy resin composition The amount is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight in total. By setting the content of the antioxidant to 0.1 parts by weight or more, oxidation of the cured product (reflector) is effectively prevented, and heat resistance and yellowing resistance tend to be further improved. On the other hand, when the content of the antioxidant is 5 parts by weight or less, coloring is suppressed and a reflector having a better hue tends to be easily obtained.

[Additive]
The curable epoxy resin composition of the present invention may contain various additives in addition to the components described above as long as the effects of the present invention are not impaired. For example, when a compound having a hydroxy group such as ethylene glycol, diethylene glycol, propylene glycol, glycerin etc. (particularly, aliphatic polyhydric alcohol, but excluding the above-mentioned polyol compound) is contained as the above additive, the reaction proceeds slowly It can be done. In addition, antifoaming agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, fluorescent whitening agents, and interfaces within limits that do not impair viscosity and light reflectivity. Conventional additives such as activators, flame retardants, colorants, ion adsorbents, UV absorbers, light stabilizers, and pigments other than white pigment (C) can be used. The content of these additives is not particularly limited, and can be appropriately selected.

As the above-mentioned fluorescent whitening agents, known to conventional fluorescent whitening agents can be used. When the curable epoxy resin composition of the present invention contains a fluorescent whitening agent, it tends to be more excellent in light reflectivity, heat resistance, light resistance and crack resistance of a cured product formed by compression molding. Examples of the fluorescent whitening agent include pyrazoline derivatives, stilbene derivatives, triazine derivatives, thiazole derivatives, benzoxazole derivatives, xanthone derivatives, triazole derivatives, oxazole derivatives, thiophene derivatives, coumarin derivatives, naphthalimide derivatives and the like.

The curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B), a white pigment (C), a curing agent (D), and a curing accelerator (F). The viscosity at 25 ° C. of the mixture comprising the alicyclic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), curing agent (D), and curing accelerator (F) is particularly limited. Although not preferred, it is preferably 5000 mPa · s or less. The curable epoxy resin composition of the present invention is a group comprising the above-mentioned siloxane derivative (G), alicyclic polyester resin (H), rubber particles other than silicone rubber particles, a silicone-based leveling agent and a fluorine-based leveling agent. At least one leveling agent selected from the group consisting of a polyol compound, an acrylic block copolymer, a stress relaxation agent (I), and / or the above-mentioned aliphatic polyhydric alcohol such as ethylene glycol (hereinafter referred to as "other optional components" (A), monoallyl diglycidyl isocyanurate compound (B), curing agent (D), curing accelerator (F), and the like. And other optional components.

On the other hand, when the curable epoxy resin composition of the present invention contains an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B), a white pigment (C), and a curing catalyst (E), The viscosity at 25 ° C. of the mixture comprising the alicyclic epoxy compound (A), the monoallyl diglycidyl isocyanurate compound (B), and the curing catalyst (E) is not particularly limited, but is preferably 5000 mPa · s or less . The curable epoxy resin composition of the present invention may contain other optional components, in which case the above-mentioned mixture is an alicyclic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), It is a mixture consisting of a curing catalyst (E) and other optional components. In addition, in this specification, the viscosity in 25 degreeC of said 2 types of mixtures may be generically called "resin viscosity."

The resin viscosity is a viscosity measured at 25 ° C. under normal pressure. The viscosity of the resin is preferably 5000 mPa · s or less, more preferably 4000 mPa · s or less, still more preferably 3500 mPa · s or less, and particularly preferably 3000 mPa · s or less. The heat resistance, light resistance, and heat resistance of the formed cured product formed by compression molding of the curable epoxy resin composition that the resin viscosity is 5000 mPa · s or less than when the resin viscosity exceeds 5000 mPa · s. Crack resistance (particularly, excellent heat resistance) tends to be further excellent. In addition, since the resin viscosity is relatively low, the content of other components such as the white pigment (C) and the inorganic filler (J) can be increased, and the light reflectivity of the cured product, heat resistance, and The light resistance tends to be further improved. The lower limit of the resin viscosity is, for example, 100 mPa · s or more. The resin viscosity is measured using, for example, a digital viscometer (model number “DVU-EII type” manufactured by Tokimec Corporation), rotor: standard 1 ° 34 ′ × R24, temperature: 25 ° C., rotation number: 0 It can be measured under the condition of 5 to 10 rpm.

The resin viscosity is, for example, a component to be used (for example, an alicyclic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), a curing agent (D), a curing accelerator (F), a curing catalyst (E) It becomes easy to obtain by using a liquid component at 25 ° C. as a siloxane derivative (G), an alicyclic polyester resin (H), a liquid stress relaxation agent (I) and the like. In addition, although a component solid at 25 ° C. may be used as the above component, the content thereof is adjusted so that the viscosity of the resin becomes 5000 mPa · s or less. Moreover, it becomes easy to obtain also by adjusting content of a rubber particle and solid stress relaxation agent (I) in the range which does not impair the effect of this invention.

The curable epoxy resin composition of the present invention can be obtained by heating to react a part of the alicyclic epoxy compound (A) and the curing agent (D) in the curable epoxy resin composition, B. It may be a curable epoxy resin composition (curable epoxy resin composition in a B-stage state) which has been staged.

As described above, since the curable epoxy resin composition of the present invention is excellent in light reflectivity, heat resistance and light resistance after curing, it is particularly preferably used as a resin composition for transfer molding or a resin composition for compression molding. it can. Among them, the curable epoxy resin composition of the present invention is a resin composition for compression molding, because it is particularly excellent in light reflectivity, heat resistance and light resistance of a cured product (reflector) formed by compression molding. Is particularly preferred.

<Method of Preparing Curable Epoxy Resin Composition>
It does not specifically limit as a manufacturing method of the curable epoxy resin composition of this invention, A well-known thru | or a usual method can be applied. Specifically, for example, a predetermined amount of alicyclic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), white pigment (C), curing agent (D), curing accelerator (F), and Optional additives are blended, or a predetermined amount of alicyclic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), white pigment (C), curing catalyst (E), and optional addition And mixing and mixing using a mixer, such as a dissolver or homogenizer, a kneader, a roll, a bead mill, a self-revolution type stirring apparatus, and the like. Moreover, after stirring and mixing, you may degas under pressure reduction or under a vacuum.

More specifically, the curable epoxy resin composition of the present invention is, for example, a cycloaliphatic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), a siloxane having two or more epoxy groups in the molecule Separately alpha agent containing a compound having an epoxy group such as derivative (G) as an essential component, and beta agent containing a curing agent (D) and a curing accelerator (F) or a curing catalyst (E) as an essential component It is possible to prepare it by a method in which the .alpha. Agent and the .beta. Agent are stirred and mixed in a predetermined ratio, and defoamed under vacuum if necessary. The alicyclic polyester resin (H) may be mixed (blended) in advance as a component of the α agent and / or the β agent, or when the α agent and the β agent are mixed, the α agent, You may mix | blend as 3rd components other than beta agent. Similarly, the white pigment (C) may be mixed (blended) in advance as a component of the α agent and / or the β agent, or when the α agent and the β agent are mixed, the α agent, β You may mix | blend as 3rd components other than an agent.

The temperature at the time of stirring and mixing when preparing the above-mentioned α-agent is not particularly limited, but it is preferably 30 to 150 ° C., more preferably 35 to 130 ° C. Further, the temperature at the time of stirring and mixing when preparing the above-mentioned β-agent (when it is composed of two or more components) is not particularly limited, but it is preferably 30 to 100 ° C, more preferably 35 to 80 ° C . For stirring and mixing, known devices, for example, various mixers such as a dissolver and a homogenizer, a kneader, a roll, a beads mill, a self-revolution type stirring device and the like can be used. Moreover, after stirring and mixing, you may degas under pressure reduction or under a vacuum.

In particular, when the curable epoxy resin composition of the present invention contains a curing agent (D) as an essential component, from the viewpoint of obtaining a uniform composition, the alicyclic polyester resin (H) and the curing agent (D) Are mixed beforehand to obtain a mixture thereof (a mixture of an alicyclic polyester resin (H) and a curing agent (D)), and then the mixture is blended with a curing accelerator (F) and other additives to obtain β Preferably, the agent is prepared and subsequently mixed by mixing the beta agent and the alpha agent. The temperature at which the alicyclic polyester resin (H) and the curing agent (D) are mixed is not particularly limited, but it is preferably 60 to 130 ° C., more preferably 90 to 120 ° C. The mixing time is not particularly limited, but is preferably 30 to 100 minutes, more preferably 45 to 80 minutes. The mixing is not particularly limited, but is preferably performed under a nitrogen atmosphere. Also, for mixing, the above-mentioned known apparatus can be used.

After mixing the alicyclic polyester resin (H) and the curing agent (D), there is no particular limitation, but even if appropriate chemical treatment (for example, hydrogenation or terminal modification of alicyclic polyester, etc.) is performed, etc. Good. In the mixture of the alicyclic polyester resin (H) and the curing agent (D), a part of the curing agent (D) is an alicyclic polyester resin (H) (for example, an alicyclic polyester resin (H) Or the like) and may react with

As a mixture of the above-mentioned alicyclic polyester resin (H) and a curing agent (D), for example, “HN-7200” (manufactured by Hitachi Chemical Co., Ltd.), “HN-5700” (manufactured by Hitachi Chemical Co., Ltd.) Commercial products such as) can also be used.

Although not particularly limited, the rubber particles may be compounded in the state of a composition dispersed in advance in the alicyclic epoxy compound (A) (the composition may be referred to as “rubber particle dispersed epoxy compound”). preferable. That is, the curable epoxy resin composition of the present invention comprises the rubber particle dispersed epoxy compound, a white pigment (C), a curing agent (D) and a curing accelerator (F), or a curing catalyst (E), It is preferable to prepare by mixing with other components as needed. By such a preparation method, in particular, the dispersibility of rubber particles in the curable epoxy resin composition can be improved. However, the blending method of the rubber particles is not limited to the above method, and it may be a blending method by itself.

(Rubber particle dispersed epoxy compound)
The rubber particle-dispersed epoxy compound is obtained by dispersing rubber particles in an alicyclic epoxy compound (A). The total amount of 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 thereof. It may be. Similarly, the rubber particles in the rubber particle-dispersed epoxy compound may be all or part of the rubber particles 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 above-mentioned reactive diluent, for example, aliphatic polyglycidyl ether having a viscosity of 200 mPa · s or less at normal temperature (25 ° C.) can be preferably used. As aliphatic polyglycidyl ethers having a viscosity (25 ° C.) of 200 mPa · s or less, for example, cyclohexane dimethanol diglycidyl ether, cyclohexane diol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether And trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether and the like.

The use amount of the reactive diluent can be appropriately adjusted and is not particularly limited, but preferably 30 parts by weight or less, more preferably 25 parts by weight or less based on 100 parts by weight of the total of the rubber particle dispersed epoxy compound. (For example, 5 to 25 parts by weight). If the amount used is 30 parts by weight or less, desired properties such as toughness (improvement in crack resistance) tend to be obtained easily.

The manufacturing method of the said rubber particle dispersion epoxy compound is not specifically limited, A well-known and usual method can be used. For example, after the rubber particles are dehydrated and dried to form a powder, they are mixed with the alicyclic epoxy compound (A) and dispersed, or the emulsion of the rubber particles and the alicyclic epoxy compound (A) are directly mixed. Then, the method of dehydrating etc. is mentioned.

The viscosity at 25 ° C. of the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 100 to 1,000,000 mPa · s, more preferably 200 to 800,000 mPa · s, and still more preferably 300 to 800,000 mPa · s. By setting the viscosity at 25 ° C. to 100 mPa · s or more, the workability at the time of casting tends to be improved, and the heat resistance and light resistance of the cured product tend to be further improved. On the other hand, by setting the viscosity at 25 ° C. to 1,000,000 mPa · s or less, the workability at the time of casting tends to be improved, and problems caused by casting defects in the cured product tend not to occur easily.

<Cured product>
By curing the curable epoxy resin composition of the present invention by heating, it is possible to obtain a cured product which is excellent in light reflectivity, and excellent in heat resistance, light resistance, and crack resistance. In addition, the hardened | cured material which hardened the curable epoxy resin composition of this invention, ie, the hardened | cured material of the curable epoxy resin composition of this invention, may be called "the hardened | cured material of this invention." The heating temperature (curing temperature) during curing is not particularly limited, but it is preferably 50 to 200 ° C., more preferably 80 to 180 ° C. Further, the heating time (curing time) at the time of curing is not particularly limited, but it is preferably 60 to 1800 seconds, more preferably 90 to 900 seconds. If the curing temperature and the curing time are lower than the lower limit of the above range, curing will be insufficient, and if the upper limit is above the above range, yellowing due to thermal decomposition will occur, which is not preferable. Although the curing conditions depend on various conditions, for example, when the curing temperature is raised, the curing time can be appropriately adjusted by shortening the curing time, and when the curing temperature is lowered, prolonging the curing time or the like. In addition, the curing process may be performed in one step (for example, only compression molding) or, for example, may be performed in multiple steps (for example, further heating in an oven as post curing (second curing) after compression molding). It is also good. When post curing is performed, the heating temperature at this time is preferably 50 to 200 ° C., more preferably 60 to 180 ° C., and more preferably about the same as the curing temperature. The post curing time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours.

The cured product of the present invention has high light reflectivity and is excellent in heat resistance, light resistance and cracking resistance. For this reason, the said hardened | cured material does not deteriorate easily and a reflectance does not fall easily with time. Therefore, the curable epoxy resin composition of the present invention is used for LED package applications (components of LED packages, for example, reflector materials in optical semiconductor devices, housing materials, etc.), applications for bonding electronic components, applications for liquid crystal displays (for example, reflection) Plates, etc., inks for white substrates, sealers, etc. can be preferably used. Among them, a curable resin composition for an LED package (in particular, a curable resin composition for a reflector in an optical semiconductor device (that is, a curable resin composition for forming a reflector)) can be particularly preferably used.

The reflectance of the cured product of the present invention is not particularly limited, but for example, the reflectance of light with a wavelength of 450 nm is preferably 90% or more, more preferably 90.5% or more. In particular, the reflectance of light of 450 to 800 nm is preferably 90% or more, more preferably 90.5% or more. The reflectance is measured, for example, using the cured product of the present invention (thickness: 3 mm) as a test piece and using a spectrophotometer (trade name "Spectrophotometer UV-2450" manufactured by Shimadzu Corporation). can do.

The retention of the reflectance of light with a wavelength of 450 nm after heating at 120 ° C. for 250 hours (sometimes referred to as “reflectance after heat aging for 250 hours”) relative to the initial reflectance ([[ The reflectance after heat aging for 250 hours] / [initial reflectance] × 100) is not particularly limited, but is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more, particularly preferably Is 98% or more. In particular, the retention for light of 450 to 800 nm is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more, and particularly preferably 98% or more. According to the curable epoxy resin composition of the present invention, the cured product formed by compression molding can have the retention of 98% or more.

The reflectance of the reflectance of light with a wavelength of 450 nm after heating at 120 ° C. for 500 hours (sometimes referred to as “the reflectance after heat aging for 500 hours”) to the initial reflectance ([ The reflectance after heat aging for 500 hours] / [initial reflectance] × 100) is not particularly limited, but is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more, particularly preferably Is 98% or more. In particular, the retention for light of 450 to 800 nm is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more, and particularly preferably 98% or more. According to the curable epoxy resin composition of the present invention, it is possible for the cured product formed by compression molding to have the retention of 90% or more.

Retention of the reflectance of the cured product of the present invention to light having a wavelength of 450 nm after irradiation with ultraviolet light having an intensity of 10 mW / cm ² for 250 hours (sometimes referred to as “reflectance after ultraviolet aging”) relative to the initial reflectance The rate ([reflectance after ultraviolet light aging] / [initial reflectance] × 100) is not particularly limited, but is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more . In particular, the retention for light of 450 to 800 nm is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.

The reflectance is measured, for example, using the cured product of the present invention (thickness: 3 mm) as a test piece and using a spectrophotometer (trade name "Spectrophotometer UV-2450" manufactured by Shimadzu Corporation). can do.

The cured product of the present invention has high light reflectivity, is excellent in heat resistance and light resistance, and is tough. For this reason, since the said hardened | cured material does not deteriorate easily, and also it is hard to produce a crack, it is hard to fall in a reflectance over time. Therefore, the curable epoxy resin composition of the present invention is used for LED package applications (components of LED packages, for example, reflector materials in optical semiconductor devices, housing materials, etc.), applications for bonding electronic components, applications for liquid crystal displays (for example, reflection) Plates, etc., inks for white substrates, sealers, etc. can be preferably used. Among them, it can be particularly preferably used as a curable resin composition for an LED package (in particular, a curable resin composition for a reflector (reflecting material) in an optical semiconductor device).

<Curable resin composition for light reflection>
The curable resin composition for light reflection of the present invention comprises the curable epoxy resin composition of the present invention. In the present specification, “curable resin composition for light reflection” means a curable resin composition capable of forming a cured product having high light reflectivity by curing, specifically, For example, it means a curable resin composition capable of forming a cured product having a reflectance of 90% or more for light with a wavelength of 450 nm. By using the curable resin composition for light reflection of the present invention, for example, a light comprising a reflector formed of a cured product excellent in various physical properties such as light reflectivity, heat resistance, light resistance, and crack resistance. A semiconductor device can be obtained. Since the reflector is unlikely to cause a decrease in reflectance over time, the light semiconductor device including the reflector has a decrease in light intensity over time, particularly even when including a high-power, high-brightness optical semiconductor device. It is difficult and can exhibit high reliability. In particular, the cured product of the present invention is excellent in crack resistance, in particular, resistance to cracking under cold temperature cycles, and has high reliability.

When the curable epoxy resin composition of the present invention is a curable resin composition for a reflector in an optical semiconductor device, the curable epoxy resin composition of the present invention is a substrate for an optical semiconductor element in an optical semiconductor device (optical semiconductor element It is a molding material (material used for molding with a metal mold etc.) used for the use which forms the reflector (light reflection member) which a mounting substrate has. Therefore, by molding (and curing) the curable epoxy resin composition of the present invention, it has high light reflectivity, is excellent in heat resistance and light resistance, and is further excellent in crack resistance (for example, high quality) A highly durable) optical semiconductor element mounting substrate can be manufactured. The reflector is a member for reflecting the light emitted from the optical semiconductor element in the optical semiconductor device to enhance the directivity and brightness of the light and to improve the light extraction efficiency. A substrate used for mounting an optical semiconductor device having at least a reflector formed of the cured product of the present invention may be referred to as "substrate for mounting an optical semiconductor device according to the present invention".

<Substrate for mounting optical semiconductor device>
The optical semiconductor element mounting substrate of the present invention is a substrate having at least a reflector (white reflector) formed of the cured product of the present invention. FIG. 1 is a schematic view showing an example of the optical semiconductor element mounting substrate of the present invention, wherein (a) is a perspective view and (b) is a cross-sectional view. In FIG. 1, 100 is a white reflector, 101 is a metal wiring (lead frame), 102 is a mounting area of the optical semiconductor device, and 103 is a package substrate. A metal wiring 101 and a white reflector 100 are attached to the package substrate 103, and the optical semiconductor element 107 is placed at the center (mounting area 102 of the optical semiconductor element) and die-bonded. And the metal wiring 101 on the package substrate 103 are connected by wire bonding. Resin, ceramic or the like is used as the material of the package substrate 103, but it may be the same as the white reflector. The upper white reflector 100 in the optical semiconductor element mounting substrate of the present invention annularly surrounds the periphery of the mounting area 102 of the optical semiconductor element, and has a concave shape inclined such that the diameter of the ring expands upward. Have. In the substrate for mounting an optical semiconductor element of the present invention, the inner surface of the above-mentioned concave shape may be formed at least by the cured product of the present invention. Further, as shown in FIG. 1, the portion surrounded by the metal wiring 101 (lower portion of 102) may be the package substrate 103 or the white reflector 100 (ie, “100/103 in FIG. 1”. “Means may be a white reflector 100 or a package substrate 103). However, the optical semiconductor element mounting substrate of the present invention is not limited to the mode shown in FIG.

As a method of forming a white reflector in the substrate for mounting an optical semiconductor element of the present invention, a known or commonly used molding method (for example, compression molding etc.) can be used, and it is not particularly limited. Such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and dam molding by dispensing, etc. (preferably compression molding). As conditions of hardening at the time of forming a reflector, it can choose suitably from conditions etc. at the time of forming the above-mentioned hardened material, for example. In the present invention, among them, heat treatment is performed in multiple stages in that it can prevent foaming due to a rapid hardening reaction and relieve stress strain due to hardening to improve toughness (crack resistance). Curing is preferred.

The optical semiconductor device mounting substrate of the present invention is used as a substrate in an optical semiconductor device, and the optical semiconductor device is mounted on the substrate to obtain the optical semiconductor device of the present invention.

<Optical semiconductor device>
The optical semiconductor device of the present invention is an optical semiconductor device provided with at least an optical semiconductor element as a light source and a reflector (reflecting material) made of the cured product of the present invention. More specifically, the optical semiconductor device of the present invention is an optical semiconductor device having at least the optical semiconductor element mounting substrate of the present invention and the optical semiconductor element mounted on the substrate. The optical semiconductor device of the present invention has a reflector formed of the cured product of the present invention as a reflector, so that the luminance of light does not easily decrease with time, and the reliability is high. FIG. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention. In FIG. 2, 100 is a white reflector, 101 is a metal wiring (lead frame), 103 is a package substrate, 104 is a bonding wire, 105 is a sealing material, 106 is a die bonding, and 107 is an optical semiconductor element (LED element). In the optical semiconductor device shown in FIG. 2, the light emitted from the optical semiconductor element 107 is reflected by the surface (reflecting surface) of the white reflector 100, so the light from the optical semiconductor element 107 is extracted with high efficiency. In addition, as shown in FIG. 2, the optical-semiconductor element in the optical semiconductor device of this invention is normally sealed by the transparent sealing material (105 in FIG. 2).

3 and 4 show another example of the optical semiconductor device of the present invention. Reference numeral 108 in FIGS. 3 and 4 denotes a heat sink (case heat sink), and by having such a heat sink 108, the heat dissipation efficiency in the optical semiconductor device is improved. FIG. 3 is an example in which the heat dissipation path of the heat sink is located immediately below the optical semiconductor device, and FIG. 4 is an example in which the heat dissipation path of the heat sink is located in the lateral direction of the optical semiconductor device [(a) is a top view, (B) shows the AA 'cross section in (a)]. The heat sink 108 protruding to the side surface of the optical semiconductor device in FIG. 4 may be referred to as a radiation fin. Also, 109 in FIG. 4 indicates a cathode mark. However, the optical semiconductor device of the present invention is not limited to the embodiments shown in FIGS.

Since the optical semiconductor device of the present invention has at least a reflector made of the cured product of the present invention, light can be emitted stably for a long period of time even when outputting high-intensity light. Furthermore, since the reflector made of the cured product of the present invention is excellent in crack resistance (in particular, crack resistance with respect to a cold cycle), problems such as a decrease in light intensity over time are less likely to occur. Therefore, the optical semiconductor device of the present invention can exhibit high reliability as an optical semiconductor device having a long life.

EXAMPLES The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples. The unit of the compounding amount of each component of the curable epoxy resin composition in Tables 1 to 7 is part by weight. In addition, silicone type leveling agents ("BYK-300", "AC FS 180"), fluorine type leveling agents ("BYK-340", "AC 110a") and stress relaxation agents ("KMP-600" in Tables 4 to 7). The blending amounts of “KMP-602”, “SF8421”, and “Y-19268” indicate the amount as a product (the amount of the product itself). In addition, “-” in Tables 1 to 7 indicates that the corresponding component was not blended.

Production Example 1
(Production of White Pigment-Containing Epoxy Resin: Examples 1 to 5)
Monoallyl diglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound ((3,4,3 ′, 4′-diepoxy) bicyclohexyl, Daicel Co., Ltd. Manufactured by Daicel Co., Ltd., according to the formulation (blending ratio) (unit: parts by weight) shown in Table 1 and stirring at 80 ° C. for 1 hour The glycidyl isocyanurate was dissolved to obtain an epoxy resin (mixture). Next, the above epoxy resin and white pigment (titanium oxide; trade name "DCF-T- 17050", manufactured by Resino Color Industrial Co., Ltd.) according to the blending formulation (blending ratio) (unit: parts by weight) shown in Table 1 Using a dissolver, they are uniformly mixed, and are kneaded using a roll mill under predetermined conditions (roll pitch: 0.2 mm, rotational speed: 25 Hz, 3 passes) to obtain a white pigment-containing epoxy resin (epoxy resin composition) The

Production Example 2
(Production of White Pigment-Containing Epoxy Resin: Comparative Examples 1 to 10)
Monoallyl diglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound (trade name “Ceroxide 2021 P”, manufactured by Daicel Co., Ltd .; trade name “EHPE3150”, Daicel Co., Ltd.), Tris glycidyl isocyanurate (trade name “TEPIC-PAS B26”, Nissan Chemical Industries, Ltd.) are mixed according to the formulation (blending ratio) (unit: parts by weight) shown in Table 1; An epoxy resin (mixture) was obtained (in the case of Comparative Examples 1, 2, 4 to 6 and 8, since the component of the epoxy resin is one kind, the mixing is not performed and it is used as the epoxy resin as it is). Next, the above epoxy resin and white pigment (titanium oxide; trade name "DCF-T- 17050", manufactured by Resino Color Industrial Co., Ltd.) according to the blending formulation (blending ratio) (unit: parts by weight) shown in Table 1 Using a dissolver, they are uniformly mixed, and are kneaded using a roll mill under predetermined conditions (roll pitch: 0.2 mm, rotational speed: 25 Hz, 3 passes) to obtain a white pigment-containing epoxy resin (epoxy resin composition) The

Production Example 3
(Production of a curing agent composition containing at least a curing agent (hereinafter referred to as “agent K”): Examples 1 to 4, Comparative Examples 1 to 4, 9)
Curing agent (acid anhydride) (Shin Nippon Rika Co., Ltd., trade name "Rikasid MH-700"), Hardening accelerator (San Apro Co., Ltd. trade name "U-CAT 18X"), additive (Japanese According to the compounding prescription (blending ratio) shown in Table 1 under the trade name "Ethylene glycol" manufactured by Kojun Chemical Industries, Ltd., a self-revolution stirring device (made by Shinky Co., Ltd., trade name "Awatori Neritaro AR-" The mixture was uniformly mixed using 250 ") and degassed to obtain a K agent.

Examples 1 to 5 and Comparative Examples 1 to 10
(Production of a curable epoxy resin composition)
The white pigment-containing epoxy resin obtained in Production Example 1, the white pigment-containing epoxy resin obtained in Production Example 2 and the product obtained in Production Example 3 so as to obtain the compounding formulation (unit: parts by weight) shown in Table 1 K agent, curing catalyst (manufactured by Sanshin Chemical Industry Co., Ltd., trade name "SunAid SI-100L"), self-revolution stirring device (made by Shinky Co., trade name "Awatori Neritaro AR-250") The mixture was uniformly mixed (2000 rpm, 5 minutes) and degassed to obtain a curable epoxy resin composition.

(Manufacturing of cured products)
The curable epoxy resin composition is sandwiched between release films made of polyester, placed in a 150 ° C. compression molding die, cured by heating and pressing at a pressure of 3.0 MPa for 600 seconds, and then post cured A cured product was obtained by carrying out (at 150 ° C. for 5 hours).

Production Example 4
(Production of White Pigment-Containing Epoxy Resin: Examples 6 to 14, Comparative Examples 11 to 21)
Monoallyl diglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound ((3,4,3 ′, 4′-diepoxy) bicyclohexyl, Daicel Co., Ltd. Manufactured by Daicel Co., Ltd .; trade name "EHPE 3150"; trade name "Dacel Co., Ltd."; Tris Glycidyl isocyanurate (trade name "TEPIC-PAS B26"; Nissan Chemical Industries Co., Ltd.) A siloxane derivative having two epoxy groups in the molecule (trade name “X-40-2678”, manufactured by Shin-Etsu Chemical Co., Ltd.), a siloxane derivative having three epoxy groups in the molecule (trade name “X -40-2720, Shin-Etsu Chemical Co., Ltd., a siloxane derivative having four epoxy groups in the molecule (trade name "X-40-2670", Shin-Etsu The monoallyl diglycidyl isocyanurate is dissolved by mixing Gakuin Industrial Co., Ltd. product according to the formulation (blending ratio) (unit: weight part) shown in Tables 2 and 3 and further stirring at 80 ° C. for 1 hour. An epoxy resin (mixture) was obtained (in the case of Comparative Examples 11 to 15, since the component of the epoxy resin was one kind, the mixing was not performed and it was used as the epoxy resin as it is). Next, the above-described epoxy resin and white pigment (titanium oxide; trade name "DCF-T- 17050", manufactured by Resino Color Industrial Co., Ltd.) are shown in Tables 2 and 3 as the blending formulation (blending ratio) (unit: parts by weight) According to the above, uniformly mixed using a dissolver, and kneaded with a roll mill under predetermined conditions (roll pitch: 0.2 mm, rotational speed: 25 Hz, 3 passes) to obtain a white pigment-containing epoxy resin (epoxy resin composition) I got

Production Example 5
(Production of Curing Agent Composition Containing Curing Agent (K Agent): Examples 6 to 14 and Comparative Examples 11 to 21)
Curing agent (acid anhydride) (trade name "Rikasid MH-700", manufactured by Hitachi Chemical Co., Ltd.), mixture of curing agent (acid anhydride) and alicyclic polyester resin (trade name "HN-7200", Hitachi Chemical Co., Ltd. product, mixture of curing agent (acid anhydride) and alicyclic polyester resin (trade name “HN-5700”, Hitachi Chemical Co., Ltd.), cure accelerator (trade name “U” -CAT 18X ", San-Apro Co., Ltd. product, additives (trade name" ethylene glycol ", Wako Pure Chemical Industries, Ltd.), the formulation shown in Tables 2 and 3 (blending ratio) (unit: parts by weight) The mixture was uniformly mixed and defoamed using a self-revolution stirring apparatus (trade name "Awatori Neritaro AR-250" manufactured by Shinky Co., Ltd.) to obtain a K agent.

Examples 6 to 14 and Comparative Examples 11 to 21
(Production of a curable epoxy resin composition)
The white pigment-containing epoxy resin obtained in Production Example 4 and the K agent obtained in Production Example 5 were mixed in a self-revolution stirring apparatus (product: The mixture was uniformly mixed (2000 rpm, 5 minutes) using the name "Awatori Neritaro AR-250" (manufactured by Shinky Co., Ltd.), and defoamed to obtain a curable epoxy resin composition.

Production Example 6
(Manufacture of rubber particles)
In a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion exchanged water and 0.68 g of sodium dioctyl sulfosuccinate were charged, 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 was added here. The mixture is stirred and emulsified for 20 minutes, and then 9.5 mg of potassium peroxodisulfate is added and stirred for 1 hour to perform the first seed polymerization, followed by addition of 180.5 mg of potassium peroxodisulfate, 5 Stir for a minute. Here, the remaining amount (about 95% by weight) of 180.5 g of butyl acrylate, 48.89 g of styrene, 7.33 g of divinylbenzene and 0.95 g of sodium dioctyl sulfosuccinate in the amount necessary to form the core portion The dissolved monomer mixture was continuously added over 2 hours, and a second seed polymerization was performed, followed by aging for 1 hour to obtain a core portion.
Next, 60 mg of potassium peroxodisulfate is added and stirred for 5 minutes, and 0.3 g of sodium dioctyl sulfosuccinate is dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid and 0.3 g of allyl methacrylate. The mixture of monomers was added continuously over 30 minutes to perform seed polymerization. Thereafter, it was aged for 1 hour to form a shell layer covering the core portion.
Then, it was cooled to room temperature (25 ° C.) and filtered through a plastic mesh with a mesh size of 120 μm to obtain a latex containing rubber particles having a core-shell structure. The obtained latex was frozen at -30.degree. C., dehydrated and washed by a suction filter, and then blow-dried at 60.degree. C. overnight to obtain rubber particles. The average particle size of the obtained rubber particles was 254 nm, and the maximum particle size was 486 nm.

The average particle size of the rubber particles, maximum particle size is dynamic light scattering method was as a measurement principle "Nanotrac ^TM" format Nanotrac particle size distribution measuring apparatus (trade name "UPA-EX150", manufactured by Nikkiso Co., Ltd. In the obtained particle size distribution curve, the cumulative average diameter at which the cumulative curve becomes 50% is the average particle diameter, and the frequency (%) of the particle size distribution measurement result is The largest particle diameter at the time of exceeding 0.00% was made into the largest particle diameter. A sample obtained by dispersing 1 part by weight of the rubber particle-dispersed epoxy compound obtained in Production Example 7 in 20 parts by weight of tetrahydrofuran was used as a sample.

Production Example 7
(Production of rubber particle dispersed epoxy compound)
Using 10 parts by weight of the rubber particles obtained in Production Example 6 in a state of being heated to 60 ° C. in a nitrogen stream, using a dissolver (1000 rpm, 60 minutes) (3,4,3 ′, 4′-diepoxy) It was dispersed in 48 parts by weight of bicyclohexyl (manufactured by Daicel Co., Ltd.) and degassed under vacuum to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C .: 3023 mPa · s).
The viscosity (25 ° C.) of the rubber particle-dispersed epoxy compound (10 parts by weight of rubber particles dispersed in 48 parts by weight of (3,4,3 ′, 4′-diepoxy) bicyclohexyl) obtained in Production Example 7 The viscosity in the above was measured using a digital viscometer (trade name “DVU-EII type”, manufactured by Tokimec Co., Ltd.).

Production Example 8
(Production of White Pigment-Containing Epoxy Resin: Examples 15 to 46)
Monoallyl diglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound ((3,4,3 ′, 4′-diepoxy) bicyclohexyl, Daicel Co., Ltd. ), A siloxane derivative having two epoxy groups in the molecule (trade name "X-40-2678", manufactured by Shin-Etsu Chemical Co., Ltd.), a siloxane derivative having three epoxy groups in the molecule (trade name) "X-40-2720", Shin-Etsu Chemical Co., Ltd.), Siloxane derivative having 4 epoxy groups in the molecule (trade name "X-40-2670", Shin-Etsu Chemical Co., Ltd.), silicone Leveling agent (trade name "BYK-300", manufactured by BIC Chemie Japan Ltd .; trade name "AC FS 180", manufactured by Algin Chemie), fluorine-based leveling agent (trade name "B "K-340", made by BIC Chemie Japan Ltd .; trade name "AC 110a", made by Algin Chemie, polycarbonate diol (trade name "PLACSEL CD220PL", made by Daicel Co., Ltd.), polytetramethylene ether glycol (trade name) "PTMG 2000", manufactured by Mitsubishi Chemical Corporation, polycaprolactone polyol (trade name "Placcel 308", manufactured by Daicel Corporation), phenoxy resin (trade name "YP-70", manufactured by Nippon Steel Chemical Co., Ltd.) , A hydroxyl group-containing long chain epoxy resin (trade name "Epototh YD-6020", manufactured by Nippon Steel Chemical Co., Ltd.), an acrylic block copolymer (trade name "nano strength M52N", manufactured by Arkema), obtained in Production Example 7 Rubber particle dispersed epoxy compound, stress relaxation agent (trade name “KMP-600”, silicone rubber Particle, Shin-Etsu Chemical Co., Ltd. product; trade name "KMP-602", silicone rubber particle, Shin-Etsu Chemical Co., Ltd. product; trade name "SF 8421", polyalkylene ether modified silicone compound represented by Formula (10) Toray Dow Corning Co., Ltd .; trade name “Y-19268”, polyalkylene ether modified silicone compound represented by the formula (10), manufactured by Momentive Performance Materials Japan (the same), Table 4 The monoallyl diglycidyl isocyanurate was dissolved by mixing according to the formulation (blending ratio) (unit: weight part) shown in 5, and stirring at 80 ° C. for 1 hour to obtain an epoxy resin (mixture). Then, the above-mentioned epoxy resin and white pigment (Titanium oxide; trade name "DCF-T-17050", manufactured by Resino Color Industrial Co., Ltd.) and inorganic filler (trade name "FB-970FD", silica (without surface treatment), average A particle size of 16.7 μm, maximum particle size of 70 μm) and Denka Co., Ltd.) are uniformly mixed using a dissolver according to the formulation (blending ratio) (unit: weight part) shown in Tables 4 and 5. The mixture was kneaded by a roll mill under predetermined conditions (roll pitch: 0.2 mm, rotational speed: 25 Hz, 3 passes) to obtain a white pigment-containing epoxy resin (epoxy resin composition).

Production Example 9
(Production of Agent K: Examples 15 to 46)
Curing agent (acid anhydride) (manufactured by Shin Nippon Rika Co., Ltd., trade name "Rikasid MH-700"), mixture of curing agent (acid anhydride) and alicyclic polyester resin (trade name "HN-7200", Hitachi Chemical Co., Ltd. product, curing accelerator (trade name "U-CAT 18X", San-Apro Ltd.), additive (trade name "ethylene glycol", Wako Pure Chemical Industries, Ltd.), According to the combination formulation (blending ratio) (unit: parts by weight) shown in Tables 4 and 5, uniform rotation using a revolution-revolution type stirring device (trade name "Awatori Neritaro AR-250, manufactured by Shinky Co., Ltd.) The mixture was mixed and degassed to obtain a K agent.

Examples 15 to 46
(Production of a curable epoxy resin composition)
The white pigment-containing epoxy resin obtained in Production Example 8 and the K agent obtained in Production Example 9 were mixed in a self-revolution stirring apparatus (product: The mixture was uniformly mixed (2000 rpm, 5 minutes) using the name "Awatori Neritaro AR-250" (manufactured by Shinky Co., Ltd.), and defoamed to obtain a curable epoxy resin composition.

Production Example 10
(Production of White Pigment-Containing Epoxy Resin: Examples 47 to 74, Comparative Examples 22 to 25)
Monoallyl diglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound ((3,4,3 ′, 4′-diepoxy) bicyclohexyl, Daicel Co., Ltd. Product name: “EHPE 3150” manufactured by Daicel Co., Ltd., tris glycidyl isocyanurate (trade name “TEPIC-PAS B26” manufactured by Nissan Chemical Industries, Ltd.), a siloxane derivative having two epoxy groups in the molecule (Trade name "X-40-2678", manufactured by Shin-Etsu Chemical Co., Ltd.), siloxane derivative having three epoxy groups in the molecule (trade name "X-40-2720", manufactured by Shin-Etsu Chemical Co., Ltd.) ), A siloxane derivative having four epoxy groups in the molecule (trade name “X-40-2670”, manufactured by Shin-Etsu Chemical Co., Ltd.), a silicone-based leveling agent (trade name) BYK-300, made by Big Chemie Japan Ltd .; trade name "AC FS 180", made by Algin Chemie, fluorine-based leveling agent (trade name "BYK-340", made by Big Chemie Japan Ltd .; trade name " AC 110a ′ ′, Algin Chemie product, polycarbonate diol (trade name “Placcel CD 220 PL”, made by Daicel Co., Ltd.), polytetramethylene ether glycol (trade name “PTMG 2000”, Mitsubishi Chemical Corp. product), polycaprolactone polyol (product name) Trade name "Placcel 308", manufactured by Daicel Co., Ltd., phenoxy resin (trade name "YP-70", manufactured by Nippon Steel Chemical Co., Ltd.), hydroxyl group-containing long chain epoxy resin (trade name "Epotote YD-6020" , Nippon Steel Chemical Co., Ltd., acrylic block copolymer (trade name) Nano strength M52N ", manufactured by Arkema), rubber particle dispersed epoxy compound obtained in Production Example 7, stress relaxation agent (trade name" KMP-600 ", silicone rubber particles, manufactured by Shin-Etsu Chemical Co., Ltd .; trade name" KMP -602 ", silicone rubber particles, manufactured by Shin-Etsu Chemical Co., Ltd .; trade name" SF8421 ", polyalkylene ether modified silicone compound represented by the formula (10), Toray Dow Corning Co., Ltd .; trade name" Y " -19268 ", the polyalkylene ether-modified silicone compound represented by the formula (10), manufactured by Momentive Performance Materials Japan (the same product), as shown in Tables 6 and 7 (blending ratio) (unit: weight) The monoallyl diglycidyl isocyanurate is dissolved by further mixing according to a part of (1) and stirring for 1 hour at 80.degree. C. Shi resin (mixture) was obtained (in Comparative Examples 22 to 25, without the mixing for components of the epoxy resin is a kind, was directly and epoxy resin). Then, the above-mentioned epoxy resin and white pigment (Titanium oxide; trade name "DCF-T-17050", manufactured by Resino Color Industrial Co., Ltd.) and inorganic filler (trade name "FB-970FD", silica (without surface treatment), average A particle diameter of 16.7 μm, maximum particle diameter of 70 μm, Denka Co., Ltd.) is uniformly mixed using a dissolver according to a blending formulation (blending ratio) (unit: weight part) shown in Tables 6 and 7, The mixture was kneaded by a roll mill under predetermined conditions (roll pitch: 0.2 mm, rotational speed: 25 Hz, 3 passes) to obtain a white pigment-containing epoxy resin (epoxy resin composition).

Production Example 11
(Production of Alicyclic Polyester Resin: Examples 48 and 73, Comparative Examples 22 to 25)
172 parts by weight of 1,4-cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 208 parts by weight of neopentyl glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, thermometer and reflux condenser 0.1 parts by weight of tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and heated to 160 ° C., and the temperature was further raised from 160 ° C. to 250 ° C. over 4 hours. Next, the pressure was reduced to 5 mmHg over 1 hour, and the pressure was further reduced to 0.3 mmHg or less, followed by reaction at 250 ° C. for 1 hour to obtain an alicyclic polyester resin.

Examples 47-74, Comparative Examples 22-25
(Production of a curable epoxy resin composition)
White pigment-containing epoxy resin obtained in Production Example 10, alicyclic polyester resin obtained in Production Example 11, curing catalyst (trade name) so as to obtain compounding formulations (unit: parts by weight) shown in Tables 6 and 7 Mix “San Aid SI-100L” (manufactured by Sanshin Chemical Industry Co., Ltd.) uniformly using a self-revolution stirring device (trade name “Awatori Neritaro AR-250, manufactured by Shinky Co., Ltd.) Defoaming (2000 rpm, 5 minutes) gave a curable epoxy resin composition.

<Evaluation>
With respect to the cured products obtained in Examples and Comparative Examples, the reflectance to light of 450 nm is measured according to the following procedure, and are cracks formed during thermal shock test (TST) during molding (cutting), reflow? It evaluated whether it was negative. The evaluation results are shown in Tables 1 to 7.

[Reflectance evaluation]
The hardened | cured material obtained by the Example and the comparative example was cut, and the test piece of thickness 3 mm was produced. Then, using a spectrophotometer (trade name "Spectrophotometer UV-2450", manufactured by Shimadzu Corporation), measure the reflectance (referred to as "initial reflectance") of each test piece for light with a wavelength of 450 nm. did. The results are shown in the "Initial reflectance" column of Tables 1-7.

[Heat resistance test (heat aging 250 hours)]
The test piece (thickness 3 mm) whose initial reflectance was measured was heated at 120 ° C. for 250 hours, and then the reflectance for light with a wavelength of 450 nm (referred to as “reflectance after heat aging (250 hours)”) was measured. Then, the reflectance retention rate (before and after heat aging; 250 hours) was calculated by the following equation. The results are shown in the column of “Reflectance retention rate before and after heating aging (250 hours)” in Tables 1 to 7.
[Reflectance retention (before and after heat aging; 250 hours)] = [reflectance after heat aging (250 hours)] / [initial reflectance] × 100

[Heat resistance test (heating aging 500 hours)]
The test piece (thickness 3 mm) whose initial reflectance was measured was heated at 120 ° C. for 500 hours, and then the reflectance for light with a wavelength of 450 nm (referred to as “reflectance after heat aging (500 hours)”) was measured. Then, the reflectance retention rate (before and after heating aging; 500 hours) was calculated by the following equation. The results are shown in the column of “Reflectance retention rate before and after heating aging (500 hours)” in Tables 1 to 7.
[Reflectance retention (before and after heat aging; 500 hours)] = [reflectance after heat aging (500 hours)] / [initial reflectance] × 100

[Light fastness test]
After irradiating an ultraviolet ray with an intensity of 10 mW / cm ² for 250 hours to a test piece (thickness 3 mm) whose initial reflectance was measured, measure the reflectance for light of 450 nm wavelength did. Then, the reflectance retention rate (before and after ultraviolet ray aging) was calculated by the following equation. The results are shown in the column of “Reflectance holding ratio before and after UV aging” in Tables 1 to 7.
[Reflectance holding ratio (before and after UV aging)] = [Reflectance after UV aging] / [Initial reflectance] × 100

[Evaluation of the occurrence of cracks during cutting (toughness evaluation)]
The hardened | cured material obtained by the Example and the comparative example was cut, and the test piece of width 5 mm * length 5 mm * thickness 3 mm was produced. A micro cutting machine (trade name "BS-300CL", manufactured by Meiwa Forcis Co., Ltd.) is used to cut the hardened material, and whether or not a crack is generated in the hardened material during cutting, It observed and confirmed using the digital microscope (brand name "VHX-900", product made from Keyence Co., Ltd.). In the column of “Number of cracks during cutting process” in Tables 1 to 7, 10 test pieces are prepared for one sample, and among them, the number of the test pieces in which the occurrence of cracks is confirmed [piece] (“number of cracks” ) Is shown as the evaluation result. In Tables 1 to 7, the case where the number of test pieces (the number of cracks) in which the occurrence of the crack was confirmed is n is shown as “n / 10”.

[Evaluation of presence or absence of cracks during reflow (tenacity evaluation)]
Using a reflow furnace (trade name “UNI-5016F”, manufactured by Nippon Antom Co., Ltd.), the test piece (5 mm wide × 5 mm long × 3 mm thick) obtained by the above-mentioned cutting processing is used. The reflow process was performed with a temperature of 5 seconds and a total reflow time of 90 seconds. After that, it was observed and confirmed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation) whether or not a crack was generated in the test piece due to the reflow process. Tables 1 to 7 show the reflow treatment of 10 test pieces per sample, and the number of pieces of test pieces (number of cracks) of which the occurrence of cracks was confirmed is shown as the evaluation results. In the column of “Number of cracks at reflow” in Tables 1 to 7, as in the case of “n / 10”, the number of test pieces (number of cracks) in which occurrence of cracks is confirmed is n. Indicated. In addition, evaluation was not implemented about what the crack generate | occur | produced at the time of cutting.

[Thermal shock test (TST)]
The test piece (width 5 mm × length 5 mm × thickness 3 mm) obtained by the above-mentioned cutting is exposed for 30 minutes in an atmosphere at −60 ° C., and then exposed for 30 minutes in an atmosphere at 150 ° C. The thermal shock with 1 cycle as the cycle was given for 200 cycles using a thermal shock tester (small thermal shock device TSE-11-A, manufactured by ESPEC Corp.). Thereafter, whether or not a crack was generated in the test piece by the thermal shock test was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation) and confirmed. In Tables 1 to 7, thermal impact tests of 10 test pieces were performed per sample, and among them, the number [pieces] (number of cracks) of the test pieces in which occurrence of a crack was confirmed is shown as an evaluation result. In the column of “Number of cracks at TST” in Tables 1 to 7, as in the case of “n / 10”, the number of test pieces (number of cracks) in which the occurrence of cracks is confirmed is n. Indicated. In addition, evaluation was not implemented about what the crack generate | occur | produced at the time of cutting.

[Comprehensive evaluation]
With an initial reflectance of 90% or more, a reflectance retention of 90% or more in a heat resistance test (heating aging for 500 hours), a reflectance retention of 90% or more in a light resistance test, and cracks during cutting Evaluation of the presence or absence (toughness evaluation), crack presence / absence evaluation (toughness evaluation) during reflow, and crack presence / absence evaluation (toughness evaluation) in the thermal shock test (TST) ○ (Good). On the other hand, the thing other than this was made into comprehensive judgment x (defect). The results are shown in the "overall judgment" column of Tables 1 to 4.

The components used in Examples and Comparative Examples are as follows.
[Epoxy resin]
(3,4,3 ′, 4′-diepoxy) bicyclohexyl, manufactured by Daicel Co., Ltd. CEL 2021 P (Ceroxide 2021 P): 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate, manufactured by Daicel Co., Ltd. MA-DGIC: monoallyl diglycidyl isocyanurate, manufactured by Shikoku Chemical Industries, Ltd. EHPE 3150: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol , Daicel Co., Ltd. TEPIC-PAS B26: Trisglycidyl isocyanurate, Nissan Chemical Industries Co., Ltd. X-40-2678: Siloxane derivative having two epoxy groups in the molecule, Shin-Etsu Chemical Co., Ltd. X -40-2720: having 3 epoxy groups in the molecule Siloxane derivative, Shin-Etsu Chemical Co., Ltd. X-40-2670: Siloxane derivative having four epoxy groups in the molecule, Shin-Etsu Chemical Co., Ltd. BYK-300: silicone leveling agent (silicone polymer) Containing leveling agent), Bic Chemie Japan KK AC FS 180: silicone leveling agent (leveling agent including silicone type polymer), Algin Chemie made BYK-340: fluorine type leveling agent (fluorinated acrylic polymer) Containing leveling agent), BIC Chemie Japan KK AC 110a: fluorine-based leveling agent (leveling agent including fluorine-containing polyether-based polymer), Algin Chemie CD 220 PL (Placcel CD 220 PL): polycarbonate diol, DAICE CO., LTD. PTMG 2000: polytetramethylene ether glycol, Mitsubishi Chemical Corp. Plaxel 308: polycaprolactone polyol, Daicel Co., Ltd. YP-70: phenoxy resin, Nippon Steel Chemical Co., Ltd. epototo YD-6020: hydroxyl group-containing length Chain epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd. M52N (nano strength M52N): acrylic block copolymer, manufactured by Arkema KMP-600: crosslinked polydimethylsiloxane having silicone resin on the surface, Shin-Etsu Chemical Co., Ltd. KMP-602: Cross-linked polydimethylsiloxane having silicone resin on the surface, Shin-Etsu Chemical Co., Ltd. SF8421: Polyalkylene ether-modified silicone compound represented by formula (10), Toray Dow Corning Co., Ltd. Made by Y-19268: Polyalkylene ether-modified silicone compound represented by (10)), Momentive Performance Materials Japan (same) manufactured by Inorganic Filler]
Silica: trade name "FB-970FD" (silica, no surface treatment, average particle diameter 16.7 μm, maximum particle diameter 70 μm), manufactured by Denka Co., Ltd. [White pigment]
Titanium oxide, trade name "DCF-T-17050", manufactured by Resino Color Industrial Co., Ltd. [K agent]
MH-700 (Rikasid MH-700): 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, Shin Nippon Chemical Co., Ltd. HN-7200: 4-methylhexahydrophthalic anhydride and alicyclic Mixture of polyester resins, Hitachi Chemical Co., Ltd. HN-5700: Mixture of 4-methylhexahydrophthalic anhydride / 3-methylhexahydrophthalic anhydride = 70/30 and alicyclic polyester resin, Hitachi Chemical 18X (U-CAT 18X) manufactured by Co., Ltd .: curing accelerator, ethylene glycol manufactured by San-Apro Co., Ltd .: manufactured by Wako Pure Chemical Industries, Ltd. [curing catalyst]
San Aid SI-100L: Arylsulfonium salt, manufactured by Sanshin Chemical Industry Co., Ltd.

As shown in Tables 1 to 7, the cured product (example) of the curable epoxy resin composition of the present invention has excellent light reflectivity, and also in cutting, reflow, and thermal shock test. It was excellent in the crack resistance especially to a thermal shock test, and was strong, without producing a crack. Furthermore, even after heat aging and ultraviolet light aging, high light reflectivity was maintained, and heat resistance and light resistance were excellent. In particular, in addition to the alicyclic epoxy compound and monoallyl diglycidyl isocyanurate, an alicyclic polyester resin (or, furthermore, an alicyclic polyester resin and a siloxane derivative having two or more epoxy groups in the molecule) ( In Examples 8, 9, 12, 14, 17, 45, 48, 73), the light reflectivity was hardly lowered even by heating for a longer time (500 hours), and exhibited extremely excellent heat resistance. .
On the other hand, the cured product (comparative example) formed from the curable epoxy resin composition not satisfying the definition of the present invention was deteriorated in light reflectivity after heat aging and ultraviolet aging, and was inferior in heat resistance and light resistance. Furthermore, it was easy to produce a crack at the time of a thermal shock test, and was inferior also in toughness.

The variations of the present invention described above are additionally described below.
[1] The following formula (I)

[Wherein, R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a , R ^10a , R ^11a , R ^12a , R ^13a , R ^14a , R ^15a , R ^16a , R ^17a and R ^18a are the same or different and each is a hydrogen atom, a halogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent (preferably Represents a hydrogen atom). ]
And a cycloaliphatic epoxy compound (A) represented by the following formula (1)

[Wherein, R ¹ and R ^{2 each} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom)]
Curable epoxy resin composition comprising: monoallyl diglycidyl isocyanurate compound (B), white pigment (C), curing agent (D), and curing accelerator (F) object.
[2] The amount (content) of the alicyclic epoxy compound (A) used is the total amount (100% by weight) of the curable epoxy resin composition excluding the white pigment (C) and the inorganic filler (J), The curable epoxy resin composition according to the above [1], which is 5 to 90% by weight (preferably 5 to 80% by weight, more preferably 5 to 70% by weight).

[3] Alicyclic epoxy compound (A) represented by the above formula (I), monoallyl diglycidyl isocyanurate compound (B) represented by the above formula (1), white pigment (C), A curable epoxy resin composition comprising: a curing catalyst (E).
[4] The amount (content) of the alicyclic epoxy compound (A) used is the total amount (100% by weight) of the curable epoxy resin composition excluding the white pigment (C) and the inorganic filler (J), The curable epoxy resin composition according to the above [3], which is 25 to 95% by weight (preferably 30 to 92% by weight, more preferably 30 to 90% by weight).

[5] The alicyclic epoxy compound (A) is represented by the following formula (I-1)

The curable epoxy resin composition according to any one of the above [1] to [4], which is a compound represented by
[6] The amount (content) of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) is 30 The curable epoxy resin composition according to any one of the above [1] to [5], which is ~ 95 wt% (preferably 35-95 wt%, more preferably 40-95 wt%).

[7] Further, an alicyclic epoxy compound other than the alicyclic epoxy compound (A) (hereinafter, may be referred to as “other alicyclic epoxy compound”), of the above-mentioned [1] to [6] The curable epoxy resin composition as described in any one.
[8] Another alicyclic epoxy compound is (i) an epoxy group (sometimes referred to as “alicyclic epoxy group”) composed of two adjacent carbon atoms constituting an alicyclic ring and an oxygen atom [7] which is at least one member selected from the group consisting of compounds having (excluding alicyclic epoxy compound (A)), and (ii) compounds in which an epoxy group is directly bonded to an alicyclic group by a single bond Curable epoxy resin composition as described in 4.
[9] The curable epoxy resin composition according to the above [8], wherein the compound having an alicyclic epoxy group is an alicyclic epoxy compound represented by the following formula (II):

[In Formula (II), X represents a linking group (a divalent group having one or more atoms). ]
[10] The curable epoxy resin composition as described in [9] above, wherein the other alicyclic epoxy compound is 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate.
[11] The amount (content) of the other alicyclic epoxy compound used is 1 to 50% by weight based on the total amount (100% by weight) of the other alicyclic epoxy compound and the alicyclic epoxy compound (A) The curable epoxy resin according to any one of the above [7] to [10], which is (preferably 5 to 40% by weight, more preferably 5 to 30% by weight, particularly preferably 5 to 20% by weight). Composition.

[12] Alicyclic epoxy compound (A): monoallyl diglycidyl isocyanurate compound (B) is 50: 50 to 95: 5 (weight ratio) (preferably 50: 50 to 90: 10 (weight ratio)) The curable epoxy resin composition according to any one of the above [1] to [11].

[13] The curable epoxy resin composition according to any one of the above [1] to [12], which is liquid at 25 ° C.
[14] The curable epoxy resin composition as described in [13] above, which has a viscosity of 1,000,000 mPa · s or less (preferably, 800,000 mPa · s or less) measured at 25 ° C. under normal pressure.

[15] The white pigment (C) is at least one selected from the group consisting of aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, silicon oxide, and inorganic hollow particles (preferably titanium oxide) The curable epoxy resin composition according to any one of the above [1] to [14].
[16] The center particle diameter of the white pigment (C) is 0.1 to 50 μm (preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, particularly preferably 0.1 to 10 μm, most preferably 0) The curable epoxy resin composition according to any one of the above [1] to [15], which is 1 to 5 μm).
[17] The use amount (blending amount) of the white pigment (C) is 80 to 500 based on 100 parts by weight of the total amount of epoxy group-containing compounds contained in the curable epoxy resin composition (total epoxy group-containing compound) The curable epoxy resin composition according to any one of the above [1] to [16], which is part by weight (preferably 90 to 400 parts by weight, more preferably 100 to 380 parts by weight).

[18] The curing agent according to the above [1], [2] or [5], wherein the curing agent (D) is an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including those in which a substituent such as an alkyl group is bonded to the ring). ] The curable epoxy resin composition according to any one of [17].
[19] The amount (content) of the curing agent (D) used is preferably 50 to 200 parts by weight (preferably 100 parts by weight) based on the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition Is 80 to 145 parts by weight). The curable epoxy resin composition according to any one of the above [1], [2] and [5] to [18].
[20] The amount (content) of the curing accelerator (F) is 0.05 to 5 parts by weight based on the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition Parts (preferably 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 2.5 parts by weight), the above [1], [2], [5] ] The curable epoxy resin composition as described in any one of--[19].

[21] The amount (content) of the curing catalyst (E) used is 0.01 to 15 parts by weight based on the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition In any one of the above [3] to [20], which is (preferably 0.01 to 12 parts by weight, more preferably 0.05 to 10 parts by weight, particularly preferably 0.1 to 10 parts by weight). Curable epoxy resin composition as described.

[22] The curable epoxy according to any one of the above [1] to [21], further comprising a siloxane derivative (G) having two or more (preferably 2 to 4) epoxy groups in the molecule. Resin composition.
[23] A siloxane derivative (G) having two or more epoxy groups in the molecule comprises 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 The curable epoxy resin composition as described in the above-mentioned [22], which is at least one selected from the group (preferably a cyclic siloxane having two or more epoxy groups in the molecule).
[24] The curable epoxy resin composition as described in [23] above, wherein the number of Si—O units forming the cyclic siloxane is 2 to 12 (preferably 4 to 8).
[25] Any one of the above [22] to [24], wherein the weight average molecular weight of the siloxane derivative (G) having two or more epoxy groups in the molecule is 100 to 3000 (preferably 180 to 2000) Curable epoxy resin composition as described in 4.
[26] The epoxy equivalent (based on JIS K 7236) of the siloxane derivative (G) having two or more epoxy groups in the molecule is 180 to 400 (preferably 240 to 400, more preferably 240 to 350), The curable epoxy resin composition according to any one of [22] to [25].
[27] Any one of the above [22] to [26], wherein the epoxy group in the siloxane derivative (G) having two or more epoxy groups in the molecule is an alicyclic epoxy group (preferably a cyclohexene oxide group) Curable epoxy resin composition as described in 4.
[28] A cyclic siloxane having two or more epoxy groups in one molecule, wherein the siloxane derivative (G) having two or more epoxy groups in the molecule is represented by the following formulas (S-1) to (S-7) The curable epoxy resin composition according to any one of the above [22] to [27], which is at least one selected from the group consisting of

[29] The used amount (content) of the siloxane derivative (G) having two or more epoxy groups in the molecule is the total amount (100% by weight) of the component (A), the component (B), and the component (G) Any of [22] to [28] above, which is 5 to 90% by weight (preferably 5 to 85% by weight, more preferably 5 to 80% by weight, and particularly preferably 8 to 75% by weight). Curable epoxy resin composition as described in one.
[30] Alicyclic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), and 2 or more epoxy groups in the molecule with respect to the total amount (100% by weight) of compounds having epoxy group (epoxy resin) The curable epoxy resin composition according to any one of the above [22] to [29], wherein the total amount of the siloxane derivative (G) having 30% by weight is 30 to 100% by weight (preferably 40 to 100% by weight). .

[31] The curable epoxy resin composition according to any one of the above [1] to [30], further comprising an alicyclic polyester resin (H).
[32] The curable epoxy resin composition as described in [31] above, wherein the alicyclic polyester resin (H) is an alicyclic polyester resin having an alicyclic ring in its main chain.
[33] The alicyclic polyester resin (H) described in the above [31] or [32], which is an alicyclic polyester resin containing at least one structural unit represented by the following formulas (2) to (4) Curable epoxy resin composition.

(Wherein, R ³ represents a linear, branched or cyclic alkylene group having 2 to 15 carbon atoms. R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched chain Or an alkyl group having 1 to 4 carbon atoms, and two selected from R ⁴ to R ⁷ may form a combined ring).
[34] Any of the above-mentioned [31] to [33], wherein the alicyclic polyester resin (H) is an alicyclic polyester resin containing at least one structural unit represented by the following formulas (5) and (6) The curable epoxy resin composition according to any one of the items.

[35] The curable epoxy resin according to any one of the above [31] to [34], wherein the number average molecular weight of the alicyclic polyester resin (H) is 300 to 100000 (preferably 300 to 30000) Composition.
[36] When the amount (content) of the alicyclic polyester resin (H) contains the curing agent (D) as an essential component, the total amount of the alicyclic polyester resin (H) and the curing agent (D) ( The curable epoxy resin composition according to any one of the above [31] to [35], which is 1 to 60% by weight (preferably 5 to 30% by weight) with respect to 100% by weight).
[37] When the amount (content) of the alicyclic polyester resin (H) contains the curing catalyst (E) as an essential component, the total amount of the alicyclic polyester resin (H) and the curing catalyst (E) ( The curable epoxy resin composition according to any one of the above [31] to [35], which is 50 to 99% by weight (preferably 65 to 99% by weight) with respect to 100% by weight).

[38] A curable epoxy resin other than the white pigment (C) and the inorganic filler (J) when the amount (content) of the alicyclic epoxy compound (A) contains the curing agent (D) as an essential component Any one of the above [22] to [37], which is 5 to 90% by weight (preferably 8 to 80% by weight, more preferably 8 to 75% by weight) based on the total amount (100% by weight) of the composition. The curable epoxy resin composition as described in 1).
[39] A curable epoxy resin other than the white pigment (C) and the inorganic filler (J) when the amount (content) of the alicyclic epoxy compound (A) contains the curing catalyst (E) as an essential component Any one of the above [22] to [37], which is 10 to 95% by weight (preferably 15 to 85% by weight, more preferably 20 to 75% by weight) based on the total amount (100% by weight) of the composition. The curable epoxy resin composition as described in 1).

[40] The curable epoxy resin composition according to any one of the above [1] to [39], further comprising rubber particles other than silicone rubber particles.
[41] Rubber particles other than silicone rubber particles are composed of a polymer containing (meth) acrylic acid ester as an essential monomer component, and have hydroxy and / or carboxy groups on the surface and have an average particle diameter of 10 to 500 nm The curable epoxy resin composition according to the above [40], which has a (preferably 20 to 400 nm) and a maximum particle diameter of 50 to 1000 nm (preferably 100 to 800 nm).
[42] The curable epoxy resin composition according to the above [40] or [41], wherein the rubber particles other than silicone rubber particles are rubber particles having a core-shell structure.
[43] The content (blending amount) of rubber particles other than silicone rubber particles is 0.5 to 30 with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. The curable epoxy resin composition according to any one of the above [40] to [42], which is a part by weight (preferably 1 to 20 parts by weight).

[44] The curable epoxy resin according to any one of the above [1] to [43], further comprising at least one leveling agent selected from the group consisting of a silicone-based leveling agent and a fluorine-based leveling agent. Composition.
[45] The content (blending amount) of the non-volatile component of the leveling agent is 0.1 to 10 parts by weight with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition The curable epoxy resin composition according to the above [44], which is a part (preferably 0.1 to 5 parts by weight, more preferably 0.1 to 4 parts by weight).

[46] The curable epoxy resin composition according to any one of the above [1] to [45], further comprising a polyol compound.
[47] The above polyol compound is at least one selected from the group consisting of polyester polyol, polyether polyol, polycarbonate polyol, phenoxy resin, bisphenol type polymer epoxy resin, polybutadiene having hydroxyl group, and acrylic polyol 46. The curable epoxy resin composition as described in 46.
[48] The curable epoxy resin composition as described in [46] or [47] above, wherein the number average molecular weight of the polyol compound is 200 to 100000 (preferably 300 to 50000, more preferably 400 to 40000).
[49] The use amount (content amount) of the polyol compound is 1 to 50 parts by weight (preferably 1.5 to 40 parts by weight) with respect to the total amount (100 parts by weight) of the component (A) and the component (B) (More preferably 5 to 30 parts by weight), the curable epoxy resin composition according to any one of the above [46] to [48].
[50] When the curable epoxy resin composition contains a siloxane derivative (G) having two or more epoxy groups in the molecule, the amount (content) of the polyol compound used is the above component (A), component (B) And 1 to 50 parts by weight (preferably 1.5 to 40 parts by weight, more preferably 5 to 30 parts by weight) based on the total amount (100 parts by weight) of the component (G) [46] The curable epoxy resin composition according to any one of [49].

[51] The curable epoxy resin composition according to any one of the above [1] to [50], further comprising an acrylic block copolymer.
[52] A polymer block [H] (hard) having a polymer block [S] (soft block) having a low glass transition temperature (Tg) and a Tg higher than the polymer block [S] The curable epoxy resin composition according to the above [51], which is a block copolymer in which blocks) are alternately arranged.
[53] The acrylic block copolymer is a triblock copolymer of the HSH structure having a polymer block [S] in the middle and having polymer blocks [H] at both ends thereof, 52. The curable epoxy resin composition as described in 52.
[54] The curable epoxy resin composition according to any one of the above [51] to [53], wherein the number average molecular weight of the acrylic block copolymer is 3000 to 500000 (preferably 30000 to 400000).
[55] The amount (content) of the acrylic block copolymer is 1 to 30 parts by weight (preferably 3 to 15 parts by weight) with respect to the total amount (100 parts by weight) of the component (A) and the component (B) The curable epoxy resin composition according to any one of the above [51] to [54], which is a part, more preferably 3 to 10 parts by weight.
[56] When the curable epoxy resin composition contains a siloxane derivative (G) having two or more epoxy groups in the molecule, the amount (content) of the acrylic block copolymer used is component (A), component (A) B) and 1 to 30 parts by weight (preferably 3 to 15 parts by weight, more preferably 3 to 10 parts by weight) based on the total amount (100 parts by weight) of the component (G) [51] The curable epoxy resin composition according to any one of [55].

[57] The curable epoxy resin composition according to any one of the above [1] to [56], further comprising a stress relaxation agent (I).
[58] At least one stress-relaxing agent (I) is preferably selected from the group consisting of silicone rubber particles (I1), silicone oil (I2), liquid rubber component (I3), and thermoplastic resin (I4) (preferably The curable epoxy resin composition as described in the above [57], which is at least one selected from the group consisting of silicone rubber particles (I1) and silicone oil (I2).
[59] The curable epoxy resin composition as described in the above [58], wherein the silicone rubber particle (I1) is a crosslinked polydimethylsiloxane having a silicone resin on its surface.
[60] The average particle size (d ₅₀ ) of the silicone rubber particles (I1) is 0.1 to 100 μm (preferably 0.5 to 50 μm), and the maximum particle size is 0.1 to 250 μm (preferably 0) The curable epoxy resin composition according to the above [58] or [59], which is 1 to 150 μm).
[61] A polyalkylene ether-modified silicone compound having a structure represented by the following formula (10), wherein the silicone oil (I2) has an epoxy equivalent of 3,000 to 15,000 (preferably 4,000 to 15,000, more preferably 5,000 to 13,000). The curable epoxy resin composition according to any one of the above [58] to [60].

[Wherein, xa is an integer of 80 to 140, ya is an integer of 1 to 5 and za is an integer of 5 to 20] R ²⁶ is an alkylene group having 2 or 3 carbon atoms (preferably a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, more preferably a trimethylene group). A is a polyalkylene ether group having a structure represented by the following formula (10a).

(Wherein, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group (preferably a methyl group).)
[62] The curable epoxy resin composition as described in [61] above, wherein the sum of a and b is an integer of 1 to 80.
[63] The content (blending amount) of the stress relaxation agent (I) is preferably 1 to 250 parts by weight (preferably 5 to 230 parts by weight, more preferably 100 parts by weight of the alicyclic epoxy compound (A). The curable epoxy resin composition according to any one of the above [57] to [62], which is 10 to 200 parts by weight).
[64] The content (blending amount) of the stress relaxation agent (I) is preferably 1 to 200 parts by weight (preferably 5 parts) per 100 parts by weight of the total amount of the compound having an epoxy group contained in the curable epoxy resin composition. The curable epoxy resin composition according to any one of the above [57] to [63], which is -150 parts by weight, more preferably 8-120 parts by weight.

[65] The curable epoxy resin composition according to any one of the above [1] to [64], further comprising an inorganic filler (J).
[66] The curable epoxy resin composition as described in the above [65], wherein the inorganic filler (J) is silica (silica filler).
[67] The curable epoxy resin composition as described in [66] above, wherein the central particle size of the silica is 0.1 to 50 μm (preferably 0.1 to 30 μm).
[68] The content (blending amount) of the inorganic filler (J) is 10 to 90% by weight (preferably 13 to 75% by weight, more preferably 10 to 90% by weight) based on the curable epoxy resin composition (100% by weight) The curable epoxy resin composition according to any one of the above [65] to [67], which is 15 to 70% by weight, more preferably 20 to 70% by weight.
[69] The content (blending amount) of the inorganic filler (J) is 10 to 1500 parts by weight (preferably 50 parts by weight) based on 100 parts by weight of the total amount of the compound having an epoxy group contained in the curable epoxy resin composition. The curable epoxy resin composition according to any one of the above [65] to [68], which is -1200 parts by weight, more preferably 100 to 1000 parts by weight.
[70] The maximum particle diameter of the white pigment (C) and the inorganic filler (J) is 200 μm or less (preferably 185 μm or less, more preferably 175 μm or less, particularly preferably 150 μm or less), and is 0.01 μm or more The curable epoxy resin composition according to any one of the above [65] to [69].

[71] The curable epoxy resin composition as described in any one of the above [1] to [70], which is a resin composition for compression molding.
[72] A cured product of the curable epoxy resin composition as described in any one of the above [1] to [71].
[73] The cured product according to the above [72], wherein the reflectance of light with a wavelength of 450 nm of the cured product is 90% or more (preferably 90.5% or more).
[74] Retainance of light with a wavelength of 450 nm after heating at 120 ° C. for 250 hours (sometimes referred to as “reflectance after heat aging for 250 hours”) relative to initial reflectivity ([250 hours heat aging] [72] or [73], wherein the later reflectance] / [initial reflectance] × 100) is 85% or more (preferably 90% or more, more preferably 95% or more, particularly preferably 98% or more). ] The hardened | cured material as described in.
[75] Retainance of light with a wavelength of 450 nm after heating at 120 ° C. for 500 hours (sometimes referred to as “reflectance after heat aging for 500 hours”) relative to initial reflectance ([500 hours heat aging] [72] to [74], wherein the later reflectance] / [initial reflectance] × 100) is 85% or more (preferably 90% or more, more preferably 95% or more, particularly preferably 98% or more). ] The hardened | cured material as described in any one.
[76] Retention of initial reflectance ([UV light] for the light with a wavelength of 450 nm after irradiation with UV light of intensity 10 mW / cm ² for 250 hours (sometimes referred to as “reflectance after ultraviolet aging”) The reflectance after aging] / [initial reflectance] × 100) is 90% or more (preferably 95% or more, more preferably 98% or more) any one of the above [72] to [75] Cured product as described in.

[77] A curable resin composition for light reflection, which comprises the curable epoxy resin composition according to any one of the above [1] to [71].
[78] An optical semiconductor device comprising at least an optical semiconductor element and a reflector comprising the cured product according to any one of the above [72] to [76].

100: White reflector 101: Metal wiring (electrode)
102: Mounting area of optical semiconductor element 103: Package substrate 104: Bonding wire 105: Sealing material of optical semiconductor element 106: Die bonding 107: Optical semiconductor element 108: Heat sink 109: Cathode mark

The curable epoxy resin composition of the present invention is used for LED package applications (components of LED packages, for example, reflector materials for optical semiconductor devices, housing materials, etc.), applications for bonding electronic components, applications for liquid crystal displays (for example, reflectors, etc.) ), Ink for white substrate, sealer, etc. can be preferably used.

Claims

Following formula (I)

[Wherein, R 1a , R 2a , R 3a , R 4a , R 5a , R 6a , R 7a , R 8a , R 9a , R 10a , R 11a , R 12a , R 13a , R 14a , R 15a , R 16a , R 17a and R 18a are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent . ]
And a cycloaliphatic epoxy compound (A) represented by the following formula (1)

[Wherein, R 1 and R 2 each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
Curable epoxy resin composition comprising: monoallyl diglycidyl isocyanurate compound (B), white pigment (C), curing agent (D), and curing accelerator (F) object.
Following formula (I)

[Wherein, R 1a , R 2a , R 3a , R 4a , R 5a , R 6a , R 7a , R 8a , R 9a , R 10a , R 11a , R 12a , R 13a , R 14a , R 15a , R 16a , R 17a and R 18a are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent . ]
And a cycloaliphatic epoxy compound (A) represented by the following formula (1)

[Wherein, R 1 and R 2 each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A curable epoxy resin composition comprising the monoallyl diglycidyl isocyanurate compound (B), a white pigment (C) and a curing catalyst (E).
The alicyclic epoxy compound (A) is represented by the following formula (I-1)

The curable epoxy resin composition according to claim 1 or 2, which is a compound represented by
The curable epoxy resin composition according to any one of claims 1 to 3, which is liquid at 25 ° C.
The curable epoxy resin composition according to any one of claims 1 to 4, further comprising a siloxane derivative (G) having two or more epoxy groups in the molecule.
The curable epoxy resin composition according to any one of claims 1 to 5, further comprising an alicyclic polyester resin (H).
The curable epoxy resin composition according to claim 6, wherein the alicyclic polyester resin (H) is an alicyclic polyester resin having an alicyclic ring in its main chain.
The curable epoxy resin composition according to any one of claims 1 to 7, further comprising rubber particles other than silicone rubber particles.
The curable epoxy resin composition according to any one of claims 1 to 8, further comprising at least one leveling agent selected from the group consisting of a silicone-based leveling agent and a fluorine-based leveling agent.
The curable epoxy resin composition according to any one of claims 1 to 9, further comprising a polyol compound.
The curable epoxy resin composition according to any one of claims 1 to 10, further comprising an acrylic block copolymer.
The curable epoxy resin composition according to any one of claims 1 to 11, further comprising a stress relaxation agent (I).
The curable epoxy resin composition according to claim 12, wherein the stress relaxation agent (I) is at least one selected from the group consisting of silicone rubber particles (I1) and silicone oil (I2).
The curable epoxy resin composition according to claim 13, wherein the silicone rubber particles (I1) are crosslinked polydimethylsiloxane having a silicone resin on the surface.
The curable epoxy resin composition according to claim 13 or 14, wherein the silicone oil (I2) is a polyalkylene ether modified silicone compound having a structure represented by the following formula (10) having an epoxy equivalent of 3000 to 15000.

[Wherein, xa is an integer of 80 to 140, ya is an integer of 1 to 5 and za is an integer of 5 to 20] R 26 is a C 2 or C 3 alkylene group. A is a polyalkylene ether group having a structure represented by the following formula (10a).

(Wherein, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group.)
The curable epoxy resin composition according to any one of claims 1 to 15, further comprising an inorganic filler (J).
A cured product of the curable epoxy resin composition according to any one of claims 1 to 16.
A curable resin composition for light reflection, comprising the curable epoxy resin composition according to any one of claims 1 to 16.
An optical semiconductor device comprising at least an optical semiconductor element and a reflector comprising the cured product of the curable resin composition for light reflection according to claim 18.