TW201739817A - Curing resin composition for light reflection and cured product thereof, and optical semiconductor device - Google Patents

Abstract

The present invention provides a curable resin composition for light reflection, which is capable of forming a cured product which has high light reflectivity, is excellent in heat resistance and light resistance, and is difficult to reduce light reflectance over time, especially by compression. When the molded product is formed into a cured product, the above effects are remarkably exhibited. The curable resin composition for light reflection is characterized by containing an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), and one or more rings in the molecule. The isomeric cyanuric acid derivative (H) of the oxyethylene ring and the oxoxane derivative (I) having two or more epoxy groups in the molecule, further containing a curing agent (E) and hardening promotion The agent (F) or the hardening catalyst (G) is liquid at 25 °C.

Description

Curing resin composition for light reflection and cured product thereof, and optical semiconductor device

The present invention relates to a curable resin composition for light reflection and a cured product thereof, and an optical semiconductor device having a reflector and an optical semiconductor element formed of the cured product. The present application claims priority from Japanese Patent Application No. 2016-025329, filed on Jan.

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 developed using light-emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources. . As such an optical semiconductor device, an optical semiconductor device is generally mounted on a substrate (an optical semiconductor element mounting substrate), and an optical semiconductor device in which the optical semiconductor device is sealed by a transparent sealing material is widely used. On the substrate of such an optical semiconductor device, a member (reflector) for reflecting light is formed in order to improve light extraction efficiency from the optical semiconductor element.

For the above reflector, high light reflectivity is required. In the past, as a constituent material of the reflector, for example, a resin composition such as an inorganic filler in which a polydecylamine resin (polyphthalamide resin) containing a terephthalic acid unit as a constituent unit is dispersed is known. (Refer to Patent Documents 1 to 3).

In addition, as a constituent material of the reflector, for example, 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 (see Patent Document 4). In addition, for example, a thermosetting resin composition for light reflection containing a thermosetting resin component and one or more kinds of filler components, and a refractive index of the entire thermosetting resin component and a refractive index of each filler component are known. The difference between the rate and the parameter calculated from the volume ratio of each filler component is controlled within a specific range (see Patent Document 5).

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

The reflector produced by the materials described in the above Patent Documents 1 to 5 is an optical semiconductor device using a high-output blue light semiconductor or a white light semiconductor as a light source due to light or heat emitted from a semiconductor element. The deterioration of the yellowing or the like is caused as time passes, and the light reflectivity is lowered as time passes. Furthermore, with the adoption of lead-free solder, there is a tendency that the heating temperature in the reflow step (solder reflow step) at the time of manufacture of the light-emitting device becomes high, and also due to the application in such a process The heat is also degraded as the above-mentioned reflector deteriorates over time, and the light reflectivity is lowered.

Therefore, the current state of the art requires a material that is excellent in heat resistance and light resistance, which is difficult to reduce light over time, even for light of higher output, shorter wavelength, or high temperature.

Further, the 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. difference.

Therefore, an object of the present invention is to provide a curable resin composition for light reflection which can form a cured product which has high light reflectivity, is excellent in heat resistance and light resistance, and is difficult to reduce light reflectance with time. In particular, when the cured product is formed by compression molding, the above effects are remarkably exhibited.

Further, another object of the present invention is to provide a cured product which is excellent in productivity, has high light reflectivity, is excellent in heat resistance and light resistance, and is difficult to reduce light reflectivity with passage of time.

Furthermore, another object of the present invention is to provide an optical semiconductor device in which the luminance of light is hard to be lowered over time and the reliability is high.

Further, in the case of the above-mentioned reflector, when stress is applied due to cutting processing or temperature change (for example, heating at a very high temperature such as a reflow step, or low-temperature cycle, etc.), cracking (cracking) is required to occur (this is also true). The characteristics are called "crack resistance" and so on. This is because if it is in the opposite When the emitter is cracked, 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 order to solve the above problems, the inventors of the present invention have intensively reviewed and found that the alicyclic epoxy compound (A), the rubber particles (B), the white pigment (C), the inorganic filler (D), and the hardener (E) are contained. And a hardening accelerator (F), an isocyanuric acid derivative (H) having one or more oxirane rings in the molecule, and a decyl alkane derivative having two or more epoxy groups in the molecule. (I), which is a liquid light-reflecting curable resin composition at 25 ° C, or an alicyclic epoxy compound (A), rubber particles (B), white pigment (C), and inorganic filler (D) ), a curing catalyst (G), an isocyanuric acid derivative (H) having one or more oxirane rings in the molecule, and a decaxane derivative having two or more epoxy groups in the molecule. The material (I) is a curable resin composition for light reflection which is liquid at 25 ° C, and is excellent in light reflectivity, heat resistance and light resistance, and it is difficult to reduce light reflectance with time. The cured product remarkably exerts the above effects particularly when a cured product is formed by compression molding. The present invention has been completed on the basis of such knowledge and knowledge.

That is, the present invention provides a curable resin composition for light reflection, which comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), and a molecule. An isomeric cyanuric acid derivative (H) having one or more oxirane rings and a fluorinated alkane derivative (I) having two or more epoxy groups in the molecule, and further containing a curing agent ( E), and a hardening accelerator (F), or a hardening catalyst (G), and is liquid at 25 °C.

Furthermore, the present invention provides a curable resin composition for light reflection, wherein the rubber particles (B) are composed of a polymer having (meth) acrylate as an essential monomer component and having a hydroxyl group and/or a carboxyl group on the surface. The rubber particles (B) have an average particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm.

Furthermore, the present invention provides a curable resin composition for light reflection, wherein the alicyclic epoxy compound (A) comprises a compound represented by the following formula (I-1);

Moreover, the present invention provides a curable resin composition for light reflection, wherein the isomeric cyanuric acid derivative (H) is a compound represented by the following formula (III-1);

In the formula (III-1), R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Furthermore, the present invention provides a curable resin composition for light reflection, wherein the white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate, and the inorganic filler is used. The agent (D) is at least one selected from the group consisting of vermiculite, alumina, tantalum nitride, aluminum nitride, and boron nitride.

Furthermore, the present invention provides the above-mentioned curable resin composition for light reflection, which is a resin composition for transfer molding or compression molding.

Moreover, the present invention provides the above-mentioned curable resin composition for light reflection, which is a resin composition for forming a reflector.

Moreover, the present invention provides a cured product which is a cured product of the curable resin composition for light reflection.

Further, an optical semiconductor device according to the present invention is characterized in that it includes at least an optical semiconductor element and a reflector formed of the cured product.

That is, the present invention relates to the following.

[1] A curable resin composition for light reflection, which comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), and has a molecule One or more isomeric cyanuric acid derivatives of the oxirane ring (H) and a oxoxane derivative (I) having two or more epoxy groups in the molecule, and further containing a curing agent (E) And a hardening accelerator (F) or a hardening catalyst (G), and it is liquid at 25 °C.

[2] The curable resin composition for light reflection according to [1], wherein the rubber particles (B) have rubber particles having a multilayer structure including a core portion having rubber elasticity and covering the core portion. At least 1 layer of shell.

[3] The curable resin composition for light reflection according to [1], wherein the rubber particles (B) are composed of a polymer having (meth) acrylate as an essential monomer component.

[4] The curable resin composition for light reflection according to any one of [2], wherein a polymer constituting a rubber-elastic core portion of the rubber particles (B) is used as a monomer component. The (meth) acrylate and one or a combination of two or more selected from the group consisting of an aromatic vinyl group, a nitrile, and a conjugated diene are contained.

[5] The curable resin composition for light reflection according to any one of [2], wherein the polymer constituting the shell layer of the rubber particles (B) is contained as a monomer component. One or a combination of two or more selected from the group consisting of acrylates and monomers selected from the group consisting of hydroxyl group-containing monomers and carboxyl group-containing monomers.

[6] The curable resin composition for light reflection according to any one of [1], wherein the rubber particles (B) have a hydroxyl group and/or a carboxyl group on the surface.

[7] The curable resin composition for light reflection according to any one of [1], wherein the rubber particles (B) have an average particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm.

The curable resin composition for light reflection according to any one of the above aspects, wherein the alicyclic epoxy compound (A) contains a compound represented by the formula (I) described later.

The epoxidized resin composition for light reflection according to any one of the above aspects, wherein the alicyclic epoxy compound (A) contains a compound represented by the formula (I-1) described later. .

[10] The curable resin composition for light reflection according to any one of [1], wherein the isomeric cyanuric acid derivative (H) is a compound represented by the formula (III) described later.

The hardenable resin composition for light reflection according to any one of the above aspects, wherein the isocyanuric acid derivative (H) is represented by the formula (III-1) described later. Compound.

[12] The curable resin composition for light reflection according to any one of [1], wherein the azide derivative (I) is a ring having two or more epoxy groups in a molecule. A halogenated alkane and/or a linear polyfluorene having two or more epoxy groups in a molecule.

[13] The curable resin composition for light reflection according to any one of the above aspects, wherein the white pigment (C) is selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate. At least one of the groups.

[14] The curable resin composition for light reflection according to any one of [1], wherein the inorganic filler (D) is selected from the group consisting of vermiculite, alumina, tantalum nitride, and nitriding. At least one of a group of aluminum and boron nitride.

[15] The curable resin composition for light reflection according to any one of [1], wherein the oxoxane derivative (I) is a oxoxane compound represented by the formula (IV) described later. .

[16] The curable resin composition for light reflection according to any one of [1] to [15], wherein the alicyclic epoxy compound (A) is used for the curable resin composition (100% by weight) The content (mixing amount) is 0.1 to 60% by weight, 0.3 to 50% by weight or 0.5 to 40% by weight.

[17] The curable resin composition for light reflection according to any one of the above-mentioned [1], wherein the content of the rubber particles (B) is blended with respect to the curable resin composition (100% by weight). The combined amount is 0.01 to 20% by weight, 0.05 to 15% by weight or 0.1 to 10% by weight.

[18] The curable resin composition for light reflection according to any one of [1] to [17], wherein the content of the white pigment (C) is blended with respect to the curable resin composition (100% by weight). The combined amount is 0.1 to 50% by weight, 1 to 40% by weight, or 5 to 35% by weight.

[19] The curable resin composition for light reflection according to any one of [1] to [18], wherein the content of the inorganic filler (D) is relative to the curable resin composition (100% by weight) ( The blending amount is 10 to 90% by weight, 13 to 75% by weight, 15 to 70% by weight or 20 to 70% by weight.

[20] The curable resin composition for light reflection according to any one of [1] to [19], wherein the content of the hardener (E) is blended with respect to the curable resin composition (100% by weight). The combined amount is 1 to 40% by weight, 3 to 35% by weight, or 5 to 30% by weight.

[21] The curable resin composition for light reflection according to any one of [1] to [20] wherein the curing accelerator (F) is present in the curable resin composition (100% by weight) ( The blending amount is 0.0001 to 5% by weight or 0.001 to 1% by weight.

[22] The curable resin composition for light reflection according to any one of [1] to [21], wherein the content of the curing catalyst (G) is (relative to the curable resin composition (100% by weight)) ( The blending amount is 0.0001 to 5% by weight or 0.001 to 1% by weight.

[23] The curable resin composition for light reflection according to any one of [1], wherein the isomeric cyanuric acid derivative (H) is used for the curable resin composition (100% by weight). The content (mixing amount) is 0.05 to 15% by weight, 0.1 to 10% by weight or 0.3 to 5% by weight.

[24] The curable resin composition for light reflection according to any one of [1] to [23] wherein the aerobic derivative (I) is the same as the curable resin composition (100% by weight) The content (mixing amount) is 0.1 to 30% by weight, 0.5 to 20% by weight or 1.0 to 10% by weight.

[25] The curable resin composition for light reflection according to any one of [1] to [24], which is a resin composition for transfer molding or compression molding.

[26] The curable resin composition for light reflection according to any one of [1] to [25], which is a resin composition for forming a reflector.

[27] A cured product of the curable resin composition for light reflection according to any one of [1] to [26].

[28] An optical semiconductor device comprising at least an optical semiconductor element and a reflector formed of a cured product of the curable resin composition for light reflection according to [27].

The curable resin composition of the present invention has the above-described configuration, and can form a cured product having high light reflectivity, excellent heat resistance and light resistance, and difficulty in reducing light reflectivity with time, especially by compression. When the molded product is formed into a cured product, the above effects are remarkably exhibited. Therefore, it is possible to provide an optical semiconductor device in which the luminance of light is hard to be lowered with time and the reliability is high.

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 <The curable resin composition for light reflection>

The curable resin composition for light reflection of the present invention (also referred to as "the curable resin composition of the present invention") is characterized by containing an alicyclic epoxy compound (A), rubber particles (B), and white pigment (C). ), an inorganic filler (D), an iso-cyanuric acid derivative (H) having one or more oxirane rings in the molecule, and an anthracene having two or more epoxy groups in the molecule. The derivative (I) further contains a curing agent (E), a curing accelerator (F), or a curing catalyst (G), and is a liquid curable resin composition at 25 ° C. In addition, the isomeric cyanuric acid derivative (H) having one or more oxirane rings in the molecule is also referred to as "isomeric cyanuric acid derivative (H)". Further, the fluorinated alkane derivative (I) having two or more epoxy groups in the molecule is also referred to as "a siloxane derivative (I)".

In other words, the curable resin composition of the present invention contains an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a hardener (E), and a hardening accelerator. (F), an isomeric cyanuric acid derivative (H), and a decyl alkane derivative (I) as essential components at 25 °C is a liquid curable resin composition for light reflection, or contains an alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), and hardening catalyst (G). A curable resin composition which is a liquid at 25 ° C as an essential component of the isocyanuric acid derivative (H) and the decyl alkane derivative (I). Further, the curable resin composition of the present invention may contain other components as needed in addition to the above-mentioned essential components. Further, the curable resin composition of the present invention can be used as a thermosetting composition (thermosetting epoxy resin composition) which can be cured by heating.

In the present specification, the term "curable resin composition for light reflection" means a curable resin composition capable of forming a cured product having light reflectivity. Specifically, for example, it means a curable resin composition capable of forming a cured product having a reflectance of 50% or more (preferably 80% or more, more preferably 90% or more) with respect to light having a wavelength of 450 nm.

The curable resin composition of the present invention tends to be suitable for compression molding because it is liquid at 25 ° C, and the cured product (reflector) has excellent 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. The conditions were measured.

The curable 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 hardener (E), and a hardening promotion. Agent (F), It becomes easy to obtain by hardening the catalyst (G) or the like. In addition, 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 resin composition of the present invention becomes liquid at 25 ° C. Further, it is also possible to easily obtain the content of the component which is solid at 25 ° C, such as rubber particles (B), white pigment (C), inorganic filler (D), etc., within the range which does not impair the effects of the present invention. .

[Cycloaliphatic epoxy compound (A)]

An alicyclic epoxy compound (alicyclic epoxy resin) (A) which is an essential component of the curable resin composition of the present invention, has at least an alicyclic ring (aliphatic hydrocarbon ring) in a molecule (in one molecule) As the compound having a structure and an epoxy group (oxiranyl group), a well-known or conventional alicyclic epoxy compound can be used. However, the alicyclic epoxy compound (A) does not include those corresponding to the isocyanuric acid derivative (H) and the decane derivative (I). Specific examples of the alicyclic epoxy compound (A) include (i) an epoxy group having an adjacent two carbon atoms and an oxygen atom constituting an alicyclic ring (alicyclic epoxy group). a compound, (ii) a compound having an epoxy group bonded directly to the alicyclic ring by a single bond.

As the compound having an alicyclic epoxy group as the above (i), a well-known or customary compound having at least one alicyclic epoxy group in the molecule can be used, and it is not particularly limited. The alicyclic epoxy group is preferably an epoxycyclohexane group from the viewpoint of curability of the curable resin composition and heat resistance and light resistance of the cured product (reflector). In particular, from the viewpoint of heat resistance and light resistance of the cured product (reflector), a compound having two or more epoxycyclohexane groups in the molecule is preferable, and the following formula (I) is more preferable. The compound shown;

In the formula (I), X represents a single bond or a linking group (having a divalent group of one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a part or all of a carbon-carbon double bond, and an epoxidized alkenyl group (also referred to as "epoxidized alkenyl group"), a carbonyl group, an ether bond, and an ester bond. And a carbonate group, a guanamine group, and a plurality of groups having such a linkage. In addition, one or more carbon atoms constituting the cyclohexane ring (epoxycyclohexane group) in the formula (I) may be bonded to a substituent such as an alkyl group.

The compound in which X in the formula (I) is a single bond may, for example, be 3,4,3',4'-dicyclooxybicyclohexane.

The divalent hydrocarbon group may, for example, be a linear or branched alkylene group having a carbon number of 1 to 18 or a divalent alicyclic hydrocarbon group. 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 a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-extended cyclohexyl group, and a 1,3-extension. a cycloalkyl group (including a cycloalkylene group) such as a cyclohexyl group, a 1,4-cyclohexylene group or a cyclohexylene group.

Examples of the alkenyl group in the epoxidized alkenyl group (epoxyalkylene group) of a part or all of the above carbon-carbon double bond include a vinyl group, a propenyl group, and a 1-butenyl group. a linear or branched alkenyl group having 2 to 8 carbon atoms, such as a 2-butenyl group, a butadienyl group, a pentenyl group, a hexenylene group, a heptenyl group, and an octenyl group. Wait. In particular, as above The epoxidized alkenyl group is preferably an epoxidized alkenyl group of a carbon-carbon double bond, more preferably an epoxidized carbon 2 to 4 alkenyl group having a carbon-carbon double bond.

The linking group in the above X is particularly preferably a linking group containing an oxygen atom, and specific examples thereof include -CO-, -O-CO-O-, -COO-, -O-, -CONH-, and epoxidation. An alkenyl group; a group having a plurality of such groups; and a group in which one or two or more of the groups are bonded to one or more of the divalent hydrocarbon groups. The divalent hydrocarbon group is exemplified above.

Representative examples of the compound represented by the above formula (I) include a compound represented by the following formula (I-1) to (I-10), and a 2,2-bis(3,4-epoxy ring). Hexyl-1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 1,2-epoxy-1,2-bis (3,4 -Epoxycyclohexane-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl)ether, and the like. Further, l and m in the following (I-5) and (I-7) each represent an integer of 1 to 30. In the following formula (I-5), R is an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an exoethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. a linear or branched alkylene group having a secondary butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. Among these, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylidene group, a propyl group or an extended isopropyl group is preferable. Each of n1 to n6 in the following formulas (I-9) and (I-10) represents an integer of 1 to 30.

(ii) The compound which has a cyclooxy group which is directly bonded to the alicyclic ring by a single bond, and the compound (epoxy resin) represented by the following formula (II), etc. are mentioned, for example.

In the above formula (II), R ¹ represents a p-valent organic group. p represents an integer from 1 to 20. The p-valent organic group may, for example, be a p-valent organic group having a structure in which p hydroxyl groups are removed from a structural formula of an organic compound having p hydroxyl groups, which will be described later.

In the formula (II), q represents an integer of 1 to 50. Further, when p is an integer of 2 or more, the plural q systems may be the same or different. The sum (sum) of q of the formula (II) is an integer of from 3 to 100.

In the formula (II), the substituent on the cyclohexane ring represented by the formula R ² represents any one of the groups represented by the following formulas (IIa) to (IIc). The binding position of R ² on the above cyclohexane ring is not particularly limited, but is usually 4 positions when the position of two carbon atoms of the cyclohexane ring bonded to the oxygen atom is 1 or 2 positions. Or a carbon atom of 5 digits. Further, when the compound represented by the formula (II) has a plurality of cyclohexane rings, the binding positions of R ² in the respective cyclohexane rings may be the same or different. At least one of R ² in the formula (II) is a group (epoxy group) represented by the formula (IIa). Further, when the compound represented by the formula (II) has two or more R ² groups, the plural R ² groups may be the same or different.

-CH=CH ₂ (IIb)

In the formula (IIc), R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, a hexyl group, an octyl group, and a 2- A linear or branched alkyl group having 1 to 20 carbon atoms such as an ethylhexyl group. Examples of the alkylcarbonyl group include a methylcarbonyl group (ethylidene group), an ethylcarbonyl group, a n-propylcarbonyl group, an isopropylcarbonyl group, a n-butylcarbonyl group, an isobutylcarbonyl group, a secondary butylcarbonyl group, and the like. A linear or branched alkylcarbonyl group having 1 to 20 carbon atoms such as a butylcarbonyl group. The arylcarbonyl group may, for example, be an arylcarbonyl group having 6 to 20 carbon atoms such as a phenylcarbonyl group (benzimidyl group), a 1-naphthylcarbonyl group or a 2-naphthylcarbonyl group.

Examples of the substituent which the above-mentioned alkyl group, alkylcarbonyl group, and arylcarbonyl group may have include a substituent having a carbon number of 0 to 20 (more preferably a carbon number of 0 to 10). Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxyl group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutyl group. An alkoxy group such as an oxy group (preferably a C _1-6 alkoxy group, more preferably a C _1-4 alkoxy group); an alkenyloxy group such as an allyloxy group (preferably a C _2-6 olefin oxygen) More preferably, it is a C _2-4 alkenyloxy group; a decyloxy group (e.g., a C _1-12 decyloxy group) such as an ethoxycarbonyl group, a propenyloxy group or a (meth) acryloxy group; An alkylthio group such as a methylthio group or an ethylthio group (preferably a C _1-6 alkylthio group, more preferably a C _1-4 alkylthio group); an olefinyl group such as an allylthio group; Is a C _2-6 alkenethio group, more preferably a C _2-4 alkylthio group; a carboxyl group; an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group or a butoxycarbonyl group (more) Preferred is a C _1-6 alkoxycarbonyl group; an amine group; a mono- or dialkylamino group such as a methylamino group, an ethylamino group, a dimethylamino group or a diethylamino group (preferably a single Or a di-C _1-6 alkylamino group; an amide group such as an acetamino group or a propylamino group (preferably a C _1-11 fluorenyl group); an ethyl oxetanyl group Etc. The oxetanyl group; acetyl, propionyl and the like acyl acyl; oxo; two or more of these as necessary via a C _1-6 alkylene group and the like are bound. Further, the substituent which the arylcarbonyl group may have may further be a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylcarbonyl group.

The ratio of the group (epoxy group) represented by the formula (IIa) to the total amount of R ² (100 mol%) in the compound represented by the formula (II) is not particularly limited, but is preferably 40 mol. More than or equal to the ear (for example, 40 to 100 mol%), more preferably 60 mol% or more, and particularly preferably 80 mol% or more. When the ratio is 40 mol% or more, the heat resistance, light resistance, mechanical properties, and the like of the cured product tend to be further increased. Further, the above ratio can be calculated, for example, by ¹ H-NMR spectrum measurement or oxirane oxygen concentration measurement.

The compound represented by the formula (II) is not particularly limited, but, for example, an organic compound [R ¹ (OH) _p ] having p hydroxyl groups in the molecule can be used as a starter (ie, the compound is Hydroxyl (active hydrogen) as a starting point for ring-opening polymerization of 1,2-epoxy-4-vinylcyclohexane (3-vinyl-7-oxabicyclo[4.1.0]heptane) (cationic polymerization) And then produced by epoxidation with an oxidizing agent.

The organic compound [R ¹ (OH) _p ] having p hydroxyl groups in the molecule may, for example, be an aliphatic alcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol or octanol; Glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol , neopentyl glycol, neopentyl glycol ester, cyclohexane dimethanol, glycerin, diglycerin, polyglycerol, trimethylolpropane, neopentyl alcohol, dipentaerythritol, hydrogenated bisphenol A, hydrogenation double Polyols such as phenol F, hydrogenated bisphenol S; polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, acrylic polyol resin, styrene-allyl alcohol copolymer resin, polyester polyol, polycaprolactone Polyol, polypropylene polyol, polytetramethylene glycol, polycarbonate polyol, polybutadiene having hydroxyl group, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, etc. An oligomer or a polymer having a hydroxyl group such as a cellulose polymer.

The above 1,2-epoxy-4-vinylcyclohexane can be produced by a well-known or customary method, and is not particularly limited, but can be obtained, for example, by a dimerization reaction via butadiene. The 4-vinylcyclohexene is obtained by partial epoxidation using an oxidizing agent such as peracetic acid. Further, as the 1,2-epoxy-4-vinylcyclohexane, a commercially available product can also be used.

Further, as the oxidizing agent, a well-known or conventional oxidizing agent such as hydrogen peroxide or an organic peracid can be used, and is not particularly limited. For example, examples of the organic peracid include performic acid, peracetic acid, perbenzoic acid, and the like. Fluorine peracetic acid and the like. Among them, peracetic acid is preferable because it is industrially inexpensive and has high stability.

In addition, the above-mentioned ring-opening polymerization and epoxidation can be carried out, for example, in accordance with a conventionally known method described in JP-A-60-161973.

The standard polystyrene-equivalent weight average molecular weight of the compound represented by the formula (II) is not particularly limited, but is preferably from 300 to 100,000, more preferably from 1,000 to 10,000. When the weight average molecular weight is 300 or more, the mechanical strength, heat resistance, and light resistance of the cured product tend to be further increased. On the other hand, when the weight average molecular weight is 100,000 or less, the viscosity is not too high, and the fluidity at the time of molding tends to be low. Further, the weight average molecular weight is determined by a gel permeation chromatography (GPC) method.

The epoxy group equivalent (epoxy equivalent) of the compound represented by the formula (II) is not particularly limited, but is preferably from 50 to 1,000, more preferably from 100 to 500. When the epoxy equivalent is 50 or more, the cured product tends to be less likely to become brittle. On the other hand, when the epoxy equivalent is 1000 or less, the mechanical strength of the cured product tends to increase. Further, the epoxy equivalent is measured in accordance with JIS K7236:2001.

In the curable resin composition of the present invention, the alicyclic epoxy compound (A) may be used alone or in combination of two or more. Further, the alicyclic epoxy compound (A) can also be produced by a known or customary method. For example, a product such as "Celloxide 2021P" or "Celloxide 2081" (above, DAICEL) can be used. Sale.

The alicyclic epoxy compound (A) preferably exhibits a liquid state at normal temperature (25 ° C) from the viewpoint of workability at the time of preparation and injection molding. By. In addition, even if the alicyclic epoxy compound (A) which is a solid at normal temperature (25 ° C) is liquid after being blended, it may be contained.

In particular, the curable resin composition of the present invention preferably contains at least (i) an alicyclic epoxy group from the viewpoint of further improving light reflectivity, heat resistance and light resistance of the cured product (reflector). More preferably, the compound further comprises (ii) a compound having an epoxy group directly bonded to the alicyclic ring by a single bond.

The content (mixing amount) of the alicyclic epoxy compound (A) in the curable resin composition of the present invention is not particularly limited, but is preferably 0.1 with respect to the curable resin composition (100% by weight). ~60% by weight, more preferably 0.3 to 50% by weight, particularly preferably 0.5 to 40% by weight. When the content of the alicyclic epoxy compound (A) is 0.1% by weight or more, the heat resistance and light resistance of the cured product (reflector) tend to be further increased. On the other hand, when the content of the alicyclic epoxy compound (A) is 60% by weight or less, the heat resistance and light resistance of the cured product (reflector) are further increased, and the cured product (reflector) is reduced. The coefficient of linear expansion tends to suppress the occurrence of defects such as warpage of the lead frame in the substrate for mounting an optical semiconductor element.

When the epoxy compound other than the alicyclic epoxy compound (A) is contained, the total amount (100% by weight) of the epoxy group-containing compound contained in the curable resin composition of the present invention is an alicyclic ring. The ratio of the oxygen compound (A) is not particularly limited, but is, for example, preferably from 1 to 90% by weight, more preferably from 5 to 80% by weight, still more preferably from 10 to 70% by weight. When it is in the above range, the heat resistance and light resistance of the cured product (reflector) tend to be further increased. Furthermore, as the curable epoxy of the present invention Examples of the epoxy group-containing compound contained in the resin composition include an alicyclic epoxy compound (A), an isocyanuric acid derivative (H), and a decane derivative (I).

In addition, in the present specification, each component contained in the curable resin composition of the present invention (for example, an alicyclic epoxy compound (A), a rubber particle (B), a white pigment (C), an inorganic filler The content of (D), hardener (E), hardening accelerator (F), hardening catalyst (G), isocyanuric acid derivative (H), decane derivative (I), etc. The total amount is 100% by weight or less, and is appropriately selected from the range described.

[Rubber particles (B)]

The rubber particles (B) which are essential components of the curable resin composition of the present invention are rubber-elastic particles. The curable resin composition of the present invention is composed of rubber particles (B) and an alicyclic epoxy compound (A), a white pigment (C), an inorganic filler (D), and an isocyanuric acid derivative (H). And the oxoxane derivative (I) is used in combination, and the cured product formed is excellent in light reflectivity, heat resistance, light resistance, and crack resistance, particularly when a cured product is formed by compression molding. The tendency to exert the above effects.

Examples of the rubber particles (B) 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 (B) preferably have a core portion having rubber elasticity and at least one layer covering the core portion from the viewpoint of the effect of good dispersibility and easy improvement in toughness (improvement in crack resistance). Rubber particles of a multilayer structure (core shell structure) composed of a shell layer (hereinafter also referred to as "Core-shell rubber particles"). From the viewpoint of further improving the heat resistance and light resistance of the cured product, the rubber particles (B) are particularly preferably composed of a polymer (polymer) having (meth) acrylate as an essential monomer component, and on the surface. A rubber particle having a hydroxyl group and/or a carboxyl group (either one or both of a hydroxyl group and a carboxyl group) as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A). In other words, the rubber particles (B) are particularly preferably core-shell type rubber particles composed of a polymer (acrylic polymer) containing (meth) acrylate as an essential monomer component. In the curable resin composition of the present invention, the rubber particles (B) may be used alone or in combination of two or more.

When the rubber particles (B) are core-shell type rubber particles, the polymer system constituting the core portion having rubber elasticity is not particularly limited, but preferably contains methyl (meth)acrylate or (meth)acrylate B. A (meth) acrylate such as an ester or a butyl (meth)acrylate is a polymer of an essential monomer component. The polymer having a rubber-elastic core portion may contain, for example, an aromatic vinyl group such as styrene or α-methylstyrene; a nitrile such as acrylonitrile or methacrylonitrile; butadiene or isoprene; A conjugated diene such as a diene; an α-olefin such as ethylene, propylene or isobutylene, or the like is used as a monomer component.

Wherein the polymer constituting the core portion having rubber elasticity as the monomer component preferably contains both (meth) acrylate and a group selected from the group consisting of aromatic vinyl groups, nitriles and conjugated dienes. One or a combination of two or more. 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) Acrylate a terpolymer such as an 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 further contain divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diallyl maleate, and cyanuric acid. A reactive crosslinking monomer having two or more reactive functional groups in the molecule such as propyl ester, diallyl phthalate or butanediol diacrylate is used as another monomer component.

The core portion can be easily adjusted by a core portion comprising a binary copolymer or a terpolymer comprising (meth) acrylate and an aromatic vinyl group (especially butyl acrylate and styrene). The point of the refractive index of the shell rubber particles is preferred.

The glass transition temperature of the polymer constituting the core portion is not particularly limited, but is preferably -100 to 10 ° C, more preferably -80 to -10 ° C, still more preferably -60 to -20 ° C. When the glass transition temperature of the above polymer is within the above range, the crack resistance of the cured product tends to increase. Further, the glass transition temperature of the polymer constituting the core portion means a calculated value calculated by the following formula (see Bull. Am. Phys. Soc., 1 (3) 123 (1956)). By the following Fox's formula, a Tg of a polymer constitutes represents a glass transition temperature of the core portion (unit: K), W _i represents relative to the total amount of the monomers constituting the polymer is the weight fraction of monomer i, wherein the polymeric The object constitutes a core portion. Further, Tg _i represents the glass transition temperature (unit: K) of the homopolymer of monomer i. The following formula of Fox indicates a formula in which the polymer constituting the core is a copolymer of monomer 1, monomer 2, ..., and monomer n.

1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+W _n /Tg _n

The glass transition temperature of the above homopolymer can be a value described in various documents, and for example, the value described in "POLYMER HANDBOOK 3rd Edition" (issued by John Wiley & Sons, Inc.) can be used. Further, as for those not described in the literature, the value of the glass transition temperature measured by the DSC method of a homopolymer obtained by polymerizing a monomer by a usual method can be employed.

The core portion can be produced by a commonly used method, and can be produced, for example, by a method of polymerizing the above monomer 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.

In addition, as the rubber particles (B), when rubber particles having no core-shell structure are used, for example, rubber particles composed only of the core portion described above can be used.

The polymer constituting the shell layer of the core-shell type rubber particles is preferably a polymer (a polymer having a different monomer composition) 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). In this way, 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 resin composition containing the core-shell type rubber particles having the shell layer can be used. Gives 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 methyl (meth)acrylate, ethyl (meth)acrylate, or butyl (meth)acrylate. (Meth) acrylate as a polymer of the necessary monomer component. 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; and the like. In the core-shell type rubber particles, it is preferable that the monomer component constituting the shell layer contains both (meth) acrylate and two or more of the above monomers alone or in combination, and particularly includes at least an aromatic vinyl group. It is preferable that the refractive index of the core-shell type rubber particles can be easily adjusted.

Further, in order to form a hydroxyl group and/or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A), the polymer constituting the shell layer preferably contains a hydroxyl group-containing compound. a monomer (for example, a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate) or a carboxyl group-containing monomer (for example, an α,β-unsaturated acid such as (meth)acrylic acid; As a monomer component, α, β-unsaturated acid anhydride or the like of maleic anhydride or the like.

The polymer constituting the shell layer is preferably a monomer component, and preferably contains at least one of (meth) acrylate and one or a combination of the above monomers. That is, the above shell layer is preferably, for example, (meth) acrylate/aromatic vinyl/hydroxyalkyl (meth) acrylate, (meth) acrylate/aromatic vinyl/α,β-unsaturated acid. a shell composed of a ternary copolymer or the like.

Further, in the same manner as the core portion, the polymer constituting the shell layer may contain divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, and horse. Reactive cross-linking monomer having two or more reactive functional groups in the molecule, such as diallyl acid, triallyl cyanurate, diallyl phthalate, butanediol diacrylate As other monomer components.

The glass transition temperature of the polymer constituting the shell layer is not particularly limited, but is preferably 20 to 200 ° C, more preferably 40 to 180 ° C, and particularly preferably 60 to 160 ° C. When the glass transition temperature of the above polymer is 20° C. or more, the heat resistance and light resistance of the cured product tend to be further increased. On the other hand, when the glass transition temperature of the above polymer is 200 ° C or lower, the dispersibility of the rubber particles (B) and the crack resistance of the cured product tend to increase. Further, the glass transition temperature of the polymer constituting the shell layer means a calculated value calculated by the above formula of Fox, and can be measured, for example, in the same manner as the glass transition temperature of the polymer constituting the core.

The core-shell type rubber particles 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; A method in which a core portion having rubber elasticity is used as a dry component, and each component constituting the shell layer is grafted and polymerized as a branch component.

The average particle diameter of the rubber particles (B) 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 (B) is not particularly limited, but is preferably 50 to 1000 nm, more preferably 100 to 800 nm. When the average particle diameter is 500 nm or less (or the maximum particle diameter is 1000 nm or less), the dispersibility of the rubber particles (B) in the cured product is increased, and the crack resistance tends to increase. On the other hand, when the average particle diameter is 10 nm or more (or the maximum particle diameter is 50 nm or more), the crack resistance of the cured product tends to increase.

The refractive index of the rubber particles (B) is not particularly limited, but is preferably 1.40 to 1.60, more preferably 1.42 to 1.58. Further, the difference between the refractive index of the rubber particles (B) and the refractive index of the cured product obtained by curing the curable resin composition (the curable resin composition of the present invention) containing the rubber particles (B) is preferably ± Within 0.03.

The refractive index of the rubber particles (B) can be obtained by, for example, injecting 1 g of the rubber particles (B) into a mold, and compression-molding at 210 ° C at 4 MPa to obtain a flat plate having a thickness of 1 mm, and cutting the longitudinally 20 mm × 6 mm from the obtained flat plate. A multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by ATAGO Co., Ltd.) was used at 20 ° C in a state where ruthenium was used as an intermediate liquid and the ruthenium was adhered to the test piece. The refractive index of the sodium D line was measured and found.

The refractive index of the cured product of the curable resin composition of the present invention can be, for example, a test piece of 20 mm in length × 6 mm in width × 1 mm in thickness, which can be obtained from the cured product obtained by the heat curing method described in the item of the following cured product. A multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by ATAGO Co., Ltd.) was used at 20 ° C in a state where ruthenium was used as an intermediate liquid and the ruthenium was adhered to the test piece. The refractive index of the sodium D line is obtained.

The content (doping amount) of the rubber particles (B) in the curable resin composition of the present invention is not particularly limited, but is preferably 0.01 to 20% by weight based on the curable resin composition (100% by weight). More preferably, it is 0.05 to 15% by weight, and particularly preferably 0.1 to 10% by weight. When the content of the rubber particles (B) is within the above range, the crack resistance of the cured product is increased, and the heat resistance and the light resistance are more excellent.

The content (doping amount) of the rubber particles (B) in the curable resin composition of the present invention is not particularly limited, but is 100% by weight based on the total amount of the epoxy group-containing compound contained in the curable resin composition. The portion is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the content of the rubber particles (B) is within the above range, the crack resistance of the cured product is increased, and the heat resistance and the light resistance are more excellent.

[white pigment (C)]

The white pigment (C) which is an essential component of the curable resin composition of the present invention mainly has a function of imparting high light reflectivity to the cured product (reflector) and reducing the coefficient of linear expansion. 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 Inorganic white pigments such as activated clay, boehmite, pseudo-boehmite, inorganic oxides, metal salts (for example, alkaline earth metal salts, etc.); styrene resin, benzoguanamine resin, urea-formalin An organic white pigment (such as a plastic pigment) such as a resin pigment such as a resin, a melamine-formalin resin or a guanamine resin; or a hollow particle having a hollow structure (balloon structure).

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. In addition, as an example 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 (D). Inorganic filler (D).

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 metals such as inorganic glass (for example, sodium citrate glass, aluminosilicate glass, sodium borosilicate glass, quartz, etc.), vermiculite, and aluminum oxide. Inorganic hollow particles (including natural materials such as white sand balls) composed of inorganic substances such as metal salts such as oxides, calcium carbonate, cesium carbonate, nickel carbonate, and calcium citrate; and styrene resins, acrylic resins, and poly Oxide resin, acrylic acid-styrene resin, vinyl chloride resin, vinylidene chloride resin, guanamine resin, urethane resin, phenol resin, styrene-conjugated diene resin Acrylic-conjugated diene resin, olefin system An organic hollow particle composed of an organic substance such as a polymer such as a resin (including a crosslinked body of such a polymer); an inorganic-organic hollow particle composed of a mixed material of an inorganic substance and an organic substance. 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, from the viewpoint of improving the reflectance, a medium having a low refractive index is preferable ( 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 with other components in the curable resin composition.

Among them, the white pigment (C) is preferred from the viewpoints of availability, heat resistance, and light resistance, high reflectance of a cured product (reflector), and an increase rate of light reflectance with respect to an added amount. It is an inorganic oxide or an inorganic hollow particle, more preferably alumina, magnesia, cerium oxide, titanium oxide, zirconium oxide, zinc oxide, barium sulfate, inorganic hollow particles, and particularly preferably titanium oxide, zirconium oxide, zinc oxide, sulfuric acid. barium. In particular, as the white pigment (C), in terms of 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, and a scaly shape. Among them, from the viewpoint of dispersibility, spherical titanium oxide is preferable, and titanium oxide having a true spherical shape (for example, spherical titanium oxide having an aspect ratio of 1.2 or less) is preferable.

The center particle diameter of the white pigment (C) is not particularly limited, but is preferably 0.1 to 50 μm from the viewpoint of improving the light reflectivity of the cured product (reflector). In particular, when titanium oxide is used as the white pigment (C), the central particle diameter of the titanium 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. Preferably, the ratio is 0.1 to 10 μm, and the optimum is 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) at an integrated value of 50% in the particle size distribution measured by the laser diffraction or scattering method.

In the curable resin composition of the present invention, the white pigment (C) may be used alone or in combination of two or more. Further, the white pigment (C) can also be produced by a well-known or conventional method. For example, the trade names "SR-1", "R-42", "R-45M", "R-650", " R-32, R-5N, GTR-100, R-62N, R-7E, R-44, R-3L, R-11P, R- 21", "R-25", "TCR-52", "R-310", "D-918", "FTR-700" (above, 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" (above, TAYCA) System), trade names "TR-600", "TR-700", "TR-750", "TR-840", "TR-900" (above, Fuji Titanium Industry Co., Ltd.), trade name "KR -310", KR-380, KR-380N, ST-410WB, ST-455, ST-455WB, ST-457SA, ST-457EC, ST-485SA15 "Rutile type titanium oxide such as "ST-486SA" and "ST-495M" (above, 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 (share) system), trade names "KA-10", "KA-15", "KA-20", "STT-65C-S", "STT- 30EHJ (above, Titanium Industry Co., Ltd.), trade names "DCF-T-17007", "DCF-T-17008", "DCF-T-17050" (above, RESINO COLOR Industrial Co., Ltd.) A commercial product such as anatase type titanium oxide.

Among them, as the white pigment (C), in particular, from the viewpoint of light reflectivity and heat resistance of the cured product (reflector), the trade names "R-62N", "CR-60", and "DCF- are preferable. T-17007", "DCF-T-17008", "DCF-T-17050", "FTR-700".

The content (mixing amount) of the white pigment (C) in the curable resin composition of the present invention is not particularly limited, but is preferably 0.1 to 50% by weight based on the curable resin composition (100% by weight). More preferably, it is 1 to 40% by weight, and particularly preferably 5 to 35% by weight. When the content of the white pigment (C) is 0.1% by weight or more, the light reflectivity of the cured product (reflector) tends to be further increased. Further, there is a tendency that heat resistance and light resistance are further increased. On the other hand, by setting the content of the white pigment (C) to 60 When the weight is less than or equal to the weight, the moldability of the cured product (reflector) is improved, and there is a tendency to be more suitable for mass production.

The content (doping amount) of the white pigment (C) in the curable resin composition of the present invention is not particularly limited, but is 100% by weight based on the total amount of the epoxy group-containing compound contained in the curable resin composition. The portion is preferably 10 to 600 parts by weight, more preferably 30 to 500 parts by weight, still more preferably 30 to 400 parts by weight. Since the content of the white pigment (C) is 10 parts by weight or more, the light reflectivity of the cured product (reflector) tends to be further increased. Further, there is a tendency that heat resistance and light resistance are further increased. On the other hand, since the content of the white pigment (C) is 600 parts by weight or less, the moldability of the cured product (reflector) is improved, and it is more suitable for mass production.

When the curable resin composition of the present invention contains titanium oxide, the ratio of titanium oxide is not particularly limited with respect to the total amount (100% by weight) of the white pigment (C) and the inorganic filler (D), but is hardened. From the viewpoint of the balance between the heat resistance of the object (reflector) and the light reflectivity, it is preferably 5 to 70% by weight, more preferably 10 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 be further increased. Further, there is a tendency that heat resistance and light 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 improved, and it is more suitable for mass production.

[Inorganic Filler (D)]

The curable resin composition of the present invention contains an inorganic filler (D) as an essential component in addition to the white pigment (C). The inorganic filler (D) mainly imparts excellent heat resistance and light resistance to a cured product (reflector). Sex (especially excellent heat resistance). 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 (D), it is also possible to impart excellent light reflectivity to a cured product (reflector).

As the inorganic filler (D), a well-known or customary inorganic filler can be used without particular limitation, and examples thereof include vermiculite, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, and magnesium carbonate. , tantalum carbide, tantalum nitride, aluminum nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium coconut stone, block Powders of talc, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline syenite, cristobalite, ochre, diatomaceous earth, talc, or the like (for example, spheroidized Beads, etc.). Moreover, as the inorganic filler (D), 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 (D), from the viewpoints of heat resistance, light resistance, and fluidity of the cured product (reflector), vermiculite, alumina, tantalum nitride, aluminum nitride, and nitride are preferable. boron.

The vermiculite is not particularly limited, and for example, well-known or conventional vermiculite such as molten vermiculite, crystalline vermiculite, and 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 improving the light reflectivity of the cured product (reflector). Further, the above-mentioned center particle diameter means a particle diameter (median diameter) at an integrated value of 50% in the particle size distribution measured by the laser diffraction or scattering method.

In addition, the inorganic filler (D) may be used singly or in combination of two or more kinds in the curable resin composition of the present invention. Further, the inorganic filler (D) 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, and 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), trade name "10μmSE-CC5" (ADMATECHS system) ), trade names "MSR-2212", "MSR-25" (above, Ronson (share) system), trade names "HS-105", "HS-106", "HS-107" (above, MICRON Commercial products such as the system).

The content (mixing amount) of the inorganic filler (D) in the curable resin composition of the present invention is not particularly limited, but is preferably 10 to 90% by weight based on the curable resin composition (100% by weight). %, better It is 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 (D) is 10% by weight or more, the heat resistance and light resistance (especially excellent heat resistance) of the cured product tend to be further increased. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and the defect such as warpage of the lead frame in the optical semiconductor element mounting substrate using the reflector tends to be difficult to occur. On the other hand, when the content of the inorganic filler (D) is 90% by weight or less, the moldability of the cured product (reflector) is improved, and it is more suitable for mass production.

The content (doping amount) of the inorganic filler (D) in the curable resin composition of the present invention is not particularly limited, but is 100% relative to the compound having an epoxy group contained in the curable resin composition. The parts by weight are preferably 10 to 1,500 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 (D) is 10 parts by weight or more, the heat resistance and light resistance (especially excellent heat resistance) of the cured product tend to be further increased. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and the defect such as warpage of the lead frame in the optical semiconductor element mounting substrate using the reflector tends to be difficult to occur. On the other hand, when the content of the inorganic filler (D) is 1,500 parts by weight or less, the moldability of the cured product (reflector) is improved, and it is more suitable for mass production.

The maximum particle diameter of the white pigment (C) and the inorganic filler (D) in the curable 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 175 μm or less. It is particularly preferably 150 μm or less. If the maximum particle diameter is 200 μm or less, it is compared with the use of a white pigment having a maximum particle diameter of more than 200 μm or none. In the case of a machine filler, there is a tendency that the heat resistance, light resistance, and crack resistance (especially excellent heat resistance) of the cured product are more excellent. Moreover, by using the white pigment (C) having a small maximum particle diameter and the inorganic filler (D), 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. In addition, the maximum particle diameter is the total maximum particle diameter of the white pigment (C) and the inorganic filler (D) which are contained in the curable resin composition of this invention. The above maximum particle size means the largest particle size in the particle size distribution measured by laser diffraction or scattering.

[hardener (E)]

The curing agent (E) in the curable resin composition of the present invention has a function of hardening the curable resin composition by reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A). compound of. The curing agent (E) is not particularly limited as long as it is a known or customary curing agent for an epoxy resin, and examples thereof include an acid anhydride (an acid anhydride curing agent), an amine (an amine curing agent), and a polycondensation agent. Amidoxime resin, imidazole (imidazole-based curing agent), polythiol (polythiol-based curing agent), phenol (phenolic curing agent), polycarboxylic acid, dicyandiamide, organic acid hydrazine, etc. .

As the acid anhydride (an acid anhydride-based curing agent) of the curing agent (E), a known or customary acid-based curing agent can be used, and it is not particularly limited, and examples thereof include methyltetrahydrophthalic anhydride ( 4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methyl hexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrogen) Phthalic anhydride, etc.), dodecenyl succinic anhydride, methyl endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrogen Phthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, diphenylketone tetracarboxylic anhydride, norbornene dianhydride, methyl norbornene dianhydride, hydrogenated methyl norbornene Anhydride, 4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecane dianhydride, methylcyclohexene tetracarboxylic anhydride, ethylene Ether-maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer, and the like. In view of the fact that the uniform curable resin composition can be efficiently prepared and mixed with the alicyclic epoxy compound (A), it is easy to be a mixture (curing agent composition) which is liquid at 25 ° C. Preferably, it is a liquid acid anhydride at 25 ° C [for example, methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl endomethylene tetrahydrobenzene Formic anhydride, etc.]. On the other hand, the acid anhydride which is solid at 25 ° C is dissolved in a liquid acid anhydride at 25 ° C to form a liquid mixture, and is hardened as a curable resin composition of the present invention. The tendency of the agent (E) to increase in handleability. The acid anhydride-based curing agent is preferably an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including a substituent having an alkyl group bonded to the ring) from the viewpoint of heat resistance and light reflectivity of the cured product. .

As the amine (amine-based curing agent) as the curing agent (E), a known or customary amine-based curing agent can be used, and it is not particularly limited, and examples thereof include ethylenediamine and diethylenetriamine. , an aliphatic polyamine such as triamethylenetetramine, tetraethyleneamine, dipropylenediamine, diethylaminopropylamine, polypropylenetriamine, etc.; menthene diamine, isophorone II Amine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperine , an alicyclic polyamine such as 3,9-bis(3-aminopropyl)-3,4,8,10-tetraoxaspiro[5,5]undecane; m-phenylenediamine, p-phenylene Diamine, toluene-2,4-diamine, toluene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltoluene-2,4-diamine, 3, Mononuclear polyamine, biphenyldiamine, 4,4-diaminodiphenylmethane, 2,5-naphthalenediamine, 2,6-naphthalene, 5-diethyltoluene-2,6-diamine An aromatic polyamine such as a diamine.

In the phenol (phenolic curing agent) as the curing agent (E), a known or customary phenolic curing agent can be used, and it is not particularly limited, and examples thereof include a novolak type phenol resin and a novolak type. Aromatic resin such as cresol resin, p-xylylene modified phenol resin, p-xylylene-m-xylylene modified phenol resin, terpene modified phenol resin, dicyclopentadiene modification Phenolic resin, trisphenol propane, and the like.

The polyamine resin which is a hardener (E) is, for example, a polyamine resin having either or both of a primary amine group and a secondary amine group in the molecule.

As the imidazole (imidazole-based curing agent) as the curing agent (E), a known or customary imidazole-based curing agent can be used, and it is not particularly limited, and examples thereof include 2-methylimidazole and 2-B. 4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium benzene Triester, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isomeric cyanurate, 2-phenylimidazolium isopolycyanate, 2 ,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-three 2,4-Diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-three Wait.

The polythiol (polythiol-based curing agent) as the curing agent (E) may, for example, be a liquid polythiol or a polysulfide resin.

Examples of the polycarboxylic acid as the curing agent (E) include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and a carboxyl group-containing polyester.

In particular, the curing agent (E) is preferably an acid anhydride (an acid anhydride-based curing agent) from the viewpoint of heat resistance, light resistance, and light reflectivity of the cured product. Further, in the curable epoxy resin composition of the present invention, the curing agent (E) may be used singly or in combination of two or more. Further, the curing agent can also be produced by a well-known or conventional method. For example, the trade names "Rikacid MH-700", "Rikacid MH-700F", "Rikacid MH-700G", "Rikacid TH", " Rikacid HH", "Rikacid HNA-100" (above, New Japan Physical and Chemical Co., Ltd.); trade name "HN-5500" (Hitachi Chemical Industry Co., Ltd.); trade name "H-TMAn-S", H-TMAn (above, Mitsubishi Gas Chemical Co., Ltd.); commercially available product such as "YH1120" (Mitsubishi Chemical Co., Ltd.).

When the curable resin composition of the present invention contains the curing agent (E), the content (mixing amount) of the curing agent (E) is not particularly limited, but is compared with the curable resin composition (100% by weight). Preferably, it is 1 to 40% by weight, more preferably 3 to 35% by weight, and particularly preferably 5 to 30% by weight. When the content of the curing agent (E) is 1% by weight or more, the curing becomes sufficient, and the crack resistance of the cured product tends to increase. On the other hand, when the content of the curing agent (E) is 40% by weight or less, it is easy to obtain a cured product (reflector) having a color tone which is further suppressed from being suppressed.

When the curable resin composition of the present invention contains the curing agent (E), the content (mixing amount) of the curing agent (E) is not particularly limited, but is epoxy with respect to the curable resin composition. The total amount of the compound of the base is 100 parts by weight, preferably 40 to 200 parts by weight, more preferably 50 to 150 parts by weight. More specifically, when an acid anhydride is used as the curing agent (E), it is preferably one equivalent per equivalent of the epoxy group in the epoxy group-containing compound contained in the curable resin composition of the present invention. It is used in a ratio of 0.5 to 1.5 equivalents. When the content of the curing agent (E) is 40 parts by weight or more, the curing becomes sufficient, and the crack resistance of the cured product tends to increase. On the other hand, when the content of the curing agent (E) is 200 parts by weight or less, it is easy to obtain a cured product (reflector) having a color tone which is further suppressed from being suppressed.

[hardening accelerator (F)]

The curable resin composition of the present invention may further contain a hardening accelerator (F). The hardening accelerator (F) is a compound having an epoxy group contained in the curable resin composition of the present invention (for example, an alicyclic epoxy compound (A), an isocyanuric acid derivative (H), and When the oxoxane derivative (I) is reacted with a curing agent such as a curing agent (E), it has a function of promoting the reaction rate. As the hardening accelerator (F), a well-known or conventional hardening accelerator can be used, and, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (for example, phenol) can be used. Salt, octoate, p-toluenesulfonate, formate, tetraphenylborate, etc.; 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (for example, phenol Salt, octoate, p-toluenesulfonate, formate, tetraphenylborate, etc.; benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N, N-dimethylcyclohexylamine and the like Alkaloid; imidazole such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphates and triphenylphosphine; tetraphenyl An antimony compound such as tetrakis(p-tolyl)borate; an organic metal salt such as tin octylate or zinc octylate; a metal chelate compound or the like.

In the curable resin composition of the present invention, the curing accelerator (F) may be used singly or in combination of two or more.

Further, the hardening accelerator (F) can also be produced by a well-known or customary method. For example, the trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", " U-CAT 18X", "12XD" (developed product) (above, SUNAPRO (share) system); trade name "TPP-K", "TPP-MK" (above, Beixing Chemical Industry Co., Ltd.); A commercial item such as "PX-4ET" (Japan Chemical Industry Co., Ltd.).

When the curable resin composition of the present invention contains the curing accelerator (F), the content (mixing amount) of the curing accelerator (F) is not particularly limited, but is relative to the curable resin composition (100% by weight). Preferably, it is 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight. When the content of the hardening accelerator (F) is 0.0001% by weight or more, the curing reaction tends to proceed more efficiently. On the other hand, when the content of the curing accelerator (F) is 5% by weight or less, the storage property of the curable resin composition is further improved, or a cured product having excellent coloration and further suppressed coloration (reflector) is easily obtained. ) The tendency.

When the curable resin composition of the present invention contains the curing accelerator (F), the content (doping amount) of the curing accelerator (F) is not particularly limited, but is contained in the curable resin composition. Epoxy The total amount of the compound is 100 parts by weight, preferably 0.05 to 15 parts by weight, more preferably 0.1 to 12 parts by weight, still more preferably 0.2 to 10 parts by weight, particularly preferably 0.25 to 8 parts by weight. When the content of the hardening accelerator (F) is 0.05 parts by weight or more, the curing reaction tends to proceed more efficiently. On the other hand, when the content of the curing accelerator (F) is 15 parts by weight or less, the storage property of the curable resin composition is further increased, or a cured product having excellent coloration which is further suppressed in coloration is easily obtained (reflection) The tendency of the device).

[hardening catalyst (G)]

The curing catalyst (G) in the curable resin composition of the present invention has a curing reaction (polymerization reaction) of a cationically polymerizable compound such as an alicyclic epoxy compound (A), which is initiated and/or promoted. A compound which acts to harden the curable resin composition. The curing catalyst (G) is not particularly limited, and examples thereof include a cationic polymerization initiator (photocationic polymerization initiator, heat) which generates a cationic species by application of light irradiation or heat treatment, and starts polymerization. a cationic polymerization initiator, etc.), or a Lewis acid-amine complex, a Bronsted acid salt, an imidazole or the like.

Examples of the photocationic polymerization initiator as the curing catalyst (G) include hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, hexafluoroarsenate, and the like, more specifically For example, a sulfonium salt such as triarylsulfonium hexafluorophosphate (for example, p-phenylthiophenyldiphenylphosphonium hexafluorophosphate) or triarylsulfonium hexafluoroantimonate (especially triarylsulfonium) can be given. Salt); diarylsulfonium hexafluorophosphate, diarylsulfonium hexafluoroantimonate, bis(dodecylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, hydrazine [4-(4-methyl) Phenyl-2- a phosphonium salt such as methylpropyl)phenyl]hexafluorophosphate; a phosphonium salt such as tetrafluorophosphonium hexafluorophosphate; a pyridinium salt such as N-hexylpyridinium tetrafluoroborate; Further, as the photocationic polymerization initiator, for example, a product name "UVACURE 1590" (manufactured by Daicel-Cytec Co., Ltd.); trade names "CD-1010", "CD-1011", and "CD-1012" can be preferably used. (The above is manufactured by SARTOMER, USA); the trade name "Irgacure 264" (manufactured by BASF Corporation); and the commercial name of "CIT-1682" (made by Japan Soda Co., Ltd.).

Examples of the thermal cationic polymerization initiator as the curing catalyst (G) include an aryldiazonium salt, an arylsulfonium salt, an arylsulfonium salt, a propadiene-ion complex, and the like. It is preferable to use the trade names "PP-33", "CP-66", "CP-77" (above ADEKA), the trade name "FC-509" (made by 3M Company), and the trade name "UVE1014" ( GE company); trade name "Sunaid SI-60L", "Sunaid SI-80L", "Sunaid SI-100L", "Sunaid SI-110L", "Sunaid SI-150L" (above, Sanxin Chemical Industry Co., Ltd.) )), a commercial item such as "CG-24-61" (manufactured by BASF Corporation). Further, examples of the thermal cationic polymerization initiator include a compound of a metal such as aluminum or titanium, a chelate compound of acetonitrile acetic acid or a diketone, a sterol compound such as triphenylnonanol, or aluminum. Or a compound of a metal such as titanium, a chelate compound of acetonitrile or a diketone, a phenolic compound such as bisphenol S, or the like.

As the Lewis acid-amine complex as the curing catalyst (G), a well-known or conventional Lewis acid-amine complex-based curing catalyst can be used, and it is not particularly limited, but for example, BF ₃ - n-hexylamine, BF ₃ - monoethylamine, BF ₃ - benzylamine, BF ₃ - diethylamine, BF ₃ - piperidine, BF ₃ - triethylamine, BF ₃ - aniline, BF ₄ - n-hexylamine, BF ₄ - monoethylamine, BF ₄ - benzylamine, BF ₄ - diethylamine, BF ₄ - piperidine, BF ₄ - triethylamine, BF ₄ - aniline, PF ₅ - ethylamine, PF ₅ - isopropylamine, PF ₅ -butylamine, PF ₅ - laurylamine, PF ₅ -benzylamine, AsF ₅ - laurylamine, and the like.

In the case of the Brucella salt which is a hardening catalyst (G), a well-known or customary Buchneric acid salt can be used, and it is not particularly limited, but examples thereof include aliphatic sulfonium salts and aromatic hydrazine salts. Salt, barium salt, barium salt, etc.

As the imidazoles to be used as the hardening catalyst (G), well-known or conventional imidazoles can be used, and it is not particularly limited, and examples thereof include 2-methylimidazole and 2-ethyl-4-methylimidazole. , 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyano Base ethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isodecyl cyanate, 2-phenylimidazolium isomeric cyanurate, 2,4-diamino- 6-[2-methylimidazolyl-(1)]-ethyl-s-three 2,4-Diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-three Wait.

In the curable resin composition of the present invention, the curing catalyst (G) may be used singly or in combination of two or more. Further, as described above, a commercially available product can also be used as the curing catalyst (G).

When the curable resin composition of the present invention contains a curing catalyst (G), the content (doping amount) of the curing catalyst (G) is not particularly limited, but is relative to the curable resin composition (100% by weight). Preferably, it is 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight. By using the curing catalyst (G) within the above range, a cured product excellent in heat resistance and light resistance can be obtained.

When the curable resin composition of the present invention contains a curing catalyst (G), the content (doping amount) of the curing catalyst (G) in the curable resin composition of the present invention is not particularly limited, but is relative to The total amount of the epoxy group-containing compound contained in the curable resin composition is 100 parts by weight, preferably 0.0001 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, particularly preferably It is 0.05 to 8 parts by weight. By using the curing catalyst (G) within the above range, a cured product excellent in heat resistance and light resistance can be obtained.

[Iso-cyanuric acid derivative (H) having one or more oxirane rings in the molecule]

The derivative of the isocyanuric acid derivative (H)-based isocyanuric acid which is an essential component of the curable resin composition of the present invention is a compound having at least one oxirane ring in the molecule. . Since the curable resin composition of the present invention contains the isocyanuric acid derivative (H), the light reflectance, heat resistance, and light resistance of the cured product are increased, and are simultaneously with the azide derivative (I) described later. It is contained in the curable resin composition, and the light reflectivity, heat resistance, and light resistance of the cured product are further increased. The number of the oxirane rings in the molecule of the isocyanuric acid derivative (H) is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3. One.

The isomeric cyanuric acid derivative (H) may, for example, be a compound represented by the following formula (III).

In the formula (III), R ⁴ to R ⁶ are the same or different and each represents a hydrogen atom or a monovalent organic group. However, at least one of R ⁴ to R ⁶ is a monovalent organic group containing an epoxy group. The monovalent organic group may, for example, be a monovalent aliphatic hydrocarbon group (for example, an alkyl group or an alkenyl group); a monovalent aromatic hydrocarbon group (for example, an aryl group or the like); a monovalent heterocyclic group; an aliphatic hydrocarbon group; A monovalent group formed by combining two or more of an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Further, the monovalent organic group may have a substituent (for example, a substituent of a hydroxyl group, a carboxyl group, a halogen atom or the like). Examples of the monovalent organic group containing an epoxy group include a monovalent group containing an epoxy group, which will be described later, such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group or an epoxycyclohexane group. Organic base, etc.

In particular, R ⁴ to R ⁶ in the formula (III) are the same or different and are a group represented by the following formula (IIIa) or a group represented by the following formula (IIIb), and at least R ⁴ to R ⁶ One is preferably a group represented by the formula (IIIa).

R ⁷ and R ⁸ in the above formula (IIIa) and formula (IIIb) are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include 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 ⁷ and R ⁸ in the formula (IIIa) and the formula (IIIb) are particularly preferably a hydrogen atom.

More specifically, the isomeric cyanuric acid derivative (H) includes a compound represented by the following formula (III-1), a compound represented by the following formula (III-2), and the following formula. A compound or the like represented by (III-3).

In the above formulae (III-1) to (III-3), R ⁷ and R ⁸ are the same or different, and are the same as those in the formula (IIIa) and the formula (IIIb).

Representative examples of the compound represented by the above formula (III-1) include monoallyl epoxypropyl isomeric cyanurate and 1-allyl-3,5-bis (2-A). Epoxypropyl)isomeric cyanurate, 1-(2-methylpropenyl)-3,5-diepoxypropyl isocyanate, 1-(2-methylpropenyl) -3,5-bis(2-methylepoxypropyl)isocyanate or the like.

Representative examples of the compound represented by the above formula (III-2) include diallyl monoepoxypropyl isomeric cyanurate and 1,3-diallyl-5-(2-methyl) Epoxypropyl)isocyanate, 1,3-bis(2-methylpropenyl)-5-epoxypropyl isocyanate, 1,3-bis(2-A) Alkyl)-5-(2-methylepoxypropyl)isocyanate or the like.

Representative examples of the compound represented by the above formula (III-3) include trisepoxypropyl isocyanurate and tris(2-methylepoxypropyl)isocyanate. .

Further, the isomeric cyanuric acid derivative (H) may be added with a compound which reacts with an epoxy group such as an alcohol or an acid anhydride, and is used in advance for modification.

In particular, the isomeric cyanuric acid derivative (H) is preferably represented by the above formula (III-1) to (III-3) from the viewpoints of light reflectivity, heat resistance and solubility of the cured product. The compound is more preferably a compound represented by the above formula (III-1). In addition, the isocyanuric acid derivative (H) may be used singly or in combination of two or more kinds in the curable resin composition of the present invention. In addition, as the isocyanuric acid derivative (H), for example, "TEPIC" (manufactured by Nissan Chemical Industries Co., Ltd.); trade names "MA-DGIC" and "DA-MGIC" (above, A commercial product such as the Shikoku Chemical Industry Co., Ltd.).

The content (doping amount) of the isocyanuric acid derivative (H) in the curable resin composition of the present invention is preferably 0.05 to 15% by weight, more preferably the composition of the curable resin composition (100% by weight). Preferably, it is 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight. When the content of the isocyanuric acid derivative (H) is within the above range, a cured product excellent in heat resistance and light resistance can be obtained.

The content (doping amount) of the isocyanuric acid derivative (H) in the curable resin composition of the present invention is not particularly limited, but is equivalent to the epoxy group contained in the curable resin composition. The total amount of the compound is 100 parts by weight, preferably 1 to 60 parts by weight, more preferably 1 to 50 parts by weight, still more preferably 1 to 30 parts by weight. When the content of the isocyanuric acid derivative (H) is within the above range, a cured product excellent in heat resistance and light resistance can be obtained.

[A halogenated alkane derivative (I) having two or more epoxy groups in the molecule]

The oxoxane derivative (I) which is an essential component of the curable resin composition of the present invention has two or more epoxy groups in the molecule and has a siloxane chain (-Si-O-Si-) A compound (a oxoxane compound) constituting a skeleton. The oxirane skeleton (Si-O-Si skeleton) in the oxoxane derivative (I) is not particularly limited, and examples thereof include a cyclic siloxane chain; linear polyfluorene, Or a polyoxane skeleton such as a cage or ladder type polysesquioxane or the like. In view of the above, the cyclooxygen skeleton is preferably a cyclic oxime skeleton and a linear chain from the viewpoint of improving light reflectivity, heat resistance, and light resistance of the cured product and suppressing reduction in luminosity of the optical semiconductor device. Polyoxygen skeleton. In other words, the cyclodecan derivative (I) is preferably a cyclic oxime having two or more epoxy groups in the molecule and a linear polyfluorene having two or more epoxy groups in the molecule. oxygen.

When the oxoxane derivative (I) is a cyclic oxirane having two or more epoxy groups in the molecule, the number of Si-O units forming the oxirane ring (equal to the formation of a siloxane chain) The number of the ruthenium atoms is not particularly limited, but is preferably from 2 to 12, more preferably from 4 to 8, from the viewpoint of improving the heat resistance and light resistance of the cured product.

The weight average molecular weight of the siloxane derivative (I) is not particularly limited, but is preferably from 100 to 3,000, more preferably from 180 to 2,000, from the viewpoint of improving heat resistance and light resistance of the cured product. Further, the above weight average molecular weight of the oxoxane derivative (I) is calculated from the molecular weight in terms of standard polystyrene measured by a GPC (gel permeation chromatography) method.

The number of the epoxy groups in the molecule of the siloxane derivative (I) is not particularly limited, but is preferably from the viewpoint of improving the heat resistance and light resistance of the cured product. 2~4 (2, 3 or 4).

The epoxy equivalent of the siloxane derivative (I) is not particularly limited, but is preferably from 180 to 2,000, more preferably from 180 to 1,500, from the viewpoint of improving the heat resistance and light resistance of the cured product. Good for 180~1000. Further, the above epoxy equivalent is a value measured in accordance with JIS K7236.

The epoxy group of the oxirane derivative (I) is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, it is preferred to form two adjacent carbon atoms constituting the alicyclic ring. An epoxy group (alicyclic epoxy group) composed of an oxygen atom, particularly preferably an epoxycyclohexane group.

The oxoxane derivative (I) may, for example, be a oxoxane compound represented by the following formula (IV).

In the formula (IV), R ^a is the same or different and represents an epoxy group-containing group or an alkyl group. However, at least two (for example, 2 to 4) of R ^a in the formula (IV) are ^a group having an epoxy group. The epoxy group-containing group includes at least one epoxy group (oxirane ring), and examples thereof include a linear or branched chain having a carbon-carbon unsaturated double bond such as an alkenyl group. An aliphatic hydrocarbon group having at least one double bond via an epoxidized group or a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond (for example, a cycloalkenyl group; a cyclohexenylethyl group or the like) An alkyl group or the like having at least one double bond epoxidized group or the like. More specifically, for example, 1,2-epoxyethyl (epoxy), 1,2-epoxypropyl, 2,3-epoxypropyl (epoxypropyl), 2,3-Epoxy-2-methylpropyl (methylepoxypropyl), 3,4-epoxybutyl, 3-glycidoxypropyl, 3,4-epoxy Cyclohexylmethyl, 2-(3,4-epoxycyclohexyl)ethyl and the like. Among them, a cyclic aliphatic group having at least one double bond of a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond is preferred. Examples of the alkyl group include a linear chain of 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group or a dodecyl group. A branched alkyl group or the like. Among them, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred.

In the formula (IV), n represents an integer of 2 to 12. In particular, n is preferably 4 to 8, more preferably 4 or 5 from the viewpoint of thermal shock resistance of the cured product, reflow resistance of the optical semiconductor device, and thermal shock resistance.

As the decane derivative (I), more specifically, for example, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4 6,6,8,8-hexamethyl-cyclotetraoxane, 4,8-bis[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-bis[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]g Base}) ethyl]-2,4,6,6,8-pentamethyl-cyclotetraoxane, 2,4,8-tri[2-(3-{oxabicyclo[4.1.0]g Base}) 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, sesquioxane having two or more epoxy groups in the molecule. More specifically, for example, a cyclic oxirane having two or more epoxy groups in the molecule represented by the following formula may be mentioned.

In addition, as the decane derivative (I), for example, a polyfluorene-containing epoxy group containing an alicyclic epoxy group described in JP-A-2008-248169, or JP-A-2008-19422 can be used. An organic polysilsesquioxane resin having at least two epoxy functional groups in one molecule.

In addition, the siloxane derivative (I) may be used singly or in combination of two or more kinds in the curable resin composition of the present invention.

The siloxane derivative (I), for example, can be obtained by the trade name "X-40-2678", "X-40-2670", or "X-" of a cyclic oxirane having two or more epoxy groups in the molecule. 40-2720" (above, Shin-Etsu Chemical Industry Co., Ltd.) Commercial products such as the system). Further, the decane derivative (I) can be produced by a known or customary method.

The content (doping amount) of the oxoxane derivative (I) in the curable resin composition of the present invention is preferably from 0.1 to 30% by weight, more preferably, based on the curable resin composition (100% by weight). 0.5 to 20% by weight, particularly preferably 1.0 to 10% by weight. When the content of the siloxane derivative (I) is controlled within the above range, the thixotropy of the curable resin composition is increased, and the heat resistance, light resistance, and light reflectivity of the cured product tend to be further increased.

The content (doping amount) of the oxoxane derivative (I) in the curable resin composition of the present invention is not particularly limited, but is equivalent to the compound having an epoxy group contained in the curable resin composition. The total amount is 100 parts by weight, preferably 5 to 99 parts by weight, more preferably 10 to 95 parts by weight, still more preferably 20 to 80 parts by weight. When the content of the siloxane derivative (I) is 5 parts by weight or more, the curability of the curable resin composition is increased, and the heat resistance, light resistance, and light reflectance of the cured product tend to increase. . On the other hand, when the content of the siloxane derivative (I) is 150 parts by weight or less, the thermal shock resistance and the adhesion property of the cured product tend to be further increased.

[release agent]

The curable resin composition of the present invention may further comprise a release agent. The continuous molding system including the mold release agent and the molding method using a mold such as transfer molding is easy, and the cured product (reflector) can be produced with high productivity. The release agent is not particularly limited, and a fluorine-based release agent (a compound containing a fluorine atom; for example, a fluorine oil or a polytetrafluoroethylene) can be used. Polyoxane a release agent (polyoxyl compound; for example, polyoxyxane oil, polyoxyxanthene wax, polyoxyxylene resin, polyorganosiloxane having a polyoxyalkylene unit, etc.), a wax-based release agent (wax; for example; , plant wax such as palm 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.), higher fatty acid ester, Higher fatty acid guanamine, mineral oil, etc.

Further, in the curable 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 resin composition of the present invention contains a release agent, the content (mixing amount) of the release agent is not particularly limited, but is equivalent to the compound having an epoxy group contained in the curable resin composition. The total amount 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 improved, and the productivity of the reflector tends to be further increased. 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 resin composition of the present invention may also contain an antioxidant. By containing an antioxidant, a cured product (reflector) having more excellent heat resistance can be produced. As the antioxidant, a well-known or conventional antioxidant can be used, and it is not particularly limited, and examples thereof include a phenolic antioxidant (phenolic compound) and a hindered amine antioxidant (hindered amine compound). A phosphorus-based antioxidant (a phosphorus-based compound) or a sulfur-based antioxidant (a sulfur-based compound).

Examples of the phenolic antioxidant include 2,6-di-tri-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tri-butyl-p-ethylphenol, and octadecyl- Monophenols such as β-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate; 2,2'-methylenebis(4-methyl-6-tertiary butyl Phenol), 2,2'-methylenebis(4-ethyl-6-tributylphenol), 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 4,4'-butylidene bis(3-methyl-6-tertiary butylphenol), 3,9-bis[1,1-dimethyl-2-{β-(3-tertiary butyl- Bisphenols such as 4-hydroxy-5-methylphenyl)propoxycarbonyl}ethyl]2,4,8,10-tetraoxaspiro[5.5]undecane; 1,1,3-three (2-methyl-4-hydroxy-5-tributylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tertiary butyl 4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tertiarybutyl-4'-hydroxyphenyl)propionate]methane, bis[3,3 '-Bis-(4'-hydroxy-3'-tris-butylphenyl)butyrate]diol, 1,3,5-tris(3',5'-di-tertiary butyl-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, three (2,4-di-tertiary butylphenyl)phosphite, cyclic neopentane tetrakis(bis-octadecyl)phosphite, cyclic neopentane tetrakis(2,4-di- Tert-butyl phenyl phosphite, cyclic neopentane tetrakis(2,4-di-tert-butyl-4-methylphenyl) phosphite, bis[2-tributyl a phosphite such as -6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]phosphite, etc.; 9,10-dihydro-9-oxa-10- Phosphenephenanthrene-10-oxide, 10-(3,5-di-tri-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxaphosphorus oxides such as oxides.

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 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), and the trade names "AO-60" and "AO-80" may be used. ADEKA Co., Ltd., phenolic antioxidant), trade name "Irgafos 168" (manufactured by BASF Corporation, phosphorus antioxidant), trade name "ADK STAB HP-10", "ADK STAB PEP-36" (ADEKA) A commercially available product such as a phosphorus-based antioxidant, trade name "HCA" (manufactured by Sanko Co., Ltd., phosphorus-based antioxidant).

When the curable resin composition of the present invention contains an antioxidant, the content (mixing amount) of the antioxidant is not particularly limited, but is 100% relative to the compound having an epoxy group contained in the curable resin composition. The parts by weight are preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight. By setting the content of the antioxidant to 0.1 part by weight or more, Further, the oxidation of the cured product (reflector) is effectively prevented, and the heat resistance and the light resistance are further increased. 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 resin composition of the present invention may contain various additives in addition to the above-described components, within a range not impairing the effects of the present invention. As the above-mentioned additive, for example, a compound having a hydroxyl group (e.g., an aliphatic polyol) such as ethylene glycol, diethylene glycol, propylene glycol or glycerin is contained, and the reaction can be carried out gently. Further, an antifoaming agent, a leveling agent, decane such as γ-glycidoxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane may be used insofar as it does not impair viscosity or light reflectivity. Conventional additives such as a coupling agent, a surfactant, a flame retardant, a colorant, an ion adsorbent, a UV absorber, a photostabilizer, and a pigment other than the white pigment (C). The content of such additives is not particularly limited and may be appropriately selected.

The curable resin composition of the present invention contains an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a hardener (E), and a hardening accelerator (F). ), when the isocyanuric acid derivative (H) and the decane derivative (I), the alicyclic epoxy compound (A), the rubber particles (B), the curing agent (E), and the hardening accelerator ( F) The mixture of the isocyanuric acid derivative (H) and the decane derivative (I) is not particularly limited in viscosity at 25 ° C, but is preferably 5,000 mPa ‧ or less. Further, the curable resin composition of the present invention may further comprise the above aliphatic polyol such as ethylene glycol. In this case, the above mixture is an alicyclic epoxy compound. (A), rubber particles (B), hardener (E), hardening accelerator (F), isomeric cyanuric acid derivative (H), decane derivative (I) and aliphatic polyol mixture.

On the other hand, the curable resin composition of the present invention contains an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing catalyst (G), When the isocyanuric acid derivative (H) and the decane derivative (I), the alicyclic epoxy compound (A), the rubber particles (B), the hardening catalyst (G), and the isocyanuric acid The viscosity of the mixture of the derivative (H) and the decane derivative (I) at 25 ° C is not particularly limited, but is preferably 5,000 mPa ‧ or less. 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 crack resistance (especially excellent heat resistance) of the cured product tend to be more excellent than when the resin viscosity exceeds 5000 mPa ‧ s. Further, since the resin has a relatively low viscosity, the content of other components such as the white pigment (C) or the inorganic filler (D) 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 resin viscosity is, for example, 100 mPa·s or more. Further, as the resin viscosity, for example, a digital viscometer (model "DVU-EII type", manufactured by TOKIMEC Co., Ltd.) can be used, and the rotor: standard 1°34 ' × R24, temperature: 25 ° C, rotation number: 0.5 to 10 rpm The conditions were measured.

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), a hardener (E), a hardening accelerator (F), and a hardening catalyst (G). ), an isocyanuric acid derivative (H), a decane derivative (I), etc.) are easily available. 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 is 5000 mPa ‧ s or less. Further, it is also possible to easily obtain the rubber particles (B) by adjusting the content of the rubber particles (B) without impairing the effects of the present invention.

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

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

The curable resin composition of the present invention is not particularly limited, but may be prepared by stirring and mixing the above components in a heated state as needed. In addition, the curable resin composition of the present invention can be used as a one-liquid composition which is used as a component in which each component is previously mixed, and can be used, for example, as two or more components to be separately stored before use. A composition of a multi-liquid system (for example, a two-liquid system) used in a ratio of mixing. The above method of stirring and mixing is not special. Other examples include a well-known or conventional stirring and mixing means such as various mixers, kneaders, rolls, bead mills, and auto-rotating stirring apparatuses such as a dissolving machine and a homogenizer. Further, after stirring and mixing, defoaming can also be carried out under vacuum.

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

(Rubber particles dispersed epoxy compound)

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

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 above 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, it tends to be easy to obtain desired properties such as improvement in toughness (crack resistance).

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 the rubber particles (B) are dehydrated and dried into a powder, mixed in the alicyclic epoxy compound (A), or dispersed, or the emulsion and the fat of the rubber particles (B) are directly mixed. The cyclic epoxy compound (A) is followed by a method of dehydrating or the like.

The viscosity of the curable 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 be further increased. 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 improved, and it is more difficult to cause a problem from the mold injection failure in the cured product.

<hardened matter>

By curing the curable resin composition of the present invention and curing it, a cured product excellent in light reflectivity and excellent in heat resistance, light resistance, and crack resistance can be obtained. Further, the cured product obtained by curing the curable resin composition of the present invention, that is, the cured product of the curable 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 becomes insufficient, and conversely, when it is higher than the upper limit of the above range, yellowing due to thermal decomposition occurs, which is not preferable. The hardening conditions depend on various conditions, but can be suitably adjusted, for example, by shortening the hardening time when the curing temperature is increased, and lengthening the hardening time when the curing temperature is lowered. 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), further 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 described above is less likely to deteriorate, and the reflectance is less likely to decrease as time passes. Therefore, the curable 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). Etc., the use of electronic components, liquid crystal display applications (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 (initial 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 93% or more, more preferably 94% or more, and particularly preferably 95% or more. In particular, the reflectance of light of 450 to 800 nm is preferably 93% or more, more preferably 94% or more, and particularly preferably 95% or more.

The reflectance of light having a wavelength of 450 nm (also referred to as "reflectance after heat aging") of the cured product of the present invention after heating at 120 ° C for 250 hours is maintained relative to the initial reflectance ([reflectance after heat aging] The [initial reflectance] × 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. In particular, the retention of light in the range of 450 to 800 nm is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. In the case of the curable resin composition according to 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 80% or more, more preferably 85% or more, and particularly preferably 90% or more. In particular, the retention of light in the range of 450 to 800 nm is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.

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

When the curable resin composition of the present invention is a curable resin composition for a reflector in an optical semiconductor device, the curable resin composition of the present invention is a molding material (a material used for molding in a mold or the like), and the molding material The use of a reflector (light reflecting member) included in a substrate (an optical semiconductor element mounting substrate) for forming an optical semiconductor element in an optical semiconductor device. Therefore, by molding (and hardening) the curable resin composition of the present invention, it is possible to manufacture a high-quality (for example, high durability) substrate for mounting an optical semiconductor element having a reflector, which has a high reflector. It is excellent in light reflectivity, heat resistance and light resistance, and is excellent in crack resistance. 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 has at least a reflector formed of a cured product of the curable resin composition of the present invention (a cured product obtained by curing the curable resin composition of the present invention) (white reflection) The substrate of the device). 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. 100 in Figure 1 represents a white reflector, 101 A metal wiring (lead frame) is shown, 102 is a mounting region of the optical semiconductor element, and 103 is 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 upper white reflector 100 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. In the substrate for mounting an optical semiconductor element of the present invention, the inner surface of the concave shape may be formed of at least a cured product of the curable resin composition of the present invention. 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.

As a method of forming the white reflector in the substrate for mounting an optical semiconductor element of the present invention, a well-known or conventional molding method (for example, compression molding) can be used, and is not particularly limited, and for example, the present invention can be used. The curable resin composition is delivered to various methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and baffle molding to be dispensed. As a curing condition at the time of forming the reflector, for example, conditions at which the above-mentioned cured product can be formed Wait for a suitable choice. In the present invention, in particular, in order to prevent foaming due to a sharp hardening reaction, stress strain due to mildening hardening, and improvement in toughness (crack resistance), it is preferred to apply heating in multiple stages. Processed to harden it step by step.

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

<Optical semiconductor device>

The optical semiconductor device of the present invention includes at least an optical semiconductor device as a light source and an optical semiconductor device having a reflector (reflective material) formed of a cured product of the curable resin composition 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 curable resin composition 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 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 Fig. 3 and Fig. 4 denote heat sinks (shell fins), and by having such heat sinks 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 one shown in FIGS. 2 to 4.

[Examples]

Hereinafter, the present invention will be described in more detail based on the examples, but the present invention is not limited by the examples. In addition, the unit of the blending amount of each component of the curable resin composition in Table 1 - Table 3 is a weight part. Further, "-" in Tables 1 to 3 means that the blending of the components is not carried out.

Manufacturing example 1 (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. A monomer mixture of 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 emulsification by stirring for 20 minutes, 9.5 mg of potassium peroxodisulfate was added, and the mixture was 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 for 2 hours, and 0.95 g was dissolved in 180.5 g of butyl acrylate, 48.89 g of styrene, and 7.33 g of divinylbenzene. A monomer mixture 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 the mixture was stirred for 5 minutes, and it was continuously added thereto for 30 minutes to dissolve 0.3 g of dioctyl group in 60 g of methyl methacrylate, 1.5 g of acrylic acid, and 0.3 g of allyl methacrylate. A monomer mixture of sodium sulfosuccinate 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, and subjected to dehydration washing with a suction filter, and then dried at 60 ° C overnight to obtain rubber particles. The obtained rubber particles had an average particle diameter of 108 nm and a maximum particle diameter of 289 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. In order to measure the sample, in the obtained particle size distribution curve, the cumulative average diameter of the particle diameter at the time point when the cumulative curve becomes 50% is regarded as the average particle diameter, and the frequency (%) of the particle size distribution measurement result exceeds 0.00%. The maximum particle size at the time point is taken as the maximum particle size. In addition, as the sample, one part by weight of the rubber particle-dispersed epoxy compound obtained in the following Production Example 2 was dispersed in 20 parts by weight of tetrahydrofuran.

Manufacturing Example 2 (Manufacture of rubber particle-dispersed epoxy compound)

5 parts by weight of the rubber particles obtained in Production Example 1 were dispersed in a dissolver (1000 rpm, 60 minutes) under a nitrogen gas flow using 100 parts by weight of a trade name "Celloxide 2021P" (with a temperature of 60 ° C). 3,4-Epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate (manufactured by DAICEL Co., Ltd.), vacuum defoaming to obtain a rubber particle-dispersed epoxy compound (in Viscosity at 25 ° C: 1036 mPa ‧ s).

Further, the rubber particle-dispersed epoxy compound obtained in Production Example 2 (a dispersion of 5 parts by weight of rubber particles in 100 parts by weight of Celloxide 2021P) was used at a viscosity of 25 ° C using a digital viscometer (trade name "DVU-" EII type", TOKIMEC (stock) system) was measured.

Manufacturing Example 3

Using a self-rotating revolution type stirring device (trade name "Defoaming Rantaro AR-250", manufactured by THINKY Co., Ltd.), the blending ratio (unit: parts by weight) shown in Tables 1 and 2 is uniformly mixed. Rikacid MH-700" (Nippon Chemical and Chemical Co., Ltd.), the product name "U-CAT 18X" (SUNAPRO (manufactured by the company)) and ethylene glycol (Wako Pure Chemical Industries, Ltd.), defoaming Hardener composition.

Example 1

According to the blending ratio (unit: parts by weight) shown in Table 1, the rubber obtained in Production Example 2 was uniformly mixed using a self-rotating revolution stirring apparatus (trade name "Defoaming Rantaro AR-250", manufactured by THINKY Co., Ltd.). Particle-dispersed epoxy compound, iso-cyanuric acid derivative (monoallyl Di-glycidyl isopropyl isocyanurate; trade name "MA-DGIC", manufactured by Shikoku Chemicals Co., Ltd.), a siloxane derivative (a derivative of oxirane having 2 epoxy groups in the molecule) The product name "X-40-2678" was subjected to defoaming to prepare a mixture. Further, the above mixing was carried out at 80 ° C for 1 hour in order to dissolve MA-DGIC.

Next, according to the blending ratio (unit: parts by weight) shown in Table 1, the above-obtained mixture and white pigment (titanium oxide; trade name "DCF-T-17050", RESINO COLOR Industrial Co., Ltd. were uniformly mixed using a dissolver. )), inorganic filler (meteorite; trade name "FB-970FD", manufactured by DENKA), by roller mill, under specified conditions (roll spacing: 0.2mm, number of revolutions: 25 Hz, 3 The channel is melt-kneaded to obtain a kneaded product.

Then, using a self-rotating revolving stirring apparatus (trade name "Defoaming Ryotaro AR-250", manufactured by THINKY Co., Ltd.), it was uniformly mixed so as to have a blending ratio (unit: parts by weight) shown in Table 1. The kneaded product obtained above and the hardener composition obtained in Production Example 3 were defoamed at 2000 rpm for 5 minutes to obtain a curable resin composition.

The curable 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 pressurized at a pressure of 3.0 MPa for 600 seconds to be hardened, and then cured. A hardened material was obtained by post-hardening (at 150 ° C for 5 hours).

Examples 2 to 14 and Comparative Examples 1 to 15

The cured product was obtained in the same manner as in Example 1 except that the blending composition of the curable resin composition was changed as shown in Table 1 or Table 2. Further, in some of the examples and comparative examples, the constituent components of the curable resin composition were replaced or combined with Production Example 2. The obtained rubber particles were dispersed in an epoxy compound, and the alicyclic epoxy compound shown in Table 1 or Table 2 was used.

Example 15

According to the blending ratio (unit: parts by weight) shown in Table 1, the rubber obtained in Production Example 2 was uniformly mixed using a self-rotating revolution stirring apparatus (trade name "Defoaming Rantaro AR-250", manufactured by THINKY Co., Ltd.). Particle-dispersed epoxy compound, iso-cyanuric acid derivative (monoallyl epoxypropyl iso-isocyanate; trade name "MA-DGIC", manufactured by Shikoku Chemical Industry Co., Ltd.), helium oxygen An alkane derivative (a halogenated alkane derivative having two epoxy groups in the molecule; trade name "X-40-2678", manufactured by Shin-Etsu Chemical Co., Ltd.) was defoamed to prepare a mixture. Further, the above mixing was carried out at 80 ° C for 1 hour in order to dissolve the MA-DGIC.

Next, according to the blending ratio (unit: parts by weight) shown in Table 1, the above-obtained mixture and white pigment (titanium oxide; trade name "DCF-T-17050", RESINO COLOR Industrial Co., Ltd. were uniformly mixed using a dissolver. )), inorganic filler (meteorite; trade name "FB-970FD", manufactured by DENKA), by roller mill, under specified conditions (roll spacing: 0.2mm, number of revolutions: 25 Hz, 3 The channel is melt-kneaded to obtain a kneaded product.

Then, using a self-rotating revolving stirring apparatus (trade name "Defoaming Ryotaro AR-250", manufactured by THINKY Co., Ltd.), it was uniformly mixed so as to have a blending ratio (unit: parts by weight) shown in Table 1. The kneaded material and the hardening catalyst (trade name "Sunaid SI-100L", manufactured by Sanshin Chemical Industry Co., Ltd.) were defoamed at 2000 rpm for 5 minutes to obtain a curable resin composition.

The curable 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 pressurized at a pressure of 3.0 MPa for 600 seconds to be hardened, and then cured. A hardened material was obtained by post-hardening (at 150 ° C for 5 hours).

Example 16 and Comparative Example 16-24

A cured product was obtained in the same manner as in Example 15 except that the blending composition of the curable resin composition was changed as shown in Tables 1 and 3. Furthermore, in some of the examples and the comparative examples, the rubber particles-dispersed epoxy compound obtained in Production Example 2 was replaced or combined as a constituent component of the curable resin composition, and the alicyclic ring shown in Table 1 or Table 3 was used. Epoxy compound.

In addition, the properties of the curable resin composition of Examples 1 to 16 and Comparative Examples 1 to 24 at 25 ° C (liquid or individual) are shown in the "Properties of the properties of the curable resin composition" in Tables 1 to 3. ).

<evaluation>

The following evaluations were carried out on the cured products obtained in the examples and the comparative examples.

[Initial reflectance]

A test piece having a length of 30 mm, a width of 30 mm, and a thickness of 3 mm was produced by cutting the cured product obtained in the examples and the comparative examples. Then, 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 Tables 1 to 3.

In addition, when the initial reflectance is 95% or more, it can be said that it is particularly excellent as a material for light reflection.

[Reflection retention before and after heating aging]

A test piece (cured material; length: 30 mm × width: 30 mm × 3 mm thick) in which the initial reflectance was evaluated was used, and the test piece was placed in a dryer at 120 ° C, and after a 250-hour stand-up test (heat resistance test), The initial reflectance was similarly measured for the reflectance of light having a wavelength of 450 nm. Then, the reflectance retention ratio (before and after heat aging) was calculated by the following formula. The results are shown in Tables 1 to 3.

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

The higher the reflectance retention ratio, the more excellent the heat resistance of the cured product. In addition, when the reflectance retention rate after heating at 120 ° C for 250 hours is 90% or more, it can be said that the heat resistance is particularly excellent as a material for light reflection.

[Reflection retention rate before and after UV aging]

A test piece (cured material; length: 30 mm × width: 30 mm × 3 mm thick) having an initial reflectance evaluation was used, and after the test piece was subjected to an ultraviolet ray having an irradiation intensity of 10 mW/cm ² for 250 hours (light resistance test), The initial reflectance was similarly measured for the reflectance of light having a wavelength of 450 nm. Then, the reflectance retention ratio (before and after ultraviolet aging) was calculated by the following formula. The results are shown in Tables 1 to 3.

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

The higher the reflectance retention ratio, the more excellent the light resistance of the cured product. In addition, when the irradiation intensity is 10 mW/cm ² and the reflectance retention ratio after 90 hours is 90% or more, it can be said that the light-reflecting material is particularly excellent in light resistance.

[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. Micro-Cutting-Machine (trade name "BS-300CL", manufactured by MEIWAFOSIS Co., Ltd.) was used for the cutting of the cured product, and it was observed with a digital microscope (trade name "VHX-900", manufactured by KEYENCE). Check if cracks occur in the hardened material during cutting. In Tables 1 to 3, 10 test pieces were prepared for each sample, and the number of test pieces (10 pieces) in which the occurrence of cracks was observed was shown as an evaluation result.

[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 observed to confirm whether or not a crack occurred in the test piece due to the reflow treatment. Each of the samples in Tables 1 to 3 was subjected to reflow treatment of 10 test pieces, and the number of test pieces in which the occurrence of cracks was observed [10 sheets] was shown as an evaluation result.

[Comprehensive judgment]

The results of the respective tests were judged to be ○ (good) by satisfying the following (1) to (5). On the other hand, in the case where any of the following (1) to (5) is not satisfied, it is judged as × (bad).

(1) Initial reflectance: light reflectance is 95% or more

(2) Reflectance retention rate before and after heating aging: reflectance retention rate is 90% or more

(3) Reflex rate retention rate before and after ultraviolet aging: reflectance retention rate is 90% or more

(4) Evaluation of cracks during cutting: The number of cracks is 0

(5) Evaluation of cracks during reflow: the number of cracks is 0

The results are displayed in the column of "Comprehensive judgment" in Tables 1 to 3.

Further, the components shown in Tables 1 to 3 will be described below.

(Rubber particles dispersed epoxy compound)

Rubber particle-dispersed epoxy compound obtained in Production Example 2

(epoxy compound)

Celloxide 2021P: trade name "Celloxide 2021P" (3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate), manufactured by DAICEL Co., Ltd.

EHPE3150: trade name "EHPE3150" (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol) , DAICEL (share) system

(isocyanuric acid derivative)

TEPIC: trade name "TEPIC" [triepoxypropyl iso-cyanurate], Nissan Chemical Industry Co., Ltd.

MA-DGIC: trade name "MA-DGIC" [monoallyl propylene oxide isopropyl isocyanurate], Shikoku Chemical Industry Co., Ltd.

DA-MGIC: trade name "DA-MGIC" [diallyl monoepoxypropyl iso-cyanurate], Shikoku Chemical Industry Co., Ltd.

(a halogen derivative)

X-40-2678: trade name "X-40-2678" (a halogenated alkane derivative having two epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd.

X-40-2720: trade name "X-40-2720" (a sulfoxane derivative having three epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd.

X-40-2670: The trade name "X-40-2670" (a sulfoxane derivative having four epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd.

(hardener composition)

MH-700: trade name "Rikacid MH-700" (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride), New Japan Physical and Chemical Co., Ltd.

18X: Product name "U-CAT 18X" (hardening accelerator), SUNAPRO (share) system

(additive)

Ethylene glycol: trade name "ethylene glycol", and Wako Pure Chemical Industries Co., Ltd. (hardening catalyst)

Sunaid SI-100L: trade name "Sunaid SI-100L", Sanshin Chemical Industry Co., Ltd.

(white pigment)

DCF-T-17050: trade name "DCF-T-17050" (titanium oxide, average particle diameter 0.3μm, maximum particle size 1μm or less), RESINO COLOR Industrial Co., Ltd.

(inorganic filler)

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

DAW-1025: trade name "DAW-1025" (alumina, average particle size 7.9μm, maximum particle size 32μm), DENKA (share) system

HF-05: trade name "HF-05" (aluminum nitride, average particle size 5μm, maximum particle size 5μm), DENKA (share) system

Industrial utilization possibility

According to the above-described configuration, the curable resin composition of the present invention can form a cured product which has high light reflectivity, is excellent in heat resistance and light resistance, and is difficult to reduce light reflectance with time. When the cured product is formed by compression molding, the above effects are remarkably exhibited. Therefore, it is possible to provide an optical semiconductor device in which the luminance of light is hard to be lowered with time and the reliability is high.

Claims (9)

A curable resin composition for light reflection, which comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), and one or more molecules in the molecule. The isomeric cyanuric acid derivative (H) of the oxirane ring and the oxoxane derivative (I) having two or more epoxy groups in the molecule, further containing a curing agent (E), and The hardening accelerator (F) or the hardening catalyst (G) is liquid at 25 °C. The curable resin composition for light reflection according to claim 1, wherein the rubber particles (B) are composed of a polymer having (meth) acrylate as an essential monomer component and having a hydroxyl group and/or a carboxyl group on the surface. The rubber particles (B) have an average particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm. The curable resin composition for light reflection according to claim 1 or 2, wherein the alicyclic epoxy compound (A) comprises a compound represented by the following formula (I-1); The curable resin composition for light reflection according to any one of claims 1 to 3, wherein the isomeric cyanuric acid derivative (H) is a compound represented by the following formula (III-1); In the formula (III-1), R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The curable resin composition for light reflection according to any one of claims 1 to 4, wherein the white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate. The inorganic filler (D) is at least one selected from the group consisting of vermiculite, alumina, tantalum nitride, aluminum nitride, and boron nitride. The curable resin composition for light reflection according to any one of claims 1 to 5, which is a resin composition for transfer molding or compression molding. The curable resin composition for light reflection according to any one of claims 1 to 6, which is a resin composition for forming a reflector. A cured product which is a cured product of the curable resin composition for light reflection according to any one of claims 1 to 7. An optical semiconductor device comprising at least an optical semiconductor element and a reflector formed of a cured product of a curable resin composition for light reflection according to claim 8.