TW201930390A - Curable epoxy resin composition, cured product thereof, and optical semiconductor device - Google Patents

Abstract

An object of the present invention is to provide a curable epoxy resin composition which is suitable for compression molding and which provides high light reflectivity, excellent heat resistance and light resistance, and excellent toughness and crack resistance, and light reflectivity. A hardened material that is not easily lowered as time passes.

The present invention provides a curable epoxy resin composition, a cured product thereof, and a semiconductor device comprising the reflector formed of the cured product, wherein the curable epoxy resin composition contains the following formula (I) The alicyclic epoxy compound (A), the isocyanuric acid monoallyl diglycidyl ester compound (B) represented by the following formula (1), the white pigment (C), the hardener (D), and the hardening Accelerator (F),

^Wherein R ^1a to 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;

[wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

Description

 Curable epoxy resin composition and 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 at least An optical semiconductor device of an optical semiconductor element and a reflector formed of the above cured material. The present application claims the priority of Japanese Patent Application No. 2017-245102 filed on Dec. 21, 2017 in Japan, the content of which is incorporated herein.

In recent years, various types of indoor or outdoor display panels, light sources for image reading, traffic signals, large-sized display units, and the like have been used as light-emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources. Progressing. As such a light-emitting device, generally, an optical semiconductor element and a transparent resin that protects the periphery of the optical semiconductor element are used, and in order to improve light extraction efficiency from the optical semiconductor element, it is widely used to reflect light. A light-emitting device for a reflector (reflective material).

It is required for the above-mentioned reflector to have high light reflectivity, and it is required to continuously exhibit such high light reflectivity continuously. Conventionally, as a constituent material of the above-mentioned reflector, a resin composition such as an inorganic filler is dispersed in a polyamide resin (polyphthalamide resin) having a terephthalic acid unit as a constituent unit. (Refer to Patent Documents 1 to 3).

In addition, as a constituent material of the above-mentioned reflector, a thermosetting resin composition for light reflection containing a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0 is known (refer to the patent literature). 4). In addition, for example, a thermosetting resin component and one or more kinds of filler components are contained, 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 are known. The calculated parameter is controlled by a thermosetting resin composition for light reflection in a specific range (see Patent Document 5). In addition, a curable resin composition for light reflection of a heteropolycyanate monoallyl diglycidyl ester compound and a white pigment is blended in an alicyclic epoxy compound (see Patent Document 6).

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2000-204244

Patent Document 2 Japanese Patent Laid-Open Publication No. 2004-75994

Patent Document 3 Japanese Patent Laid-Open Publication No. 2006-257314

Patent Document 4 Japanese Patent Laid-Open Publication No. 2010-235753

Patent Document 5 Japanese Patent Laid-Open Publication No. 2010-235756

Patent Document 6 International Publication WO2013/008680 Booklet

However, the reflector made of the above-mentioned polyimide resin described in Patent Documents 1 to 3 is particularly used in a light-emitting device using a high-output blue light semiconductor or a white light semiconductor as a light source due to the light semiconductor element. Light or heat deteriorates with yellowing or the like as time passes, and there is a problem that sufficient light reflectivity cannot be maintained. Further, in the tendency that the heating temperature in the reflow step (solder reflow step) at the time of manufacture of the light-emitting device becomes higher with the use of lead-free solder, the above-mentioned reflector is caused by heat applied in such a process As time passes, it deteriorates, and the problem of reduced light reflectivity also occurs.

Further, in the reflector formed of the cured product of the thermosetting resin composition for light reflection described in Patent Documents 4 and 5, isomeric isocyanuric acid glycidyl ester is used as a main component of the thermosetting resin. The heat resistance is insufficient, and the light reflectivity is lowered as time passes due to heat generated from the optical semiconductor element or heat in the reflow step. In the reflector formed of the cured product of the curable resin composition for light reflection described in Patent Document 6, the heat resistance is improved as compared with Patent Documents 1 to 5, but the high output of the optical semiconductor device is high. Under the long-term use, there is a problem of reduced light reflectivity.

Further, the above reflector is generally produced by delivering a material (resin composition) for forming the reflector to transfer molding or compression molding. However, since the conventional resin composition for forming a reflector is suitable for transfer molding, the reflector formed of the resin composition is excellent in heat resistance, but the reflector formed by compression molding is often heat resistant. Poor.

Further, in addition to the above-mentioned heat resistance and light resistance, the above-mentioned reflector is required to be applied with stress due to cutting processing or temperature change (for example, heating at a very high temperature such as a reflow step, or a heat cycle). It is less prone to cracks (cracks) (also known as "crack resistance"). If a crack occurs in the reflector, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it is difficult to secure the reliability of the light-emitting device. In the reflector formed of the cured product of the curable resin composition for light reflection described in Patent Document 6, there is a problem that cracks are likely to occur due to a heat cycle or the like.

Therefore, the current state requires a material which is suitable for compression molding, and can form a poor condition such as deterioration or cracking even due to higher output, short-wavelength light or high temperature, hot and cold cycle, etc., and light reflectability is not easy to pass over time. The reduced reflector is excellent in heat resistance and light resistance, and is excellent in toughness and crack resistance.

Accordingly, an object of the present invention is to provide a curable epoxy resin composition which is suitable for compression molding and which provides high light reflectivity, excellent heat resistance and light resistance, and excellent toughness and crack resistance. A hardened material whose reflectance is not easily lowered as time passes.

Further, another object of the present invention is to provide a cured product obtained by curing the curable epoxy resin composition, which has high light reflectivity, excellent heat resistance and light resistance, and is tough and resistant to turtles. Excellent cracking, light reflectivity is not easy to decrease with time.

Further, another object of the present invention is to provide a light-reflecting resin composition for light reflection which can obtain an optical semiconductor device which suppresses a decrease in luminance of light over time.

Further, another object of the present invention is to provide an optical semiconductor device in which the luminance of light is less likely to decrease with time and has high reliability.

In order to solve the above problems, the inventors of the present invention have intensively reviewed and found that a specific alicyclic epoxy compound, a isocyanuric acid monoallyl diglycidyl ester compound, and a white pigment are contained as essential components, and further, it is hardened. The hardening epoxy resin composition of the agent and the hardening accelerator or the curing catalyst has high light reflectivity, excellent heat resistance and light resistance, and is excellent in toughness and crack resistance, and light reflectability is not easy with time. After the reduction. Furthermore, the present inventors have found that a specific alicyclic epoxy compound, a isocyanuric acid monoallyl diglycidyl ester compound, and a cyclooxygen derivative having two or more epoxy groups in a molecule are contained. An alicyclic polyester resin and a white pigment as essential components, further comprising a hardener and a hardening epoxy resin composition of a hardening accelerator or a curing catalyst, in particular, a cured product having high light reflectivity It is excellent in heat resistance and light resistance, and is excellent in toughness and crack resistance, and it is difficult to reduce light reflectivity with time. The present invention has been completed on the basis of such knowledge and knowledge.

In other words, the present invention provides a curable epoxy resin composition comprising the alicyclic epoxy compound (A) represented by the following formula (I) and isomeric cyanide represented by the following formula (1). Acid monoallyl diglycidyl ester compound (B), white pigment (C), hardener (D) and hardening accelerator (F),

^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 , ^R17a and ^R18a are the same or different and represent 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];

[wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

Moreover, the present invention provides a curable epoxy resin composition characterized by containing an alicyclic epoxy compound (A) represented by the alicyclic epoxy compound (A) represented by the following formula (I), and The isocyanuric acid monoallyl diglycidyl ester compound (B), the white pigment (C) and the hardening catalyst (E) represented by the formula (1),

^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 , ^R17a and ^R18a 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],

[wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

Furthermore, the curable epoxy resin composition according to the above formula, wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (I-1).

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

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

A curable epoxy resin composition as described above is provided, which further comprises an alicyclic polyester resin (H).

Further, a curable epoxy resin composition as described above, wherein the alicyclic polyester resin (H) is an alicyclic polyester resin having an alicyclic ring in a main chain, is provided.

The curable epoxy resin composition as described above is further provided, which further comprises rubber particles other than the polyoxyxylene rubber particles.

The curable epoxy resin composition as described above is further provided, which further comprises at least one leveling agent selected from the group consisting of a polyoxonium-based leveling agent and a fluorine-based leveling agent.

A curable epoxy resin composition as described above is provided, which further comprises a polyol compound.

A curable epoxy resin composition as described above is provided, which further comprises an acrylic block copolymer.

A curable epoxy resin composition as described above is provided, which further comprises a stress relieving agent (I).

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

The polyoxyxylene rubber particles (I1) may be a crosslinked polydimethyl siloxane having a polyoxyxylene resin on its surface.

The polyoxyxane oil (I2) may be a polyalkylene ether modified polyoxonium compound having a structure represented by the following formula (10) having an epoxy equivalent of 3,000 to 15,000 epoxy equivalents of 3,000 to 15,000;

[wherein, xa is an integer of 80 to 140, ya is an integer of 1 to 5, za is an integer of 5 to 20; R ²⁶ is an alkylene group having 2 or 3 carbon atoms; and A has the following formula (10a) a polyalkylene ether group of the structure shown;

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

A curable epoxy resin composition as described above is provided, which further comprises an inorganic filler (J).

Further, the present invention provides a cured product which is a cured product of the aforementioned curable epoxy resin composition.

Moreover, the present invention provides a curable resin composition for light reflection, which comprises the above-described curable epoxy resin composition.

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

The curable epoxy resin composition of the present invention has the above-described configuration, and the curable epoxy resin composition is suitable for compression molding, and is cured to obtain a cured product having high light reflectivity, and further heat resistance and light resistance. Excellent in properties, strong and resistant to cracks, so light reflectivity is not easy to decrease with time. Therefore, the curable epoxy resin composition of the present invention is suitable for various applications related to optical semiconductor devices, and is particularly applicable to a light-reflecting curable resin composition for LED packaging. In addition, the reflector (reflective material) formed of the cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention can exhibit high light reflectivity for a long period of time, so at least An optical semiconductor device having a long life of an optical semiconductor device (light-emitting device) including an optical semiconductor element and the above-described reflector can exhibit high reliability.

100‧‧‧White reflector

101‧‧‧Metal wiring (electrode)

102‧‧‧ Mounting area of optical semiconductor components

103‧‧‧Package substrate

104‧‧‧bonding line

105‧‧‧ Sealing materials for optical semiconductor components

106‧‧‧ die bonding

107‧‧‧Optical semiconductor components

108‧‧‧ Heat sink

109‧‧‧cathode marking

FIG. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention. The left side view (a) is an oblique view, and the right side view (b) is a cross-sectional view.

Fig. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention.

Fig. 3 is a schematic view showing a further example of the optical semiconductor device of the present invention (a cross-sectional view; a case having a heat sink).

Fig. 4 is a schematic view showing another example of the optical semiconductor device of the present invention (when a heat sink (heat sink fin) is provided). The diagram on the left side (a) is the upper view, and the diagram on the right side (b) is the A-A' cross-sectional view in (a).

Form of implementing the invention  <Curable epoxy resin composition>  

The curable epoxy resin composition of the present invention contains 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 , ^R17a and ^R18a 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]

The alicyclic epoxy compound (A) shown, the following formula (1)

[wherein, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]

a resin composition of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B), a white pigment (C), a curing agent (D), and a curing accelerator (F) as essential components, or the above The alicyclic epoxy compound (A) represented by the formula (I), the isocyanuric acid monoallyl diglycidyl ester compound (B) represented by the above formula (1), the white pigment (C) and the hardening The catalyst (E) is a resin composition as an essential component. Further, the curable epoxy resin composition of the present invention may contain other components as needed in addition to the above-mentioned essential components. Further, the curable epoxy resin composition of the present invention can be used as a thermosetting composition (thermosetting epoxy resin composition) which is cured by heating and can be converted into a cured product.

In addition, the term "curable resin composition for light reflection" as used herein means 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 light of 450 nm or more at a wavelength of 50% or more (particularly, 90% or more) 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 the cured product (reflector) tends to have light reflectivity and is excellent in heat resistance and light resistance. In the present specification, the phrase "liquid at 25 ° C" means that the viscosity measured at 25 ° C under normal pressure is 1,000,000 mPa ‧ or less (preferably 800,000 mPa ‧ s or less). Further, for the viscosity, for example, a digital viscometer (model "DVU-EII type", manufactured by TOKIMEC Co., Ltd.) can be used, and the rotor is: standard 1° 34' × R24, temperature: 25 ° C, rotation number: 0.5 to 10 rpm. Determined under conditions.

The curable epoxy resin composition of the present invention which is liquid at 25 ° C can be used, for example, by using a component which is liquid at 25 ° C as a component (for example, an alicyclic epoxy compound (A), a liquid stress relieving agent. (I), a hardener (E), a hardening accelerator (F), a hardening catalyst (G), etc. are easily obtained. Further, as the above-mentioned component, a component which is solid at 25 ° C may be used, but the content thereof is adjusted so that the curable epoxy resin composition of the present invention becomes liquid at 25 ° C. Further, the rubber particles, the white pigment (C), the inorganic filler (J), the solid stress relieving agent (I), and the like may be solid at 25 ° C without departing from the effects of the present invention. It is easy to obtain as a component.

 [Cycloaliphatic epoxy compound (A)]  

The alicyclic epoxy compound (A) constituting the curable epoxy resin composition of the present invention is a compound represented by the following formula (I).

The curable epoxy resin composition of the present invention contains the above alicyclic epoxy compound (A), and the cured product has high light reflectivity, excellent heat resistance and light resistance, and is tough and crack resistant. Excellent, especially with a tendency to improve the resistance to cracking of the hot and cold cycle.

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 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.

In the formula (1), a halogen atom of R ^1a to R ^18a contains a fluorine, chlorine, bromine or iodine atom. Examples of the hydrocarbon group of the "hydrocarbon group having an oxygen atom or a halogen atom" include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a bond having two or more of these groups. Examples of the aliphatic hydrocarbon group include a linear group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a hexyl group, an octyl group or a decyl group. a branched alkyl group (for example, an alkyl group having 1 to 10 carbon atoms, preferably about 1 to 5 carbon atoms); an alkenyl group such as a vinyl group or an allyl group (for example, a carbon number of 2 to 10, preferably An alkenyl group having a carbon number of from 2 to 5 or the like; an alkynyl group such as an ethynyl group (for example, an alkynyl group having a carbon number of 2 to 10, preferably a carbon number of about 2 to 5). Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a cycloalkenyl group; a bridged cyclic group group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the hydrocarbon group having an oxygen atom include a group in which an oxygen atom is present in a carbon chain of the hydrocarbon group (for example, an alkoxyalkyl group such as a methoxymethyl group or an ethoxymethyl group). Examples of the hydrocarbon group having a halogen atom include one or more hydrogen atoms (such as a fluorine, chlorine, bromine or iodine atom) of the hydrogen atom of the hydrocarbon group such as a chloromethyl group, a trifluoromethyl group or a chlorophenyl group. ) the base replaced. Examples of the alkoxy group of the "alkoxy group having a substituent" include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and the like, and a carbon number of 1 to 10 (preferably An alkoxy group having a carbon number of about 1 to 5). Examples of the substituent of the alkoxy group include the above-mentioned halogen atom and the like.

Among the alicyclic epoxy compounds (A) represented by the formula (I), a compound represented by the following formula (I-1) in which all of R ^1a to R ^18a have a hydrogen atom is preferred.

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

The amount (content) of the alicyclic epoxy compound (A) is not particularly limited, but in the case where the curable epoxy resin composition of the present invention contains the curing agent (D) as an essential component, it is relative to the white pigment. (C) and the entire amount of the curable epoxy resin composition other than the inorganic filler (J) (100% by weight), preferably 5 to 90% by weight, more preferably 5 to 80% by weight, particularly preferably 5 to 70% weight%. On the other hand, in the case where the curable epoxy resin composition of the present invention contains the curing catalyst (E) as an essential component, the curable epoxy resin other than the white pigment (C) and the inorganic filler (J) The total amount (100% by weight) of the composition, the amount (content) of the alicyclic epoxy compound (A) is preferably from 25 to 95% by weight, more preferably from 30 to 92% by weight, particularly preferably from 30 to 90% by weight. .

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

Further, the alicyclic epoxy compound (A) is based on the total amount (100% by weight) of the alicyclic epoxy compound (A) and the isomeric cyanuric acid monoallyl diglycidyl ester compound (B). The amount of use (content) is not particularly limited, but is preferably from 30 to 95% by weight, more preferably from 35 to 95% by weight, still more preferably from 40 to 95% by weight. When the amount of the alicyclic epoxy compound (A) used is less than 30% by weight, the solubility of the isocyanuric acid monoallyl diglycidyl ester compound (B) is insufficient, and it is easy to stand at room temperature. The situation of precipitation. On the other hand, when the amount of the alicyclic epoxy compound (A) used exceeds 95% by weight, the toughness of the cured product is lowered, and cracking is likely to occur.

The curable epoxy resin composition of the present invention may contain an alicyclic epoxy compound other than the alicyclic epoxy compound (A) within the range which does not impair the effects of the present invention (hereinafter, also referred to as "other An alicyclic epoxy compound").

The other alicyclic epoxy compound is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in a molecule (within one molecule), and is a compound other than the alicyclic epoxy compound (A). More specifically, among other alicyclic epoxy compounds, for example, (i) an epoxy group having two carbon atoms adjacent to each other constituting an alicyclic ring and an oxygen atom (also referred to as "alicyclic ring" The compound of the epoxy group ") (except for the alicyclic epoxy compound (A)), and (ii) the compound in which the epoxy group is directly bonded to the alicyclic ring by a single bond or the like. However, among other alicyclic epoxy compounds, a nonoxyl derivative (G) having two or more epoxy groups in the molecule to be described later is not included.

(i) A compound having an epoxy group (alicyclic epoxy group) composed of two carbon atoms and an oxygen atom adjacent to each other in the alicyclic ring can be arbitrarily selected from known or used. Wherein, the compound preferably has an epoxy group composed of two adjacent carbon atoms and an oxygen atom of a cyclohexane ring, that is, a compound having an epoxycyclohexane group (alicyclic epoxy compound). .

(i) a compound having an epoxy group (alicyclic epoxy group) composed of two carbon atoms adjacent to an alicyclic ring and an oxygen atom, particularly in terms of heat resistance and light resistance, preferably lower An alicyclic epoxy compound (alicyclic epoxy resin) represented by the formula (II).

In the formula (II), X represents a linking group (having a divalent group of one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether group (ether bond), a thioether group (thioether bond), an ester group (ester bond), a carbonate group (carbonate bond), and a guanamine group. (Amidoxime bond), and a plurality of links have such a base. Further, one or more carbon atoms constituting the alicyclic ring (alicyclic epoxy group) of the formula (II) may be bonded to a substituent such as an alkyl group.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having a carbon number of 1 to 18, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group, and a trimethylene group. Base. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentyl group, 1,3-cyclopentyl group, cyclopentylene group, 1,2-extended cyclohexyl group, and 1,3-extension ring. A divalent cycloalkylene group (including a cycloalkylene group) such as a hexyl group, a 1,4-cyclohexylene group or a cyclohexylene group.

The above-mentioned linking group X is particularly preferably a linking group containing an oxygen atom, and specific examples thereof include -CO-(carbonyl), -O-CO-O-(carbonate group), and -COO-( Ester group), -O-(ether group), -CONH-(nonylamino group), a plurality of groups having such a group bonded thereto, 1 or 2 or more of these groups and 1 or 2 of a divalent hydrocarbon group More than one of the connected bases. Examples of the divalent hydrocarbon group include the above-exemplified ones.

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 such a compound, for example, a commercial item such as "Celloxide 2021P" or "Celloxide 2081" (manufactured by DAICEL Co., Ltd.) can be used. Further, l and m in the following formulae (II-5) and (II-7) 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 examples thereof include a methylene group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. A linear or branched alkyl group having a secondary butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methylene group, an ethyl group, a propyl group and an isopropyl group is preferable. Further, n1 to n6 in the following formulae (II-9) and (II-10) each represent an integer of 1 to 30.

The compound represented by the following formula (III) is exemplified as the compound in which the epoxy group is directly bonded to the alicyclic ring by a single bond.

In the 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 the p-valent alcohol [R'-(OH) _p ] include an alcohol having 1 to 15 carbon atoms, and more specifically, 2,2-bis(hydroxymethyl)-1-buty. A polyol such as an alcohol or the like. p is preferably from 1 to 6, and n is preferably from 1 to 30. When p is 2 or more, the n series in the base of each (in the parentheses) may be the same or different. Specific examples of the above compound include 1,2-epoxy-4-(2-oxiranyl)cyclohexane of 2,2-bis(hydroxymethyl)-1-butanol. The product is sold under the trade name "EHPE3150" (DAICEL).

Other alicyclic epoxy compounds may be used alone or in combination of two or more. Among the above, as the other alicyclic epoxy compound, a 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexane represented by the above formula (II-1) is particularly preferred. Alkyl carboxylate, trade name "Celloxide 2021P".

When the curable epoxy resin composition of the present invention contains other alicyclic epoxy compounds, the total amount (100% by weight) relative to the other alicyclic epoxy compound and the alicyclic epoxy compound (A) The amount (content) of the other 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. Good is 5~20% 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 are lowered, and light reflectability with time is lowered or cracking is likely to occur due to thermal cycle. Happening.

 [Iso-cyanuric acid monoallyl diglycidyl ester compound (B)]  

The isocyanuric acid monoallyl diglycidyl ester compound (B) constituting the curable epoxy resin composition of the present invention is represented by the 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. a linear or branched alkyl group. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. R ¹ and R ² in the above formula (1) are particularly preferably a hydrogen atom.

Typical examples of the isocyanuric acid monoallyl diglycidyl ester compound (B) include isoallyl cyanuric monoglycidyl diglycidyl ester and 1-allyl-3,5-double. (2-methylepoxypropyl)isomeric cyanurate, 1-(2-methylpropenyl)-3,5-diepoxypropyl isocyanate, 1-(2- Methylpropenyl)-3,5-bis(2-methylepoxypropyl)isocyanate or the like. Further, the isocyanuric acid monoallyl diglycidyl ester compound (B) may be used alone or in combination of two or more.

The isocyanuric acid monoallyl diglycidyl ester compound (B) can be arbitrarily mixed in the range of the above-mentioned alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) and the different The ratio of the cyanuric acid monoallyl diglycidyl ester compound (B) is not particularly limited, but the alicyclic epoxy compound (A): isocyanuric acid monoallyl diglycidyl ester compound ( B) is preferably 50:50 to 95:5 (weight ratio), more preferably 50:50 to 90:10 (weight ratio). Outside of this range, it is difficult to obtain the solubility of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B).

The isocyanuric acid monoallyl diglycidyl ester compound (B) may be previously added with a compound which reacts with an epoxy group such as an alcohol or an acid anhydride, and is used for modification.

 [white pigment (C)]  

The white pigment (C) which is an essential component of the curable epoxy resin composition of the present invention is a cured product obtained by curing the curable epoxy resin composition, and functions to exhibit high light reflectivity. . As the white pigment (C), a well-known or conventional white pigment can be used without particular limitation, and examples thereof include glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acid clay, and activity. Inorganic white pigments such as white earth, boehmite, pseudo-boehmite, inorganic oxides, metal salts such as alkaline earth metal salts; styrene resin, benzoguanamine resin, urea-formalin resin, melamine- An organic white pigment (such as a plastic pigment) such as a resin pigment such as a fumarin resin or a guanamine resin; or a hollow particle having a hollow structure (balloon structure). These white pigments can be used individually or in combination of 2 or more types.

As the white pigment (C), in order to increase the reflectance of the reflector, it is preferred to use a white pigment having a high refractive index, for example, a white pigment having a refractive index of 1.5 or more. However, a white pigment having a hollow particle structure has a surface reflectance which is very large because a gas having a low refractive index is contained inside (core), so that the shell portion can also be composed of a material having a refractive index of less than 1.5. Further, among those who are examples of the white pigment (C), those having an index of 1.5 or more as the white pigment (C) and those having a refractive index of less than 1.5 are also regarded as the inorganic filler (J). Inorganic filler (J).

Examples of the inorganic oxide include alumina (alumina), magnesium oxide, cerium oxide, and titanium oxide (for example, rutile-type titanium oxide, anatase-type titanium oxide, brookite-type titanium oxide, etc.), Zirconium oxide, zinc oxide, and the like. Moreover, examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium citrate, calcium citrate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, barium sulfate, and the like. . In addition, examples of the metal salt other than the alkaline earth metal salt include aluminum niobate, aluminum hydroxide, and zinc sulfide.

The hollow particles are not particularly limited, and examples thereof include metal oxidation by inorganic glass (for example, sodium citrate glass, aluminosilicate glass, sodium borosilicate glass, quartz, etc.), vermiculite, alumina, or the like. Inorganic hollow particles (including natural materials such as white sand balls) composed of inorganic substances such as metal salts such as calcium carbonate, barium carbonate, nickel carbonate, and calcium citrate; and styrene resins, acrylic resins, and polyfluorenes. Oxygen resin, acrylic acid-styrene resin, vinyl chloride resin, vinylidene chloride resin, guanamine resin, urethane resin, phenol resin, styrene-conjugated diene resin, An organic hollow particle composed of an organic material such as an acrylic acid-conjugated diene resin or an olefin resin (including a crosslinked body of such a polymer); and an inorganic material composed of a mixed material of an inorganic material and an organic material - Organic hollow particles, etc. Further, the hollow particles may be composed of a single material or may be composed of two or more materials. Further, the hollow portion (the space inside the hollow particles) of the hollow particles may be in a vacuum state or may be filled with a medium, but in particular, a medium having a low refractive index is preferable from the viewpoint of improving the reflectance ( For example, hollow particles filled with an inert gas such as nitrogen or argon or air.

Further, the white pigment (C) may also be subjected to a well-known or conventional surface treatment [for example, a surface treatment agent such as a metal oxide, a decane coupling agent, a titanium coupling agent, an organic acid, a polyhydric alcohol, a polyfluorene oxide or the like. Surface treatment, etc.]. By applying such a surface treatment, it is possible to improve the compatibility or dispersibility of the white pigment (C) in the curable epoxy resin composition with other components.

In particular, the white pigment (C) is preferably an inorganic oxide or an inorganic hollow particle from the viewpoint of availability, heat resistance, and light resistance, and more preferably contains alumina, magnesia, cerium oxide, and titanium oxide. One or more white pigments of a group of zirconium oxide, cerium oxide, and inorganic hollow particles. In particular, as the white pigment (C), at a point having a higher refractive index, titanium oxide is preferred.

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

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

The amount (mixing amount) of the white pigment (C) used in the curable epoxy resin composition of the present invention is not particularly limited, but is equivalent to the epoxy group-containing compound contained in the curable epoxy resin composition. The total amount (all of the epoxy group-containing compounds) is preferably from 80 to 500 parts by weight, more preferably from 90 to 400 parts by weight, even more preferably from 100 to 380 parts by weight, based on 100 parts by weight. When 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 is more than 500 parts by weight, the toughness of the cured product tends to decrease.

Further, the white pigment (C) can be produced by a known or customary production method. Further, as the white pigment (C), a commercially available product can be used. For example, the trade names "SR-1", "R-42", "R-45M", "R-650", and "R-32" can be used. "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, 堺Chemical Industries, Inc.), trade name "Tipaque 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, Ishihara Industry Co., Ltd.), trade names "JR-301", "JR-403", "JR-405", "JR-600A" , "JR-605", "JR-600E", "JR-603", "JR-805", "JR-806", "JR-701", "JRNC", "JR-800", "JR" (The above, TAYCA (share) system), trade names "TR-600", "TR-700", "TR-750", "TR-840", "TR-900" (above, Fuji Titanium Industry Co., Ltd.) (product) "KR-310", "KR-380", "KR-380N" (above, Titanium Industry Co., Ltd.), products Name "ST-410WB", "ST-455", "ST-455WB", "ST-457SA", "ST-457EC", "ST-485SA15", "ST-486SA", "ST-495M" (above) , rutile type titanium oxide such as Titanium Industry Co., Ltd.; trade names "A-110", "TCA-123E", "A-190", "A-197", "SA-1", "SA" -1L", "SSP Series", "CSB Series" (above, 堺Chemical Industries Co., Ltd.), trade names "JA-1", "JA-C", "JA-3" (above, TAYCA) )), the product name "KA-10", "KA-15", "KA-20", "STT-65C-S", "STT-30EHJ" (above, Titanium Industry Co., Ltd.), trade name Anatase-type titanium oxide such as "DCF-T-17007", "DCF-T-17008", and "DCF-T-17050" (above, RESINO COLOR Industrial Co., Ltd.).

 [hardener (D)]  

The curing agent (D) constituting the curable epoxy resin composition of the present invention serves as a function of hardening a compound having an epoxy group. As the curing agent (D), a curing agent known or customary as a curing agent for an epoxy resin can be used. In particular, the curing agent (D) is preferably a liquid acid anhydride at 25 ° C, and more specifically, examples thereof include methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride. Dodecenyl succinic anhydride, methyl endomethylene tetrahydrophthalic anhydride, and the like. Further, for example, an acid anhydride which is solid at room temperature (about 25 ° C) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or methylcyclohexene dicarboxylic anhydride, It can also be dissolved in a liquid acid anhydride at normal temperature (about 25 ° C) to form a liquid mixture, and is preferably used as a curing agent (D). Further, the curing agent (D) may be used singly or in combination of two or more. The curing agent (D) is particularly preferably an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including a substituent in which an alkyl group or the like is bonded to a ring) from the viewpoint of heat resistance, light resistance, and crack resistance. ).

Further, in the present invention, the product name "Rikacid MH-700" (manufactured by Shin-Nihon Chemicals Co., Ltd.), and the product name "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.) can be used as the curing agent (D). ) and other commercial products.

The amount (content) of the curing agent (D) is not particularly limited, but is preferably 50% based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. 200 parts by weight, more preferably 80 to 145 parts by weight. More specifically, it is preferably used in an amount of from 0.5 to 1.5 equivalents per equivalent of the epoxy group in the epoxy group-containing compound 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, the curing is insufficient, and the strength of the cured product tends to be lowered. On the other hand, when the amount of the curing agent (D) used is more than 200 parts by weight, the cured product may be colored and the hue may be deteriorated.

 [hardening accelerator (F)]  

In the curable epoxy resin composition of the present invention, the curing accelerator (F) is a compound having a function of promoting the curing rate when the compound having an epoxy group is cured by the curing agent (D). As the curing accelerator (F), a known or conventional hardening accelerator can be used without particular limitation, and examples thereof include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and a salt thereof (for example, a phenate, an octanoate, a p-toluenesulfonate, a formate, a tetraphenylborate, etc.); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and a salt thereof (for example, a phenate, caprylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); benzyldimethylamine, 2,4,6-gin (dimethylamino) a tertiary amine such as phenol or N,N-dimethylcyclohexylamine; 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, etc. Imidazoles; phosphines such as phosphates and triphenylphosphine; antimony compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organometallic salts such as tin octylate and zinc octoate; metal chelates. Further, the curing accelerator (F) may be used alone or in combination of two or more.

Further, in the present invention, as the curing accelerator (F), the trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", or the like may be used. "12XD (developed product)" (above, SUNAPRO (share) system), trade name "TPP-K", "TPP-MK" (above, Beixing Chemical Industry Co., Ltd.), trade name "PX-4ET" ( A commercial product such as the Japan Chemical Industry Co., Ltd.).

The amount (content) of the curing accelerator (F) is not particularly limited, but is preferably 0.05 with respect to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. ~5 parts by weight, more preferably 0.1 to 3 parts by weight, particularly preferably 0.2 to 3 parts by weight, 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 amount of the curing accelerator (F) used is more than 5 parts by weight, the cured product may be colored and the hue may be deteriorated.

 [hardening catalyst (E)]  

The curable epoxy resin composition of the present invention may further comprise a hardening catalyst (E) instead of the above-mentioned hardener (D). Similarly to the case of using the curing agent (D), the curing reaction of the epoxy group-containing compound can be carried out by using the curing catalyst (E) to obtain a cured product. The curing catalyst (E) is not particularly limited. For example, a cationic catalyst (cationic polymerization initiator) which can generate a cationic species by application of ultraviolet irradiation or heat treatment and which can start polymerization can be used.

Examples of the cationic catalyst that generates a cationic species by ultraviolet irradiation include hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, and hexafluoroarsenate. These cationic catalysts can be used singly or in combination of two or more. As the cation catalyst, for example, a product name "UVACURE 1590" (manufactured by Daicel-Cytec Co., Ltd.), trade names "CD-1010", "CD-1011", and "CD-1012" (above, USA) can be preferably used. Manufactured by SARTOMER, the product name is "Irgacure 264" (CIBA Japan Co., Ltd.), and the product name is "CIT-1682" (made by Japan Soda Co., Ltd.).

Examples of the cationic catalyst which generates a cationic species by heat treatment include an aryldiazonium salt, an aryl iodonium salt, an arylsulfonium salt, an allene-ion complex, and the like. These cationic catalysts can be used singly or in combination of two or more. As the cation catalyst, for example, the product names "PP-33", "CP-66", "CP-77" (above, ADEKA), and the product name "FC-509" (3M) can be preferably used. System), product name "UVE1014" (GE system), trade name "Sunaid SI-60L", "Sunaid SI-80L", "Sunaid SI-100L", "Sunaid SI-110L", "Sunaid SI-150L" ( In the above, Sanshin Chemical Industry Co., Ltd., a commercial product such as "CG-24-61" (CIBA Japan Co., Ltd.). As the cation catalyst, a compound of a metal such as aluminum or titanium, a chelating compound of acetonitrile acetic acid or a diketone, a sterol compound such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and B may be further used. A chelating compound of indole acetic acid or a diketone, a compound of a phenol such as bisphenol S, or the like.

The amount (content) of the curing catalyst (E) is not particularly limited, but is preferably 0.01 with respect to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. It is preferably from 15 to 12 parts by weight, more preferably from 0.05 to 10 parts by weight, particularly preferably from 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 further comprise a fluorinated alkane derivative (G) and/or an alicyclic polyester resin (H) having two or more epoxy groups in the molecule. In particular, the curable epoxy resin composition of the present invention preferably contains a fluorinated alkane derivative (G) and an alicyclic polyester resin (H) having two or more epoxy groups in the molecule. In other words, the curable epoxy resin composition of the present invention preferably contains at least the alicyclic epoxy compound (A) represented by the above formula (I) and the isomeric cyanuric monoolefin represented by the above formula (1). a propyl diglycidyl ester compound (B), a decane derivative (G) having two or more epoxy groups in the molecule, an alicyclic polyester resin (H), a white pigment (E), and a hardener (F) a resin composition of the hardening accelerator (H), or at least the alicyclic epoxy compound (A) represented by the above formula (I), and the isomeric cyanuric acid represented by the above formula (1) Allyl diglycidyl ester compound (B), a decane derivative (G) having two or more epoxy groups in the molecule, an alicyclic polyester resin (H), a white pigment (E), and hardening The resin composition of the catalyst (G).

 [a oxane 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 fluorinated alkane derivative (G) having two or more epoxy groups in a molecule (in one molecule). The fluorinated alkane 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 fluorinated alkane derivative (G) having two or more epoxy groups in the molecule serves to increase the heat resistance, light resistance, and crack resistance of the cured product, and to suppress the decrease in the illuminance of the optical semiconductor device.

The oxoxane skeleton in the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, and examples thereof include a cyclic oxirane skeleton and a linear polycondensation. A polyoxyalkylene skeleton such as a ruthenium or a cage or ladder type polyasesquioxane. In particular, the naphthene skeleton is preferably a cyclic siloxane skeleton or a linear polyfluorene skeleton from the viewpoint of increasing the heat resistance and light resistance of the cured product and suppressing the decrease in luminosity. In other words, the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule is preferably a cyclic oxirane having two or more epoxy groups in the molecule, and has 2 in the molecule. More than one linear polyoxyl group of epoxy groups. In addition, the decane derivative (G) having two or more epoxy groups in the molecule may be used singly or in combination of two or more.

When the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule is a cyclic siloxane having two or more epoxy groups in the molecule, the Si-O forming the siloxane ring The number of the units (equivalent to the number of the ruthenium atoms forming the siloxane ring) is not particularly limited, but is preferably from 2 to 12, more preferably 4 from the viewpoint of increasing the heat resistance and light resistance of the cured product. ~8.

The weight average molecular weight of the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but is preferably from the viewpoint of improving heat resistance and light resistance of the cured product. 100~3000, more preferably 180~2000. In addition, the weight average molecular weight of the oxoxane derivative (G) having two or more epoxy groups in the molecule can be, for example, a GPC (gel permeation chromatography) method as a standard polystyrene equivalent value. Determination.

The number of epoxy groups (the number of epoxy groups in one molecule) of the oxoxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited as long as it is two or more. However, from the viewpoint of increasing the heat resistance and light resistance of the cured product, it is preferably 2 to 4.

The epoxy equivalent of the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule (in accordance with JIS K7236) is not particularly limited, but the heat resistance and light resistance of the cured product are increased. Preferably, it is 180 to 400, more preferably 240 to 400, and particularly preferably 240 to 350.

The epoxy group in the oxoxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but is preferably from the viewpoint of improving heat resistance and light resistance of the cured product. It is an epoxy group (alicyclic epoxy group) which is composed of two adjacent carbon atoms and an oxygen atom which constitute an aliphatic ring, and particularly preferably an epoxycyclohexane group.

Specific examples of the fluorinated alkane 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-cyclotetraoxane, 4,8-di[2-(3-{oxabicyclo[4.1.0] Heptyl})ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetraoxane, 2,4-di[2-(3-{oxabicyclo[4.1.0] Heptyl})ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 4,8-di[2-(3-{oxabicyclo[ 4.1.0] heptyl}) ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,8-tri[2-(3 -{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetraoxane, 2,4,8-tri[2-(3 -{oxabicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,6,8-tetra [2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetraoxane, oxime sesquioxide with epoxy group Alkane, etc. More specifically, for example, a cyclic oxirane having two or more epoxy groups in one molecule represented by the following formulas (S-1) to (S-7) may be mentioned.

In addition, as the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule, for example, an alicyclic epoxy group-containing polyfluorene oxide resin described in JP-A-2008-248169 may be used. Or an organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule as described in JP-A-2008-19422.

The fluorinated alkane derivative (G) having two or more epoxy groups in the molecule may, for example, be a cyclic oxirane having two or more epoxy groups in the molecule. 40-2678" (Shin-Etsu Chemical Industry Co., Ltd.), trade name "X-40-2670" (Shin-Etsu Chemical Industry Co., Ltd.), trade name "X-40-2720" (Shin-Etsu Chemical Industry Co., Ltd.) ) and other commercial products.

The amount (content) of the oxoxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but is relative to the component (A), the component (B), and the component (G). The total amount (100% by weight) is preferably 5 to 90% by weight, more preferably 5 to 85% by weight, still more preferably 5 to 80% by weight, particularly preferably 8 to 75% by weight. When the amount of the oxoxane 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 lowered. On the other hand, when the amount of the oxoxane derivative (G) having two or more epoxy groups in the molecule is more than 90% by weight, the crack resistance of the cured product may be lowered.

An alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound (B), and a total amount (100% by weight) of the epoxy group-containing compound (epoxy resin) The total amount of the decane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but is preferably from the viewpoint of improvement in heat resistance, light resistance, and crack resistance. 30% by weight or more (for example, 30 to 100% by weight), particularly preferably 40% by weight or more.

 [Cycloaliphatic Polyester Resin (H)]  

The alicyclic polyester resin (H) is a polyester resin having at least an alicyclic structure (aliphatic ring structure). The alicyclic polyester resin (H) serves to increase the heat resistance, light resistance, and crack resistance of the cured product, and to suppress the decrease in the illuminance of the optical semiconductor device. In particular, the alicyclic polyester resin (H) is preferably an alicyclic ring having an alicyclic ring (alicyclic structure) in the main chain from the viewpoint of an increase in heat resistance, light resistance, and crack resistance of the cured product. Polyester. That is, the alicyclic polyester resin (H) is preferably a polyester resin constituting a polymer main chain from a part or all of carbon atoms constituting the alicyclic ring. Further, the alicyclic polyester resin (H) may be used singly or in combination of two or more.

The alicyclic structure in the alicyclic polyester resin (H) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure or a bridged cyclic hydrocarbon structure (for example, a bicyclic hydrocarbon), and the like. The alicyclic ring (the carbon-carbon bond constituting the alicyclic ring) is a saturated monocyclic hydrocarbon structure or a saturated bridged cyclic hydrocarbon structure composed of a carbon-carbon single bond. Further, the alicyclic structure in the alicyclic polyester resin (H) may be introduced into any one of a constituent unit derived from a dicarboxylic acid and a constituent unit derived from a diol, or may be introduced into both. There are no special restrictions.

The alicyclic polyester resin (H) has a constituent unit derived from a monomer component having an alicyclic structure. The monomer having the above alicyclic structure is exemplified by a diol or a dicarboxylic acid having a known or customary alicyclic structure, and is not particularly limited, and examples thereof include 1,2-cyclohexanedicarboxylic acid. 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, hepic acid, 1, a dicarboxylic acid having an alicyclic structure such as 4-decahydronaphthalene dicarboxylic acid, 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid or 2,7-decahydronaphthalene dicarboxylic acid Acid (also including a derivative of an acid anhydride or the like); 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentane dimethanol, 1,3-cyclopentane dimethanol, 5-membered cyclic diol such as bis(hydroxymethyl)tricyclo[5.2.1.0]nonane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 6-membered ring of 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis-(4-hydroxycyclohexyl)propane, etc. A diol having an alicyclic structure such as an alcohol or hydrogenated bisphenol A (including such derivatives) and the like.

The alicyclic polyester resin (H) may also have a constituent unit derived from a monomer component having no alicyclic structure. The monomer component having no 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. a derivative containing an acid anhydride or the like); an aliphatic dicarboxylic acid such as adipic acid, sebacic acid, sebacic acid, succinic acid, fumaric acid or maleic acid (including a derivative such as an acid anhydride); , propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexane Alcohol, 3-methylpentanediol, diethylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3 - propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc. Alcohol (also including such derivatives) and the like. Further, in the monomer component having no alicyclic structure, a suitable substituent (for example, an alkyl group, an alkoxy group, a halogen atom or the like) is bonded to the above dicarboxylic acid or two having no alicyclic structure. Alcohol.

The ratio of the monomer unit having an alicyclic ring is not particularly limited with respect to all the monomer units (all monomer components) (100 mol%) constituting the alicyclic polyester resin (H), but is preferably 10 More than Mole (for example, 10 to 80 mol%), more preferably 25 to 70 mol%, and particularly preferably 40 to 60 mol%. When the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, and crack resistance of the cured product may be lowered.

The alicyclic polyester resin (H) is particularly preferably an alicyclic polyester resin containing at least one of the constituent units represented by the following formulas (2) to (4).

(wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched carbon number; The alkyl group of 1 to 4, the two selected from R ⁴ to R ⁷ may also be bonded to form a ring).

(wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched carbon number; The alkyl group of 1 to 4, the two selected from R ⁴ to R ⁷ may also be bonded to form a ring).

(wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched carbon number; The alkyl group of 1 to 4 may also form a ring formed by two bonds selected from R ⁴ to R ⁷ ).

Preferred examples of the structural unit represented by the above formulas (2) to (4) include 4-methyl-1,2-cyclohexanedicarboxylic acid represented by the following formula (5). And a constituent unit of ethylene glycol. The alicyclic polyester resin (H) having such a constituent unit can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride and ethylene glycol.

In addition, as another preferable example of the structural unit represented by the above formulas (2) to (4), for example, 1,4-cyclohexanedicarboxylic acid and a new one represented by the following formula (6) are mentioned. a constituent unit of pentanediol. The alicyclic polyester resin (H) having such a structural unit is obtained, for example, by polycondensation of 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.

Further, 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 a hydroxyl group or a carboxyl group is suitably modified (for example, a terminal hydroxyl group via a monocarboxylic acid) A structure in which an acid or an acid anhydride is esterified, or a structure in which a terminal carboxyl group is esterified with an alcohol, etc.).

When the alicyclic polyester resin (H) has the constituent units represented by the above formulas (2) to (4), the total amount of the constituent units (the total content; all the monomer units constituting the constituent unit) is It is not particularly limited, but is preferably 20 mol with respect to all constituent units of the alicyclic polyester resin (H) (100 mol%; all monomer units constituting the alicyclic polyester resin (H)). More than % (for example, 20 to 100% by mole), more preferably 50 to 100% by mole, and particularly preferably 80 to 100% by mole. 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 from 300 to 100,000, more preferably from 300 to 30,000. When the number average molecular weight of the alicyclic polyester resin (H) is less than 300, the toughness of the cured product is insufficient, and the crack resistance is lowered. On the other hand, if the number average molecular weight of the alicyclic polyester resin (H) exceeds 100,000, the compatibility with other components (for example, the hardener (D)) is lowered, and the mechanical properties of the cured product are adversely affected. The case of reduced crack resistance. Further, the number average molecular weight of the alicyclic polyester resin (H) is measured, for example, by a GPC (gel permeation chromatography) method as a standard polystyrene equivalent value.

In addition, the alicyclic polyester resin (H) may be used alone or in combination of two or more.

The alicyclic polyester resin (H) is not particularly limited and can be produced by a known or customary method. More specifically, for example, the above-mentioned dicarboxylic acid and a diol can be polycondensed by a usual method to obtain an alicyclic polyester resin (H), and the above dicarboxylic acid derivative can also be obtained by a usual method. (Acid anhydride, ester, hydrazine halide, etc.) obtained by polycondensation with a diol.

In the curable epoxy resin composition of the present invention, the blending amount (content) of the alicyclic polyester resin (H) is not particularly limited, but when the hardener (D) is used as an essential component, The total amount (100% by weight) of the alicyclic polyester resin (H) and the hardener (D) is preferably from 1 to 60% by weight, more preferably from 5 to 30% by weight. When the blending amount of the alicyclic polyester resin (H) is less than 1% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the blending amount of the alicyclic polyester resin (H) exceeds 60% by weight, the heat resistance of the cured product may be lowered.

On the other hand, when the hardening epoxy resin composition of the present invention contains the curing catalyst (E) as an essential component, the blending amount (content) of the alicyclic polyester resin (H) is not particularly limited. However, it is preferably 50 to 99% by weight, and more preferably 65 to 99% by weight based on the total amount (100% by weight) of the alicyclic polyester resin (H) and the curing catalyst (E). When the blending amount of the alicyclic polyester resin (H) is less than 50% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the blending amount of the alicyclic polyester resin (H) exceeds 99% by weight, the heat resistance of the cured product may be lowered.

 [leveling agent]  

The curable epoxy resin composition of the present invention preferably further comprises at least one leveling selected from the group consisting of a polyfluorene-based leveling agent (polyoxane-based leveling agent) and a fluorine-based leveling agent. Agent. Since the curable epoxy resin composition of the present invention contains the above-mentioned leveling agent, a cured product capable of exhibiting higher heat resistance, light resistance and crack resistance can be formed, and an optical semiconductor device produced by using the cured product is more It is not easy to cause a decrease in luminosity as time passes.

 (polyoxane leveling agent)  

The above polyoxygen-based leveling agent is a leveling agent containing a compound having a polyoxyalkylene skeleton. As the polyfluorene-based leveling agent, a well-known or conventional polyfluorinated leveling agent can be used, and is not particularly limited. For example, the product names "BYK-300", "BYK-301/302", and " BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322, BYK-323, BYK- 325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-341", "BYK-344", "BYK-345/346", "BYK-" 347", "BYK-348", "BYK-349", "BYK-370", "BYK-375", "BYK-377", "BYK-378", "BYK-UV3500", "BYK-UV3510" , "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" (above, BYK Chemical ‧ Japan (share) system), trade name "AC FS 180", "AC FS 360" "AC S 20" (above, manufactured by Algin Chemie), trade name "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403" "Polyflow KL-404" (above, Kyoeisha Chemical Co., Ltd.), trade name KP-323", "KP-326", "KP-341", "KP-104", "KP-110", "KP-112" (above, Shin-Etsu Chemical Co., Ltd.), trade name "LP" -7001", "LP-7002", "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 Commercial products such as ADDITIVE and "56 ADDITIVE" (above, Toray Dow Corning Co., Ltd.).

The compound having a polyoxyalkylene skeleton is particularly preferably a polyfluorene-based polymer having at least a structural unit (repeated structural unit) represented by the following formula (7) (except for the component (C)). That is, the polyfluorinated leveling agent is preferably a leveling agent containing at least the above polyfluorene-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 (n-butyl group), an isobutyl group, a secondary butyl group, and a tertiary butyl group. a linear or branched alkyl group having 1 to 30 carbon atoms such as a pentyl group.

In the above R ⁸ , the substituent which the linear or branched alkyl group may have is not particularly limited, and examples thereof include a hydroxyl group which can be protected by a protective group [for example, a hydroxyl group, a substituted oxy group (for example, Alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; and a carboxyl group which can be protected by a protecting group [for example, a -COOR ^a group or the like: R ^a represents a hydrogen atom or an alkane. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, and a hexyl group. Chain or branched alkyl], propylene fluorenyl, methacryl fluorenyl, acryloxy, methacryloxy, vinyl, propenyl, epoxy, epoxypropyl, and the like.

R ⁹ in the above formula (7) represents 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 in the above 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), and an isobutyl group. a linear or branched alkyl group having 1 to 30 carbon atoms such as a secondary butyl group, a tertiary butyl group or a pentyl group. Further, 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.

In the above R ⁹ , the substituent which the linear or branched alkyl group may have and the substituent which the aralkyl group may have are not particularly limited, and examples thereof include the substituents exemplified in the above R ⁸ . Wait.

The organic group containing a polyether chain in the above R ⁹ is a monovalent organic group containing at least a polyether structure. The polyether structure in the organic group containing the polyether chain is not particularly limited as long as it has a complex ether bond structure, and examples thereof include a polyethylene glycol structure (polyethylene oxide structure). , a polypropylene glycol structure (polypropylene oxide structure), a polytetramethylene glycol (polytetramethylene glycol) structure, a polyether structure derived from a plurality of alkanediols (or alkylene oxides) (for example, poly(propylene glycol) / Glycol) structure, etc.) Polyoxyalkylene structure. Further, in the polyether structure derived from a plurality of kinds of alkanediols, the addition form of each alkanediol may be a block type (block copolymerization type) or a random type (random copolymerization type).

The organic group containing the polyether chain may be an organic group formed only of the above polyether structure, or may have one or two or more and one or two or more linking groups having the above polyether structure (having one The organic group of the structure to which the above-mentioned divalent group of atoms is attached. Examples of the linking group in the organic group containing the polyether chain include a divalent hydrocarbon group (especially a linear or branched alkyl group), a thioether group (-S-), and an ester group (-COO). -), amidino group (-CONH-), a carbonyl group (-CO-), a carbonate group (-OCOO-), a bond of two or more of these groups, and the like.

Further, the above-mentioned organic group containing a polyether chain may have a substituent exemplified in the above R ⁸ (for example, a hydroxyl group, a carboxyl group, an acryl fluorenyl group, a methacryl fluorenyl group, an acryloxy group, a methacryl oxime). The oxy group, the vinyl group, the acryl group or the like, for example, the organic group having a polyether structure as described above, and the terminal (the end portion on the opposite side to the ruthenium atom in the formula (7)) has the above substituent. Organic base and so on.

The organic group containing a polyester chain in the above R ⁹ is a monovalent organic group containing at least a polyester structure. The polyester structure in the organic group containing the polyester chain is not particularly limited as long as it has a complex ester bond, and examples thereof include an aliphatic polyester structure and an alicyclic polyester structure. An aromatic polyester structure, an aliphatic/aromatic polyester structure, an aliphatic/alicyclic polyester structure, an alicyclic/aromatic polyester structure, and the like.

More specifically, the polyester structure is, for example, a polyester structure formed by polymerization of a polycarboxylic acid (particularly a dicarboxylic acid) and a polyhydric alcohol (especially a diol). The 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 an acid anhydride or an ester). Derivatives; aliphatic dicarboxylic acids (including derivatives of anhydrides or esters, etc.) of adipic acid, azelaic acid, sebacic acid, succinic acid, fumaric acid, maleic acid, etc.; 1,2-ring Hexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, norbornene diacid, 1,4-decahydronaphthalene dicarboxylic acid, 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid, 2,7-decahydronaphthalene dicarboxylic acid, etc. having an alicyclic structure A dicarboxylic acid (including a derivative such as an acid anhydride or an ester) or the like. The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, and 2,3-butanediol. , 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, hexanediol (2-methylpentyl) Alkane-2,4-diol), 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5- Pentandiol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,8-octane Glycol, 1,12-dodecanediol, xylylene glycol, 1,3-dihydroxyacetone, polybutadiene diol, ethylene oxide adduct of bisphenol A, bisphenol A a diol such as a propylene oxide adduct (including such derivatives); 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentane dimethanol, 1, 5-membered cyclohexane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1-cyclopentane dimethanol, bis(hydroxymethyl)tricyclo[5.2.1.0]decane , 4-cyclohexanediol, 1,2-cyclohexane Methanol (1,2-dimethylolcyclohexane), 1,3-cyclohexanedimethanol (1,3-dimethylolcyclohexane), 1,4-cyclohexanedimethanol (1, 6-membered ring diol such as 4-dihydroxymethylcyclohexane), 2,2-bis-(4-hydroxycyclohexyl)propane, diol having an alicyclic structure such as hydrogenated bisphenol A (also including 3, etc.), glycerol, trimethylolpropane, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, neopentyl alcohol, etc. The above hydroxyl group polyol (including such derivatives) and the like. Each of the above polyester structures may be formed of a single polyol or a polycarboxylic acid, or may be formed of two or more kinds of polyhydric alcohols or polycarboxylic acids.

Moreover, as the polyester structure, for example, a polyester structure formed by polymerization of a hydroxycarboxylic acid and a polymerization (open-loop polymerization) of a lactone of a cyclic ester of a hydroxycarboxylic acid may be mentioned. Polyester structure, etc. The hydroxycarboxylic acid is not particularly limited, and examples thereof include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid (salicylic acid), and 3-methoxy-4-hydroxybenzoic acid (vanillic acid). ), 4-methoxy-3-hydroxybenzoic acid (isovanaic acid), 3,5-dimethoxy-4-hydroxybenzoic acid (syringic acid), 2,6-dimethoxy-4-hydroxybenzene Formic 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-phenyl)propane a hydroxyaromatic carboxylic acid such as 2-enol acid (ferulic acid) or 3-(4-hydroxyphenyl)-2-propenone acid (coumaric acid); glycolic acid, lactic acid, tartaric acid, citric acid, etc. A hydroxy aliphatic carboxylic acid or the like. The lactone is not particularly limited, and examples thereof include γ-butyrolactone, δ-valerolactone, ε-caprolactone, ξ-heptanolactone, and η-octanolactone. Each of the above polyester structures may be formed of a single hydroxycarboxylic acid or a lactone, or each of them may be formed of two or more kinds of hydroxycarboxylic acids and lactones.

Further, the polyester structure is not limited to the above-exemplified structure, and may be, for example, a polyester structure formed by polymerization of the above polycarboxylic acid and a polyhydric alcohol, and polymerization by a hydroxycarboxylic acid. Two or more kinds of polyester structures formed by polymerization of lactones.

The organic group containing the polyester chain may be an organic group formed only of the above polyester structure, or may have a structure in which one or two or more of the above polyester structures are bonded to one or two or more linking groups. Organic base. Examples of the linking group in the organic group containing the polyester chain include a divalent hydrocarbon group (particularly, a linear or branched alkyl group), a thioether group (-S-), and an ester group (-COO). -), amidino group (-CONH-), a carbonyl group (-CO-), a carbonate group (-OCOO-), a bond of two or more of these groups, and the like.

Further, the above organic group containing a polyester chain may have a substituent exemplified in the above R ⁸ (for example, a hydroxyl group, a carboxyl group, an acryl fluorenyl group, a methacryl fluorenyl group, an acryloxy group, a methacryl oxime). The oxy group, the vinyl group, the acryl group or the like, for example, the organic group having a polyester structure as described above, and the terminal (the end portion on the opposite side to the ruthenium atom in the formula (7)) has the above substituent. Organic base and so on.

The polyfluorene-based polymer may be a polymer having only the structural unit represented by the formula (7) as a repeating structural unit, or may be a structural unit other than the structural unit represented by the formula (7) as a repeating structural unit. polymer. The structural unit other than the structural unit represented by the formula (7) in the above polyfluorinated polymer is not particularly limited, and examples thereof include a structural unit having a hydroquinone group (Si—H). In addition, the polyfluorene-based polymer may be a polymer having only one structural unit represented by the formula (7), or may be a polymer having two or more structural units represented by the formula (7). Further, it may be a polymer having two or more structural units other than the structural unit represented by the formula (7).

Specific examples of the polyfluorene-based polymer include polymers represented by the following formulas (7a) to (7e) (polydimethyl siloxane or modified polydimethyl siloxane) Wait.

The polyfluorene-based polymer represented by the above formula (7a) is polydimethylsiloxane. X1 (the number of repetitions of the dimethyl fluorenyl structural unit [-Si(CH ₃ ) ₂ -O-]) in the formula (7a) is not particularly limited, but is preferably 2 to 3,000, more preferably 3 ~1500.

The polyfluorene-based polymer represented by the above formula (7b) is a polyether modified product of a polydimethylsiloxane having a polyether structure introduced into a 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. In addition, examples of the substituent in R ¹¹ include the substituents exemplified in the above R ⁸ . M1 (the number of repetitions of the methylene structural unit) in the formula (7b) is not particularly limited, and may be appropriately selected, for example, from the range of 1 to 30. Further, n1 (the number of repetitions of the oxyethylene structural unit or the oxypropylene structural unit) is not particularly limited, and may be appropriately selected, for example, from the range of 2 to 3,000. Further, y1 in the formula (7b) (the number of repeating of the structural unit including the polyether structure (polyether side chain)) is not particularly limited, but is preferably from 1 to 3,000, more preferably from 3 to 1,500. Further, x2 (the number of repetitions of the dimethyloxy group) is not particularly limited, but is preferably 2 to 3,000, more preferably 3 to 1,500. Further, in the polyfluorene-based polymer represented by the formula (7b), the addition form of the structural unit having a polyether structure and the dimethyl methoxy structural unit may be a block type or a random type. Further, when y1 is an integer of 2 or more, the structural unit having a polyether structure surrounded by the brackets of y1 may be the same or different.

The polyfluorene-based polymer represented by the above formula (7c) is a long-chain alkyl group of a polydimethylsiloxane having an alkyl group having a longer chain than a methyl group introduced into a side chain of polydimethylsiloxane. Modified body (polymethylalkyl oxane). R ¹² in the formula (7c) represents a linear or branched alkyl group having 2 or more carbon atoms. The y2 (the number of repetitions of the methylalkyl fluorenyl structural unit) in the formula (7c) is not particularly limited, but is preferably from 2 to 3,000, more preferably from 3 to 1,500. Further, x3 (the number of repetitions of the dimethyloxy group) is not particularly limited, but is preferably 0 to 3,000, more preferably 2 to 1,500. Further, in the polyfluorene-based polymer represented by the formula (7c), the addition form of the methylalkyl fluorenyl structural unit and the dimethyl methoxy structural unit may be a block type, or It is a random type. Further, the methylalkyloxy group structure units surrounded by the brackets of y2 may be the same or different.

The polyoxymethylene-based polymer represented by the above formula (7d) is an aralkyl modified body of polydimethylsiloxane having an aralkyl group introduced into a side chain of polydimethylsiloxane. M2 (the number of repetitions of the methylene structural unit) in the formula (7d) is not particularly limited, and may be appropriately selected, for example, from the range of 1 to 30. Further, y3 (the number of repeating of the methyl aralkyloxy group) is not particularly limited, but is preferably 2 to 3,000, more preferably 3 to 1,500. Further, x4 (the number of repetitions of the dimethyloxy group) is not particularly limited, but is preferably from 0 to 3,000, more preferably from 2 to 1,500. Further, in the polyfluorene-based polymer represented by the formula (7d), the addition form of the methyl aralkyl fluorenyl structural unit and the dimethyl fluorenyl structural unit may be a block type, and Can be a random type. Further, the methyl aralkyloxy group structure units surrounded by the brackets of y3 may be the same or different.

The polyoxymethylene-based polymer represented by the above formula (7e) is a polyester modified body of a polydimethylsiloxane having a polyester structure introduced into a 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 (for example, 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. In addition, examples of the substituent in R ¹⁵ include the substituents exemplified in the above R ⁸ . M3 (the number of repetitions of the methylene structural unit) in the formula (7e) is not particularly limited, and may be appropriately selected, for example, from the range of 1 to 30. Further, n2 (the number of repetitions of the condensation structure of the polyhydric alcohol and the polycarboxylic acid) is not particularly limited, and may be appropriately selected, for example, from the range of 2 to 3,000. Further, y4 in the formula (7e) (the number of repeating of the structural unit including the polyester structure (polyester side chain)) is not particularly limited, but is preferably from 1 to 3,000, more preferably from 3 to 1,500. Further, x5 (the number of repetitions of the dimethyloxy group) is not particularly limited, but is preferably 2 to 3,000, more preferably 3 to 1,500. Further, in the polyfluorene-based polymer represented by the formula (7e), the addition form of the structural unit having a polyester structure and the dimethyl methoxy structural unit may be a block type or a random type. type. Further, when y4 is an integer of 2 or more, the structural unit containing the polyester structure surrounded by the brackets of y4 may be the same or different.

The polyoxosiloxane-based polymer can be obtained by a known or customary production method, and the production method thereof is not particularly limited, and for example, a single sheet having a structure corresponding to the structural unit represented by the formula (7) can be used. a method of bulk polymerization, or a reactive group of a polyfluorene-based polymer having a reactive group in a side chain (polydimethyloxane having a reactive group in a side chain, etc.), having a specific structure The compound (for example, a compound having a polyether structure or a polyester structure) is reacted and bonded, and the like. Further, as the polyfluorene-based polymer, a commercially available product can also be used.

 (fluorine leveling agent)  

The fluorine-based leveling agent is a leveling agent containing a compound having a fluorinated alkyl group in which a part or all of a hydrogen atom of an alkyl group is substituted with a fluorine atom. As the fluorine-based leveling agent, a fluorine-based leveling agent which is known or conventionally used can be used, and it is not particularly limited. For example, the product name "BYK-340" (BYK Chemical ‧ Japan Co., Ltd.) and the product name can be used. AC 110a", "AC 100a" (above, manufactured by Algin Chemie), trade name "Megafac F-114", "Megafac F-410", "Megafac F-444", "Megafac EXP TP-2066", "Megafac F -430", "Megafac F-472SF", "Megafac F-477", "Megafac F-552", "Megafac F-553", "Megafac F-554", "Megafac F-555", "Megafac R-" 94", "Megafac RS-72-K", "Megafac RS-75", "Megafac F-556", "Megafac EXP TF-1367", "Megafac EXP TF-1437", "Megafac F-558", " Megafac EXP TF-1537" (above, DIC (share) system), trade name "FC-4430", "FC-4432" (above, Sumitomo 3M (share) system), trade name "Ftergent 100", "Ftergent 100C" , Ftergent 110, Ftergent 150, Ftergent 150CH, Ftergent AK, Ftergent 501, Ftergent 250, Ftergent 251, Ftergent 222F", "Ftergent 208G", "Ftergent 300", "Ftergent 310", "Ftergent 400SW" (above, NEOS (share) system), trade name "PF-136A", "PF-156A", "PF-151N" "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-651", "PF-652" (above, Bukchon Chemical Industry Co., Ltd.) Commercial products.

The compound having a fluorinated alkyl group is particularly preferably a fluorine-containing acrylic polymer having at least a structural unit (repeated structural unit) represented by the following formula (8), and having at least the following formula (9) A fluorine-containing polyether polymer of a structural unit (repeated structural unit). In other words, 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) represents a linear or branched alkyl group having 1 to 4 carbon atoms which may be a part or all of a hydrogen atom, a fluorine atom or a hydrogen atom. 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, a secondary butyl group, and a tertiary butyl group.

R ¹⁷ in the above formula (8) represents a fluorinated alkyl group (an alkyl group in which one or all of hydrogen atoms are substituted by a fluorine atom). The fluorinated alkyl group is not particularly limited, and examples thereof include difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3- Tetrafluoropropyl, perfluoroethylmethyl, 2,2,3,3,4,4-hexafluorobutyl, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl, 1,1-dimethyl-2,2,3,3,3-pentafluoropropyl, 2-(perfluoropropyl)ethyl, 2,2,3,3,4,4,5,5- Octafluoropentyl, 1,1-dimethyl-2,2,3,3,4,4-hexafluorobutyl, 1,1-dimethyl-2,2,3,3,4,4, 4-heptafluorobutyl, 2-(perfluorobutyl)ethyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, perfluoropentylmethyl, 1 ,1-dimethyl-2,2,3,3,4,4,5,5-octafluoropentyl, 1,1-dimethyl-2,2,3,3,4,4,5, 5,5-nonafluoropentyl, 2-(perfluoropentyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7-dodefluoroheptyl, Perfluorohexylmethyl, 2-(perfluorohexyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorooctyl, Perfluoroheptylmethyl, 2-(perfluoroheptyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Hexadecafluorodecyl, perfluorooctylmethyl, 2-(perfluorooctyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8, 8,9,9,10,10-octadecylfluorenyl, perfluorodecylmethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4, 4 ,4-heptafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 3,3,4,4,5,5,6,6,7,7, a linear or branched alkyl group having 1 to 30 carbon atoms substituted by a fluorine atom of a hydrogen atom such as 8,8,8-tridecafluorooctyl; trifluoromethyl, pentafluoroethyl, and Fluorylpropyl, heptafluoroisopropyl, nonafluoro-n-butyl, nonafluoroisobutyl, nonafluoro-tert-butyl, nonafluorotributyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl And a linear or branched perfluoroalkyl group having 1 to 30 carbon atoms such as perfluorooctyl group, perfluorodecyl group or perfluorodecyl group. Among them, as the above R ¹⁷ , a perfluoroalkyl group is preferred.

In addition, the fluorine-containing acrylic polymer may be a polymer having only a structural unit represented by the formula (8) as a repeating structural unit, or may be a structural unit other than the structural unit represented by the formula (8). a polymer of structural units. In addition, the fluorine-containing acrylic polymer may be a polymer having only one structural unit represented by the formula (8), or may be a polymer having two or more structural units represented by the formula (8). Further, it may be a polymer having two or more structural units other than the structural unit represented by the formula (8).

The structural unit other than the structural unit represented by the formula (8) which is contained in the fluorine-containing acrylic polymer is not particularly limited, and examples thereof include a monomer component (monomer component) which is an acrylic polymer. Or a structural unit of a conventional monomer or the like. Examples of the monomer include acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and amyl acrylate (including those having a functional group such as a hydroxyl group or a carboxyl group); a methacrylate such as an ester, ethyl methacrylate, propyl methacrylate or butyl methacrylate (including a functional group having a hydroxyl group or a carboxyl group); acrylamide, N-methyl acrylamide And other acrylamides; methacrylamides such as methacrylamide; allyl compounds; vinyl compounds such as aromatic vinyl compounds, vinyl ethers, and vinyl esters. Further, a polyalkylene glycol ether, an ester of acrylic acid or methacrylic acid, or the like may be used as the above monomer.

Specific examples of the fluorine-containing acrylic polymer include a fluorine-containing acrylic polymer represented by the following formula (8a).

R ¹⁸ in the formula (8a) represents a hydrogen atom or a methyl group. Further, 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, and a secondary group. a linear or branched alkyl group having 1 to 30 carbon atoms such as a benzyl group, a tributyl group or a pentyl group.

R ²⁰ in the formula (8a) represents a hydrogen atom or a methyl group. Further, R ²¹ represents a perfluoroalkyl group. The perfluoroalkyl group is not particularly limited, and examples thereof include a perfluoroalkyl group exemplified as R ^{17 in} the above formula (8).

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 containing the polyether chain is not particularly limited, and examples thereof include those exemplified as R ⁹ in the above formula (7).

r, s and t in the formula (8a) each represent an integer of 1 to 3,000.

The fluorine-containing acrylic polymer can be obtained by a known or customary production method, and the production method thereof is not particularly limited. For example, a monomer which gives a structural unit represented by the formula (8) by polymerization can be used (for example, It is produced by a method of polymerization such as perfluoroalkyl acrylate or perfluoroalkyl methacrylate. Further, as the fluorine-containing acrylic polymer, a commercially available product can also be used.

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

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 a part or all of a hydrogen atom substituted by a fluorine atom, and examples thereof include those exemplified as R ¹⁷ in the above formula (8). . Among them, as the above R ²⁵ , an alkyl group in which a part of a hydrogen atom is substituted with a fluorine atom is preferred.

The z (the number of repetitions of the methylene structural unit) in the above formula (9) represents an integer of from 1 to 30. Among them, an integer of 1 to 10 is preferred.

In addition, the fluorine-containing polyether polymer may be a polymer having only a structural unit represented by the formula (9) as a repeating structural unit, or may be a structural unit other than the structural unit represented by the formula (9). Repeat the polymer of the structural unit. In addition, the fluorine-containing polyether polymer may be a polymer having only one structural unit represented by the formula (9), or may be a polymer having two or more structural units represented by the formula (9). . Further, it may be a polymer having two or more structural units other than the structural unit represented by the formula (9).

The fluorine-containing polyether polymer may have a structural unit other than the structural unit represented by the formula (9), and is not particularly limited, and examples thereof include an oxyethylene unit [-OCH ₂ CH ₂ -], oxypropylene. An oxyalkylene structural unit or the like of the unit [-OCH(CH ₃ )CH ₂ -].

Specific examples of the structural unit represented by the above formula (9) include a structural unit represented by the following formula and the like. R ²⁶ in the following formula represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a n-butyl group or the like). R ²⁵ and z in the following formula are the same as described above.

Specific examples of the fluorine-containing polyether polymer include a fluorine-containing polyether polymer represented by the following formula (9a).

In the formula (9a), u, v and w each represent an integer of from 1 to 50. The sum of u and w is preferably an integer of 2 to 80, more preferably an integer of 4 to 30, and particularly 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 fluorine-containing polyether polymer can be obtained by a known or customary production method, and the production method thereof is not particularly limited, and for example, a monomer which gives a structural unit represented by the formula (9) by polymerization can be used (for example) For example, a cyclic ether compound such as an epoxy compound or an oxetane compound is produced by a method such as polymerization (for example, ring-opening polymerization). Further, as the fluorine-containing polyether polymer, a commercially available product can also be used.

The non-volatile content (doping amount) of the leveling agent in the curable epoxy resin composition of the present invention is not particularly limited, but is an epoxy group contained in the curable epoxy resin composition. The total amount (100 parts by weight) of the compound is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.1 to 4 parts by weight. When the content of the leveling agent (in terms of nonvolatile matter) is less than 0.1 part by weight, the crack resistance of the cured product may be lowered. On the other hand, when the content of the leveling agent (in terms of nonvolatile matter) exceeds 10 parts by weight, the heat resistance of the cured product may be lowered.

In particular, in the curable epoxy resin composition of the present invention, the content (doping amount) of the polyfluorene-based polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer is not particularly However, it is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. It is preferably 0.1 to 4 parts by weight. When the content of the polyfluorene-based polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer is less than 0.1 part by weight, the crack resistance of the cured product may be lowered. 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 (the amount of the above-mentioned polyfluorinated polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer) means that the above-mentioned polyoxyl polymerization is contained. In the case of two or more kinds of the fluorine-containing acrylic polymer and the fluorine-containing polyether polymer, the total content (total content) of these.

When the curable epoxy resin composition of the present invention contains the specific leveling agent described above, the reflector formed of the cured product of the resin composition can exhibit higher heat resistance and crack resistance, so that it is suppressed. The illuminance of the optical semiconductor device of the reflector decreases with time (in particular, the illuminance of the optical semiconductor device that emits high-intensity light decreases). It is presumed that such an effect is obtained by blending a leveling agent to improve the adhesion of the curable epoxy resin composition (or a cured product thereof) of the present invention to a sealing material (a sealing resin of an optical semiconductor element).

 [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 capable of exhibiting higher heat resistance and crack resistance by containing the above polyol compound, and an optical semiconductor device produced using the cured product is less likely to occur. The luminosity decreases as time passes. The polyol compound is a polymer (oligomer or polymer) having a number average molecular weight of 200 or more in a molecule (in one molecule), and includes, for example, a polyether polyol or a polyester polyol. Polycarbonate polyols and the like. Further, the above polyol compounds may be used singly or in combination of two or more.

The hydroxyl group (two or more hydroxyl groups) of the above polyol compound may be an alcoholic hydroxyl group or a phenolic hydroxyl group. In addition, 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) of the polyol compound is not particularly limited, but from the viewpoint of reactivity with the curing agent, etc., it is preferably present at least at the end of the polyol (polymeric main) The end of the chain) is particularly preferably present at least at both ends of the polyol.

The polyol compound may be a solid or liquid, as long as it is a curable epoxy resin composition which can be formed into a liquid after being blended with other components.

The number average molecular weight of the above polyol compound is not particularly limited as long as it is 200 or more, but is preferably 200 to 100,000, more preferably 300 to 50,000, and particularly preferably 400 to 40,000. If the number average molecular weight is less than 200, peeling of the hardened material or cracking in the hardened material may occur when the solder is reflowed. On the other hand, when the number average molecular weight exceeds 100,000, the liquid curable epoxy resin composition may be precipitated or may not be dissolved. Further, the number average molecular weight of the above polyol compound means a number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

The polyhydric alcohol compound is, for example, a polyester polyol (including a polyester polyol oligomer) having an ester skeleton (polyester skeleton) in a molecule, and a polyether skeleton (polyether skeleton) in a molecule. An ether polyol (including a polyether polyol oligomer), a polycarbonate polyol having a carbonate skeleton (polycarbonate skeleton) in a molecule (including a polycarbonate polyol oligomer), and the like. The polyhydric alcohol compound may further contain, for example, a phenoxy resin, a bisphenol type polymer epoxy resin having an epoxy equivalent of more than 1000 g/eq., a polybutadiene having a hydroxyl group, an acrylic polyol, or the like.

The polyester polyol may, for example, be a polyester polyol obtained by condensation polymerization (for example, transesterification) of a polyhydric alcohol, a polycarboxylic acid (polybasic acid) or a hydroxycarboxylic acid, or by a lactone. A polyester polyol or the like obtained by ring-opening polymerization.

Examples of the polyol constituting the monomer component of the polyester polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 2-methyl-1,3-propanediol, and 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, 2,3,5-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 Cyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dodecanediol, polybutadiene diol, neopentyl glycol, Tetramethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-dihydroxyacetone, hexanediol, 1,2,6-hexanetriol, ditrimethylolpropane , mannitol, sorbitol, neopentyl alcohol, and the like. Examples of the polycarboxylic acid constituting the monomer component of the polyester polyol include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, sebacic acid, and lemon. Acid, 2,6-naphthalene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, 1,10-decane dicarboxylic acid, methyl hexahydrophthalic anhydride, Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and the like. Examples of the hydroxycarboxylic acid include lactic acid, malic acid, glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of the lactones include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

The above polyester polyol can be produced by a known or customary production method, and is not particularly limited. For example, it can be obtained by condensation polymerization (polycondensation) of the above polyol with a polycarboxylic acid, and condensation polymerization of the above hydroxycarboxylic acid. It is produced by ring-opening polymerization of the above lactones. The conditions at the time of polymerization are also not particularly limited, and can be appropriately selected from known or customary reaction conditions. Further, as the above polyol, polycarboxylic acid, or hydroxycarboxylic acid, a derivative which is well known or conventionally used (for example, a hydroxyl group via a mercapto group, an alkoxycarbonyl group, an organic mercapto group, an alkoxyalkyl group, or an oxygen group) may be used. A derivative protected by a heterocycloalkyl group or the like, or a carboxyl group derived from a derivative such as an alkyl ester, an acid anhydride or an oxidized halide, or the like).

As the polyester polyol, for example, "Placcel 205", "Placcel 205H", "Placcel 205U", "Placcel 205BA", "Placcel 208", "Placcel 210", "Placcel 210CP", "Placcel 210BA" can be used. , "Placcel 212", "Placcel 212CP", "Placcel 220", "Placcel 220CPB", "Placcel 220NP1", "Placcel 220BA", "Placcel 220ED", "Placcel 220EB", "Placcel 220EC", "Placcel 230" "Placcel 230CP", "Placcel 240", "Placcel 240CP", "Placcel 210N", "Placcel 220N", "Placcel L205AL", "Placcel L208AL", "Placcel L212AL", "Placcel L220AL", "Placcel L230AL" , "Placcel 305", "Placcel 308", "Placcel 312", "Placcel L312AL", "Placcel 320", "Placcel L320AL", "Placcel L330AL", "Placcel 410", "Placcel 410D", "Placcel 610" , "Placcel P3403", "Placcel CDE9P" (above, DAICEL (share) system) and other commercial products.

Examples of the polyether polyol include a polyether polyol obtained by an addition reaction of a cyclic ether compound to a polyhydric alcohol, a polyether polyol obtained by ring-opening polymerization of an alkylene oxide, and the like. .

More specifically, examples of the polyether polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol (propylene glycol), 2-methyl-1,3-propanediol, and 1,3-propanediol. , 1,4-butanediol (tetramethylene glycol), 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5- Pentyl glycol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1, 6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,2-Dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dodecanediol, polybutadiene Glycol, neopentyl glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-dihydroxyacetone, hexanediol, 1,2,6-hexanetriol, ditrimethylolpropane, a polyol of a polyol such as mannitol, sorbitol or neopentyl alcohol; the above polyols and ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-ring An adduct of an alkylene oxide such as oxybutane, 2,3-butylene oxide, tetrahydrofuran or epichlorohydrin; or a cyclic ether such as tetrahydrofuran A cyclic polymer (for example, polytetramethylene glycol) or the like.

The above polyether polyol can be produced by a known or customary production method, and is not particularly limited. For example, it can be subjected to an addition reaction (open-loop addition polymerization) of a cyclic ether compound to a polyol, and an epoxy resin. It is produced by ring-opening polymerization (homopolymerization or copolymerization) of an alkane. The conditions at the time of polymerization are also not particularly limited, and can be appropriately selected from known or customary reaction conditions.

As the polyether polyol, for example, the trade name "PEP-101" (FREUND Industries Co., Ltd.), the trade name "Adeka Pluronic L", "Adeka Pluronic P", "Adeka Pluronic F", "Adeka Pluronic R" can be used. "Adeka Pluronic TR", "Adeka PEG" (above, Adeka), trade name "PEG#1000", "PEG#1500", "PEG#11000" (above, Nippon Oil Co., Ltd.) ), trade names "Newpol PE-34", "Newpol PE-61", "Newpol PE-78", "Newpol PE-108", "PEG-200", "PEG-600", "PEG-2000", "PEG-6000", "PEG-10000", "PEG-20000" (above, Sanyo Chemical Industry Co., Ltd.), trade name "PTMG1000", "PTMG1800", "PTMG2000" (above, Mitsubishi Chemical Corporation) (available from the company), "PTMG Prepolymer" (Mitsubishi Resin Co., Ltd.).

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

The above polycarbonate polyol may be the same as the usual method for producing a polycarbonate polyol by phosgene method or using a carbonate such as dimethyl carbonate, diethyl carbonate or diphenyl carbonate. In the case of the above-mentioned Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. And then synthesized. Since the carbonate bond in the above polycarbonate polyol is less susceptible to thermal decomposition, the resin cured product containing a polycarbonate polyol exhibits excellent stability even under high temperature and high humidity.

Examples of the polyol used in the carbonic acid exchange reaction together with the above-described dialkyl carbonate or diphenyl carbonate include 1,6-hexanediol, ethylene glycol, diethylene glycol, and 1,3-propanediol. , 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4- Cyclohexanedimethanol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, butadienediol, neopentyl glycol, tetramethylene glycol, Propylene glycol, dipropylene glycol, and the like.

As the polycarbonate polyol, for example, "Placcel CD205PL", "Placcel CD205HL", "Placcel CD210PL", "Placcel CD210HL", "Placcel CD220PL", and "Placcel CD220HL" can be used (above, DAICEL) ), trade names "UH-CARB50", "UH-CARB100", "UH-CARB300", "UH-CARB90(1/3)", "UH-CARB90(1/1)", "UC-CARB100" ( The above-mentioned cities such as Ube Industries Co., Ltd., and the product names "PCDL T4671", "PCDL T4672", "PCDL T5650J", "PCDL T5651", and "PCDL T5652" (above, Asahi Kasei Chemicals Co., Ltd.) Sale.

As the polyol compound other than the polyether polyol, the polyester polyol, and the polycarbonate polyol, for example, "YP-50", "YP-50S", "YP-55U", and "YP-70" can be used. "ZX-1356-2", "YPB-43C", "YPB-43M", "FX-316", "FX-310T40", "FX-280S", "FX-293", "YPS-007A30" Benzene resin such as "TX-1016" (above, Nippon Steel Chemical Co., Ltd.), trade name "jER1256", "jER4250", "jER4275" (above, Mitsubishi Chemical Co., Ltd.); Epotohto YD-014, Epotohto YD-017, Epotohto YD-019, Epotohto YD-020G, Epotohto YD-904, Epotohto YD-907, Epotohto YD-6020 The above, the Nippon Steel Chemical Co., Ltd., the product names "jER1007", "jER1009", "jER1010", "jER1005F", "jER1009F", "jER1006FS", "jER1007FS" (above, Mitsubishi Chemical Corporation) a bisphenol type high molecular epoxy resin having an epoxy equivalent of more than 1000 g/eq.; trade names "Poly bd R-45HT", "Poly bd R-15HT", "Poly ip", "KRASOL" (above) Idemitsu Kosan Co., Ltd., trade name "α-ω polybutadiene diol G-1000", "α-ω polybutadiene diol G-2000", "α-ω polybutadiene II Polybutadiene having a hydroxyl group such as alcohol G-3000" (above, manufactured by Nippon Soda Co., Ltd.); trade names "Hitaloid 3903", "Hitaloid 3904", "Hitaloid 3905", "Hitaloid 6500", "Hitaloid" 6500B", "Hitaloid 3018X" (above, Hitachi Chemical Co., Ltd.), trade name "Acrydic DL-1537", "Acrydic BL-616", "Acrydic AL-1157", "Acrydic A-322", " Acrydic A-817", "Acrydic A-870", "Acrydic A-859-B", "Acrydic A-829", "Acrydic A-49-394-IM" (above, DIC) Commercial products such as acrylic polyols such as "Dianal SR-1346", "Dianal SR-1237", and "Dianal AS-1139" (above, manufactured by Mitsubishi Rayon Co., Ltd.).

The amount (content) of the polyol compound to be used is not particularly limited, but is preferably 1 to 50 parts by weight, more preferably 1 to 50 parts by weight, based on the total amount of the component (A) and the component (B). 1.5 to 40 parts by weight, particularly 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 excessively lowered, and the volume change due to heating is large, and the light semiconductor device may not be lit or the like. When the content of the polyol compound is less than 1 part by weight, the light reflectivity may be easily lowered as time passes.

When the curable epoxy resin composition of the present invention contains a nonoxyl derivative (G) having two or more epoxy groups in the molecule, the amount (content) of the polyol compound used is not particularly limited. The total amount (100 parts by weight) of the component (A), the component (B) and the component (G) is preferably 1 to 50 parts by weight, more preferably 1.5 to 40 parts by weight, particularly preferably 5 parts by weight. 30 parts by weight. When the content of the polyol compound exceeds 50 parts by weight, the Tg of the cured product is excessively lowered, and the volume change due to heating is large, and the light semiconductor device may not be lit or the like. When the content of the polyol compound is less than 1 part by weight, the light reflectivity may be easily lowered as time passes.

 [Acrylic block copolymer]  

The curable epoxy resin composition of the present invention preferably further comprises 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 manufactured using the curable epoxy resin composition, particularly in the case of high brightness and high output There is also a tendency that the luminosity is not easily lowered. In other words, the cured product obtained by curing the curable epoxy resin composition of the present invention by using the acrylic block copolymer can exhibit higher levels of heat resistance, light resistance, and crack resistance.

The above acrylic block copolymer is a block copolymer containing an acrylic monomer as an essential monomer component. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and ethyl methacrylate. (meth)acrylic acid alkyl ester such as n-butyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, octadecyl methacrylate; (meth) acrylate having an alicyclic structure such as ester or cyclohexyl methacrylate; (meth) acrylate having an aromatic ring such as benzyl methacrylate; 2-trifluoroethyl methacrylate; a (fluoro)alkyl ester of (meth)acrylic acid; a carboxyl group-containing acrylic monomer having a carboxyl group in a molecule such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride; 2-hydroxyethyl acrylate, acrylic acid 2 -Hydroxypropyl ester, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, mono(meth) acrylate of glycerol An acrylic monomer having a hydroxyl group and having a hydroxyl group in the molecule An acrylic monomer having an epoxy group in a molecule such as glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate or the like; An allyl-containing acrylic monomer having an allyl group in the molecule, such as an ester or allyl methacrylate; γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxyl Acrylic acid-containing acrylic monomer having a hydrolyzable mercapto group in a molecule such as propyltriethoxydecane; 2-(2'-hydroxy-5'-methylpropenyloxyethylphenyl)-2H - a benzotriazole-based benzotriazole-based ultraviolet absorbing acrylic monomer or the like having an ultraviolet absorbing group.

Further, in the above acrylic block copolymer, a monomer other than the above acrylic monomer may be used as a monomer component. Examples of the monomer other than the acrylic monomer include an aromatic vinyl compound such as styrene or α-methylstyrene, a conjugated diene such as butadiene or isoprene, ethylene or propylene. An olefin such as isobutylene.

The acrylic block copolymer is not particularly limited, and examples thereof include a diblock copolymer composed of two polymer blocks or a triblock copolymer composed of three polymer blocks. A multi-block copolymer composed of four or more polymer blocks.

Among them, the acrylic block copolymer is preferably a polymer block [S] (soft block) having a low glass transition temperature (Tg) from the viewpoint of improvement in heat resistance, light resistance, and crack resistance. a block copolymer alternately arranged with a polymer block [H] (hard block) having a higher Tg than the polymer block [S], more preferably having a polymer block [S] in the middle thereof A triblock copolymer having an HSH structure of a polymer block [H] at both ends. Further, the Tg of the polymer constituting the polymer block [S] of the above acrylic block copolymer is not particularly limited, but is preferably less than 30 °C. Further, the Tg of the polymer constituting the polymer block [H] is not particularly limited, but is preferably 30 ° C or higher. When the above acrylic block copolymer has a plurality of polymer blocks [H], the respective polymer blocks [H] may have the same composition or may be different. Similarly, when the above acrylic block copolymer has a plurality of polymer blocks [S], the respective polymer blocks [S] may have the same composition or may be different.

In the above-mentioned acrylic block copolymer (such as a triblock copolymer of the above-described HSH structure), the monomer component constituting the polymer block [H] is not particularly limited, and examples thereof include Tg of a homopolymer. More specifically, the monomer of 30 ° C or more may, for example, be methyl methacrylate, styrene, acrylamide or acrylonitrile. On the other hand, the acrylic block copolymer is not particularly limited as a monomer component constituting the polymer block [S], and examples thereof include a monomer having a Tg of less than 30 ° C in a homopolymer. Specific examples thereof include C _2-10 alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate, butadiene (1,4-butadiene).

A preferred example of the acrylic block copolymer in the curable epoxy resin composition of the present invention is, for example, a polymer composed of the above polymer block [S] having butyl acrylate (BA) as a main monomer. The polymer block [H] is a polymer composed of methyl methacrylate (MMA) as a main monomer, and polymethyl methacrylate-block-polybutyl acrylate-block-polymethacrylate is exemplified. Methyl methacrylate terpolymer (PMMA-b-PBA-b-PMMA) and the like. The above PMMA-b-PBA-b-PMMA is preferred in terms of improvement in heat resistance, light resistance and crack resistance. In addition, the PMMA-b-PBA-b-PMMA may have a hydrophilic group (for example, a hydroxyl group, a carboxyl group, or the like) for the purpose of improving the compatibility with the component (A) and the component (B) as needed. A monomer such as an amine group such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or (meth)acrylic acid is copolymerized in the PMMA block and/or the PBA block.

The number average molecular weight of the above acrylic block copolymer is not particularly limited, but is preferably from 3,000 to 500,000, more preferably from 30,000 to 400,000. When the number average molecular weight is less than 3,000, the toughness of the cured product is insufficient, and the crack resistance is lowered. On the other hand, when the number average molecular weight exceeds 500,000, the compatibility with the alicyclic epoxy compound (A) is lowered, and the mechanical properties of the cured product are adversely affected and the crack resistance is lowered.

The above acrylic block copolymer can be produced by a method of producing a well-known or conventional block copolymer. As a method for producing the above-mentioned acrylic block copolymer, in particular, from the viewpoint of easily controlling the molecular weight, molecular weight distribution, terminal structure and the like of the acrylic block copolymer, living polymerization (active radical polymerization, living anionic polymerization, active cation) is preferred. Aggregation, etc.). The above living polymerization can be carried out by a well-known or customary method.

Further, as the acrylic block copolymer, for example, "Nanostrength M52N", "Nanostrength M22N", "Nanostrength M51", "Nanostrength M52", "Nanostrength M53" (made by ARKEMA, PMMA-b-PBA-) can also be used. b-PMMA), a commercial item such as "Nanostrength E21" and "Nanostrength E41" (manufactured by ARKEMA, PSt (polystyrene)-b-PBA-b-PMMA).

The amount (content) of the acrylic block copolymer is not particularly limited, but is preferably from 1 to 30 parts by weight, based on the total amount (100 parts by weight) of the component (A) and the component (B). It is preferably from 3 to 15 parts by weight, particularly preferably from 3 to 10 parts by weight. When the amount of the acrylic block copolymer used is less than 1 part by weight, the toughness of the cured product is insufficient, and heat resistance and light resistance are lowered. On the other hand, when the amount of the acrylic block copolymer used exceeds 30 parts by weight, the compatibility with the alicyclic epoxy compound (A) is lowered, and the crack resistance of the cured product may be lowered.

When the curable epoxy resin composition of the present invention contains a nonoxyl derivative (G) having two or more epoxy groups in the molecule, the amount (content) of the 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, even more preferably 3 to 15 parts by weight, based on the total amount (100 parts by weight) of the component (A), the component (B) and the component (G). 3 to 10 parts by weight. When the amount of the acrylic block copolymer used is less than 1 part by weight, the toughness of the cured product is insufficient, and heat resistance and light resistance are lowered. On the other hand, when the amount of the acrylic block copolymer used exceeds 30 parts by weight, the compatibility with the alicyclic epoxy compound (A) is lowered, and the crack resistance of the cured product may be lowered.

 [Rubber particles other than polyoxyethylene rubber particles]  

The curable epoxy resin composition of the present invention may further contain rubber particles other than the polyoxyethylene rubber particles (hereinafter also referred to as "rubber particles"). Examples of the rubber particles include granular NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and granular SBR (styrene-butadiene rubber). Rubber particles. The rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and a shell layer covering at least one layer of the core portion. The rubber particles are particularly preferably composed of a polymer (polymer) containing (meth) acrylate as an essential monomer component, and have a hydroxyl group and/or a carboxyl group (either or both of a hydroxyl group and a carboxyl group) as energy on the surface. A rubber particle having a functional group reactive with a compound having an epoxy group such as an alicyclic epoxy compound (A). When the hydroxyl group and/or the carboxyl group are not present on the surface of the rubber particles, there is a case where cracks are likely to occur in the cured product.

The polymer constituting the rubber-elastic core portion of the rubber particles is not particularly limited, but is preferably methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate. The (meth) acrylate is used as an essential monomer component. The polymer constituting the rubber-elastic core portion may further contain, for example, an aromatic vinyl (aromatic vinyl compound) such as styrene or α-methylstyrene, or a nitrile such as acrylonitrile or methacrylonitrile. A conjugated diene such as butadiene or isoprene, ethylene, propylene or isobutylene is used as a monomer component.

Among them, the polymer constituting the rubber-elastic core portion is preferably a monomer component, preferably a (meth) acrylate and a group selected from the group consisting of an aromatic vinyl group, a nitrile, and a conjugated diene. One type or two or more types are combined and included. In other words, examples of the polymer constituting the core portion include a (meth) acrylate/aromatic vinyl group, a binary copolymer such as a (meth) acrylate/conjugated diene; and (meth)acrylic acid. a terpolymer such as an ester/aromatic vinyl/conjugated diene or the like. Further, the polymer constituting the core portion may contain polyoxymethylene or polyurethane such as polydimethyl siloxane or polyphenylmethyl siloxane.

The polymer constituting the core portion may contain, as other monomer components, divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, and maleic acid diene. a reactive cross-linking monomer having two or more reactive functional groups in one monomer (one molecule) such as ester, triallyl cyanurate, diallyl phthalate or butanediol diacrylate body.

The core portion of the above rubber particles is preferably a binary copolymer of (meth) acrylate/aromatic vinyl (particularly, butyl acrylate/styrene) or (methyl) from the viewpoint of heat resistance. a core portion of a terpolymer of an acrylate/aromatic vinyl/reactive crosslinkable monomer (particularly, butyl acrylate/styrene/divinylbenzene).

The core portion of the rubber particles can be produced by a commonly used method, for example, by a method of polymerizing the above monomers by an emulsion polymerization method. In the emulsion polymerization method, the entire amount of the above monomers may be added in a batch to be polymerized, or a part of the above monomers may be polymerized, and the remainder may be continuously or intermittently added to be polymerized, and seed particles may also be used. Aggregation method.

The polymer constituting the shell layer of the rubber particles is preferably a polymer different from the polymer constituting the core portion. 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, at the interface with the alicyclic epoxy compound (A), the adhesion can be improved, and the cured product obtained by hardening the curable epoxy resin composition containing the core-shell type rubber particles having the shell layer can be improved. It can exert excellent crack resistance. Further, it is also possible to prevent a decrease in the glass transition temperature of the cured product.

The polymer constituting the shell layer preferably contains a (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate as an essential monomer component. Things. For example, when butyl acrylate is used as the (meth) acrylate in the core portion, as the monomer component of the polymer constituting the shell layer, for example, (meth) acrylate other than butyl acrylate is preferably used ( For example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl methacrylate, etc.). Examples of the monomer component which may be contained in addition to the (meth) acrylate include an aromatic vinyl group such as styrene or α-methyl styrene, a nitrile such as acrylonitrile or methacrylonitrile. In the above-mentioned rubber particles, the monomer component constituting the shell layer is preferably contained alone or in combination of two or more kinds together with the (meth) acrylate, and particularly preferably from the viewpoint of heat resistance. Contains at least an aromatic vinyl group.

Further, the polymer constituting the shell layer is a functional group which can react with a compound having an epoxy group such as an alicyclic epoxy compound (A) in order to form a hydroxyl group and/or a carboxyl group as a monomer component. Preferably, it is a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, or an α,β-unsaturated acid such as (meth)acrylic acid or a maleic anhydride. A monomer such as an unsaturated acid anhydride.

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

Further, the polymer constituting the shell layer may contain divinylbenzene, allyl (meth)acrylate, and the like as the other monomer component, in addition to the above-mentioned monomers. Diol (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butanediol diacrylate, etc. in 1 monomer (1 molecule a reactive crosslinking monomer having two or more reactive functional groups.

The rubber particles (rubber particles having a core-shell structure) are obtained by coating the core portion with a shell layer. The method of coating the core portion with a shell layer may, for example, be a method of coating a polymer constituting the shell layer on the surface of a core portion having rubber elasticity obtained by the above method; The core portion having rubber elasticity is used as a dry component, and a method of graft polymerization of each component constituting the shell layer as a branch component is used.

The average particle diameter of the rubber particles is not particularly limited, but is preferably from 10 to 500 nm, more preferably from 20 to 400 nm. Further, the maximum particle diameter of the rubber particles is not particularly limited, but is preferably from 50 to 1,000 nm, more preferably from 100 to 800 nm. When the average particle diameter is more than 500 nm or the maximum particle diameter is more than 1000 nm, the dispersibility of the rubber particles in the cured product is lowered, and the crack resistance is lowered. On the other hand, when the average particle diameter is less than 10 nm or the maximum particle diameter is less than 50 nm, it may be difficult to obtain an effect of increasing the crack resistance of the cured product.

The content (doping amount) of the rubber particles in the curable epoxy resin composition of the present invention is not particularly limited, but is equivalent to the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition. (100 parts by weight), preferably 0.5 to 30 parts by weight, 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 is more than 30 parts by weight, the heat resistance of the cured product tends to decrease.

 [stress mitigator (I)]  

The curable epoxy resin composition of the present invention preferably contains a stress relieving agent (I). The stress relieving agent (I) is a compound which can alleviate internal stress in the hardened material. The curable epoxy resin composition of the present invention is composed of a stress relieving agent (I) and an alicyclic epoxy compound (A), an isomeric cyanuric acid monoallyl diglycidyl ester compound (B), and white The pigment (C) is used in combination, and even if the amount of the white pigment (C) or the inorganic filler (J) described later is increased, it can be compression-molded, and the light-reflective and heat-resistant of the cured product formed by compression molding can be used. The tendency to be excellent in light and light resistance. Further, the stress relaxation agent (I) can alleviate the internal stress of the cured product, and the warpage of the molded article due to compression molding can be reduced.

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

The polyoxyxylene rubber particles (I1) are not particularly limited, and examples thereof include those composed of polyoxymethane such as polymethyl siloxane or polymethyl phenyl siloxane.

Further, the polyoxyalkylene constituting the polyoxyxylene rubber particles (I1) is preferably a cross-linker. The crosslinked polyoxyalkylene is not particularly limited, and examples thereof include a condensation reaction by a decyl group or the like, a radical reaction of a mercapto fluorenyl group with a vinyl fluorenyl group, a vinyl fluorenyl group and a hydroquinone group. a polysiloxane or the like which is crosslinked by an addition reaction or the like (SiH group). However, from the viewpoint of reactivity and reaction steps, it is preferred to polymerize a vinyl group-containing organic polyoxane with an organic hydrogen. The polyoxyalkylene which is crosslinked by the addition reaction of oxane in the presence of a platinum-based catalyst.

Moreover, the polyfluorene oxide rubber particles (I1) may be surface-treated from the viewpoint of improving affinity and dispersibility with the resin composition and adjusting the viscosity of the resin composition after dispersion. The surface treatment state is not particularly limited, and examples thereof include polyoxyethylene rubber particles coated with methyl methacrylate and polyoxyethylene rubber particles coated with a polyoxyxylene resin.

The average particle diameter (d ₅₀ ) of the polyoxyxene rubber particles (I1) is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm. Further, the maximum particle diameter of the polyoxyxylene rubber particles (I1) is not particularly limited, but is preferably 0.1 to 250 μm, more preferably 0.1 to 150 μm. When the average particle diameter is 100 μm or less (or the maximum particle diameter is 250 μm or less), the crack resistance of the cured product tends to increase. On the other hand, when the average particle diameter is 0.1 μm or more (or the maximum particle diameter is 0.1 μm or more), the dispersibility of the above-mentioned polyoxyxylene rubber particles (I1) tends to increase.

Further, the shape of the polyoxyxene rubber particles (I1) is not particularly limited, but is preferably spherical from the viewpoint of improving workability.

The polyoxyethylene rubber particles (I1) are preferably formed of a crosslinked polyoxyalkylene from the viewpoint of forming a cured product excellent in light reflectivity, heat resistance and light resistance by compression molding. Or the surface coated with the polyoxyxene resin, wherein from the viewpoint of the compatibility of the resin component with the polyoxyxylene rubber particles (I1), it is particularly preferred to coat the crosslinked poly 2 with a polyoxyl resin. The surface of methyl oxa oxide.

In the curable epoxy resin composition of the present invention, the polyoxyxylene rubber particles (I1) may be used alone or in combination of two or more. In addition, the polyfluorene oxide rubber particles (I1) can be produced by a known method or a conventional method. For the production method, for example, a polyoxyxene rubber produced by the method described in JP-A-7-196815 can be used. Particles, or the trade names "KMP-600", "KMP-601", "KMP-602", "KMP-605", "X-52-7030", "KMP-597", "KMP-598" And "KMP-594", "X-52-875", "KMP-590", "KMP-701" (above, Shin-Etsu Chemical Co., Ltd.) and other commercial products.

The polyoxyxane oil (I2) is not particularly limited, and examples thereof include non-modified polyoxyphthalic acid oil and modified polyoxygenated oil.

The non-modified polyfluorene oxide oil is not particularly limited, and examples thereof include a polydimethylsiloxane type, a polymethylhydroquinane type, and a polymethylphenyloxane type.

The modified polyoxygenated oil is not particularly limited, and for example, a reactive polyoxyxene oil reactive with an epoxy resin and a non-reactive polyoxygenated oil having no reactivity with an epoxy resin can be used. One. Examples of the reactive polysiloxane oil include an amine group modified type, an epoxy group modified type, a carboxyl group modified type, a methanol modified type, a methacrylic modified type, a thiol modified type, and a phenol modified type. Type and so on. Examples of the non-reactive polyoxygenated oil include a polyalkylene ether modified type, a methylstyryl modified type, an alkyl modified type, a fatty acid ester modified type, and an alkoxy modified type. , fluorine modified type and so on. Further, the reactive polyfluorene oxide oil may have a non-reactive modified group, and examples thereof include a polyalkylene ether-amine-modified polyoxyxane oil, and a polyalkylene ether-epoxy modified polyfluorene. Oxygen oil or the like, preferably having an epoxy group with an alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound (B), a decane derivative (G) or the like The compound is reactive and can control the flow or viscosity of the polyalkylene ether-epoxy modified polyoxyxide.

The polyfluorene oxide (I2) is preferably a polyalkylene ether-epoxy modified polycondensate from the viewpoint of forming a cured product excellent in light reflectivity, heat resistance and light resistance by compression molding. An oxygenated oil, particularly preferably a polyalkylene oxide modified polyoxosiloxane having an epoxy equivalent of from 3,000 to 15,000 and having a structure represented by the following formula (10) (hereinafter, also referred to as "polyalkylene ether" Polyoxygenated compound (10)").

In the above formula (10), R ²⁶ is an alkylene group having 2 or 3 carbon atoms. Examples of the alkylene group having 2 or 3 carbon atoms include methylmethylene, dimethylmethylene, ethylidene, propylidene and trimethylene, and a trimethylene group is preferred.

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 structural systems in the brackets with ya may be the same or different.

In the above formula (10), za represents an integer of 5-20. Furthermore, the structural systems in brackets with za may be the same or different.

In the above formula (10), A is a polyalkylene ether group having a structure represented by the following formula (10a).

In the above formula (10a), a and b are each independently an integer of 0 to 40. Since a is 40 or less, the water resistance of the cured product tends to increase.

On the other hand, since b is 40 or less, the fluidity of the curable epoxy resin composition tends to increase.

The total of a and b is not particularly limited, but is preferably an integer of from 1 to 80. Since the total of a and b is within this range, it becomes easy to control the water resistance of the cured product and the fluidity of the curable epoxy resin composition.

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 either a random type or a block type as long as two trimethylsulfonyl groups in the formula (10) are present at both ends. Further, the addition form of each structural unit in the above formula (10a) may be a random type or a block type as long as B has a terminal. Further, the order of arrangement of each structural unit in the above formulas (10) and (10a) is also not particularly limited.

The epoxy equivalent of the above polyalkylene ether modified polyoxyl compound (10) is, as described above, from 3,000 to 15,000, preferably from 4,000 to 15,000, more preferably from 5,000 to 13,000. Since the epoxy equivalent is 3,000 or more, the stress inside the cured product tends to be more moderate. On the other hand, since the epoxy equivalent is 15,000 or less, the compatibility with the resin tends to increase.

Further, the epoxy equivalent of the polyalkylene ether modified polysiloxane (10) can be measured in accordance with JIS K 7236:2001.

In the curable epoxy resin composition of the present invention, the polyoxygenated oil (I2) may be used alone or in combination of two or more. In addition, the polyoxygenated oil (I2) can be produced by a well-known or conventional method, and for example, a polyoxygenated oil (I2) produced by the method described in JP-A-2008-201904 can be used. Or you may use a commercial item such as "SF8421" (made by Toray Dow Corning Co., Ltd.) and the trade name "Y-19268" (Momentive Performance Materials ‧ Japan (same))

The liquid rubber component (I3) is not particularly limited, and examples thereof include polybutadiene, maleated polybutadiene, acrylated polybutadiene, methacrylated polybutadiene, and a ring. Oxidized polybutadiene, acrylonitrile butadiene rubber, carboxyl terminal acrylonitrile butadiene rubber, amine terminal acrylonitrile butadiene rubber, vinyl terminal acrylonitrile butadiene rubber, styrene butadiene rubber Wait.

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 a polyimide resin, a polyamide resin, a polyether quinone resin, a polyester resin, a polyester phthalimide resin, and a phenoxy resin. , polyfluorene resin, polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, and the like. Among these, from the viewpoint of heat resistance, a phenoxy resin or a polyimide resin is preferred. These thermoplastic resins may be used alone or in combination of two or more.

The glass transition temperature (Tg) of the thermoplastic resin (I4) is not particularly limited, but is preferably 200 ° C or lower.

The above-mentioned stress relieving agent (I) may be used alone or in combination of two or more.

The stress relaxation agent (I) is preferably selected from the group consisting of polyfluorene oxide rubber particles (I1) and polycondensate from the viewpoint of forming a cured product excellent in light reflectivity, heat resistance and light resistance by compression molding. At least one of the group of the oxime oil (I2), particularly as the polyoxyxene rubber particles (I1), is preferably a crosslinked polydimethyl siloxane having a polyfluorene resin on the surface as a poly The oxime oil (I2), preferably a polyalkylene ether modified polyoxime compound (10).

The content (mixing amount) of the stress relieving agent (I) of the present invention is not particularly limited, but is preferably 1 to 250 parts by weight, more preferably 100 parts by weight of the alicyclic epoxy compound (A). It is 5 to 230 parts by weight, preferably 10 to 200 parts by weight. By setting the content of the stress relieving agent (I) to 1 part by weight or more, even if the amount of the white pigment (C) or the inorganic filler (J) to be described later is increased, the molding can be carried out, and the formed cured product can be formed. The light reflectivity, heat resistance and light resistance tend to increase. Further, the warpage of the molded article is alleviated, and the dimensional stability tends to increase. On the other hand, when the content of the stress relieving agent (I) is 250 parts by weight or less, the curability of the curable epoxy resin composition tends to increase.

The content (mixing amount) of the stress relieving agent (I) of the present invention is not particularly limited, but is preferably 100 parts by weight based on the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition. It is 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, and particularly preferably 8 to 120 parts by weight. By setting the content of the stress relieving agent (I) to 1 part by weight or more, even if the amount of the white pigment (C) or the inorganic filler (J) to be described later is increased, the molding can be carried out, and the formed cured product can be formed. The light reflectivity, heat resistance, and light resistance of the cured product tend to increase. Further, the warpage of the formed product is alleviated, and the dimensional stability is increased. On the other hand, when the content of the stress relieving agent (I) is 200 parts by weight or less, the curability of the curable epoxy resin composition tends to increase.

 [Inorganic Filler (J)]  

The curable epoxy resin composition of the present invention preferably further contains an inorganic filler (J) in addition to the white pigment (C). In the case where the curable epoxy resin composition is formed by compression molding, the inorganic filler (J) imparts excellent heat resistance and light resistance (especially, excellent heat resistance) to the formed cured product. Further, it has the effect of reducing the linear expansion ratio of the cured product (reflector). Further, depending on the type of the inorganic filler (J), there is a case where excellent light reflectivity can be imparted to the cured product (reflector).

As the inorganic filler (J), a well-known or customary inorganic filler can be used without particular limitation, and examples thereof include vermiculite, zircon, calcium silicate, calcium phosphate, tantalum carbide, tantalum nitride, and nitriding. Aluminum, boron nitride, iron oxide, aluminum oxide, magnesite, talc, spinel, clay, dolomite, hydroxyapatite, nepheline syenite, cristobalite, ash stone, diatomaceous earth, etc. Powder, or a molded body thereof (for example, spheroidized beads, etc.) or the like. Moreover, as the inorganic filler (J), a surface treatment person or the like which is known or conventionally used for the above-mentioned inorganic filler may be mentioned. Among them, as the inorganic filler (J), from the viewpoint of heat resistance (especially, yellowing resistance), light resistance, and fluidity of the cured product (reflector), vermiculite, tantalum nitride, aluminum nitride, or the like is preferable. Boron nitride is more preferably vermiculite (fossil filler).

The vermiculite is not particularly limited, and for example, well-known or conventional vermiculite such as molten vermiculite, crystalline vermiculite, or high-purity synthetic vermiculite can be used. Further, as the vermiculite, a surface treatment which is well known or conventionally applied [for example, a surface treatment agent such as a metal oxide, a decane coupling agent, a titanium coupling agent, an organic acid, a polyhydric alcohol, a polyfluorene oxide or the like may be used. Surface treatment, etc.].

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

The center particle diameter of the vermiculite is not particularly limited, but is preferably from 0.1 to 50 μm, more preferably from 0.1 to 30 μm, from the viewpoint of an increase in light reflectivity of the cured product (reflector). Further, the above-mentioned center particle diameter means a particle diameter (median diameter) of 50% of the cumulative value in the particle size distribution measured by the laser diffraction ‧ scattering method.

Further, in the curable epoxy resin composition of the present invention, the inorganic filler (J) may be used alone or in combination of two or more. Further, the inorganic filler (J) can also be produced by a well-known or conventional manufacturing method. For example, the trade names "FB-910", "FB-940", "FB-950", and "FB-105" can also be used. "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", trade names "DAW-03DC", "DAW-0525", "DAW- DAW series such as 1025", trade name "SGP" (above, DENKA (share) system), trade name "HF-05" (TOKUYAMA (share) system), product name "10μmSE-CC5" (ADMATECHS (share) system ), trade name "MSR-2212", "MSR-25" (above, Ronson (share) system), trade name "HS-105", "HS-106", "HS-107" (above, MICRON Commercial products such as the system).

The content (mixing amount) of the inorganic filler (J) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably a curable epoxy resin composition (100% by weight). 10 to 90% by weight, more preferably 13 to 75% by weight, particularly preferably 15 to 70% by weight, particularly preferably 20 to 70% by weight. When the content of the inorganic filler (J) is 10% by weight or more, even when a curable epoxy resin composition is formed by compression molding, heat resistance and light resistance of the formed cured product (especially, excellent heat resistance) are obtained. Sexuality) is a higher tendency. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and the optical semiconductor element mounting substrate using the reflector tends to be inconvenient in warpage such as warpage of the lead frame. 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 increased, which tends to be more suitable for mass production.

The content (mixing amount) of the inorganic filler (J) in the curable epoxy resin composition of the present invention is not particularly limited, but is equivalent to the epoxy group contained in the curable epoxy resin composition. The total amount of the compound is 100 parts by weight, preferably 10 to 1500 parts by weight, more preferably 50 to 1200 parts by weight, still more preferably 100 to 1000 parts by weight. When the content of the inorganic filler (J) is 10 parts by weight or more, when the curable epoxy resin composition is formed by compression molding, the heat resistance and light resistance (especially, excellent heat resistance) of the cured product are increased. High tendency. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and the optical semiconductor element mounting substrate using the reflector tends to be inconvenient in warpage such as warpage of the lead frame. On the other hand, since the content of the inorganic filler (J) is 1,500 parts by weight or less, the moldability of the cured product (reflector) is increased, which tends to be more suitable for mass production.

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, and particularly preferably It is 175 μm or less, and particularly preferably 150 μm or less. When the maximum particle diameter is 200 μm or less, the heat resistance and light resistance of the cured product formed by compression molding of the curable epoxy resin composition are compared with the case of using a white pigment or an inorganic filler having a maximum particle diameter of more than 200 μm. The tendency to be excellent in properties and crack resistance (especially, excellent heat resistance). Moreover, by using the white pigment (C) having a small maximum particle diameter and the inorganic filler (J), the content of these can be increased, and the light reflectivity, heat resistance, and light resistance of the cured product tend to be further increased. The lower limit of the above maximum particle diameter is, for example, 0.01 μm or more. Further, the maximum particle diameter is the total maximum particle diameter of the white pigment (C) and the inorganic filler (J) contained in the curable epoxy resin composition of the present invention. The above maximum particle size means the largest particle size in the particle size distribution measured by the laser diffraction ‧ 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, but From the viewpoint of the balance between the heat resistance (yellowing resistance) of the cured product (reflector) and the light reflectivity, it is preferably 5 to 70% by weight, more preferably 5 to 60% by weight. When the ratio of the titanium oxide is 5% by weight or more, the light reflectivity of the cured product (reflector) tends to increase. Further, there is a tendency that heat resistance (especially, yellowing resistance) and light resistance (particularly, ultraviolet resistance) are further increased. On the other hand, when the ratio of the titanium oxide is 70% by weight or less, the moldability of the cured product (reflector) is increased, which tends to be more suitable for mass production.

 [release agent]  

The curable epoxy resin composition of the present invention may further comprise a release agent. By including a mold release agent, it is easy to form a continuous molding system using a molding method of a mold such as transfer molding, and it is possible to produce a cured product (reflector) with high productivity. As the release agent, a well-known or conventional release agent can be used, and it is not particularly limited, and examples thereof include a fluorine-based release agent (a compound containing a fluorine atom; for example, a fluorine oil or a polytetrafluoroethylene), and a polycondensation agent. Oxygen-based mold release agent (polyoxyl compound; for example, polyoxyxane oil, polyoxyxanthene wax, polyoxyxylene resin, polyorganosiloxane having polyoxyalkylene unit, etc.), wax-based release agent (wax) For example; vegetable wax such as carnauba wax, animal wax such as wool wax, paraffin wax such as paraffin wax, polyethylene wax, oxidized polyethylene wax, etc.), higher fatty acid or salt thereof (for example, metal salt, etc.), high fat Acid esters, higher fatty acid decylamine, mineral oil, and the like.

Further, in the curable epoxy resin composition of the present invention, the release agent may be used singly or in combination of two or more. Further, the release agent can also be produced by a known or customary method, and a commercially available product can also be used.

When the moldable agent of the curable epoxy resin composition of the present invention contains a release agent, the content (mixing amount) of the release agent is not particularly limited, but is epoxy with respect to the composition of the curable epoxy resin. The total amount of the compound of the group is 100 parts by weight, preferably 1 to 12 parts by weight, more preferably 2 to 10 parts by weight. When the content of the release agent is 1 part by weight or more, the mold release property of the cured product (reflector) is further increased, and the productivity of the reflector tends to be higher. On the other hand, when the content of the release agent is 12 parts by weight or less, it is possible to ensure good adhesion of the reflector in the substrate for mounting an optical semiconductor element to the lead frame.

 [Antioxidants]  

The curable epoxy resin composition of the present invention may also contain an antioxidant. By containing an antioxidant, a cured product (reflector) which is more excellent in heat resistance (particularly, yellowing resistance) can be produced. The antioxidant is not particularly limited as long as it is a known or customary antioxidant, and examples thereof include a phenolic antioxidant (phenolic compound), a hindered amine antioxidant (hindered amine compound), and a phosphorus antioxidant ( Phosphorus-based compound, sulfur-based antioxidant (sulfur-based compound), and the like.

Examples of the phenolic antioxidant include 2,6-ditributylbutyl cresol, butylated hydroxyanisole, 2,6-ditributylbutylethylphenol, and octadecyl-β-. Monophenols such as (3,5-ditributyl-4-hydroxyphenyl)propionate; 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-ethyl-6-tertiary butylphenol), 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 4,4 '-Butylene bis(3-methyl-6-tertiary butyl phenol), 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxyl) Bisphenols of -5-methylphenyl)propenyloxy}ethyl]2,4,8,10-tetraoxaspiro[5.5]undecane; 1,1,3-tri(2- Methyl-4-hydroxy-5-tributylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-ditributyl-4-hydroxyl) Benzyl)benzene, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-( 4'-hydroxy-3'-tertiary butylphenyl)butyrate]diol, 1,3,5-tris(3',5'-ditributyl-4-'-hydroxybenzyl)- S-three - 2,4,6-(1H,3H,5H) triketone, a polymer type phenol such as tocopherol, and the like.

Examples of the hindered amine-based antioxidant include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[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-piperidinyl sebacate, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, and the like.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisononyl phosphite, tris(nonylphenyl) phosphite, and diisodecyl phenyl. Pentaerythritol phosphite, tris(2,4-ditributylphenyl)phosphite, cyclic neopentane tetrakis(bis-octadecyl)phosphite, cyclic neopentane tetrakis (2,4-ditributylphenyl)phosphite, cyclic neopentyltetrakis(2,4-ditributyl-4-methylphenyl)phosphite, double [2 a phosphite such as tributyl butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]phosphite; 9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-ditributyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phospha An oxaphosphorus phenanthrene oxide such as phenanthrene-10-oxide.

Examples of the sulfur-based antioxidant include dodecanethiol, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and Stearyl-3,3'-thiodipropionate and the like.

In the curable epoxy resin composition of the present invention, the antioxidant may be used singly or in combination of two or more. Further, the antioxidant may be produced by a known or customary method. For example, the trade name "Irganox 1010" (a phenolic antioxidant manufactured by BASF Corporation), the trade name "AO-60", and "AO-80" may be used. (shared by ADEKA, phenolic antioxidant), trade name "Irgafos 168" (manufactured by BASF Corporation, phosphorus antioxidant), trade name "ADK STAB HP-10", "ADK STAB PEP-36" ((share) ADEKA A commercially available product such as a phosphorus-based antioxidant, a product name "HCA" (manufactured by Sanko Co., Ltd., a phosphorus-based antioxidant).

The curable epoxy resin composition of the present invention contains an antioxidant, and the content (doping amount) of the antioxidant is not particularly limited, but is equivalent to the epoxy group-containing compound contained in the curable epoxy resin composition. The total amount is 100 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight. When the content of the antioxidant is 0.1 part by weight or more, oxidation of the cured product (reflector) is effectively prevented, and heat resistance and yellowing resistance tend to increase. 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 above components insofar as the effects of the present invention are not impaired. As the above-mentioned additive, for example, a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or glycerin (particularly an aliphatic polyol; except for the above polyol compound) can be used to carry out the reaction smoothly. Further, an antifoaming agent, a decane coupling agent such as γ-glycidoxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane, or fluorene may be used insofar as the viscosity or the light reflectance is not impaired. Conventional additives such as optical brighteners, surfactants, flame retardants, colorants, ion adsorbents, ultraviolet absorbers, light stabilizers, and pigments other than white pigment (C). The content of such additives is not particularly limited and may be appropriately selected.

As the above fluorescent whitening agent, a well-known or conventional fluorescent whitening agent can be used. When the curable epoxy resin composition of the present invention contains a fluorescent whitening agent, the cured product formed by compression molding tends to be more excellent in light reflectivity, heat resistance, light resistance, and crack resistance. Examples of the fluorescent whitening agent include a pyrazoline derivative, a stilbene derivative, and the like. Derivatives, thiazole derivatives, benzo Azole derivatives, Ketone derivatives, triazole derivatives, An azole derivative, a thiophene derivative, a coumarin derivative, a naphthoquinone imine derivative, or the like.

The curable epoxy resin composition of the present invention contains an alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound (B), a white pigment (C), and a hardener (D). And the hardening accelerator (F), comprising an alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound (B), a hardener (D), and a hardening accelerator (F) The viscosity of the mixture at 25 ° C is not particularly limited, but is preferably 5,000 mPa ‧ or less. Further, the curable epoxy resin composition of the present invention may further comprise rubber particles other than the above-described decane derivative (G), alicyclic polyester resin (H), and polyoxyxylene rubber particles, and may be selected from the group consisting of At least one of a leveling agent, a polyol compound, an acrylic block copolymer, a stress relieving agent (I), and/or an ethylene glycol, etc., of the group of the polyoxygen-based leveling agent and the fluorine-based leveling agent a polyol (hereinafter referred to as "other optional component"). In this case, the above mixture contains an alicyclic epoxy compound (A) and a isocyanuric acid monoallyl diglycidyl ester compound (B). ), a hardener (D), a hardening accelerator (F), and other mixtures of any of the ingredients.

On the other hand, the curable epoxy resin composition of the present invention contains an alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound (B), a white pigment (C), and When the catalyst (E) is cured, the viscosity of the mixture of the alicyclic epoxy compound (A), the isocyanuric acid monoallyl diglycidyl ester compound (B) and the hardening catalyst (E) at 25 ° C is included. It is not particularly limited, but is preferably 5000 mPa·s or less. The curable epoxy resin composition of the present invention may further contain other optional components. In this case, the above mixture contains an alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound. (B), a mixture of hardening catalyst (E) and other optional ingredients. Further, in the present specification, the viscosity of the above two mixtures at 25 ° C is also collectively referred to as "resin viscosity".

The above resin viscosity is a viscosity measured at 25 ° C under normal pressure. The resin viscosity is preferably 5,000 mPa ‧ or less, more preferably 4,000 mPa ‧ s or less, still more preferably 3,500 mPa ‧ s or less, and particularly preferably 3,000 mPa ‧ s or less. When the resin viscosity is 5,000 mPa ‧ s or less, the heat resistance, light resistance, and anti-turtle of the cured product formed by compression molding the curable epoxy resin composition are compared with the case where the resin viscosity exceeds 5000 mPa ‧ s Cracking (especially, excellent heat resistance) tends to be more excellent. Further, since the resin has a relatively low viscosity, the content of other components such as the white pigment (C) or the inorganic filler (J) can be increased, and the light reflectivity, heat resistance, and light resistance of the cured product tend to be further increased. The lower limit of the above resin viscosity is, for example, 100 mPa ‧ s or more. Further, the resin viscosity may be, for example, a digital viscometer (model "DVU-EII type", manufactured by TOKIMEC Co., Ltd.), and the rotor: standard 1° 34' × R24, temperature: 25 ° C, rotation number: 0.5 to 10 rpm Determined under the conditions.

The resin viscosity can be, for example, a component which is liquid at 25 ° C as a component to be used (for example, an alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound (B), Hardener (D), hardening accelerator (F), hardening catalyst (E), decane derivative (G) and alicyclic polyester resin (H), liquid stress relieving agent (I), etc.) And easy to get. Further, as the above component, a component which is solid at 25 ° C may be used, but the content thereof is preferably adjusted so that the resin viscosity becomes 5000 mPa ‧ s or less. Moreover, it is easy to obtain by adjusting the content of the rubber particles and the solid stress relieving agent (I) within the range not impairing the effects of the present invention.

Further, the curable epoxy resin composition of the present invention may be obtained by partially reacting one of the alicyclic epoxy compound (A) and the curing agent (D) in the curable epoxy resin composition by heating. A B-staged curable epoxy resin composition (curable epoxy resin composition in a B-stage state).

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

 <Modulation method of curable epoxy resin composition>  

The method for producing the curable epoxy resin composition of the present invention is not particularly limited, and a well-known or conventional method can be employed. Specifically, for example, a specific amount of an alicyclic epoxy compound (A), an isomeric cyanuric monoallyl diglycidyl ester compound (B), a white pigment (C), and a hardener may be mentioned. (D), a hardening accelerator (F) and any additives, or a specific amount of an alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound (B), white A method of stirring and mixing the pigment (C), the curing catalyst (E), and any additives, using various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a spinning and agitating stirring device, and the like. Wait. Further, after stirring and mixing, it may be defoamed under reduced pressure or under vacuum.

More specifically, the curable epoxy resin composition of the present invention can be prepared, for example, by separately comprising: an alicyclic epoxy compound (A), an isocyanuric acid monoallyl diglycidyl ester compound (B) And an epoxy group-containing compound having two or more epoxy groups, such as a cyclooxyalkyl derivative (G), as an essential component, and a hardener (D) and a hardening accelerator ( F), or the β agent which hardens the catalyst (E) as an essential component; stirs in a specific ratio, mixes the α agent and the β agent, and modulates it by defoaming under vacuum as needed. Further, the alicyclic polyester resin (H) may be previously mixed (blended) as a constituent component of the alpha agent and/or the beta agent, or may be used as an alpha agent or a beta agent when the alpha agent and the beta agent are mixed. The third component is blended outside. In addition, the white pigment (C) may be mixed (blended) as a constituent component of the alpha agent and/or the beta agent in advance, and may be used as a third component other than the alpha agent and the beta agent when the alpha agent and the beta agent are mixed. Ingredient blending.

The temperature at the time of mixing and mixing of the above-mentioned α agent is not particularly limited, but is preferably 30 to 150 ° C, more preferably 35 to 130 ° C. Further, the temperature at the time of mixing and mixing of the above-mentioned β agent (when two or more components are used) is not particularly limited, but is preferably 30 to 100 ° C, more preferably 35 to 80 ° C. In the stirring and mixing, well-known apparatuses such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a spinning and agitating stirring apparatus, and the like can be used. Further, after stirring and mixing, it may be defoamed under reduced pressure or under vacuum.

In particular, when the curable epoxy resin composition of the present invention contains the curing agent (D) as an essential component, it is preferred to premix the alicyclic polyester resin (H) from the viewpoint of obtaining a uniform composition. And the hardener (D), after obtaining a mixture of the above (a mixture of the alicyclic polyester resin (H) and the hardener (D)), blending the hardening accelerator (F) or other additives in the mixture The β agent is prepared and then prepared by mixing the β agent with the α agent. The temperature at which the alicyclic polyester resin (H) and the curing agent (D) are mixed is not particularly limited, but is preferably 60 to 130 ° C, more preferably 90 to 120 ° C. The mixing time is not particularly limited, but is preferably from 30 to 100 minutes, more preferably from 45 to 80 minutes. The mixing system is not particularly limited, but is preferably carried out under a nitrogen atmosphere. Further, in the mixing, the above-mentioned well-known apparatus can be used.

After mixing the alicyclic polyester resin (H) and the curing agent (D), although it is not particularly limited, it may be further subjected to a suitable chemical treatment (for example, hydrogenation or terminal modification of an alicyclic polyester, etc.) Wait. Further, in the mixture of the above alicyclic polyester resin (H) and the hardener (D), a part of the hardener (D) may also be combined with the alicyclic polyester resin (H) (for example, alicyclic polymerization) The hydroxyl group of the ester resin (H) is reacted.

As a mixture of the alicyclic polyester resin (H) and the curing agent (D), for example, "HN-7200" (manufactured by Hitachi Chemical Co., Ltd.) and "HN-5700" (Hitachi Chemical Industry Co., Ltd.) Commercial products such as shares).

The rubber particles are preferably blended in a state in which the composition is previously dispersed in the alicyclic epoxy compound (A) (this composition is also referred to as "rubber particle-dispersed epoxy compound"). . That is, the curable epoxy resin composition of the present invention is preferably obtained by mixing the above rubber particle-dispersed epoxy compound, white pigment (C), hardener (D), hardening accelerator (F), or hardening catalyst ( E), modulated with other components as needed. By such a preparation method, the dispersibility of the rubber particles in the curable epoxy resin composition can be particularly improved. However, the method of blending the rubber particles is not limited to the above method, and a method of blending them alone may be employed.

 (Rubber particles dispersed epoxy compound)  

The rubber particle-dispersed epoxy compound is obtained by dispersing rubber particles in the alicyclic epoxy compound (A). In addition, the alicyclic epoxy compound (A) in the rubber particle-dispersed epoxy compound may be a full amount of the alicyclic epoxy compound (A) constituting the curable epoxy resin composition, or may be a part thereof. the amount. Similarly, the rubber particles in the rubber particle-dispersed epoxy compound may be the total amount of the rubber particles constituting the curable epoxy resin composition, or may be a part of the amount.

The viscosity of the rubber particle-dispersed epoxy compound can be adjusted, for example, by using a reactive diluent in combination (that is, the rubber particle-dispersed epoxy compound may further contain a reactive diluent). As the reactive diluent, for example, an aliphatic polyepoxypropyl ether having a viscosity at room temperature (25 ° C) of 200 mPa ‧ s or less can be preferably used. Examples of the aliphatic polyepoxypropyl ether having a viscosity (25 ° C) of 200 mPa·s or less include cyclohexane dimethanol diepoxypropyl ether, cyclohexanediol diepoxypropyl ether, and new Pentylene glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, polypropylene glycol diepoxypropyl ether, and the like.

The amount of the reactive diluent to be used is not particularly limited, and is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, based on 100 parts by weight of the total amount of the rubber particles-dispersed epoxy compound. For example, 5 to 25 parts by weight). When the amount is 30 parts by weight or less, the desired properties such as toughness (increased crack resistance) tend to be easily obtained.

The method for producing the rubber particle-dispersed epoxy compound is not particularly limited, and a conventionally known method can be used. For example, a method in which rubber particles are dehydrated and dried into a powder, mixed in an alicyclic epoxy compound (A), or dispersed, or an emulsion in which rubber particles are directly mixed with an alicyclic epoxy compound ( A), followed by dehydration and the like.

The viscosity of the curable epoxy resin composition of the present invention at 25 ° C is not particularly limited, but is preferably from 100 to 1,000,000 mPa ‧ , more preferably from 200 to 800,000 mPa ‧ , and particularly preferably from 300 to 800,000 mPa ‧ s. When the viscosity at 25 ° C is 100 mPa ‧ s or more, the workability at the time of injection molding is increased, and the heat resistance and light resistance of the cured product tend to increase. On the other hand, when the viscosity at 25 ° C is 1,000,000 mPa ‧ s or less, the workability at the time of injection molding is increased, or the cured product is less likely to cause a defect due to mold injection failure.

 <hardened matter>  

By curing the curable epoxy resin composition of the present invention and curing it, a cured product excellent in light reflectivity, excellent in heat resistance, light resistance, and crack resistance can be obtained. In addition, the cured product obtained by hardening the curable epoxy resin composition of the present invention, that is, the cured product of the curable epoxy resin composition of the present invention is also referred to as "the cured product of the present invention". The heating temperature (hardening temperature) at the time of hardening is not particularly limited, but is preferably 50 to 200 ° C, more preferably 80 to 180 ° C. Further, the heating time (hardening time) at the time of curing is not particularly limited, but is preferably 60 to 1800 seconds, more preferably 90 to 900 seconds. When the hardening temperature and the hardening time are less than the lower limit of the above range, the hardening is insufficient, and when it is higher than the upper limit of the above range, yellowing occurs due to thermal decomposition, which is not preferable. The curing conditions depend on various conditions. For example, the curing time can be shortened by increasing the curing temperature, lowering the curing temperature, increasing the curing time, and the like. Further, the hardening treatment may be carried out in one stage (for example, compression molding only), or may be carried out, for example, as a plurality of stages (for example, after compression molding, as post-hardening (secondary hardening), heating in an oven or the like). Further, in the case of post-hardening, the heating temperature at this time is preferably 50 to 200 ° C, more preferably 60 to 180 ° C, and particularly preferably the same temperature as the curing temperature. Further, the time for post-hardening is preferably from 0.5 to 10 hours, more preferably from 1 to 8 hours.

The cured product of the present invention has high light reflectivity and is excellent in heat resistance and light resistance. Therefore, the cured product is less likely to deteriorate, and the reflectance is less likely to decrease as time passes. Therefore, the curable epoxy resin composition of the present invention can be preferably used as an LED package (a constituent material of an LED package, such as a reflector material in an optical semiconductor device, a case material, etc.), an adhesive use of an electronic component, and a liquid crystal display. Uses (for example, reflectors, etc.), inks for white substrates, sealants, and the like. In particular, a curable resin composition for LED packaging (particularly, a curable resin composition for a reflector in an optical semiconductor device (that is, a curable resin composition for forming a reflector)) can be used.

The reflectance of the cured product of the present invention is not particularly limited. For example, the reflectance of light having a wavelength of 450 nm is preferably 90% or more, and 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. In addition, the above-mentioned reflectance can be measured, for example, by using a spectrophotometer (trade name "Spectrophotometer UV-2450", manufactured by Shimadzu Corporation).

The reflectance of light of a wavelength of 450 nm (also referred to as "reflectance after 250 hours of heat aging") of the cured product of the present invention after heating at 120 ° C for 250 hours is relative to the initial reflectance ([250 The reflectance after heating and aging for an hour]/[initial reflectance]×100) is not particularly limited, but is preferably 85% or more, more preferably 90% or more, particularly preferably 95% or more, and particularly preferably 98%. In particular, the retention of light in the case of 450 to 800 nm is preferably 85% or more, more preferably 90% or more, particularly preferably 95% or more, particularly preferably 98% or more. The hardenable ring according to the present invention The oxygen resin composition can be made 98% or more by the cured product formed by compression molding.

The reflectance of light having a wavelength of 450 nm (also referred to as "reflectance after 500 hours of heat aging") of the cured product of the present invention after heating at 120 ° C for 500 hours is maintained at an initial reflectance ([500 hours after heat aging) The reflectance] / [initial reflectance] × 100) is not particularly limited, but is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more, and particularly preferably 98% or more. In particular, the retention of light in the case of 450 to 800 nm is preferably 85% or more, more preferably 90% or more, particularly 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 above-described retention ratio of 90% or more.

The cured product of the present invention has a reflectance against light of a wavelength of 450 nm (also referred to as "reflectance after ultraviolet aging") after maintaining ultraviolet light having an intensity of 10 mW/cm ² for 250 hours (% of ultraviolet light aging) ([UV The reflectance after aging] / [initial reflectance] × 100) is not particularly limited, but is preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more. In particular, the retention of light in the case of 450 to 800 nm is preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more.

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

The cured product of the present invention has high light reflectivity, is excellent in heat resistance and light resistance, and is tough. Therefore, the cured product is less likely to deteriorate, and the reflectance is less likely to decrease as time passes. Therefore, the curable epoxy resin composition of the present invention can be preferably used as an LED package (a constituent material of an LED package, such as a reflector material in an optical semiconductor device, a case material, etc.), an adhesive use of an electronic component, and a liquid crystal display. Uses (for example, reflectors, etc.), inks for white substrates, sealants, and the like. Among them, a curable resin composition for LED packaging (particularly, a curable resin composition for a reflector (reflecting material) in an optical semiconductor device) can be preferably used.

 <The 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 addition, the term "curable resin composition for light reflection" as used in the present specification 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 light having a wavelength of 450 nm of 90% or more. By using the curable resin composition for light reflection of the present invention, for example, an optical semiconductor device having a reflector formed of a cured product excellent in physical properties such as light reflectivity, heat resistance, light resistance, and crack resistance can be obtained. . In the above-mentioned reflector, since the reflectance is less likely to decrease with time, the optical semiconductor device including the reflector has a high optical output and high luminance, and the illuminance is less likely to decrease with time. High reliability. In particular, the cured product of the present invention is excellent in crack resistance, particularly excellent in crack resistance against hot and cold 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 molding material (used in a material molded by a mold or the like). The molding material is used for forming a reflector (light reflecting member) included in a substrate (an optical semiconductor element mounting substrate) of an optical semiconductor device in an optical semiconductor device. Therefore, by molding (and hardening) the curable epoxy resin composition of the present invention, it is possible to produce a high quality having excellent light reflectivity, excellent heat resistance and light resistance, and excellent crack resistance. (For example, a highly durable) substrate for mounting an optical semiconductor element. In addition, the reflector is a member for reflecting light emitted from the optical semiconductor element in the optical semiconductor device, improving directivity and brightness of light, and improving light extraction efficiency. A substrate on which a semiconductor element having at least a reflector formed of a cured product of the present invention is mounted is also referred to as a "substrate for mounting an optical semiconductor element of the present invention".

 <Semiconductor element mounting substrate>  

The substrate for mounting an optical semiconductor element of the present invention is a substrate having at least a reflector (white reflector) formed of the cured product of the present invention. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention, wherein (a) is a perspective view and (b) is a cross-sectional view. In Fig. 1, 100 denotes a white reflector, 101 denotes a metal wiring (lead frame), 102 denotes a mounting region of the optical semiconductor element, and 103 denotes a package substrate. Further, the metal wiring 101 and the white reflector 100 are mounted on the package substrate 103, and the optical semiconductor element 107 and the die bonding are placed at the center (the mounting region 102 of the optical semiconductor element), and the optical semiconductor device 107 and the package are mounted. The metal wirings 101 on the substrate 103 are connected by wire bonding. As the material of the package substrate 103, a resin, a ceramic, or the like is used, but the same as the white reflector. The white reflector 100 on the upper side of the optical semiconductor element mounting substrate of the present invention surrounds the periphery of the mounting region 102 of the optical semiconductor element in a ring shape, and has a concave shape that is inclined such that the diameter of the ring is enlarged upward. The substrate for mounting an optical semiconductor element of the present invention may be formed by at least the cured surface of the present invention as long as the inner surface of the concave shape is formed. Further, as shown in FIG. 1, the portion (the lower portion of the 102) surrounded by the metal wiring 101 may be the package substrate 103, and the white reflector 100 may be used (that is, the "100/103" in FIG. It can be a white reflector 100 or a package substrate 103). However, the substrate for mounting an optical semiconductor element of the present invention is not limited to the one shown in FIG.

The method of forming the white reflector in the substrate for mounting an optical semiconductor element of the present invention can be a well-known or conventional molding method (for example, compression molding), and is not particularly limited, and examples thereof include hardening of the present invention. The epoxy resin composition is supplied to a method of various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and baffle molding to be dispensed (preferably, compression molding). The curing condition at the time of forming the reflector can be suitably selected, for example, from the conditions at the time of forming the cured product described above. In the present invention, in particular, in order to prevent foaming due to a sharp hardening reaction, to alleviate stress strain due to hardening, and to improve toughness (crack resistance), it is preferable to apply heat treatment in multiple stages. It hardens in stages.

By using the optical semiconductor element mounting substrate of the present invention as a substrate in an optical semiconductor device, an optical semiconductor device of the present invention can be obtained by mounting an optical semiconductor device on the substrate.

 <Optical semiconductor device>  

The optical semiconductor device of the present invention is an optical semiconductor device including at least an optical semiconductor element as a light source and a reflector (reflective material) formed of the cured product of the present invention. More specifically, the optical semiconductor device of the present invention includes at least the optical semiconductor device mounting substrate of the present invention and the optical semiconductor device mounted on the substrate. In the optical semiconductor device of the present invention, since the reflector formed of the cured product of the present invention is used as a reflector, the brightness of light is less likely to 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 denotes a white reflector, 101 denotes a metal wiring (lead frame), 103 denotes a package substrate, 104 denotes a bonding wire, 105 denotes a sealing material, 106 denotes a die bonding, and 107 denotes an optical semiconductor component (LED component). In the optical semiconductor device shown in FIG. 2, the light emitted from the optical semiconductor element 107 is reflected on the surface (reflecting surface) of the white reflector 100, so that the light from the optical semiconductor element 107 is taken out with high efficiency. Further, as shown in Fig. 2, the optical semiconductor element in the optical semiconductor device of the present invention is usually sealed by a transparent sealing material (105 in Fig. 2).

3 and 4 are views showing another example of the optical semiconductor device of the present invention. 108 in Figs. 3 and 4 denotes a heat sink (shell heat sink), and by having such a heat sink 108, heat dissipation efficiency in the optical semiconductor device is increased. 3 is an example in which the heat dissipation path of the heat sink is located directly under the optical semiconductor element, 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) represents an upper view, and (b) represents (a) A-A' section view]. The heat sink 108 on the side of the protruding optical semiconductor device of FIG. 4 is also referred to as a heat sink fin. Further, 109 in Fig. 4 denotes a cathode mark. However, the optical semiconductor device of the present invention is not limited to the ones shown in FIGS. 2 to 4.

Since the optical semiconductor device of the present invention has at least a reflector formed of the cured product of the present invention, even when high-intensity light is output, it is possible to stably emit light for a long period of time. Further, since the reflector formed of the cured product of the present invention is excellent in crack resistance (especially, crack resistance against hot and cold cycles), it is less likely to cause problems such as a decrease in illuminance with time. Therefore, the optical semiconductor device of the present invention can exhibit high reliability as a long-life optical semiconductor device.

Example

Hereinafter, the present invention will be described in more detail based on the examples, but the present invention is not limited by the examples. The unit of the blending amount of each component of the curable epoxy resin composition in Tables 1 to 7 is part by weight. In addition, the polyfluorene-based leveling agents in Tables 4 to 7 ("BYK-300", "AC FS 180"), fluorine-based leveling agents ("BYK-340", "AC 110a"), stress relaxation The blending amount of the agent ("KMP-600", "KMP-602,", "SF8421", "Y-19268")) indicates the amount of the product (the amount of the product itself). Further, "-" in Tables 1 to 7 indicates that the blending of the components is not carried out.

 Manufacturing example 1    (Manufacture of epoxy resin containing white pigment: Examples 1 to 5)  

According to the blending formula (mixing ratio) shown in Table 1 (unit: parts by weight), mixed isoallyl cyanuryl diglycidyl ester (trade name "MA-DGIC", Shikoku Chemical Industry Co., Ltd. )), an alicyclic epoxy compound ((3,4,3',4'-dicyclooxy)bicyclohexane, manufactured by DAICEL Co., Ltd.; trade name "Celloxide 2021P", manufactured by DAICEL Co., Ltd.) After stirring at 80 ° C for 1 hour, the isomeric cyanuric acid monoallyl diglycidyl ester was dissolved to obtain an epoxy resin (mixture). Next, according to the blending formula (mixing ratio) shown in Table 1 (unit: parts by weight), the above epoxy resin and white pigment (titanium oxide; trade name "DCF-T-17050" were uniformly mixed using a dissolver. , RESINO COLOR industrial (stock) system, by a roller mill, under the specified conditions (roll spacing: 0.2mm, number of revolutions: 25 Hz, through 3 times), to obtain epoxy resin containing white pigment ( Epoxy resin composition).

 Manufacturing Example 2    (Manufacture of epoxy resin containing white pigment: Comparative Examples 1 to 10)  

According to the blending formula (mixing ratio) shown in Table 1 (unit: parts by weight), mixed isoallyl cyanuryl diglycidyl ester (trade name "MA-DGIC", Shikoku Chemical Industry Co., Ltd. )), an alicyclic epoxy compound (trade name "Celloxide 2021P", manufactured by DAICEL (trade name); trade name "EHPE3150", manufactured by DAICEL), and isomeric cyanuric acid glycidyl ester (trade name " TEPIC-PAS B26", manufactured by Nissan Chemical Industries Co., Ltd.), obtained epoxy resin (mixture) (in the case of Comparative Examples 1, 2, 4 to 6, and 8, since the composition of the epoxy resin is one, it is not This mixing was carried out directly to form an epoxy resin. Next, according to the blending formula (mixing ratio) shown in Table 1 (unit: parts by weight), the above epoxy resin and white pigment (titanium oxide; trade name "DCF-T-17050" were uniformly mixed using a dissolver. , RESINO COLOR industrial (stock) system, by a roller mill, under the specified conditions (roll spacing: 0.2mm, number of revolutions: 25 Hz, through 3 times), to obtain epoxy resin containing white pigment ( Epoxy resin composition).

 Manufacturing Example 3    (Manufacture of at least a hardener composition containing a curing agent (hereinafter referred to as "K agent"): Examples 1 to 4, Comparative Examples 1 to 4, 9)  

According to the blending formula (mixing ratio) shown in Table 1, a hardening agent (anhydride) was uniformly mixed using a self-rotating revolution type stirring device (manufactured by THINKY Co., Ltd., trade name "Defoaming Rantaro AR-250") New Japan Physicochemical Co., Ltd., trade name "Rikacid MH-700"), hardening accelerator (SUNAPRO (share), trade name "U-CAT 18X"), additive (Wako Pure Chemical Industries, Ltd.), products The name "ethylene glycol" is defoamed to obtain a K agent.

 Examples 1 to 5 and Comparative Examples 1 to 10    (Manufacture of curable epoxy resin composition)  

In a blending formulation (unit: parts by weight) shown in Table 1, a self-rotating revolution type stirring device (manufactured by THINKY Co., Ltd., trade name "Defoaming Ryotaro AR-250") was uniformly mixed (2000 rpm). 5 minutes) The epoxy resin containing the white pigment obtained in Production Example 1, the epoxy resin containing the white pigment obtained in Production Example 2, the K agent obtained in Production Example 3, and the curing catalyst (manufactured by Sanshin Chemical Industry Co., Ltd.) The product name "Sunaid SI-100L" was defoamed to obtain a curable epoxy resin composition.

 (Manufacture of hardened material)  

The curable epoxy resin composition was sandwiched between a release film made of a polyester, placed in a mold for compression molding at 150 ° C, and heated and pressed at a pressure of 3.0 MPa for 600 seconds to be hardened. Then, by performing post-hardening (150 ° C, 5 hours), a cured product was obtained.

 Manufacturing Example 4    (Manufacture of epoxy resin containing white pigment: Examples 6 to 14, Comparative Examples 11 to 21)  

According to the blending formula (mixing ratio) shown in Tables 2 and 3 (unit: parts by weight), mixed isocyanuric acid monoglycidyl diglycidyl ester (trade name "MA-DGIC", Shikoku Chemical Industry Co., Ltd. (manufactured by the company), an alicyclic epoxy compound ((3,4,3',4'-dicyclooxy)bicyclohexane, manufactured by DAICEL Co., Ltd.; trade name "Celloxide 2021P", DAICEL (share) Product name: "EHPE3150", manufactured by DAICEL Co., Ltd.), isocyanuric acid glycidyl ester (trade name "TEPIC-PAS B26", manufactured by Nissan Chemical Industries Co., Ltd.), and has 2 rings in the molecule. A oxooxane derivative (trade name "X-40-2678", manufactured by Shin-Etsu Chemical Co., Ltd.) and a siloxane derivative having three epoxy groups in the molecule (trade name "X-40") -2720", Shin-Etsu Chemical Co., Ltd.), a cyclooxyl derivative having four epoxy groups in the molecule (trade name "X-40-2670", manufactured by Shin-Etsu Chemical Co., Ltd.), After stirring at 80 ° C for 1 hour, the isomeric cyanuric acid monoallyl diglycidyl ester was dissolved to obtain an epoxy resin (mixture) (in the case of Comparative Examples 11 to 15, since the composition of the epoxy resin was one, Do not carry out the mixing directly Made of epoxy resin sample). Next, according to the blending formula (mixing ratio) shown in Tables 2 and 3 (unit: parts by weight), the above epoxy resin and white pigment (titanium oxide; trade name "DCF-T-" were uniformly mixed using a dissolver. 17050", RESINO COLOR Industrial Co., Ltd.), which is kneaded under a specified condition (roll spacing: 0.2 mm, number of revolutions: 25 Hz, 3 times) by a roll mill to obtain an epoxy containing white pigment. Resin (epoxy resin composition).

 Manufacturing Example 5    (Manufacture of hardener composition (K agent) containing at least a hardener: Examples 6 to 14, Comparative Examples 11 to 21)  

According to the blending formula (mixing ratio) shown in Tables 2 and 3 (unit: parts by weight), use a self-rotating revolution type stirring device (trade name "Defoaming Rantaro AR-250", manufactured by THINKY Co., Ltd.), uniform Mixture of hardener (anhydride) (trade name "Rikacid MH-700", manufactured by Hitachi Chemical Co., Ltd.), hardener (anhydride) and alicyclic polyester resin (trade name "HN-7200", Hitachi Chemical Industry Co., Ltd., a mixture of a curing agent (anhydride) and an alicyclic polyester resin (trade name "HN-5700", manufactured by Hitachi Chemical Co., Ltd.), and a hardening accelerator (trade name "U-CAT") 18X", manufactured by SUNAPRO Co., Ltd., and an additive (trade name "ethylene glycol", manufactured by Wako Pure Chemical Industries, Ltd.), and defoamed to obtain K agent.

 Examples 6 to 14 and Comparative Examples 11 to 21    (Manufacture of curable epoxy resin composition)  

In a blending formula (unit: parts by weight) shown in Tables 2 and 3, a self-rotating revolution type stirring device (trade name "Defoaming Ryotaro AR-250", manufactured by THINKY Co., Ltd.) was used, and the mixture was uniformly mixed. (2000 rpm, 5 minutes) The epoxy resin containing the white pigment obtained in Production Example 4 and the K agent obtained in Production Example 5 were defoamed to obtain a curable epoxy resin composition.

 (Manufacture of hardened material)  

The curable epoxy resin composition was sandwiched between a release film made of a polyester, placed in a mold for compression molding at 150 ° C, and heated and pressed at a pressure of 3.0 MPa for 600 seconds to be hardened. Then, by performing post-hardening (150 ° C, 5 hours), a cured product was obtained.

 Manufacturing Example 6    (Manufacture of rubber particles)  

500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were placed in a 1 L polymerization vessel equipped with a reflux condenser, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. Between 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene, which is equivalent to about 5% by weight of the amount required for forming the core portion of the rubber particles, is added thereto. After the monomer mixture was stirred for 20 minutes and emulsified, 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour to carry out initial seed polymerization. Next, 180.5 mg of potassium peroxodisulfate was added and stirred for 5 minutes. The remainder (approximately 95% by weight) of the amount required to form the core portion was continuously added over 2 hours from 180.5 g of butyl acrylate, 48.89 g of styrene, and 7.33 g of divinylbenzene. A monomer mixture obtained by dissolving 0.95 g of sodium dioctylsulfosuccinate was subjected to the second seed polymerization, followed by aging for 1 hour to obtain a core portion.

Next, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes, in which 30 minutes of continuous addition was carried out by dissolving 0.3 g of methyl methacrylate, 1.5 g of acrylic acid, and 0.3 g of allyl methacrylate. A monomer mixture of sodium dioctylsulfosuccinate of g is subjected to seed polymerization. Then, it was aged for 1 hour to form a shell layer covering the core portion.

Subsequently, the mixture was cooled to room temperature (25 ° C), and filtered through a plastic mesh having a pore size of 120 μm to obtain a latex containing rubber particles having a core-shell structure. The obtained latex was frozen at a negative temperature of 30 ° C, dehydrated and washed with a suction filter, and then air-dried at 60 ° C for one day and night to obtain rubber particles. The obtained rubber particles had an average particle diameter of 254 nm and a maximum particle diameter of 486 nm.

In addition, the average particle diameter and the maximum particle diameter of the rubber particles are Nanotrac particle size distribution measuring apparatus (product name "UPA-EX150", "Nikko" (shared ^{) in the} form of "NanotracTM" using the dynamic light scattering method as the measurement principle. The following sample was measured. For the obtained particle size distribution curve, the cumulative average diameter of the particle diameter at the time point when the cumulative curve became 50% was taken as the average particle diameter, and the frequency (%) of the particle size distribution measurement result exceeded 0.00%. The maximum particle size at the time point is taken as the maximum particle size. In addition, as the sample, 1 part by weight of the rubber particle-dispersed epoxy compound obtained in Production Example 7 was dispersed in 20 parts by weight of tetrahydrofuran.

 Manufacturing Example 7    (Manufacture of rubber particle-dispersed epoxy compound)  

Under a nitrogen stream, 10 parts by weight of the rubber particles obtained in Production Example 6 were dispersed in 48 parts by weight (3, 4, 3' using a dissolver (1000 rpm, 60 minutes) while being heated to 60 °C. In a 4'-dicyclooxy)bicyclohexane (manufactured by DAICEL Co., Ltd.), vacuum defoaming was carried out to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C: 3023 mPa ‧ s).

Further, the rubber particles obtained in Production Example 7 were dispersed in an epoxy compound (10 parts by weight of rubber particles were dispersed in 48 parts by weight of (3,4,3',4'-diepoxy)bicyclohexane) The viscosity (viscosity at 25 ° C) was measured using a digital viscometer (trade name "DVU-EII type", manufactured by TOKIMEC Co., Ltd.).

 Manufacturing Example 8    (Manufacture of epoxy resin containing white pigment: Examples 15 to 46)  

According to the blending formula (mixing ratio) shown in Tables 4 and 5 (unit: parts by weight), mixed isocyanuric acid monoallyl diglycidyl ester (trade name "MA-DGIC", Shikoku Chemical Industry Co., Ltd. (manufactured by the company), an alicyclic epoxy compound ((3,4,3',4'-dicyclooxy)bicyclohexane, manufactured by DAICEL), having two epoxy groups in the molecule a decane derivative (trade name "X-40-2678", manufactured by Shin-Etsu Chemical Co., Ltd.) and a siloxane derivative having three epoxy groups in the molecule (trade name "X-40-2720" , Shin-Etsu Chemical Co., Ltd.), a cyclooxygen derivative having four epoxy groups in the molecule (trade name "X-40-2670", manufactured by Shin-Etsu Chemical Co., Ltd.) Flat agent (trade name "BYK-300", BYK Chemical ‧ Japan (share) system; product name "AC FS 180", manufactured by Algin Chemie), fluorine-based leveling agent (trade name "BYK-340", BYK Chemical ‧ Japanese (stock) system; trade name "AC 110a", manufactured by Algin Chemie), polycarbonate diol (trade name "Placcel CD220PL", manufactured by DAICEL Co., Ltd.), polytetramethylene ether glycol (trade name " PTMG2000", manufactured by Mitsubishi Chemical Corporation), polycaprolactone polyol ( Product name "Placcel 308", DAICEL (manufactured by DAICEL), phenoxy resin (trade name "YP-70", manufactured by Nippon Steel Chemical Co., Ltd.), long-chain epoxy resin containing hydroxyl group (trade name "Epotohto YD-" 6020", Nippon Steel Chemical Co., Ltd.), acrylic block copolymer (trade name "Nanostrength M52N", manufactured by ARKEMA), rubber particle-dispersed epoxy compound obtained in Production Example 7, and stress relieving agent (trade name "KMP" -600", polyoxyethylene rubber particles, manufactured by Shin-Etsu Chemical Co., Ltd.; trade name "KMP-602", polyoxyn rubber particles, Shin-Etsu Chemical Co., Ltd.; trade name "SF8421", formula (10) The polyalkylene ether modified polyoxosiloxane shown, manufactured by Toray Dow Corning Co., Ltd.; trade name "Y-19268", polyalkylene ether modified polyoxonium compound represented by formula (10) Momentive Performance Materials (manufactured by Japan) was stirred at 80 ° C for 1 hour to dissolve isocyanuric acid monoallyl diglycidyl ester to obtain an epoxy resin (mixture). Next, according to the blending formula (mixing ratio) shown in Tables 4 and 5 (unit: parts by weight), the above epoxy resin and white pigment (titanium oxide; trade name "DCF-T-" were uniformly mixed using a dissolver. 17050", RESINO COLOR Industrial Co., Ltd.) and inorganic filler (trade name "FB-970FD", vermiculite (no surface treatment), average particle size 16.7μm, maximum particle size 70μm), manufactured by DENKA Co., Ltd.) The mixture was kneaded under a specified condition (roll pitch: 0.2 mm, number of revolutions: 25 Hz, three times) by a roll mill to obtain an epoxy resin (epoxy resin composition) containing a white pigment.

 Manufacturing Example 9    (Manufacture of K agent: Examples 15 to 46)  

According to the blending formula (mixing ratio) shown in Tables 4 and 5 (unit: parts by weight), a self-rotating revolution type stirring device (trade name "Defoaming Rantaro AR-250", manufactured by THINKY Co., Ltd.) is used. a mixture of a ground-mixing hardener (anhydride) (manufactured by Nippon Chemical and Chemical Co., Ltd., trade name "Rikacid MH-700"), a hardener (anhydride) and an alicyclic polyester resin (trade name "HN-7200", Hitachi Chemical Co., Ltd., a hardening accelerator (trade name "U-CAT 18X", manufactured by SUNAPRO), and additives (trade name "ethylene glycol", and Wako Pure Chemical Industries, Ltd.) Defoaming gives K agent.

 Examples 15 to 46    (Manufacture of curable epoxy resin composition)  

The white pigment-containing epoxy resin obtained in Production Example 8 was uniformly mixed (2000 rpm, 5 minutes) in a blending formula (unit: parts by weight) as shown in Tables 4 and 5, using a self-rotating revolution stirring apparatus. The K agent obtained in Production Example 9 was defoamed to obtain a curable epoxy resin composition.

 (Manufacture of hardened material)  

The curable epoxy resin composition was sandwiched between a release film made of a polyester, placed in a mold for compression molding at 150 ° C, and heated and pressed at a pressure of 3.0 MPa for 600 seconds to be hardened. Then, by performing post-hardening (150 ° C, 5 hours), a cured product was obtained.

 Manufacturing Example 10    (Manufacture of epoxy resin containing white pigment: Examples 47 to 74, Comparative Examples 22 to 25)  

According to the blending formula (mixing ratio) shown in Tables 6 and 7 (unit: parts by weight), mixed isocyanuric acid monoglycidyl diglycidyl ester (trade name "MA-DGIC", Shikoku Chemical Industry Co., Ltd. (manufactured by the company), alicyclic epoxy compound ((3,4,3',4'-dicyclooxy)bicyclohexane, manufactured by DAICEL (stock); trade name "EHPE3150", DAICEL (share) system ), isocyanuric acid glycidyl ester (trade name "TEPIC-PAS B26", manufactured by Nissan Chemical Industries Co., Ltd.), and a cyclooxygen derivative having two epoxy groups in the molecule (trade name "X" -40-2678", Shin-Etsu Chemical Co., Ltd.), a siloxane derivative having three epoxy groups in the molecule (trade name "X-40-2720", manufactured by Shin-Etsu Chemical Co., Ltd.), A fluorinated alkane derivative having four epoxy groups in the molecule (trade name "X-40-2670", manufactured by Shin-Etsu Chemical Co., Ltd.) and a polyfluorene-based leveling agent (trade name "BYK-300" , BYK Chemical ‧ Japan (share) system; trade name "AC FS 180", made by Algin Chemie), fluorine-based leveling agent (trade name "BYK-340", BYK chemistry ‧ Japan (share) system; product name "AC 110a", manufactured by Algin Chemie), polycarbonate diol (trade name) Placcel CD220PL", manufactured by DAICEL Co., Ltd.), polytetramethylene ether glycol (trade name "PTMG2000", manufactured by Mitsubishi Chemical Corporation), polycaprolactone polyol (trade name "Placcel 308", DAICEL ( )), phenoxy resin (trade name "YP-70", Nippon Steel Chemical Co., Ltd.), long-chain epoxy resin containing hydroxyl (trade name "Epotohto YD-6020", Nippon Steel Chemical ( (Production), acrylic block copolymer (trade name "Nanostrength M52N", manufactured by ARKEMA), rubber particle-dispersed epoxy compound obtained in Production Example 7, stress relieving agent (trade name "KMP-600", polyoxyxene rubber Particles, Shin-Etsu Chemical Co., Ltd.; trade name "KMP-602", polyoxyn rubber particles, Shin-Etsu Chemical Co., Ltd.; trade name "SF8421", polyalkylene ether shown in formula (10) Modified polyoxyl compound, manufactured by Toray Dow Corning Co., Ltd.; trade name "Y-19268", polyalkylene ether modified polyoxane compound represented by formula (10), Momentive Performance Materials ‧ Japan )), and further stirred at 80 ° C for 1 hour to dissolve the isomeric cyanuric acid monoallyl diglycidyl ester to obtain an epoxy resin (mixed) ) (In the case of Comparative Examples 22 to 25, since the epoxy resin as a component, it does not carry out the mixing, the epoxy resin thus created directly). Next, according to the blending formula (mixing ratio) shown in Tables 6 and 7 (unit: parts by weight), the above epoxy resin and white pigment (titanium oxide; trade name "DCF-T-" were uniformly mixed using a dissolver. 17050", RESINO COLOR Industrial Co., Ltd.) and inorganic filler (trade name "FB-970FD", vermiculite (no surface treatment), average particle size 16.7μm, maximum particle size 70μm), manufactured by DENKA Co., Ltd.) The mixture was kneaded under a specified condition (roll pitch: 0.2 mm, number of revolutions: 25 Hz, three times) by a roll mill to obtain an epoxy resin (epoxy resin composition) containing a white pigment.

 Manufacturing Example 11    (Manufacture 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 (Tokyo Chemicals Co., Ltd.) were placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser. Industrial Co., Ltd., 0.1 part by weight of tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 160 ° C, and further heated from 160 ° C to 250 ° C in 4 hours. Subsequently, the pressure was reduced to 5 mmHg over 1 hour, and the pressure was reduced to 0.3 mmHg or less, and then reacted at 250 ° C for 1 hour to obtain an alicyclic polyester resin.

 Examples 47 to 74 and Comparative Examples 22 to 25    (Manufacture of curable epoxy resin composition)  

In a blending formula (unit: parts by weight) shown in Tables 6 and 7, a self-rotating revolution type stirring device (trade name "Defoaming Rantaro AR-250", manufactured by THINKY Co., Ltd.) was used, and the mixture was uniformly mixed. (2000 rpm, 5 minutes) The epoxy resin containing the white pigment obtained in Production Example 10, the alicyclic polyester resin obtained in Production Example 11, and the curing catalyst (trade name "Sunaid SI-100L", Sanshin Chemical Industry Co., Ltd. )), defoaming to obtain a curable epoxy resin composition.

 (Manufacture of hardened material)  

The curable epoxy resin composition was sandwiched between a release film made of a polyester, placed in a mold for compression molding at 150 ° C, and heated and pressed at a pressure of 3.0 MPa for 600 seconds to be hardened. Then, by performing post-hardening (150 ° C, 5 hours), a cured product was obtained.

 <evaluation>  

For the cured products obtained in the examples and the comparative examples, the reflectance of light at 450 nm was measured according to the following procedure, and whether cracks occurred during molding (cutting), during reflow, and during thermal shock test (TST) were performed. Evaluation. The evaluation results are shown in Tables 1 to 7.

 [reflectance evaluation]  

A test piece having a thickness of 3 mm was produced by cutting the cured product obtained in the examples and the comparative examples. Next, the reflectance (as "initial reflectance") of each test piece for light having a wavelength of 450 nm was measured using a spectrophotometer (trade name "Spectrophotometer UV-2450", manufactured by Shimadzu Corporation). The results are shown in the column of "Initial reflectance" in Tables 1 to 7.

 [heat resistance test (heat aging 250 hours)]  

The test piece (thickness: 3 mm) in which the initial reflectance was measured was heated at 120 ° C for 250 hours, and then the reflectance of light at a wavelength of 450 nm (the "reflectance after heat aging (250 hours)") was measured. Then, the reflectance retention ratio (before and after heat aging; 250 hours) was calculated by the following formula. The results are shown in the columns of "Reflection retention rate before and after heating aging (250 hours)" in Tables 1 to 7.

[Reflection retention rate (before and after heating aging; 250 hours)] = [reflectance after heat aging (250 hours)] / [initial reflectance] × 100

 [heat resistance test (heat aging 500 hours)]  

The test piece (thickness: 3 mm) in which the initial reflectance was measured was heated at 120 ° C for 500 hours, and then the reflectance of light at a wavelength of 450 nm (measured as "reflectance after heat aging (500 hours)") was measured. Then, the reflectance retention ratio (before and after heating aging; 500 hours) was calculated by the following formula. The results are shown in the columns of "Reflection retention rate before and after heating aging (500 hours)" in Tables 1 to 7.

[Reflection retention rate (before and after heating aging; 500 hours)] = [reflectance after heat aging (500 hours)] / [initial reflectance] × 100

 [Light resistance test]  

The test piece (thickness: 3 mm) in which the initial reflectance was measured was irradiated with ultraviolet rays having a intensity of 10 mW/cm ² for 250 hours, and then the reflectance for light having a wavelength of 450 nm (as "reflectance after ultraviolet aging") was measured. Then, the reflectance retention ratio (before and after ultraviolet aging) was calculated by the following formula. The results are shown in the columns of "Resistance retention rate before and after UV aging" in Tables 1 to 7.

[Reflection retention rate (before and after UV aging)] = [Reflectance after ultraviolet aging] / [Initial reflectance] × 100

 [Evaluation of cracks during cutting (strength evaluation)]  

A test piece having a width of 5 mm, a length of 5 mm, and a thickness of 3 mm was produced by cutting the cured product obtained in the examples and the comparative examples. In the cutting process of the above-mentioned cured product, a micro-cutting machine (trade name "BS-300CL", manufactured by MEIWAFOSIS Co., Ltd.) was used to observe and confirm with a digital microscope (trade name "VHX-900", manufactured by KEYENCE Co., Ltd.). Whether cracks occur in the hardened material during cutting. In the column of "the number of cracks during cutting" in Tables 1 to 7, 10 test pieces were prepared for each sample, and the number of test pieces in which cracks occurred was confirmed (referred to as "the number of cracks"). It is expressed as an evaluation result. In addition, in Tables 1 to 7, the number of test pieces (the number of cracks) in which cracking occurred was confirmed to be n in the form of "n/10".

 [Evaluation of cracks during reflow (evaluation of toughness)]  

For the test piece (width: 5 mm × length: 5 mm × thickness: 3 mm) obtained by the above-mentioned cutting, a reflow furnace (trade name "UNI-5016F", manufactured by ANTOM Co., Ltd.) was used, and 260 ° C was taken as the highest temperature. In seconds, the total reflow time is set to 90 seconds, and the reflow process is applied. Then, a digital microscope (trade name "VHX-900", manufactured by KEYENCE Co., Ltd.) was used to observe and confirm whether or not a crack occurred in the test piece due to the reflow treatment. In Tables 1 to 7, 10 test pieces were reflowed for each sample, and the number of test pieces (the number of cracks) in which cracks were confirmed was indicated as an evaluation result. In the column of "the number of cracks in the reflow process" in Tables 1 to 7, the number of test pieces (the number of cracks) in which cracking occurred was confirmed to be n in the form of "n/10". Further, in the case where cracks have occurred during the cutting process, the evaluation is not performed.

 [thermal shock test (TST)]  

For the test piece obtained by the above-described cutting process (width 5 mm × length 5 mm × thickness 3 mm), it was exposed to an environment of -60 ° C for 30 minutes, and then exposed to an environment of 150 ° C for 30 minutes as a heat of 1 cycle. For the impact, 200 cycles were given using a thermal shock tester (ESPEC (small) cold thermal shock device TSE-11-A). Then, a digital microscope (trade name "VHX-900", manufactured by KEYENCE Co., Ltd.) was observed to confirm whether or not a crack occurred in the test piece due to the thermal shock test. In Tables 1 to 7, a thermal shock test of 10 test pieces was carried out for each sample, and the number of test pieces (the number of cracks) in which cracks were confirmed was shown as an evaluation result. In the column of "the number of cracks in the TST" in Tables 1 to 7, the number of the test pieces (the number of cracks) in which cracking occurred was confirmed to be n in the form of "n/10". Further, in the case where cracks have occurred during the cutting process, the evaluation is not performed.

 [Overview]  

When the initial reflectance is 90% or more, the reflectance retention rate is 90% or more in the heat resistance test (heating aging for 500 hours), and the reflectance retention rate in the light resistance test is 90% or more, and there is no crack evaluation during cutting. (Strength toughness evaluation), whether there is crack evaluation (reinforcement evaluation) during reflow, and whether or not crack evaluation (toughness evaluation) is used in thermal shock test (TST), the number of cracks is 0 as a comprehensive judgment ○ (good) . On the other hand, the other is regarded as a comprehensive judgment × (bad). The results are displayed in the column of "Comprehensive judgment" in Tables 1 to 4.

Further, the components used in the examples and comparative examples are as follows.

 [Epoxy resin]  

(3,4,3',4'-diepoxy)bicyclohexane, DAICEL (share) system

CEL2021P (Celloxide 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, manufactured by DAICEL

MA-DGIC: Isopropyl cyanurate monoallyl diglycidyl ester, Siguo Chemical Industry Co., Ltd.

EHPE3150: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by DAICEL

TEPIC-PAS B26: isomeric cyanuric acid glycidyl ester, manufactured by Nissan Chemical Industry Co., Ltd.

X-40-2678: a decane derivative having two epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

X-40-2720: a decane derivative having three epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

X-40-2670: a decane derivative having four epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

BYK-300: Polyoxane leveling agent (containing leveling agent for polyfluorene-based polymer), BYK Chemical ‧ Japan (share) system

AC FS 180: Polyoxane leveling agent (leveling agent containing polyfluorene-based polymer), manufactured by Algin Chemie

BYK-340: Fluorine leveling agent (containing leveling agent for fluorine-containing acrylic polymer), BYK Chemical ‧ Japan (share) system

AC 110a: Fluorine leveling agent (leveling agent containing fluorine-containing polyether polymer), manufactured by Algin Chemie

CD220PL (Placcel CD220PL): polycarbonate diol, DAICEL (stock) system

PTMG2000: polytetramethylene ether glycol, Mitsubishi Chemical Co., Ltd.

Placcel 308: polycaprolactone polyol, DAICEL (stock) system

YP-70: phenoxy resin, Nippon Steel Chemical Co., Ltd.

Epotohto YD-6020: Long-chain epoxy resin with hydroxyl group, Nippon Steel Chemical Co., Ltd.

M52N (Nanostrength M52N): acrylic block copolymer, manufactured by ARKEMA

KMP-600: cross-linked polydimethyl siloxane with polyoxyl resin on the surface, Shin-Etsu Chemical Co., Ltd.

KMP-602: crosslinked polydimethyl siloxane with polyoxyl resin on the surface, Shin-Etsu Chemical Co., Ltd.

SF8421: polyalkylene ether modified polyoxonium compound represented by formula (10), manufactured by Toray Dow Corning Co., Ltd.

Y-19268: polyalkylene ether modified polyoxonium compound represented by formula (10), Momentive Performance Materials ‧ Japan (same) system

 [Inorganic filler]  

Meteorite: trade name "FB-970FD" (meteorite, no surface treatment, average particle size 16.7μm, maximum particle size 70μm), DENKA (share) system

 [white pigment]  

Titanium oxide, trade name "DCF-T-17050", RESINO COLOR industrial (share) system

 [K agent]  

MH-700 (Rikacid MH-700): 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30, New Japan Physical and Chemical Co., Ltd.

HN-7200: a mixture of 4-methylhexahydrophthalic anhydride and an alicyclic polyester resin, manufactured by Hitachi Chemical Co., Ltd.

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

18X (U-CAT 18X): hardening accelerator, manufactured by SUNAPRO

Ethylene glycol: Wako Pure Chemical Industries Co., Ltd.

 [hardening catalyst]  

Sunaid SI-100L: aryl sulfonium salt, 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 does not crack at the time of cutting, reflow, and thermal shock test. Especially for the thermal shock test, it has excellent crack resistance and is tough. Further, after heat aging and ultraviolet aging, high light reflectivity is maintained, and heat resistance and light resistance are excellent. In particular, in addition to the alicyclic epoxy compound and the isoallyl diglycidyl isocyanurate, an alicyclic polyester resin (or an alicyclic polyester resin or a molecule) is further included. In the case of the oxoxane derivative having two or more epoxy groups in the above (Examples 8, 9, 12, 14, 17, 45, 48, and 73), even if heating is performed for a longer period of time (500 hours), The light reflectivity is also hardly lowered, and the heat resistance is extremely excellent.

On the other hand, the cured product (comparative example) formed of the curable epoxy resin composition which does not satisfy the requirements of the present invention has a low light reflectivity after heat aging and ultraviolet aging, and is inferior in heat resistance and light resistance. Furthermore, cracks are likely to occur during the thermal shock test, and the toughness is also poor.

The modifications of the invention described above are attached below.

[1] A curable epoxy resin composition comprising an alicyclic epoxy compound (A) represented by the following formula (I) and an isomeric cyanuric acid represented by the following formula (1) Allyl diglycidyl ester compound (B), white pigment (C), hardener (D) and hardening accelerator (F),

^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 , ^R17a and ^R18a 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 (preferably a hydrogen atom)];

[wherein, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom)].

[2] The curable epoxy resin composition according to the above [1], wherein the total amount (100% by weight) of the curable epoxy resin composition other than the white pigment (C) and the inorganic filler (J) is fat The amount (content) of the cyclic epoxy compound (A) used is 5 to 90% by weight (preferably 5 to 80% by weight, more preferably 5 to 70% by weight).

[3] A curable epoxy resin composition comprising the alicyclic epoxy compound (A) represented by the above formula (I) and the isomeric cyanuric monoallyl represented by the above formula (1) A bisglycidyl ester compound (B), a white pigment (C) and a hardening catalyst (E).

[4] The curable epoxy resin composition according to the above [3], wherein the total amount (100% by weight) of the curable epoxy resin composition other than the white pigment (C) and the inorganic filler (J) is fat The amount (content) of the cyclic epoxy compound (A) used is 25 to 95% by weight (preferably 30 to 92% by weight, more preferably 30 to 90% by weight).

[5] The curable epoxy resin composition according to any one of the above [1], wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (I-1) .

[6] The curable epoxy resin composition according to any one of the above [1] to [5], wherein the alicyclic epoxy compound (A) and the isomeric cyanuric acid monoallyl condensed water are used. The total amount (100% by weight) of the glyceride compound (B) and the amount (content) of the alicyclic epoxy compound (A) are from 30 to 95% by weight (preferably from 35 to 95% by weight, more preferably 40) ~95% by weight).

[7] The curable epoxy resin composition according to any one of the above [1] to [6] further comprising an alicyclic epoxy compound other than the alicyclic epoxy compound (A) (hereinafter also It is called "other alicyclic epoxy compounds").

[8] The curable epoxy resin composition according to [7] above, wherein the other alicyclic epoxy compound is selected from the group consisting of (i) having two carbon atoms and oxygen atoms adjacent to each other to constitute an alicyclic ring. a compound constituting an epoxy group (also referred to as "alicyclic epoxy group") (except for the alicyclic epoxy compound (A)) and (ii) a compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond At least one of the groups.

[9] The curable epoxy resin composition according to the above [8], wherein (i) the compound having an alicyclic epoxy group is an alicyclic epoxy compound represented by the following formula (II);

In the formula (II), X represents a linking group (having a divalent group of one or more atoms)].

[10] The curable epoxy resin composition according to [9] above, wherein the other alicyclic epoxy compound is 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane Alkyl carboxylate.

[11] The curable epoxy resin composition according to any one of the above [7] to [10], wherein the total amount of the alicyclic epoxy compound and the alicyclic epoxy compound (A) is relative to (100% by weight), the amount (content) of the other alicyclic epoxy compound is from 1 to 50% by weight (preferably from 5 to 40% by weight, more preferably from 5 to 30% by weight, particularly preferably from 5 to 5% by weight) 20% by weight).

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

[13] The curable epoxy resin composition according to any one of [1] to [12] above which is liquid at 25 °C.

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

[15] The curable epoxy resin composition according to any one of [1] to [14] wherein the white pigment (C) is selected from the group consisting of alumina, magnesia, cerium oxide, titanium oxide, and zirconia. One or more (preferably titanium oxide) of the group of cerium oxide and inorganic hollow particles.

[16] The curable epoxy resin composition according to any one of [1] to [15] wherein the white pigment (C) has a central particle diameter of 0.1 to 50 μm (preferably 0.1 to 30 μm, more preferably It is 0.1 to 20 μm, particularly preferably 0.1 to 10 μm, and most preferably 0.1 to 5 μm).

[17] The curable epoxy resin composition according to any one of the above [1], wherein the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition (all) 100 parts by weight of the epoxy group-containing compound and the white pigment (C) are used in an amount of 80 to 500 parts by weight (preferably 90 to 400 parts by weight, more preferably 100 to 380 parts by weight).

[18] The curable epoxy resin composition according to any one of the above [1], wherein the hardener (D) is an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid. (Also includes a substituent in which an alkyl group or the like is bonded to the ring).

[19] The curable epoxy resin composition according to any one of the above [1], wherein the curable epoxy resin composition has a ring The total amount (100 parts by weight) of the compound of the oxy group and the amount (content) of the curing agent (D) are 50 to 200 parts by weight (preferably 80 to 145 parts by weight).

[20] The curable epoxy resin composition according to any one of the above [1], wherein the curable epoxy resin composition has a ring The total amount (100 parts by weight) of the compound of the oxy group and the amount (content) of the curing accelerator (F) are 0.05 to 5 parts by weight (preferably 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, particularly Good is 0.25~2.5 parts by weight).

[21] The curable epoxy resin composition according to any one of the above [3], wherein the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition is 100%. The amount (content) of the hardening catalyst (E) is 0.01 to 15 parts by weight (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) .

[22] The curable epoxy resin composition according to any one of the above [1], which further comprises two or more (preferably two to four) epoxy groups in the molecule. A halogen derivative (G).

[23] The curable epoxy resin composition according to the above [22], wherein the oxoxane derivative (G) having two or more epoxy groups in the molecule is selected from the group consisting of two or more molecules included in the molecule. At least one of a group of an epoxy group-containing cyclic siloxane and a linear polyoxyl group having two or more epoxy groups in the molecule (preferably having two or more epoxies in the molecule) Base cyclic oxane).

[24] The curable epoxy resin composition according to the above [23], wherein the number of Si-O units forming the cyclic siloxane is 2 to 12 (preferably 4 to 8).

[25] The curable epoxy resin composition according to any one of the above [22], wherein the weight average of the oxoxane derivative (G) having two or more epoxy groups in the molecule The molecular weight is from 100 to 3,000 (preferably from 180 to 2,000).

[26] The curable epoxy resin composition according to any one of the above [22], wherein the epoxy group of the oxoxane derivative (G) having two or more epoxy groups in the molecule The equivalent (according to JIS K7236) is 180 to 400 (preferably 240 to 400, more preferably 240 to 350).

[27] The curable epoxy resin composition according to any one of the above [22], wherein the ring of the oxoxane derivative (G) having two or more epoxy groups in the molecule The oxy group is an alicyclic epoxy group (preferably an epoxycyclohexane group).

[28] The curable epoxy resin composition according to any one of the above [22], wherein the oxoxane derivative (G) having two or more epoxy groups in the molecule is selected from the group consisting of At least one of the group of cyclic oxiranes having two or more epoxy groups in one molecule represented by the following formulas (S-1) to (S-7) is contained.

[29] The curable epoxy resin composition according to any one of the above [22], wherein the total amount of the component (A), the component (B), and the component (G) is 100% by weight. The amount (content) of the decane derivative (G) having two or more epoxy groups in the molecule is 5 to 90% by weight (preferably 5 to 85% by weight, more preferably 5 to 80%) % by weight, particularly preferably 8 to 75% by weight).

[30] The curable epoxy resin composition according to any one of the above [22] to [29] wherein the fat is relative to the total amount (100% by weight) of the epoxy group-containing compound (epoxy resin) The total amount of the cyclic epoxy compound (A), the isomeric cyanuric acid monoallyl diglycidyl ester compound (B), and the oxoxane derivative (G) having two or more epoxy groups in the molecule It is 30 to 100% by weight (preferably 40 to 100% by weight).

[31] The curable epoxy resin composition according to any one of [1] to [30] further comprising an alicyclic polyester resin (H).

[32] The curable epoxy resin composition according to the above [31], wherein the alicyclic polyester resin (H) is an alicyclic polyester resin having an alicyclic ring in the main chain.

[33] The curable epoxy resin composition according to the above [31], wherein the alicyclic polyester resin (H) contains at least one of the following formulas (2) to (4). An alicyclic polyester resin constituting the unit;

(wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched carbon number; 1 to 4 alkyl groups, two selected from R ⁴ to R ⁷ may also be bonded to form a ring);

(wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched carbon number; 1 to 4 alkyl groups, two selected from R ⁴ to R ⁷ may also be bonded to form a ring);

(wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched carbon number; The alkyl group of 1 to 4 may also form a ring formed by two bonds selected from R ⁴ to R ⁷ ).

The curable epoxy resin composition according to any one of the above aspects, wherein the alicyclic polyester resin (H) contains at least one of the following formulas (5) and (6). The alicyclic polyester resin constituting the unit shown.

[35] The curable epoxy resin composition according to any one of [31] to [34] wherein the alicyclic polyester resin (H) has a number average molecular weight of 300 to 100,000 (preferably 300~). 30000).

[36] The curable epoxy resin composition according to any one of the above [31] to [35] wherein, when the hardener (D) is used as an essential component, the alicyclic polyester resin (H) is used. The blending amount (content) of the alicyclic polyester resin (H) is from 1 to 60% by weight (preferably from 5 to 30% by weight) based on the total amount (100% by weight) of the curing agent (D).

[37] The curable epoxy resin composition according to any one of the above [31], wherein the hardening catalyst (E) is used as an essential component with respect to the alicyclic polyester resin (H). The total amount (content) of the alicyclic polyester resin (H) is 50 to 99% by weight (preferably 65 to 99% by weight) based on the total amount (100% by weight) of the curing catalyst (E).

[38] The curable epoxy resin composition according to any one of the above [22], wherein the hardener (D) is used as an essential component, relative to the white pigment (C) and the inorganic filler. The total amount (100% by weight) of the curable epoxy resin composition other than (J), and the amount (content) of the alicyclic epoxy compound (A) used is 5 to 90% by weight (preferably 8 to 80% by weight, More preferably 8 to 75% by weight).

[39] The curable epoxy resin composition according to any one of [22] to [37], wherein the hardening catalyst (E) is used as an essential component, relative to the white pigment (C) and the inorganic filler The total amount (100% by weight) of the curable epoxy resin composition other than the agent (J), and the amount (content) of the alicyclic epoxy compound (A) used is 10 to 95% by weight (preferably 15 to 85% by weight) More preferably, it is 20 to 75% by weight).

[40] The curable epoxy resin composition according to any one of the above [1] to [39] further comprising rubber particles other than the polyoxyethylene rubber particles.

[41] The curable epoxy resin composition according to the above [40], wherein the rubber particles other than the polyoxyxylene rubber particles are composed of a polymer having (meth) acrylate as a necessary monomer component. The surface has a hydroxyl group and/or a carboxyl group, and has an average particle diameter of 10 to 500 nm (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], wherein the rubber particles other than the polyoxyxylene rubber particles are rubber particles having a core-shell structure.

[43] The curable epoxy resin composition according to any one of the above [40], wherein the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition is 100%. The content (mixing amount) of the rubber particles other than the polyoxyethylene rubber particles is 0.5 to 30 parts by weight (preferably 1 to 20 parts by weight).

The curable epoxy resin composition according to any one of the above aspects, further comprising at least one selected from the group consisting of a polyfluorene-based leveling agent and a fluorine-based leveling agent. 1 leveling agent.

[45] The curable epoxy resin composition according to the above [44], wherein the above-mentioned leveling agent is the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. The content of the nonvolatile matter (dosage amount) is 0.1 to 10 parts by weight (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 [1] to [45] further comprising a polyol compound.

[47] The curable epoxy resin composition according to [46] above, wherein the polyol compound is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, phenoxy resins, and bisphenols. At least one of a group of a molecular epoxy resin, a polybutadiene having a hydroxyl group, and an acrylic polyol.

[48] The curable epoxy resin composition according to the above [46] or [47] wherein the polyol compound has a number average molecular weight of from 200 to 100,000 (preferably from 300 to 50,000, more preferably from 400 to 40,000).

[49] The curable epoxy resin composition according to any one of the above [46], wherein the polyol compound is a total amount (100 parts by weight) based on the total amount of the component (A) and the component (B). The amount (content) used is 1 to 50 parts by weight (preferably 1.5 to 40 parts by weight, more preferably 5 to 30 parts by weight).

[50] The curable epoxy resin composition according to any one of the above [4], wherein the curable epoxy resin composition contains oxygen having two or more epoxy groups in the molecule. In the case of the alkane derivative (G), the amount (content) of the polyol compound is from 1 to 50 parts by weight based on the total amount (100 parts by weight) of the component (A), the component (B) and the component (G). It is preferably 1.5 to 40 parts by weight, more preferably 5 to 30 parts by weight.

[51] The curable epoxy resin composition according to any one of [1] to [50] further comprising an acrylic block copolymer.

[52] The curable epoxy resin composition according to the above [51], wherein the acrylic block copolymer is preferably a polymer block [S] (soft block) having a low glass transition temperature (Tg) and having a Tg A block copolymer in which polymer blocks [H] (hard blocks) are alternately arranged higher than the polymer block [S].

[53] The curable epoxy resin composition according to the above [52], wherein the acrylic block copolymer has a polymer block [S] in the middle, and has a polymer block [H] at both ends thereof. Structured triblock copolymer.

[54] The curable epoxy resin composition according to any one of [51] to [53] wherein the acrylic block copolymer has a number average molecular weight of from 3,000 to 500,000 (preferably from 30,000 to 400,000).

[55] The curable epoxy resin composition according to any one of the above [51], wherein the acrylic block is a total amount (100 parts by weight) based on the total amount of the component (A) and the component (B). The amount (content) of the copolymer used is 1 to 30 parts by weight (preferably 3 to 15 parts by weight, more preferably 3 to 10 parts by weight).

The curable epoxy resin composition according to any one of the above aspects, wherein the curable epoxy resin composition contains oxygen having two or more epoxy groups in the molecule. In the case of the alkane derivative (G), the amount (content) of the acrylic block copolymer is from 1 to 30 parts by weight based on the total amount (100 parts by weight) of the component (A), the component (B) and the component (G). (preferably 3 to 15 parts by weight, more preferably 3 to 10 parts by weight).

[57] The curable epoxy resin composition according to any one of [1] to [5], further comprising a stress relaxation agent (I).

[58] The curable epoxy resin composition according to the above [57], wherein the stress relieving agent (I) is selected from the group consisting of polyfluorene oxide rubber particles (I1), polyoxygenated oil (I2), and liquid rubber component. At least one of the group of (I3) and the thermoplastic resin (I4) (preferably at least one selected from the group consisting of polyoxyxylene rubber particles (I1) and polyoxygenated oil (I2)).

[59] The curable epoxy resin composition according to the above [58], wherein the polyfluorene oxide rubber particles (I1) are crosslinked polydimethyloxane having a polyfluorene resin on its surface.

[60] The curable epoxy resin composition according to the above [58] or [59] wherein the polyoxyn rubber particles (I1) have an average particle diameter (d ₅₀ ) of 0.1 to 100 μm (preferably 0.5 to 50 μm). The maximum particle size is 0.1 to 250 μm (preferably 0.1 to 150 μm).

[61] The curable epoxy resin composition according to any one of [58], wherein the polyfluorene oxide (I2) is an epoxy equivalent of from 3,000 to 15,000 (preferably from 4,000 to 15,000). More preferably, it is a 5,000 to 13,000) polyalkylene ether modified polyoxime compound having a structure represented by the following formula (10);

[wherein, xa is an integer of 80 to 140, ya is an integer of 1 to 5, za is an integer of 5 to 20; and R ²⁶ is an alkylene group having 2 or 3 carbon atoms (preferably a methylmethylene group, a dimethylmethylene group, an ethylidene group, a propylidene group, a trimethylene group, more preferably a trimethylene group; and 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; and B is a hydrogen atom or a methyl group (preferably a methyl group))].

[62] The curable epoxy resin composition according to [61] above, wherein a total of a and b is an integer of from 1 to 80.

[6] The curable epoxy resin composition according to any one of the above [57], wherein the content of the stress relieving agent (I) is 100 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A). The blending amount is 1 to 250 parts by weight (preferably 5 to 230 parts by weight, more preferably 10 to 200 parts by weight).

[64] The curable epoxy resin composition according to any one of the above [5], wherein the total amount of the compound having an epoxy group contained in the curable epoxy resin composition is 100% by weight. The content (mixing amount) of the stress relieving agent (I) is 1 to 200 parts by weight (preferably 5 to 150 parts by weight, more preferably 8 to 120 parts by weight).

[65] The curable epoxy resin composition according to any one of [1] to [64] further comprising an inorganic filler (J).

[66] The curable epoxy resin composition according to [65] above, wherein the inorganic filler (J) is vermiculite (a vermiculite filler).

[67] The curable epoxy resin composition according to [66] above, wherein the vermiculite has a center particle diameter of 0.1 to 50 μm (preferably 0.1 to 30 μm).

[68] The curable epoxy resin composition according to any one of the above [65], wherein the content of the inorganic filler (J) is relative to the curable epoxy resin composition (100% by weight). The blending amount is 10 to 90% by weight (preferably 13 to 75% by weight, more preferably 15 to 70% by weight, still more preferably 20 to 70% by weight).

[69] The curable epoxy resin composition according to any one of the above [65], wherein the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition is 100% by weight. The content (mixing amount) of the inorganic filler (J) is 10 to 1500 parts by weight (preferably 50 to 1200 parts by weight, more preferably 100 to 1000 parts by weight).

[70] The curable epoxy resin composition according to any one of the above [65], wherein the white pigment (C) and the inorganic filler (J) have a maximum particle diameter of 200 μm or less (preferably 185 μm or less, more preferably 175 μm or less, particularly preferably 150 μm or less, and 0.01 μm or more.

[71] The curable epoxy resin composition according to any one of [1] to [70] which is a resin composition for compression molding.

[72] A cured product of the curable epoxy resin composition according to any one of the above [1] to [71].

[73] The cured product according to [72] above, wherein the cured product has a reflectance of light of a wavelength of 450 nm of 90% or more (preferably 90.5% or more).

[74] The cured product according to [72] or [73] above, wherein the reflectance of light having a wavelength of 450 nm after heating at 120 ° C for 250 hours (also referred to as "reflectance after heating for 250 hours" is relative to The initial reflectance retention rate ([250 hours after heat aging] / [initial reflectance] × 100) is 85% or more (preferably 90% or more, more preferably 95% or more, particularly preferably 98%). the above).

[75] The cured product according to any one of the above [72] to [74], which has a reflectance of light having a wavelength of 450 nm after heating at 120 ° C for 500 hours (also referred to as "reflectance after 500 hours of heat aging" The retention ratio with respect to the initial reflectance ([reflectance after 500 hours of heat aging] / [initial reflectance] × 100) is 85% or more (preferably 90% or more, more preferably 95% or more). Good is 98% or more).

[76] The cured product according to any one of the above [72] to [75], which has a reflectance to light of a wavelength of 450 nm after ultraviolet light having an irradiation intensity of 10 mW/cm ² for 250 hours (also referred to as "ultraviolet aging" The retention ratio of the subsequent reflectance ") to the initial reflectance ([reflectance after ultraviolet aging] / [initial reflectance] × 100) is 90% or more (preferably 95% or more, more preferably 98% or more). ).

[77] A curable resin composition for light reflection, comprising 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 formed of the cured product according to any one of the above [72] to [76].

Industrial utilization possibility

The curable epoxy resin composition of the present invention can be preferably used as an LED package (a constituent material of an LED package, such as a reflector material or an outer casing material in an optical semiconductor device), an adhesive use of an electronic component, or a liquid crystal display. (for example, a reflector, etc.), an ink for a white substrate, a sealant, or the like.

Claims (19)

A curable epoxy resin composition comprising an alicyclic epoxy compound (A) represented by the following formula (I) and an isomeric cyanuric monoallyl group represented by the following formula (1) a diglycidyl ester compound (B), a white pigment (C), a hardener (D), and a hardening accelerator (F), ^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 , ^R17a and ^R18a are the same or different and represent 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]; [wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. A curable epoxy resin composition comprising an alicyclic epoxy compound (A) represented by the alicyclic epoxy compound (A) represented by the following formula (I), and the following formula (1) The isomeric cyanuric acid monoallyl diglycidyl ester compound (B), white pigment (C) and hardening catalyst (E), ^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 , ^R17a and ^R18a 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], [wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. The curable epoxy resin composition according to claim 1 or 2, wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (I-1),  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, which further comprises a oxoxane 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, which further comprises an alicyclic polyester resin (H).    The curable epoxy resin composition of claim 6, wherein the alicyclic polyester resin (H) is an alicyclic polyester resin having an alicyclic ring in the main chain.    The curable epoxy resin composition according to any one of claims 1 to 7, which further comprises rubber particles other than the polyoxyethylene rubber particles.    The curable epoxy resin composition according to any one of claims 1 to 8, which further comprises at least one leveling agent selected from the group consisting of a polyfluorene-based leveling agent and a fluorine-based leveling agent.    The curable epoxy resin composition according to any one of claims 1 to 9, which further comprises a polyol compound.    The curable epoxy resin composition according to any one of claims 1 to 10, which further comprises an acrylic block copolymer.    The curable epoxy resin composition according to any one of claims 1 to 11, which further comprises a stress relieving agent (I).    The curable epoxy resin composition according to claim 12, wherein the stress relieving agent (I) is at least one selected from the group consisting of polyoxyxylene rubber particles (I1) and polyoxygenated oil (I2).    The curable epoxy resin composition according to claim 13, wherein the polyoxyxylene rubber particles (I1) are crosslinked polydimethyloxane having a polyoxyxylene resin on its surface.   The curable epoxy resin composition according to claim 13 or 14, wherein the polyoxyalkylene oil (I2) is an epoxy equivalent having a structure represented by the following formula (10) in an epoxy equivalent of from 3,000 to 15,000. Polyoxygenated compound; [wherein, xa is an integer of 80 to 140, ya is an integer of 1 to 5, za is an integer of 5 to 20; R ²⁶ is an alkylene group having 2 or 3 carbon atoms; and A has the following formula (10a) a polyalkylene ether group of the structure shown; (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, which further comprises an inorganic filler (J).    A cured product which is 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, which comprises the curable epoxy resin composition according to any one of claims 1 to 16.    An optical semiconductor device comprising a reflector formed of at least an optical semiconductor element and a cured product of a curable resin composition for light reflection according to claim 18.