WO2017138491A1 - Curable resin composition for reflecting light, cured product thereof, and optical semiconductor device - Google Patents

Abstract

A curable resin composition for reflecting light is provided which is capable of forming a cured product which exhibits high light reflectance, and excellent heat resistance and light resistance, and which has a light reflectance which does not readily deteriorate over time, said curable resin composition exhibiting this remarkable effect particularly when used to form a cured product by way of compression moulding. This curable resin composition for reflecting light is characterized by: including an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), an isocyanuric acid derivative (H) having at least one oxirane ring in a molecule thereof, and a siloxane derivative (I) having at least two epoxy groups in a molecule thereof; further including a curing agent (E), and a curing accelerator (F), or a curing catalyst (G); and being liquid at 25˚C.

Description

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

The present invention relates to a light-reflective curable resin composition and a cured product thereof, and an optical semiconductor device having a reflector formed of the cured product and an optical semiconductor element. This application claims the priority of Japanese Patent Application No. 2016-025329 for which it applied to Japan on February 12, 2016, and uses the content here.

2. Description of the Related Art In recent years, in various indoor or outdoor display boards, image reading light sources, traffic signals, large display units, etc., light emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources have been increasingly adopted. . As such an optical semiconductor device, in general, an optical semiconductor device in which an optical semiconductor element is mounted on a substrate (substrate for mounting an optical semiconductor element) and the optical semiconductor element is sealed with a transparent sealing material is widespread. is doing. On the substrate in such an optical semiconductor device, a member (reflector) for reflecting light is formed in order to improve the extraction efficiency of light emitted from the optical semiconductor element.

The reflector is required to have high light reflectivity. Conventionally, as a constituent material of the reflector, for example, a resin composition in which an inorganic filler or the like is dispersed in a polyamide resin (polyphthalamide resin) having a terephthalic acid unit as an essential constituent unit is known. (See Patent Documents 1 to 3).

In addition, as the constituent material of the reflector, for example, a thermosetting resin for light reflection containing a specific ratio of a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0, for example. Resin compositions are known (see Patent Document 4). Furthermore, for example, it contains a thermosetting resin component and one or more filler components, the difference between the refractive index of the entire thermosetting resin component and the refractive index of each filler component, and the volume of each filler component There is known a thermosetting resin composition for light reflection in which a parameter calculated from a ratio is controlled within a specific range (see Patent Document 5).

JP 2000-204244 A JP 2004-75994 A JP 2006-257314 A JP 2010-235753 A JP 2010-235756 A

Reflectors made from the materials described in Patent Documents 1 to 5 described above are yellowed over time due to light and heat emitted from a semiconductor element in an optical semiconductor device using a high-power blue light semiconductor or white light semiconductor as a light source. Etc., and the light reflectivity decreases with time. Furthermore, with the adoption of lead-free solder, the heating temperature in the reflow process (solder reflow process) during the manufacture of the light-emitting device tends to be higher, and the reflector is also deteriorated over time due to the heat applied in such a manufacturing process. There was also a problem that the light reflectivity was deteriorated due to deterioration.

For this reason, the present situation is that a material excellent in heat resistance and light resistance in which light reflectivity is less likely to deteriorate with time even for higher output, shorter wavelength light and high temperature is required.

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

Therefore, an object of the present invention is to form a cured product having high light reflectivity, excellent heat resistance and light resistance, and light reflectivity is less likely to deteriorate with time, and in particular, a cured product is formed by compression molding. It is in providing the curable resin composition for light reflections which the said effect is exhibited notably at the time.
Another object of the present invention is to provide a cured product having excellent productivity, high light reflectivity, excellent heat resistance and light resistance, and the light reflectivity is less likely to deteriorate with time. .
Furthermore, another object of the present invention is to provide a highly reliable optical semiconductor device in which the luminance of light is less likely to decrease over time.

Furthermore, the above reflector is less susceptible to cracking when subjected to stress due to cutting or temperature change (for example, heating at a very high temperature such as a reflow process or a cooling cycle). Such a characteristic is sometimes referred to as “crack resistance”). This is because if the reflector is cracked, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it is difficult to ensure the reliability of the light emitting device.

As a result of intensive studies to solve the above problems, the present inventors have found that the alicyclic epoxy compound (A), the rubber particles (B), the white pigment (C), the inorganic filler (D), and the curing agent (E). , A curing accelerator (F), an isocyanuric acid derivative (H) having one or more oxirane rings in the molecule, and a siloxane derivative (I) having two or more epoxy groups in the molecule, which are liquid at 25 ° C. A certain light-reflective curable resin composition, or alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), curing catalyst (G), 1 in the molecule A light-reflective curable resin composition containing an isocyanuric acid derivative (H) having one or more oxirane rings and a siloxane derivative (I) having two or more epoxy groups in the molecule and being liquid at 25 ° C. is high. Light reflective and heat resistant And excellent light resistance, light reflectivity can be formed a cured product hardly decreases with time, the effect was found to be remarkably exhibited particularly when forming a cured product compression molding. The present invention has been completed based on these findings.

That is, the present invention relates to an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), an isocyanuric acid derivative (H) having one or more oxirane rings in the molecule. ) And a siloxane derivative (I) having two or more epoxy groups in the molecule, and further contains a curing agent (E) and a curing accelerator (F) or a curing catalyst (G), 25 Provided is a light-reflective curable resin composition characterized by being liquid at a temperature of 0 ° C.

Further, in the present invention, the rubber particle (B) is composed of a polymer containing (meth) acrylic acid ester as an essential monomer component, and has a hydroxy group and / or a carboxy group on the surface, and the rubber particle (B Is provided with a mean particle size of 10 to 500 nm and a maximum particle size of 50 to 1000 nm.

で表される化合物を含む光反射用硬化性樹脂組成物を提供する。 Further, according to the present invention, the alicyclic epoxy compound (A) is represented by the following formula (I-1):

The curable resin composition for light reflection containing the compound represented by these is provided.

［式（ＩＩＩ－１）中、Ｒ⁷及びＲ⁸は、同一又は異なって、水素原子又は炭素数１～８のアルキル基を示す。］
で表される化合物である光反射用硬化性樹脂組成物を提供する。 Further, in the present invention, the isocyanuric acid derivative (H) is represented by the following formula (III-1):

[In 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 which is a compound represented by these is provided.

Further, in the present invention, 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 (D) is silica, Provided is a curable resin composition for light reflection, which is at least one selected from the group consisting of alumina, silicon nitride, aluminum nitride, and boron nitride.

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

Furthermore, this invention provides the said curable resin composition for light reflections which is a resin composition for reflector formation.

The present invention also provides a cured product of the light reflecting curable resin composition.

The present invention also provides an optical semiconductor device comprising at least an optical semiconductor element and a reflector made of the cured product.

That is, the present invention relates to the following.
[1] Alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), isocyanuric acid derivative (H) having one or more oxirane rings in the molecule, and Contains a siloxane derivative (I) having two or more epoxy groups in the molecule, and further contains a curing agent (E) and a curing accelerator (F) or a curing catalyst (G), and is liquid at 25 ° C. A curable resin composition for light reflection, characterized by:
[2] The light reflection according to [1], wherein the rubber particle (B) is a rubber particle having a multilayer structure including a core portion having rubber elasticity and at least one shell layer covering the core portion. Curable resin composition.
[3] The curable resin composition for light reflection according to [1] or [2], wherein the rubber particles (B) are composed of a polymer having (meth) acrylic acid ester as an essential monomer component.
[4] The polymer constituting the rubber-elastic core portion of the rubber particle (B) is selected from the group consisting of aromatic vinyl, nitrile, and conjugated diene together with (meth) acrylic acid ester as a monomer component. The curable resin composition for light reflection according to any one of [2] or [3], which includes one or a combination of two or more.
[5] The polymer constituting the shell layer of the rubber particles (B) is one or two selected from the group consisting of a hydroxy group-containing monomer and a carboxy group-containing monomer together with a (meth) acrylic acid ester as a monomer component The light-reflective curable resin composition according to any one of [2] to [4], including the above in combination.
[6] The light-reflective curable resin composition according to any one of [1] to [5], wherein the rubber particles (B) have a hydroxy group and / or a carboxy group on the surface.
[7] The light-reflective curable resin according to any one of [1] to [6], wherein the rubber particles (B) have an average particle size of 10 to 500 nm and a maximum particle size of 50 to 1000 nm. Composition.
[8] The light-reflective curable resin composition according to any one of [1] to [7], wherein the alicyclic epoxy compound (A) includes a compound represented by the following formula (I): .
[9] The light-reflective curable resin according to any one of [1] to [8], wherein the alicyclic epoxy compound (A) includes a compound represented by the following formula (I-1): Composition.
[10] The curable resin composition for light reflection according to any one of [1] to [9], wherein the isocyanuric acid derivative (H) is a compound represented by the following formula (III).
[11] The curable resin composition for light reflection according to any one of [1] to [10], wherein the isocyanuric acid derivative (H) is a compound represented by the following formula (III-1): .
[12] The siloxane derivative (I) is a cyclic siloxane having two or more epoxy groups in the molecule and / or a linear silicone having two or more epoxy groups in the molecule. The curable resin composition for light reflection as described in any one.
[13] The white pigment (C) according to any one of [1] to [12], wherein the white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate. Curable resin composition for light reflection.
[14] In any one of [1] to [13], the inorganic filler (D) is at least one selected from the group consisting of silica, alumina, silicon nitride, aluminum nitride, and boron nitride. The curable resin composition for light reflection as described.
[15] The curable resin composition for light reflection according to any one of [1] to [14], wherein the siloxane derivative (I) is a siloxane compound represented by the following formula (IV).
[16] The content (blending amount) of the alicyclic epoxy compound (A) is 0.1 to 60% by weight, 0.3 to 50% by weight with respect to the curable resin composition (100% by weight). Or the curable resin composition for light reflection according to any one of [1] to [15], which is 0.5 to 40% by weight.
[17] The content (blending amount) of the rubber particles (B) is 0.01 to 20% by weight, 0.05 to 15% by weight, or 0 with respect to the curable resin composition (100% by weight). The curable resin composition for light reflection according to any one of [1] to [16], which is 1 to 10% by weight.
[18] The content (blending amount) of the white pigment (C) is 0.1 to 50% by weight, 1 to 40% by weight, or 5 to 35 with respect to the curable resin composition (100% by weight). The light-reflective curable resin composition according to any one of [1] to [17], which is wt%.
[19] The content (blending amount) of the inorganic filler (D) is 10 to 90% by weight, 13 to 75% by weight, 15 to 70% by weight with respect to the curable resin composition (100% by weight). Or the curable resin composition for light reflection according to any one of [1] to [18], which is 20 to 70% by weight.
[20] The content (blending amount) of the curing agent (E) is 1 to 40% by weight, 3 to 35% by weight, or 5 to 30% by weight with respect to the curable resin composition (100% by weight). The curable resin composition for light reflection according to any one of [1] to [19].
[21] The content (blending amount) of the curing accelerator (F) is 0.0001 to 5% by weight, or 0.001 to 1% by weight with respect to the curable resin composition (100% by weight). The light-reflective curable resin composition according to any one of [1] to [20].
[22] The content (blending amount) of the curing catalyst (G) is 0.0001 to 5% by weight or 0.001 to 1% by weight with respect to the curable resin composition (100% by weight). The curable resin composition for light reflection according to any one of [1] to [21].
[23] The content (blending amount) of the isocyanuric acid derivative (H) is 0.05 to 15% by weight, 0.1 to 10% by weight with respect to the curable resin composition (100% by weight), or The curable resin composition for light reflection according to any one of [1] to [22], which is 0.3 to 5% by weight.
[24] The content (blending amount) of the siloxane derivative (I) is 0.1 to 30% by weight, 0.5 to 20% by weight, or 1 with respect to the curable resin composition (100% by weight). The light-reflective curable resin composition according to any one of [1] to [23], which is 0.0 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 light-reflective curable resin composition according to any one of [1] to [26].
[28] An optical semiconductor device comprising at least an optical semiconductor element and a reflector made of a cured product of the curable resin composition for light reflection described in [27].

Since the curable resin composition of the present invention has the above-described configuration, it can form a cured product having high light reflectivity, excellent heat resistance and light resistance, and light reflectivity hardly decreasing over time. Especially, when the cured product is formed by compression molding, the above-mentioned effect is remarkably exhibited. Therefore, it is possible to provide a highly reliable optical semiconductor device in which the luminance of light hardly decreases over time.

It is the schematic which shows an example of the board | substrate for optical semiconductor element mounting of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. It is the schematic (sectional drawing) which shows an example of the optical semiconductor device of this invention. It is the schematic (sectional drawing; when it has a heat sink) which shows another example of the optical semiconductor device of this invention. It is the schematic (when it has a heat sink (radiation fin)) which shows another example of the optical semiconductor device of this invention. The left figure (a) is a top view, and the right figure (b) is a cross-sectional view along AA 'in (a).

<Curable resin composition for light reflection>
The light-reflective curable resin composition of the present invention (sometimes simply referred to as “the curable resin composition of the present invention”) includes an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C ), An inorganic filler (D), an isocyanuric acid derivative (H) having one or more oxirane rings in the molecule, and a siloxane derivative (I) having two or more epoxy groups in the molecule, and a curing agent A curable resin composition containing (E) and a curing accelerator (F) or a curing catalyst (G) and being liquid at 25 ° C. The isocyanuric acid derivative (H) having one or more oxirane rings in the molecule may be referred to as “isocyanuric acid derivative (H)”. Further, the siloxane derivative (I) having two or more epoxy groups in the molecule may be referred to as “siloxane derivative (I)”.

In other words, the curable resin composition of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing agent (E), and a curing accelerator. (F), isocyanuric acid derivative (H), and siloxane derivative (I) as essential components, a light-reflective curable resin composition that is liquid at 25 ° C., or an alicyclic epoxy compound (A), rubber particles ( B), a white pigment (C), an inorganic filler (D), a curing catalyst (G), an isocyanuric acid derivative (H), and a siloxane derivative (I) as essential components, a curable resin composition that is liquid at 25 ° C. It is a thing. In addition, the curable resin composition of this invention may contain the other component as needed other than the said essential component. In addition, the curable resin composition of this invention can be used as a thermosetting composition (thermosetting epoxy resin composition) which can form hardening by heating.

In the present specification, the “curable resin composition for light reflection” refers to a curable resin composition capable of forming a cured product having light reflectivity. Specifically, for example, it refers to 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.

Since the curable resin composition of the present invention is liquid at 25 ° C., it tends to be suitable for compression molding, and the cured product (reflector) tends to have excellent light reflectivity and excellent heat resistance and light resistance. There is. In the present specification, “liquid at 25 ° C.” means that the viscosity measured at 25 ° C. at normal pressure is 1000000 mPa · s or less (preferably 800000 mPa · s or less). The above viscosity is measured using, for example, a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24, temperature: 25 ° C., rotational speed: 0.00. It can be measured at 5 to 10 rpm.

The curable resin composition of the present invention which is liquid at 25 ° C. includes, for example, components (for example, alicyclic epoxy compound (A), curing agent (E), curing accelerator (F), curing catalyst (G) and the like. ), It is easy to obtain by using a liquid component at 25 ° C. In addition, although a solid component may be used as a said component at 25 degreeC, the content is adjusted so that the curable resin composition of this invention may become a liquid state at 25 degreeC. It can also be obtained by adjusting the content of components that are solid at 25 ° C., such as rubber particles (B), white pigment (C), and inorganic filler (D), within a range that does not impair the effects of the present invention. It becomes easy.

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (alicyclic epoxy resin) (A), which is an essential component of the curable resin composition of the present invention, has an alicyclic (aliphatic hydrocarbon ring) structure and epoxy in the molecule (in one molecule). It is a compound which has a group (oxiranyl group) at least, and a publicly known thru / or usual alicyclic epoxy compound can be used. However, those corresponding to the isocyanuric acid derivative (H) and the siloxane derivative (I) are excluded from the alicyclic epoxy compound (A). More specifically, as the alicyclic epoxy compound (A), for example, (i) an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring And (ii) a compound having an epoxy group directly bonded to the alicyclic ring with a single bond.

As the above-mentioned (i) compound having an alicyclic epoxy group, a known or conventional compound having one or more alicyclic epoxy groups in the molecule can be used, and it is not particularly limited. The alicyclic epoxy group is preferably a cyclohexene oxide group from the viewpoints 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 a cured product (reflector), a compound having two or more cyclohexene oxide groups in the molecule is preferable, and a compound represented by the following formula (I) is more preferable.

In formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized (sometimes referred to as an “epoxidized alkenylene group”), a carbonyl group, Examples include an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (I).

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

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

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

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

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

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

In the above formula (II), R ¹ represents a p-valent organic group. p represents an integer of 1 to 20. Examples of the p-valent organic group include a p-valent organic group having a structure formed by removing p hydroxy groups from the structural formula of an organic compound having p hydroxy groups described later.

In the formula (II), q represents an integer of 1 to 50. In addition, when p is an integer greater than or equal to 2, several q may be the same and may differ. The sum (total) of q in the formula (II) is an integer of 3 to 100.

In the formula (II), R ² is a substituent on the cyclohexane ring shown in the formula, and represents any of the groups represented by the following formulas (IIa) to (IIc). The bonding position of R ² on the cyclohexane ring is not particularly limited. Usually, when the positions of the two carbon atoms of the cyclohexane ring bonded to the oxygen atom are the 1st and 2nd positions, the 4th or 5th carbon atom It is. When the compound represented by the formula (II) has a plurality of cyclohexane rings, the bonding positions of R ² in each cyclohexane ring may be the same or different. At least one R ² in the formula (II) is a group (epoxy group) represented by the formula (IIa). In the case where the compound represented by the formula (II) has two or more R ^2, to a plurality of R ² may be the same or different.

In 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 methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl. Examples thereof include straight-chain or branched alkyl groups having 1 to 20 carbon atoms. Examples of the alkylcarbonyl group include methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl. Examples thereof include a linear or branched alkyl-carbonyl group having 1 to 20 carbon atoms such as a carbonyl group. Examples of the arylcarbonyl group include arylcarbonyl groups having 6 to 20 carbon atoms such as a phenylcarbonyl group (benzoyl group), 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, and the like.

Examples of the substituent that the above-described alkyl group, alkylcarbonyl group, and arylcarbonyl group may have include a substituent having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms). Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Preferably C _1-6 alkoxy group, more preferably C _1-4 alkoxy group); alkenyloxy group such as allyloxy group (preferably C _2-6 alkenyloxy group, more preferably C _2-4 alkenyloxy group) An acyloxy group such as an acetyloxy group, a propionyloxy group and a (meth) acryloyloxy group (preferably a C _1-12 acyloxy group); a mercapto group; an alkylthio group such as a methylthio group and an ethylthio group (preferably a C _1-6 alkylthio group) group, more preferably a C _1-4 alkylthio group); allyl alkenylthio such groups (Preferably C _2-6 alkenylthio group, more preferably C _2-4 alkenylthio group); carboxy; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, an alkoxycarbonyl group (preferably C such as butoxycarbonyl group _1-6 alkoxy-carbonyl group); amino group; mono- or dialkylamino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group (preferably mono- or di-C _1-6 alkylamino group); acetyl An acylamino group such as an amino group or a propionylamino group (preferably a C _1-11 acylamino group); an oxetanyl group-containing group such as an ethyl oxetanyloxy group; an acyl group such as an acetyl group or a propionyl group; an oxo group; It includes groups attached via a C _1-6 alkylene group optionally It is. In addition, examples of the substituent that the above-described arylcarbonyl group may have include the above-described substituted or unsubstituted alkyl group and the above-described substituted or unsubstituted alkylcarbonyl group.

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

The compound represented by the formula (II) is not particularly limited. For example, an organic compound [R ¹ (OH) _p ] having p hydroxy groups in the molecule is used as an initiator (ie, the hydroxy group of the compound). (Starting with active hydrogen)), 1,2-epoxy-4-vinylcyclohexane (3-vinyl-7-oxabicyclo [4.1.0] heptane) is subjected to ring-opening polymerization (cationic polymerization), and then Manufactured by epoxidation with an oxidizing agent.

Examples of the organic compound [R ¹ (OH) _p ] having p hydroxy groups in the molecule include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol; ethylene 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, cyclohexanedi Methanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, water Polyhydric alcohols such as 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 Examples thereof include oligomers or polymers having a hydroxy group such as polybutadiene having a hydroxy group, cellulose, cellulose acetate, cellulose acetate butyrate, and cellulose-based polymers such as hydroxyethyl cellulose.

The 1,2-epoxy-4-vinylcyclohexane can be produced by a known or commonly used method, and is not particularly limited. For example, 4-vinylcyclohexene obtained by dimerization reaction of butadiene is replaced with an oxidizing agent such as peracetic acid. Obtained by partial epoxidation using. Moreover, as 1,2-epoxy-4-vinylcyclohexane, a commercially available product can be used.

The oxidant may be a known or conventional oxidant such as hydrogen peroxide or organic peracid, and is not particularly limited. Examples of the organic peracid include performic acid, peracetic acid, peroxygen. Examples include benzoic acid and trifluoroperacetic acid. Among them, peracetic acid is preferable because it is industrially available at low cost and has high stability.

The above ring-opening polymerization and epoxidation can be carried out more specifically according to well-known and conventional methods described in, for example, 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 300 to 100,000, more preferably 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 improved. On the other hand, when the weight average molecular weight is 100,000 or less, the viscosity does not become too high and the fluidity during molding tends to be maintained low. The weight average molecular weight is measured by a gel permeation chromatography (GPC) method.

The equivalent (epoxy equivalent) of the epoxy group of the compound represented by the formula (II) is not particularly limited, but is preferably 50 to 1000, more preferably 100 to 500. When the epoxy equivalent is 50 or more, the cured product tends not to be brittle. On the other hand, when the epoxy equivalent is 1000 or less, the mechanical strength of the cured product tends to be improved. The epoxy equivalent is measured according to JIS K7236: 2001.

In the curable resin composition of the present invention, the alicyclic epoxy compound (A) can be used singly or in combination of two or more. The alicyclic epoxy compound (A) can also be produced by a known or conventional method. For example, commercial names such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) are available. Can also be used.

The alicyclic epoxy compound (A) preferably exhibits a liquid state at normal temperature (25 ° C.) from the viewpoint of workability during preparation and casting. Moreover, even if it is an alicyclic epoxy compound (A) which is solid at normal temperature (25 degreeC), as long as it shows liquid state after mix | blending, you may contain.

Especially, the curable resin composition of this invention contains at least the compound which has (i) alicyclic epoxy group from a viewpoint which the light reflectivity of a hardened | cured material (reflector), heat resistance, and light resistance improve more. More preferably, it further includes (ii) a compound having an epoxy group directly bonded to the alicyclic ring with a single bond.

The content (blending amount) of the alicyclic epoxy compound (A) in the curable resin composition of the present invention is not particularly limited, but is 0.1 to 60 with respect to the curable resin composition (100% by weight). % By weight is preferable, more preferably 0.3 to 50% by weight, still more preferably 0.5 to 40% by weight. By setting the content of the alicyclic epoxy compound (A) to 0.1% by weight or more, the heat resistance and light resistance of the cured product (reflector) tend to be further improved. On the other hand, by setting the content of the alicyclic epoxy compound (A) to 60% by weight or less, the heat resistance and light resistance of the cured product (reflector) are further improved, the linear expansion coefficient is reduced, and the optical semiconductor element is mounted. There is a tendency that the occurrence of defects such as lead frame warpage in the circuit board is suppressed.

When the epoxy compound other than the alicyclic epoxy compound (A) is contained, the alicyclic epoxy compound (A) with respect to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition of the present invention. The ratio is not particularly limited, but is preferably 1 to 90% by weight, more preferably 5 to 80% by weight, and still more preferably 10 to 70% by weight. By making it in the said range, there exists a tendency for the heat resistance and light resistance of hardened | cured material (reflector) to improve more. In addition, as a compound which has an epoxy group contained in the curable epoxy resin composition of this invention, an alicyclic epoxy compound (A), an isocyanuric acid derivative (H), a siloxane derivative (I), etc. are mentioned, for example. .

In addition, in this specification, each component (for example, alicyclic epoxy compound (A), rubber particle (B), white pigment (C), inorganic filler (D) contained in the curable resin composition of the present invention. , Curing agent (E), curing accelerator (F), curing catalyst (G), isocyanuric acid derivative (H), siloxane derivative (I), etc.), respectively, so that the total content is 100% by weight or less. In addition, it can select suitably from the description range.

[Rubber particles (B)]
The rubber particles (B) that are essential components of the curable resin composition of the present invention are particles having rubber elasticity. In the curable resin composition of the present invention, the rubber particles (B) are alicyclic epoxy compound (A), white pigment (C), inorganic filler (D), isocyanuric acid derivative (H), and siloxane derivative (I). ), The cured product formed is excellent in light reflectivity, heat resistance, light resistance, and crack resistance, and the above effect is remarkably exhibited particularly when the cured product is formed by compression molding. Tend.

Examples of the rubber particles (B) include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxy group NBR (CTBN), metal-free NBR, particulate SBR (styrene-butadiene rubber). . The rubber particles (B) have a core part having rubber elasticity and at least one shell covering the core part from the viewpoint of good dispersibility and an effect of improving toughness (crack resistance improvement). Rubber particles having a multilayer structure (core-shell structure) composed of layers (hereinafter sometimes referred to as “core-shell type rubber particles”) are preferred. From the viewpoint of further improving the heat resistance and light resistance of the cured product, the rubber particles (B) are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component, and an alicyclic ring on the surface. Rubber particles having a hydroxy group and / or a carboxy group (either one or both of a hydroxy group and a carboxy group) as a functional group capable of reacting with a compound having an epoxy group such as the formula epoxy compound (A) are preferred. That is, the rubber particles (B) are particularly preferably core-shell type rubber particles composed of a polymer (acrylic polymer) containing (meth) acrylic acid ester as an essential monomer component. In the curable resin composition of the present invention, the rubber particles (B) can be used singly or in combination of two or more.

When the rubber particles (B) are core-shell type rubber particles, the polymer constituting the core portion having rubber elasticity is not particularly limited, but methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic A polymer containing a (meth) acrylic acid ester such as butyl acid as an essential monomer component is preferable. The polymer constituting the core part having rubber elasticity includes, for example, aromatic vinyl such as styrene and α-methylstyrene; nitrile such as acrylonitrile and methacrylonitrile; conjugated diene such as butadiene and isoprene; ethylene, propylene, An α-olefin such as isobutene may be included as a monomer component.

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

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

The core-shell type rubber is preferably a core portion composed of a binary or ternary copolymer containing (meth) acrylic acid ester and aromatic vinyl (particularly butyl acrylate and styrene). This is preferable in that the refractive index of the particles can be easily adjusted.

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., and further preferably −60 to −20 ° C. There exists a tendency for the crack resistance of hardened | cured material to improve by making the glass transition temperature of the said polymer into the said range. In addition, the glass transition temperature of the polymer which comprises the said core part means the calculated value calculated by the formula of the following Fox (refer Bull. Am. Phys. Soc., 1 (3) 123 (1956)). Wherein the following Fox, Tg glass transition temperature (unit: K) of the polymer constituting the core portion indicates, W _i is the weight fraction of the monomer i for the monomer total amount constituting the polymer constituting the core portion Indicates the rate. Further, Tg _i is the glass transition temperature of the homopolymer of monomer i (unit: K) shows a. The following Fox formula shows the formula when 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
As the glass transition temperature of the homopolymer, values described in various documents can be adopted, for example, values described in “POLYMER HANDBOOK 3rd edition” (published by John Wiley & Sons, Inc.) can be adopted. In addition, about the thing which is not described in literature, the value of the glass transition temperature measured by DSC method of the homopolymer obtained by superposing | polymerizing a monomer by a conventional method is employable.

The core part can be produced by a commonly used method. For example, the core part can be produced by a method of polymerizing the monomer by an emulsion polymerization method. In the emulsion polymerization method, the whole amount of the monomer may be charged all at once and polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently for polymerization. Further, a polymerization method using seed particles may be used.

In addition, when using the rubber particle which does not have a core shell structure as a rubber particle (B), the rubber particle etc. which consist only of the said core part can be used, for example.

The polymer constituting the shell layer of the core-shell type rubber particles is preferably a polymer different from the polymer constituting the core portion (a polymer having a different monomer composition). Further, as described above, the shell layer preferably has a hydroxy group and / or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A). Thereby, especially with respect to the hardened | cured material which can improve adhesiveness in an interface with an alicyclic epoxy compound (A), and hardened the curable resin composition containing the core-shell type rubber particle which has this shell layer Excellent crack resistance can be exhibited. Moreover, the fall of the glass transition temperature of hardened | cured material can also be prevented.

The polymer constituting the shell layer is preferably a polymer containing (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate as an essential monomer component. . For example, when butyl acrylate is used as the (meth) acrylic acid ester in the core portion, as a monomer component of the polymer constituting the shell layer, for example, (meth) acrylic acid esters other than butyl acrylate (for example, ( (Meth) methyl acrylate, ethyl (meth) acrylate, butyl methacrylate, etc.) are preferably used. Examples of the monomer component that may be contained in addition to the (meth) acrylic acid ester include aromatic vinyl such as styrene and α-methylstyrene; nitrile such as acrylonitrile and methacrylonitrile. In the core-shell type rubber particle, it is preferable that the monomer component constituting the shell layer includes the (meth) acrylic acid ester alone or in combination of two or more, particularly at least aromatic vinyl. It is preferable in that the refractive index of the core-shell type rubber particles can be easily adjusted.

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

The polymer constituting the shell layer preferably contains, as a monomer component, one or two or more selected from the above monomers in combination with (meth) acrylic acid ester. That is, the shell layer is composed of, for example, a ternary copolymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / α, β-unsaturated acid. A shell layer composed of a polymer or the like is preferable.

Further, the polymer constituting the shell layer includes, as the other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, trimethyl, as well as the above-described monomer. A reactive crosslinking monomer having two or more reactive functional groups may be contained in the molecule such as allyl cyanurate, diallyl phthalate, butylene glycol diacrylate.

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 still more preferably 60 to 160 ° C. By setting the glass transition temperature of the polymer to 20 ° C. or higher, the heat resistance and light resistance of the cured product tend to be further improved. On the other hand, when the glass transition temperature of the polymer is 200 ° C. or lower, the dispersibility of the rubber particles (B) and the crack resistance of the cured product tend to be improved. In addition, the glass transition temperature of the polymer which comprises the said shell layer means the calculated value computed by the said Formula of Fox, For example, it can measure similarly to the glass transition temperature of the polymer which comprises the above-mentioned core.

Core-shell type rubber particles are obtained by covering the core part with a shell layer. Examples of the method for coating the core part with the shell layer include a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a polymer constituting the shell layer; Examples thereof include a graft polymerization method in which the core portion having rubber elasticity is a trunk component and each component constituting the shell layer is a branch component.

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

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. 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 It is preferably within ± 0.03.

The refractive index of the rubber particles (B) is, for example, 1 g of rubber particles (B) is cast into a mold and compression molded at 210 ° C. and 4 MPa to obtain a flat plate having a thickness of 1 mm. × A 6 mm wide test piece was cut out, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, Atago Co., Ltd.) was used in a state where the prism and the test piece were in close contact using monobromonaphthalene as an intermediate solution. And the refractive index at 20 ° C. and sodium D line can be measured.

The refractive index of the cured product of the curable resin composition of the present invention is, for example, a test piece having a length of 20 mm × width of 6 mm × thickness of 1 mm from a cured product obtained by the heat curing method described in the section of cured product below. Using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate solution, 20 It can obtain | require by measuring the refractive index in C, sodium D line | wire.

The content (blending amount) of the rubber particles (B) in the curable resin composition of the present invention is not particularly limited, but is 0.01 to 20% by weight with respect to the curable resin composition (100% by weight). Preferably, it is 0.05 to 15% by weight, more preferably 0.1 to 10% by weight. By making content of a rubber particle (B) into the said range, there exists a tendency which the crack resistance of hardened | cured material improves and heat resistance and light resistance are more excellent.

The content (blending amount) of the rubber particles (B) in the curable resin composition of the present invention is not particularly limited, but with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition, The amount is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight. By making content of a rubber particle (B) into the said range, there exists a tendency which the crack resistance of hardened | cured material improves and heat resistance and 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 imparts high light reflectivity to the cured product (reflector), and also functions to reduce its linear expansion coefficient. Have. As the white pigment (C), known or commonly used white pigments can be used, and are not particularly limited. For example, glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acidic clay, active Inorganic white pigments such as clay, boehmite, pseudoboehmite, inorganic oxides, metal salts [for example, alkaline earth metal salts]; styrene resins, benzoguanamine resins, urea-formalin resins, melamine-formalin resins, amides Organic white pigments (plastic pigments, etc.) such as resin pigments such as resin-based resins; hollow particles having a hollow structure (balloon structure), and the like.

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

Examples of the inorganic oxide include aluminum oxide (alumina), magnesium oxide, antimony oxide, titanium oxide [eg, rutile titanium oxide, anatase titanium oxide, brookite titanium oxide, etc.], zirconium oxide, zinc oxide, and the like. Can be mentioned. Examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, and sulfuric acid. Barium etc. are mentioned. Examples of the metal salt other than the alkaline earth metal salt include aluminum silicate, aluminum hydroxide, and zinc sulfide.

Although it does not specifically limit as said hollow particle, For example, inorganic glass [For example, silicate glass, aluminum silicate glass, sodium borosilicate glass, quartz, etc.], metal oxides, such as silica and alumina, calcium carbonate, barium carbonate, Inorganic hollow particles composed of inorganic materials such as nickel carbonate, calcium silicate and other metal salts (including natural products such as shirasu balloon); styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride -Based resins, vinylidene chloride-based resins, amide-based resins, urethane-based resins, phenol-based resins, styrene-conjugated diene-based resins, acrylic-conjugated diene-based resins, olefin-based polymers (including cross-linked products of these polymers), etc. Organic hollow particles composed of organic materials; hybrid materials of inorganic and organic materials Configured inorganic Ri - organic hollow particles, and the like. In addition, the said hollow particle may be comprised from the single material, and may be comprised from 2 or more types of materials. In addition, the hollow portion of the hollow particles (the space inside the hollow particles) may be in a vacuum state or may be filled with a medium. However, particularly from the viewpoint of improving the reflectance, the refractive index is low. Hollow particles filled with a medium (for example, an inert gas such as nitrogen or argon or air) are preferred.

The white pigment (C) is subjected to a known or conventional surface treatment [for example, a surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone]. It may be what was done. By performing such a surface treatment, there are cases where compatibility and dispersibility with other components in the curable resin composition can be improved.

Among these, as the white pigment (C), from the viewpoint of availability, heat resistance, light resistance, and high reflectance of the cured product (reflector) and light reflectance increase rate with respect to the addition amount, inorganic oxides, inorganic Hollow particles are preferred, more preferably aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, barium sulfate, inorganic hollow particles, and more preferably titanium oxide, zirconium oxide, zinc oxide, barium sulfate. In particular, the white pigment (C) is preferably titanium oxide because it has a higher refractive index.

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 scale shape. Among them, spherical titanium oxide is preferable from the viewpoint of dispersibility, and spherical titanium oxide (for example, spherical titanium oxide having an aspect ratio of 1.2 or less) is particularly 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 center 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, and still more preferably 0. .1 to 20 μm, particularly preferably 0.1 to 10 μm, most preferably 0.1 to 5 μm. On the other hand, when hollow particles (particularly inorganic hollow particles) are used as the white pigment (C), the center 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. In addition, the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.

In the curable resin composition of the present invention, the white pigment (C) can be used alone or in combination of two or more. The white pigment (C) can also be produced by a known or conventional method. For example, 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 "(manufactured by Sakai Chemical Industry Co., Ltd.) -50 "," CR-50-2 "," CR-60 "," CR-60-2 "," CR-63 "," CR-80 "," CR-90 "," CR-90-2 " "," CR-93 "," CR-95 "," CR-97 "(manufactured by Ishihara Sangyo 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" (manufactured by Teika Co., Ltd.), trade names "TR-600", "TR-700", "TR-750", "TR-840", "TR-900 (Fuji Titanium Industry Co., Ltd.), trade names “KR-310”, “KR-380”, “KR-380N”, “ST-410WB”, “ST-455”, “ST-455WB” , “ST-457SA”, “ST-457EC”, “ST-485SA15”, “ST-486SA”, “ST-495M” (above, manufactured by Titanium Industry Co., Ltd.), etc .; A-110 "," TCA-123 " "," A-190 "," A-197 "," SA-1 "," SA-1L "," SSP series "," CSB series "(above, manufactured by Sakai Chemical Industry Co., Ltd.) "JA-1", "JA-C", "JA-3" (manufactured by Teika Co., Ltd.), trade names "KA-10", "KA-15", "KA-20", "STT-65C" -S "," STT-30EHJ "(above, manufactured by Titanium Industry Co., Ltd.), trade names" DCF-T-17007 "," DCF-T-17008 "," DCF-T-17050 "(above, Resino Color Industries) Commercial products such as anatase-type titanium oxide such as (manufactured by Co., Ltd.) can also be used.

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

The content (blending amount) of the white pigment (C) in the curable resin composition of the present invention is not particularly limited, but is 0.1 to 50% by weight with respect to the curable resin composition (100% by weight). Preferably, it is 1 to 40% by weight, more preferably 5 to 35% by weight. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more by making content of a white pigment (C) 0.1 weight% or more. Moreover, there exists a tendency for heat resistance and light resistance to improve more. On the other hand, when the content of the white pigment (C) is 60% by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.

The content (blending amount) of the white pigment (C) in the curable resin composition of the present invention is not particularly limited, but is based on 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition. The amount 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. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more because content of a white pigment (C) is 10 weight part or more. Moreover, there exists a tendency for heat resistance and light resistance to improve more. On the other hand, when the content of the white pigment (C) is 600 parts by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.

When titanium oxide is contained in the curable resin composition of the present invention, the ratio of titanium oxide to the total amount (100% by weight) of the white pigment (C) and the inorganic filler (D) is not particularly limited, but a cured product ( From the viewpoint of the balance between heat resistance and light reflectivity of the reflector, the content is preferably 5 to 70% by weight, more preferably 10 to 60% by weight. By making the ratio of titanium oxide 5% by weight or more, the light reflectivity of the cured product (reflector) tends to be further improved. Moreover, there exists a tendency for heat resistance and light resistance to improve more. On the other hand, by setting the proportion of titanium oxide to 70% by weight or less, the moldability of the cured product (reflector) is improved and tends to be 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 separately from the white pigment (C). The inorganic filler (D) mainly imparts excellent heat resistance and light resistance (particularly excellent heat resistance) to the cured product (reflector). Moreover, it has the function to reduce the linear expansion coefficient of hardened | cured material (reflector). Moreover, depending on the kind of inorganic filler (D), the light reflectivity excellent with respect to hardened | cured material (reflector) may be provided.

As the inorganic filler (D), a known or conventional inorganic filler can be used, and is not particularly limited. For example, silica, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, Silicon nitride, aluminum nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, fosterite, steatite, spinel, clay, kaolin, dolomite , Hydroxyapatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, talc and the like, or moldings thereof (for example, spherical beads). Examples of the inorganic filler (D) include those obtained by subjecting the above-described inorganic filler to a known or conventional surface treatment. Among these, silica, alumina, silicon nitride, aluminum nitride, and boron nitride are preferable as the inorganic filler (D) from the viewpoint of heat resistance, light resistance, and fluidity of the cured product (reflector).

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

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

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

In the curable resin composition of the present invention, the inorganic filler (D) can be used alone or in combination of two or more. The inorganic filler (D) can also be produced by a known or conventional production method. For example, trade names “FB-910”, “FB-940”, “FB-950”, “FB-105” can be used. "," FB-105FD "," FB-5D "," FB-8S "," FB-7SDC "," FB-5SDC "," FB-3SDC "," FB-9FDC "," FB-7FDC ", FB series such as “FB-5FDC”, “FB-970FD”, “FB-975FD”, “FB-950FD”, “FB-40RFD”, product names “DAW-03DC”, “DAW-0525”, “DAW DAW series such as “-1025”, trade name “SGP” (manufactured by Denka), trade name “HF-05” (manufactured by Tokuyama), trade name “10 μm SE-CC5” (Admatech) Product names “MSR-2212”, “MSR-25” (above, manufactured by Tatsumori Co., Ltd.), product names “HS-105”, “HS-106”, “HS-107” (above, Micron) Commercially available products such as those manufactured by the company may also be used.

The content (blending 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 with respect to the curable resin composition (100% by weight). More preferably, it is 13 to 75% by weight, more preferably 15 to 70% by weight, and still more preferably 20 to 70% by weight. By setting the content of the inorganic filler (D) to 10% by weight or more, the heat resistance and light resistance (particularly excellent heat resistance) of the cured product tend to be further improved. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and problems such as lead frame warpage in an optical semiconductor element mounting substrate using the reflector tend not 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 tends to be more suitable for mass production.

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

The maximum particle size 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, still more preferably 175 μm or less, particularly Preferably it is 150 micrometers or less. When the maximum particle size is 200 μm or less, the cured product has heat resistance, light resistance, and crack resistance (especially excellent heat resistance) as compared with the case of using a white pigment or an inorganic filler having a maximum particle size exceeding 200 μm. ) Tends to be even better. Further, by using the white pigment (C) and the inorganic filler (D) having a small maximum particle size, it is possible to increase their contents, and the light reflectivity, heat resistance and light resistance of the cured product are further increased. There is a tendency to improve. The lower limit of the maximum particle size is, for example, 0.01 μm or more. The maximum particle size is the total maximum particle size of the white pigment (C) and the inorganic filler (D) contained in the curable resin composition of the present invention. The maximum particle size means the maximum particle size in the particle size distribution measured by the laser diffraction / scattering method.

[Curing agent (E)]
The curing agent (E) in the curable resin composition of the present invention is a compound having a function of curing the curable resin composition by reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A). is there. As the curing agent (E), a known or conventional epoxy resin curing agent can be used, and is not particularly limited. For example, acid anhydrides (acid anhydride curing agents), amines (amine curing) Agents), polyamide resins, imidazoles (imidazole-based curing agents), polymercaptans (polymercaptan-based curing agents), phenols (phenol-based curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides and the like.

As the acid anhydrides (acid anhydride curing agents) as the curing agent (E), known or conventional acid anhydride curing agents can be used, and are not particularly limited. For example, methyltetrahydrophthalic anhydride (4 -Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride), dodecenyl succinic anhydride, methyl Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydrous Nadic acid, methyl nadic acid anhydride, hydrogenated methyl Nadic acid anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride Examples include acid copolymers and alkylstyrene-maleic anhydride copolymers. Above all, from the viewpoint of efficiently preparing a uniform curable resin composition, from the viewpoint of easily mixing with the alicyclic epoxy compound (A) to form a liquid mixture (curing agent composition) at 25 ° C., 25 Preference is given to acid anhydrides [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] that are liquid at ° C. On the other hand, for the acid anhydride that is solid at 25 ° C., for example, the curing agent (E) in the curable resin composition of the present invention is prepared by dissolving in a liquid acid anhydride at 25 ° C. to form a liquid mixture. As a result, the handling property tends to be improved. As the acid anhydride curing agent, from the viewpoint of heat resistance and light reflectivity of the cured product, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those having a substituent such as an alkyl group bonded to the ring) are preferable. .

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

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

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

As the imidazole (imidazole curing agent) as the curing agent (E), a known or commonly used imidazole curing agent can be used, and 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-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanate 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]- And ethyl-s-triazine.

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

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

Among these, as the curing agent (E), acid anhydrides (acid anhydride curing agents) are preferable from the viewpoints of heat resistance, light resistance, and light reflectivity of the cured product. In addition, the hardening | curing agent (E) can also be used individually by 1 type in the curable resin composition of this invention, and can also be used in combination of 2 or more type. The curing agent can be produced by a known or conventional method. For example, trade names “Licacid MH-700”, “Licacid MH-700F”, “Licacid MH-700G”, “Licacid TH”, “Licacid CI” "HH", "Licacid HNA-100" (manufactured by Shin Nippon Rika Co., Ltd.); trade name "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.); trade names "H-TMAn-S", "H Commercially available products such as “TMAn” (Mitsubishi Gas Chemical Co., Ltd.); trade name “YH1120” (Mitsubishi Chemical Co., Ltd.) can also be used.

When the curable resin composition of this invention contains a hardening | curing agent (E), content (blending amount) of a hardening | curing agent (E) is although it does not specifically limit, With respect to curable resin composition (100 weight%) The content is preferably 1 to 40% by weight, more preferably 3 to 35% by weight, and still more preferably 5 to 30% by weight. By setting the content of the curing agent (E) to 1% by weight or more, the curing becomes more sufficient, and the crack resistance of the cured product tends to be improved. On the other hand, by setting the content of the curing agent (E) to 40% by weight or less, there is a tendency that a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained.

When the curable resin composition of the present invention contains a curing agent (E), the content (blending amount) of the curing agent (E) is not particularly limited, but has an epoxy group contained in the curable resin composition. The amount is preferably 40 to 200 parts by weight, more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the total amount of the compound. More specifically, when acid anhydrides are used as the curing agent (E), 0.5 to 0.5 per equivalent of epoxy group in the compound having all epoxy groups contained in the curable resin composition of the present invention. It is preferable to use it at a ratio of 1.5 equivalents. By setting the content of the curing agent (E) to 40 parts by weight or more, the curing becomes more sufficient and the crack resistance of the cured product tends to be improved. On the other hand, by setting the content of the curing agent (E) to 200 parts by weight or less, there is a tendency that a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained.

[Curing accelerator (F)]
The curable resin composition of the present invention may contain a curing accelerator (F). The curing accelerator (F) is a compound having an epoxy group contained in the curable resin composition of the present invention (for example, alicyclic epoxy compound (A), isocyanuric acid derivative (H), and siloxane derivative (I)). Is a compound having a function of accelerating the reaction rate when reacting with a curing agent such as curing agent (E). As the curing accelerator (F), a known or conventional curing accelerator can be used. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, phenol) Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, Octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, etc. Secondary amines; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Ether, phosphines such as triphenyl phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p- tolyl) borate, organometallic salts such as zinc octylate and tin octylate; metal chelate and the like.

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

Further, the curing accelerator (F) can be produced by a known or conventional method. For example, trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “12XD” (developed product) (San Apro Co., Ltd.); trade names “TPP-K”, “TPP-MK” (Hokuko Chemical Co., Ltd.); Commercial products such as the name “PX-4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) can also be used.

When the curable resin composition of the present invention contains a curing accelerator (F), the content (blending amount) of the curing accelerator (F) is not particularly limited, but the curable resin composition (100% by weight). The content is preferably 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight. By setting the content of the curing accelerator (F) to 0.0001% by weight or more, the curing reaction tends to proceed more efficiently. On the other hand, by setting the content of the curing accelerator (F) to 5% by weight or less, the storability of the curable resin composition is further improved, or a cured product (reflector) that is more suppressed in coloring and excellent in hue. There is a tendency to obtain easily.

When the curable resin composition of the present invention contains a curing accelerator (F), the content (blending amount) of the curing accelerator (F) is not particularly limited, but is an epoxy group contained in the curable resin composition. Is 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, and most preferably 0.25 parts by weight with respect to 100 parts by weight of the total amount of the compounds having the above. ~ 8 parts by weight. By setting the content of the curing accelerator to 0.05 parts by weight or more, the curing reaction tends to proceed more efficiently. On the other hand, by setting the content of the curing accelerator to 15 parts by weight or less, the storability of the curable resin composition is further improved, or a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained. Tend.

[Curing catalyst (G)]
The curing catalyst (G) in the curable resin composition of the present invention is a curable resin by initiating and / or accelerating a curing reaction (polymerization reaction) of a cationically polymerizable compound such as an alicyclic epoxy compound (A). It is a compound having a function of curing the composition. The curing catalyst (G) is not particularly limited. For example, a cationic polymerization initiator (photo cationic polymerization initiator, thermal cationic polymerization) that initiates polymerization by generating cationic species by performing light irradiation, heat treatment, or the like. Initiators, etc.), Lewis acid / amine complexes, Bronsted acid salts, imidazoles and the like.

Examples of the photocationic polymerization initiator as the curing catalyst (G) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically. For example, triarylsulfonium hexafluorophosphate (eg, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate), sulfonium salts such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salts); diaryl iodonium hexafluorophosphate Diaryl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodine Iodonium salts such as nium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; pyridinium salts such as N-hexylpyridinium tetrafluoroborate It is done. Examples of the cationic photopolymerization initiator include, for example, trade names “UVACURE 1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, the United States). Commercial products such as Sartomer); trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.

Examples of the thermal cationic polymerization initiator as the curing catalyst (G) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33”, “CP-66”. "CP-77" (manufactured by ADEKA); trade name "FC-509" (manufactured by 3M); trade name "UVE1014" (manufactured by GE); trade name "Sun-Aid SI-60L" “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-150L” (manufactured by Sanshin Chemical Industry Co., Ltd.); trade name “CG-24-61” ( Commercially available products such as BASF) can be preferably used. Further, as the thermal cationic polymerization initiator, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketone Examples thereof include a compound of a chelate compound with a phenol and a phenol such as bisphenol S.

As the Lewis acid / amine complex as the curing catalyst (G), a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited. 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 etc. are mentioned.

As the Bronsted acid salt as the curing catalyst (G), known or commonly used Bronsted acid salts can be used, and are not particularly limited. For example, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphoniums. Examples include salts.

As the imidazole as the curing catalyst (G), known or conventional imidazoles can be used, and are not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl Imidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4 - Amino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine, etc. Is mentioned.

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

When the curable resin composition of the present invention contains a curing catalyst (G), the content (blending amount) of the curing catalyst (G) is not particularly limited, but relative to the curable resin composition (100% by weight). The content is preferably 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 having excellent heat resistance and light resistance can be obtained.

When the curable resin composition of the present invention contains a curing catalyst (G), the content (blending amount) of the curing catalyst (G) in the curable resin composition of the present invention is not particularly limited. The amount is preferably 0.0001 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, and still more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the composition. Particularly preferred is 0.05 to 8 parts by weight. By using the curing catalyst (G) within the above range, a cured product having excellent heat resistance and light resistance can be obtained.

[Isocyanuric acid derivative (H) having one or more oxirane rings in the molecule]
The isocyanuric acid derivative (H) that is an essential component of the curable resin composition of the present invention is a derivative of isocyanuric acid and is a compound having at least one oxirane ring in the molecule. When the curable resin composition of the present invention contains the isocyanuric acid derivative (H), the light reflectivity, heat resistance, and light resistance of the cured product are improved, and the curable resin composition is simultaneously formed with the siloxane derivative (I) described later. By being contained in, the light reflectivity, heat resistance, and light resistance of the cured product are further improved. The number of oxirane rings in the molecule of the isocyanuric acid derivative (H) may be one or more and is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3.

Examples of the isocyanuric acid derivative (H) include compounds represented by the following formula (III).

In 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. Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group); a monovalent aromatic hydrocarbon group (for example, an aryl group); A cyclic group; a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The monovalent organic group may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom). Examples of the monovalent organic group containing an epoxy group include a monovalent organic group containing an epoxy group described later such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group, and a cyclohexene oxide group.

In particular, R ⁴ ~ R ⁶ in formula (III) may be the same or different, a group represented by the group or the following formula represented by the following formula (IIIa) (IIIb), the R ⁴ ~ R ⁶ At least one is preferably a group represented by the formula (IIIa).

R ⁷ and R ⁸ in the above formulas (IIIa) and (IIIb) are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, octyl and the like. Examples thereof include a chain or branched alkyl group. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable. R ⁷ and R ^{8 in} formula (IIIa) and formula (IIIb) are particularly preferably hydrogen atoms.

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

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

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

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

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

The above isocyanuric acid derivative (H) can be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.

Among these, the isocyanuric acid derivative (H) is preferably a compound represented by the above formulas (III-1) to (III-3) from the viewpoint of light reflectivity, heat resistance, and solubility of the cured product. A compound represented by the above formula (III-1) is preferable. In addition, in the curable resin composition of this invention, an isocyanuric acid derivative (H) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Examples of the isocyanuric acid derivative (H) include trade names “TEPIC” (manufactured by Nissan Chemical Industries, Ltd.); trade names “MA-DGIC”, “DA-MGIC” (above, Shikoku Kasei Kogyo Co., Ltd.) (Commercially available) can also be used.

The content (blending 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 relative to the curable resin composition (100% by weight). Is 0.1 to 10% by weight, more preferably 0.3 to 5% by weight. By setting the content of the isocyanuric acid derivative (H) within the above range, a cured product having excellent heat resistance and light resistance can be obtained.

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

[Siloxane derivative (I) having two or more epoxy groups in the molecule]
The siloxane derivative (I), which is an essential component of the curable resin composition of the present invention, has a skeleton composed of siloxane bonds (—Si—O—Si—) having two or more epoxy groups in the molecule. It is a compound (siloxane compound). The siloxane skeleton (Si—O—Si skeleton) in the siloxane derivative (I) is not particularly limited, and examples thereof include cyclic siloxane skeletons; linear silicones, cage-type and ladder-type polysilsesquioxanes, and the like. Examples include a polysiloxane skeleton. Among these, as the siloxane skeleton, a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the light reflectivity, heat resistance, and light resistance of the cured product and suppressing the light intensity reduction of the optical semiconductor device. That is, the siloxane derivative (I) is preferably a cyclic siloxane having two or more epoxy groups in the molecule and a linear silicone having two or more epoxy groups in the molecule.

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

The weight average molecular weight of the siloxane derivative (I) is not particularly limited, but is preferably 100 to 3000, more preferably 180 to 2000, from the viewpoint of improving the heat resistance and light resistance of the cured product. In addition, the said weight average molecular weight of siloxane derivative (I) is computed from the molecular weight of standard polystyrene conversion measured by GPC (gel permeation chromatography) method.

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

The epoxy equivalent of the siloxane derivative (I) is not particularly limited, but is preferably 180 to 2000, more preferably 180 to 1500, and still more preferably 180 to 1000 from the viewpoint of improving the heat resistance and light resistance of the cured product. . The epoxy equivalent is a value measured according to JIS K7236.

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

Examples of the siloxane derivative (I) include a siloxane compound represented by the following formula (IV).

In formula (IV), R ^a is the same or different and represents an epoxy group-containing group or an alkyl group. Provided that at least two R ^a in formula (IV) (e.g., 2 to four) is a group containing an epoxy group. The above-mentioned group containing an epoxy group is a group containing at least one epoxy group (oxirane ring). For example, a linear or branched aliphatic group having a carbon-carbon unsaturated double bond such as an alkenyl group. A group in which at least one double bond of a hydrocarbon group is epoxidized, or a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond (for example, a cycloalkenyl group; a cyclohexenylethyl group, etc. A group in which at least one double bond of the alkenylalkyl group or the like is epoxidized. More specifically, for example, 1,2-epoxyethyl group (epoxy group), 1,2-epoxypropyl group, 2,3-epoxypropyl group (glycidyl group), 2,3-epoxy-2-methylpropyl Groups (methyl glycidyl group), 3,4-epoxybutyl group, 3-glycidyloxypropyl group, 3,4-epoxycyclohexylmethyl group, 2- (3,4-epoxycyclohexyl) ethyl group and the like. Among them, a group in which at least one double bond of a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond is epoxidized is preferable. Examples of the alkyl group include straight-chain or branched chain groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group. An alkyl group etc. are mentioned. Of these, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.

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 and thermal shock resistance of the optical semiconductor device.

More specifically, examples of the siloxane derivative (I) include 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6. , 8,8-Hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,2,4,6,6,8- Hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6,8-dipropyl-2,4,6,8-tetramethyl- Cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetra Siloxane, 2,4,8-tri [2- (3- {Oxavicic [4.1.0] Heptyl}) ethyl] -2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tri [2- (3- {oxabicyclo [4.1. 0] heptyl}) ethyl] -6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetra [2- (3- {oxabicyclo [4.1. 0] heptyl}) ethyl] -2,4,6,8-tetramethyl-cyclotetrasiloxane, silsesquioxane having two or more epoxy groups in the molecule, and the like. More specifically, for example, a cyclic siloxane having two or more epoxy groups in the molecule represented by the following formula.

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

In the curable resin composition of the present invention, the siloxane derivative (I) can be used alone or in combination of two or more.

Siloxane derivatives (I) are, for example, trade names “X-40-2678”, “X-40-2670”, “X-40-2720” (and above) which are cyclic siloxanes having two or more epoxy groups in the molecule. Commercial products such as Shin-Etsu Chemical Co., Ltd.) are available. The siloxane derivative (I) can be produced by a known or conventional method.

The content (blending amount) of the siloxane derivative (I) in the curable resin composition of the present invention is preferably 0.1 to 30% by weight, more preferably relative to the curable resin composition (100% by weight). It is 0.5 to 20% by weight, more preferably 1.0 to 10% by weight. By controlling the content of the siloxane derivative (I) 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 improved.

The content (blending amount) of the siloxane derivative (I) in the curable resin composition of the present invention is not particularly limited, but with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition, The amount is preferably 5 to 99 parts by weight, more preferably 10 to 95 parts by weight, and still more preferably 20 to 80 parts by weight. By setting the content of the siloxane derivative (I) to 5 parts by weight or more, the thixotropy of the curable resin composition increases, and the heat resistance, light resistance, and light reflectivity of the cured product tend to be further improved. . On the other hand, when the content of the siloxane derivative (I) is 150 parts by weight or less, the thermal shock resistance and adhesiveness of the cured product tend to be further improved.

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

In the curable resin composition of the present invention, one type of release agent can be used alone, or two or more types can be used in combination. Moreover, a mold release agent can also be manufactured by a well-known thru | or usual method, and a commercial item can also be used for it.

When the curable resin composition of the present invention contains a release agent, the content (blending amount) of the release agent is not particularly limited, but the total amount of compounds having epoxy groups contained in the curable resin composition is 100. The amount is preferably 1 to 12 parts by weight, more preferably 2 to 10 parts by weight with respect to parts by weight. By making content of a mold release agent 1 weight part or more, there exists a tendency which the mold release property of hardened | cured material (reflector) improves more and the productivity of a reflector improves more. On the other hand, when the content of the release agent is 12 parts by weight or less, there is a tendency that good adhesion to the lead frame of the reflector in the substrate for mounting an optical semiconductor element can be secured.

[Antioxidant]
The curable resin composition of the present invention may contain an antioxidant. By containing an antioxidant, it becomes possible to produce a cured product (reflector) with even better heat resistance. As the antioxidant, known or commonly used antioxidants can be used, and are not particularly limited. For example, phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), phosphorus System antioxidants (phosphorus compounds), sulfur antioxidants (sulfur compounds), and the like.

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

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

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

Examples of the sulfur-based antioxidant include dodecanethiol, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate Is mentioned.

In the curable resin composition of the present invention, the antioxidant can be used alone or in combination of two or more. Antioxidants can also be produced by known or conventional methods. For example, trade names “Irganox 1010” (manufactured by BASF, phenolic antioxidants), trade names “AO-60”, “AO-80”. ”(Manufactured by ADEKA Corporation, phenolic antioxidant), trade name“ Irgafos168 ”(manufactured by BASF, phosphorous antioxidant), trade names“ ADK STAB HP-10 ”,“ ADEKA STAB PEP-36 ”(Corporation) Commercial products such as ADEKA (phosphorus antioxidant) and trade name “HCA” (manufactured by Sanko Co., Ltd., phosphorus antioxidant) can also be used.

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

[Additive]
The curable resin composition of the present invention may contain various additives in addition to the above-described components as long as the effects of the present invention are not impaired. For example, when a compound having a hydroxy group (especially an aliphatic polyhydric alcohol) such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained as the additive, the reaction can be allowed to proceed slowly. In addition, antifoaming agents, leveling agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, and surfactants, as long as the viscosity and light reflectivity are not impaired. Conventional additives such as flame retardants, colorants, ion adsorbents, ultraviolet absorbers, light stabilizers, and pigments other than the white pigment (C) can be used. The content of these additives is not particularly limited and can be appropriately selected.

The curable resin composition of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing agent (E), and a curing accelerator (F). , Isocyanuric acid derivative (H), and siloxane derivative (I), alicyclic epoxy compound (A), rubber particle (B), curing agent (E), curing accelerator (F), isocyanuric acid derivative The viscosity at 25 ° C. of the mixture comprising (H) and the siloxane derivative (I) is not particularly limited, but is preferably 5000 mPa · s or less. In addition, the curable resin composition of the present invention may contain the above-described aliphatic polyhydric alcohol such as ethylene glycol. In this case, the above-described mixture includes the alicyclic epoxy compound (A), rubber particles ( B), a curing agent (E), a curing accelerator (F), an isocyanuric acid derivative (H), a siloxane derivative (I), and an aliphatic polyhydric alcohol.

On the other hand, the curable resin composition of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing catalyst (G), an isocyanuric acid derivative ( In the case of containing H) and a siloxane derivative (I), it comprises an alicyclic epoxy compound (A), rubber particles (B), a curing catalyst (G), an isocyanuric acid derivative (H), and a siloxane derivative (I). The viscosity of the mixture at 25 ° C. is not particularly limited, but is preferably 5000 mPa · s or less. In the present specification, the viscosity at 25 ° C. of the above-mentioned two kinds of mixtures may be collectively referred to as “resin viscosity”.

The resin viscosity is a viscosity measured at 25 ° C. at normal pressure. The resin viscosity is preferably 5000 mPa · s or less, more preferably 4000 mPa · s or less, further preferably 3500 mPa · s or less, and particularly preferably 3000 mPa · s or less. When the resin viscosity is 5000 mPa · s or less, the heat resistance, light resistance, and crack resistance (particularly excellent heat resistance) of the cured product tend to be more excellent than when the resin viscosity exceeds 5000 mPa · s. is there. Further, since the resin viscosity is relatively low, it is possible to increase the content of other components such as white pigment (C) and inorganic filler (D), and the light reflectivity, heat resistance and light resistance of the cured product. There is a tendency for sex to be further improved. The lower limit of the resin viscosity is, for example, 100 mPa · s or more. The resin viscosity is measured using, for example, a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24, temperature: 25 ° C., rotational speed: 0 It can be measured under the condition of 5 to 10 rpm.

The resin viscosity is, for example, the components used (for example, alicyclic epoxy compound (A), curing agent (E), curing accelerator (F), curing catalyst (G), isocyanuric acid derivative (H), and siloxane derivative. (I), etc.) can be easily obtained by using a liquid component at 25 ° C. In addition, although a solid component may be used as said component at 25 degreeC, the content is adjusted so that the said resin viscosity may be 5000 mPa * s or less. Moreover, it becomes easy to obtain by adjusting content of a rubber particle (B) within the range which does not impair the effect of this invention.

The curable resin composition of the present invention is obtained by heating and reacting a part of the alicyclic epoxy compound (A) and the curing agent (E) in the curable resin composition to be a B-stage. It may be a curable resin composition (a curable resin composition in a B-stage state).

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

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

Although not particularly limited, the rubber particles (B) are blended in a state of being preliminarily dispersed in the alicyclic epoxy compound (A) (the composition may be referred to as “rubber particle dispersed epoxy compound”). It is preferable to do. That is, the curable resin composition of the present invention includes the rubber particle-dispersed epoxy compound, the white pigment (C), the inorganic filler (D), the curing agent (E) and the curing accelerator (F), or It is preferable to prepare by mixing the curing catalyst (G) and other components as necessary. Such a preparation method can particularly improve the dispersibility of the rubber particles (B) in the curable resin composition. However, the blending method of the rubber particles (B) is not limited to the above method, and may be a method of blending alone.

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

The viscosity of the rubber particle-dispersed epoxy compound can be adjusted, for example, by using a reactive diluent together (that is, the rubber particle-dispersed epoxy compound may further contain a reactive diluent). As the reactive diluent, for example, an aliphatic polyglycidyl ether having a viscosity at room temperature (25 ° C.) of 200 mPa · s or less can be preferably used. Examples of the aliphatic polyglycidyl ether having a viscosity (25 ° C.) of 200 mPa · s or less include cyclohexanedimethanol diglycidyl ether, cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. , Trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, and the like.

The amount of the reactive diluent used can be appropriately adjusted and is not particularly limited, but is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, with respect to 100 parts by weight of the total amount of the rubber particle-dispersed epoxy compound. (For example, 5 to 25 parts by weight). When the amount used is 30 parts by weight or less, desired performance such as improvement of toughness (crack resistance) tends to be easily obtained.

The method for producing the rubber particle-dispersed epoxy compound is not particularly limited, and a well-known and commonly used method can be used. For example, after the rubber particles (B) are dehydrated and dried to form a powder, the rubber particles (B) are mixed and dispersed in the alicyclic epoxy compound (A), or the emulsion of the rubber particles (B) and the alicyclic epoxy compound (A And the like, followed by dehydration and the like.

The viscosity of the curable resin composition of the present invention at 25 ° C. is not particularly limited, but is preferably 100 to 1000000 mPa · s, more preferably 200 to 800000 mPa · s, and still more preferably 300 to 800000 mPa · s. By setting the viscosity at 25 ° C. to 100 mPa · s or more, workability during casting is improved, and heat resistance and light resistance of the cured product tend to be further improved. On the other hand, when the viscosity at 25 ° C. is set to 1000000 mPa · s or less, workability during casting is improved, and defects due to casting defects tend not to occur in the cured product.

<Hardened product>
By curing the curable resin composition of the present invention by heating, a cured product having excellent light reflectivity and excellent heat resistance, light resistance, and crack resistance can be obtained. A cured product obtained by curing the curable resin composition of the present invention, that is, a cured product of the curable resin composition of the present invention may be referred to as “cured product of the present invention”. The heating temperature (curing temperature) during curing is not particularly limited, but is preferably 50 to 200 ° C, more preferably 80 to 180 ° C. Further, the heating time (curing time) at the time of curing is not particularly limited, but is preferably 60 to 1800 seconds, and more preferably 90 to 900 seconds. When the curing temperature and the curing time are lower than the lower limit of the above range, curing is insufficient, and when the curing temperature and the curing time are higher than the upper limit of the above range, yellowing due to thermal decomposition occurs. Although the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased. Further, the curing process may be performed in one stage (for example, compression molding only), for example, in multiple stages (for example, further heating in an oven or the like as post-curing (secondary curing) after compression molding). Also good. When post-curing is performed, the heating temperature at this time is preferably 50 to 200 ° C., more preferably 60 to 180 ° C., and more preferably about the same as the curing temperature. The post-curing time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours.

The cured product of the present invention has high light reflectivity and is excellent in heat resistance and light resistance. For this reason, the said hardened | cured material does not deteriorate easily and a reflectance does not fall easily with time. Therefore, the curable resin composition of the present invention is used for LED packages (component materials for LED packages, such as reflector materials and housing materials for optical semiconductor devices), adhesive applications for electronic components, and liquid crystal display applications (for example, reflectors). Etc.), and can be preferably used as white substrate ink, sealer and the like. Especially, it can use especially preferably as curable resin composition for LED packages (especially curable resin composition for reflectors in an optical semiconductor device (that is, curable resin composition for forming reflectors)).

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 still more preferably. 95% or more. In particular, the reflectance of light at 450 to 800 nm is preferably 93% or more, more preferably 94% or more, and still more preferably 95% or more.

The retention ratio of the light reflectance at a wavelength of 450 nm after heating for 250 hours at 120 ° C. (sometimes referred to as “reflectance after heat aging”) to the initial reflectance ([heat aging (Reflectance after) / [Initial reflectance] × 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. In particular, the retention in the case of 450 to 800 nm light is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. According to the curable resin composition of the present invention, the cured product formed by compression molding can have the above-mentioned retention rate of 90% or more.

Maintaining the reflectance of the cured product of the present invention with respect to light having a wavelength of 450 nm after irradiation with ultraviolet rays having an intensity of 10 mW / cm ² for 250 hours (sometimes referred to as “reflectance after ultraviolet ray aging”) relative to the initial reflectance. The rate ([reflectance after ultraviolet ray aging] / [initial reflectivity] × 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. . In particular, the retention in the case of 450 to 800 nm light is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.

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

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 substrate of an optical semiconductor element (for mounting an optical semiconductor element) in an optical semiconductor device. This is a molding material (material used for molding with a mold or the like) used for forming a reflector (light reflecting member) included in the substrate. Therefore, by molding (and curing) the curable resin composition of the present invention, it has high light reflectivity, excellent heat resistance and light resistance, and has a high-quality reflector having excellent crack resistance. A substrate for mounting an optical semiconductor element (for example, highly durable) can be manufactured. The reflector is a member for reflecting light emitted from the optical semiconductor element in the optical semiconductor device to increase the directivity and luminance of the light and improve the light extraction efficiency. A substrate used for mounting an optical semiconductor element having at least a reflector formed of the cured product of the present invention may be referred to as “optical semiconductor element mounting substrate of the present invention”.

<Optical semiconductor device mounting substrate>
The substrate for mounting an optical semiconductor element of the present invention is a reflector (white reflector) formed of a cured product of the curable resin composition of the present invention (cured product obtained by curing the curable resin composition of the present invention). Is a substrate having at least FIG. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention, where (a) is a perspective view and (b) is a cross-sectional view. In FIG. 1, 100 is a white reflector, 101 is a metal wiring (lead frame), 102 is an optical semiconductor element mounting region, and 103 is a package substrate. A metal wiring 101 and a white reflector 100 are attached to the package substrate 103. An optical semiconductor element 107 is placed in the center (optical semiconductor element mounting region 102) and die-bonded. And the metal wiring 101 on the package substrate 103 are connected by wire bonding. As the material of the package substrate 103, resin, ceramic, or the like is used, but it may be the same as the white reflector. The upper white reflector 100 in the optical semiconductor element mounting substrate of the present invention has a concave shape that surrounds the optical semiconductor element mounting region 102 in an annular shape and is inclined so that the diameter of the ring increases upward. Have. The substrate for mounting an optical semiconductor element of the present invention is only required to have the inner surface of the concave shape formed of at least a cured product of the curable resin composition of the present invention. Further, as shown in FIG. 1, the portion surrounded by the metal wiring 101 (the lower part of 102) may be the package substrate 103 or the white reflector 100 (that is, “100/103 in FIG. 1). "Means the white reflector 100 or the package substrate 103). However, the optical semiconductor element mounting substrate of the present invention is not limited to the embodiment shown in FIG.

As a method for forming a white reflector in the substrate for mounting an optical semiconductor element of the present invention, a known or conventional molding method (for example, compression molding or the like) can be used, and is not particularly limited. Examples include a method of subjecting the functional resin composition to various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and dam molding by dispensing. The curing conditions for forming the reflector can be appropriately selected from, for example, the conditions for forming the cured product described above. In the present invention, among other things, it is possible to prevent foaming due to a rapid curing reaction, relax stress strain due to curing, and improve toughness (crack resistance). It is preferable to cure it.

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

<Optical semiconductor device>
The optical semiconductor device of the present invention is an optical semiconductor device comprising at least an optical semiconductor element as a light source and a reflector (reflecting material) made of a cured product of the curable resin composition of the present invention. More specifically, the optical semiconductor device of the present invention is an optical semiconductor device having at least the optical semiconductor element mounting substrate of the present invention and an optical semiconductor element mounted on the substrate. Since the optical semiconductor device of the present invention has a reflector formed of a cured product of the curable resin composition of the present invention as a reflector, the luminance of light is unlikely 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 is a white reflector, 101 is a metal wiring (lead frame), 103 is a package substrate, 104 is a bonding wire, 105 is a sealing material, 106 is die bonding, and 107 is an optical semiconductor element (LED element). In the optical semiconductor device shown in FIG. 2, the light emitted from the optical semiconductor element 107 is reflected by the surface (reflecting surface) of the white reflector 100, so that the light from the optical semiconductor element 107 is extracted with high efficiency. As shown in FIG. 2, the optical semiconductor element in the optical semiconductor device of the present invention is usually sealed with a transparent sealing material (105 in FIG. 2).

3 and 4 are diagrams showing another example of the optical semiconductor device of the present invention. Reference numeral 108 in FIGS. 3 and 4 denotes a heat sink (case heat sink), and by having such a heat sink 108, the heat radiation efficiency in the optical semiconductor device is improved. FIG. 3 is an example in which the heat dissipation path of the heat sink is located immediately below the optical semiconductor element, and FIG. 4 is an example in which the heat dissipation path of the heat sink is positioned in the lateral direction of the optical semiconductor device [(a) is a top view, (B) shows a cross-sectional view along AA ′ in (a)]. The heat sink 108 protruding from the side surface of the optical semiconductor device in FIG. 4 may be referred to as a heat radiating fin. Further, reference numeral 109 in FIG. 4 denotes a cathode mark. However, the optical semiconductor device of the present invention is not limited to the embodiment shown in FIGS.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In Tables 1 to 3, the unit of the amount of each component of the curable resin composition is parts by weight. In Tables 1 to 3, “-” means that the component was not blended.

Production Example 1
(Manufacture of rubber particles)
In a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Here, a monomer mixture composed of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion of the rubber particles. Were added together and emulsified by stirring for 20 minutes, and then 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour to perform the first seed polymerization. Subsequently, 180.5 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, the remaining amount (about 95% by weight) of butyl acrylate 180.5 g, styrene 48.89 g, divinylbenzene 7.33 g and 0.95 g sodium dioctyl sulfosuccinate required to form the core portion. A monomer mixture obtained by dissolving sucrose was continuously added over 2 hours to perform seed polymerization for the second time, and then aged for 1 hour to obtain a core part.
Next, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, 0.3 g of sodium dioctylsulfosuccinate was dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid and 0.3 g of allyl methacrylate. The monomer mixture was continuously added over 30 minutes to perform seed polymerization. Then, it aged for 1 hour and formed the shell layer which coat | covers a core part.
Next, the mixture was cooled to room temperature (25 ° C.) and filtered through a plastic mesh having an opening of 120 μm to obtain a latex containing rubber particles having a core-shell structure. The obtained latex was frozen at −30 ° C., dehydrated and washed with a suction filter, and then blown and dried at 60 ° C. overnight to obtain rubber particles. The resulting rubber particles had an average particle size of 108 nm and a maximum particle size of 289 nm.

The average particle size and the maximum particle size of the rubber particles are determined based on a nanotrac ^™ particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle. ) Was used to measure the sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is 0 The maximum particle size at the time of exceeding 0.000 was defined as the maximum particle size. In addition, as said sample, what disperse | distributed 1 weight part of rubber particle dispersion | distribution epoxy compounds obtained by the following manufacture example 2 to 20 weight part of tetrahydrofuran was used.

Production Example 2
(Manufacture of rubber particle-dispersed epoxy compounds)
Using a dissolver with 5 parts by weight of the rubber particles obtained in Production Example 1 heated to 60 ° C. in a nitrogen stream, the product name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4) -Epoxy) cyclohexanecarboxylate (manufactured by Daicel Corporation) and dispersed in 100 parts by weight (1000 rpm, 60 minutes) and vacuum degassed to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C .: 1036 mPa · s). It was.
The viscosity at 25 ° C. of the rubber particle-dispersed epoxy compound obtained in Production Example 2 (5 parts by weight of rubber particles dispersed in 100 parts by weight of ceroxide 2021P) is a digital viscometer (trade name “DVU”). -EII ", manufactured by Tokimec Co., Ltd.).

Production Example 3
In the blending ratios (unit: parts by weight) shown in Table 1 and Table 2, the product name “Licacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.) and the product name “U-CAT 18X” (manufactured by San Apro Co., Ltd.) And ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) are uniformly mixed using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.) It foamed and the hardening | curing agent composition was obtained.

Example 1
According to the blending ratio (unit: parts by weight) shown in Table 1, the rubber particle-dispersed epoxy compound obtained in Production Example 2, isocyanuric acid derivative (monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, Shikoku Kasei Kogyo Co., Ltd. ), A siloxane derivative (a siloxane derivative having two epoxy groups in the molecule; a trade name “X-40-2678”, a self-revolving stirrer (a trade name “Awatori Nerita AR-250”, The mixture was uniformly mixed and defoamed using a product manufactured by Shinky Co., Ltd., and the mixture was stirred 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 mixture obtained above, white pigment (titanium oxide; trade name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd.), inorganic filling The agent (silica; trade name “FB-970FD”, manufactured by Denka Co., Ltd.) is uniformly mixed using a dissolver, and is subjected to predetermined conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3) by a roll mill. The kneaded product was obtained by melt kneading in a pass.
Next, the kneaded product obtained above and the curing agent composition obtained in Production Example 3 so as to have the blending ratio (unit: parts by weight) shown in Table 1 were mixed with a self-revolving stirrer (trade name “Awatori” The mixture was uniformly mixed (2000 rpm, 5 minutes) using Nertaro AR-250 "(Sinky Corp.) and defoamed to obtain a curable resin composition.
The curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., heated and pressurized at a pressure of 3.0 MPa for 600 seconds, and then post-cured (5 at 150 ° C. Time), a cured product was obtained.

Examples 2 to 14 and Comparative Examples 1 to 15
A cured product was obtained in the same manner as in Example 1 except that the composition of the curable resin composition was changed as shown in Table 1 or Table 2. In some examples and comparative examples, as a constituent component of the curable resin composition, the alicyclic ring shown in Table 1 or Table 2 is used instead of or in addition to the rubber particle-dispersed epoxy compound obtained in Production Example 2. The formula epoxy compound was used.

Example 15
According to the blending ratio (unit: parts by weight) shown in Table 1, the rubber particle-dispersed epoxy compound obtained in Production Example 2, isocyanuric acid derivative (monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, Shikoku Kasei Kogyo Co., Ltd. )), A siloxane derivative (a siloxane derivative having two epoxy groups in the molecule; trade name “X-40-2678”, manufactured by Shin-Etsu Chemical Co., Ltd.), a self-revolving stirrer (trade name “Awatori” Using Nertaro AR-250 "(manufactured by Shinky Co., Ltd.), the mixture was uniformly mixed and defoamed to prepare a mixture. The above mixing was carried out with stirring 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 mixture obtained above, white pigment (titanium oxide; trade name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd.), inorganic filling The agent (silica; trade name “FB-970FD”, manufactured by Denka Co., Ltd.) is uniformly mixed using a dissolver, and is subjected to predetermined conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3) by a roll mill. The kneaded product was obtained by melt kneading in a pass.
Next, the kneaded product obtained above so as to have the blending ratio (unit: parts by weight) shown in Table 1 and the curing catalyst (trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd.) Using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), uniformly mix (2000 rpm, 5 minutes), defoam, and curable resin composition Obtained.
The curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., heated and pressurized at a pressure of 3.0 MPa for 600 seconds, and then post-cured (5 at 150 ° C. Time), a cured product was obtained.

Example 16 and Comparative Examples 16 to 24
A cured product was obtained in the same manner as in Example 15 except that the composition of the curable resin composition was changed as shown in Tables 1 and 3. In some examples and comparative examples, the alicyclic rings shown in Table 1 or Table 3 are used instead of or in addition to the rubber particle-dispersed epoxy compound obtained in Production Example 2 as a constituent of the curable resin composition. The formula epoxy compound was used.

The properties (liquid or solid) at 25 ° C. of the curable resin compositions in Examples 1 to 16 and Comparative Examples 1 to 24 are shown in “Properties of Curable Resin Composition” in Tables 1 to 3.

<Evaluation>
The following evaluation was implemented about the hardened | cured material obtained by the Example and the comparative example.

[Initial reflectance]
The cured products obtained in the examples and comparative examples were cut to prepare test pieces having a length of 30 mm × width of 30 mm × thickness of 3 mm. Next, using a spectrophotometer (trade name “Spectrophotometer UV-2450”, manufactured by Shimadzu Corporation), the reflectance (referred to as “initial reflectance”) of each test piece with respect to light having a wavelength of 450 nm is measured. did. The results are shown in Tables 1 to 3.
If the initial reflectance is 95% or more, it can be said that the material is particularly excellent as a light reflecting material.

[Reflectance retention before and after heat aging]
Using a test piece (cured product; length 30 mm × width 30 mm × 3 mm thickness) on which the initial reflectance was evaluated, the test piece was placed in a dryer at 120 ° C. and allowed to stand for 250 hours (heat resistance test). After the measurement, the reflectance of light having a wavelength of 450 nm was measured in the same manner as the initial reflectance. And the reflectance maintenance factor (before and after heating aging) was computed by the following formula. The results are shown in Tables 1 to 3.
[Reflectance retention ratio (before and after heating aging)] = ([Reflectance after heating aging] / [Initial reflectance]) × 100
It is suggested that the higher the reflectance retention, the better the cured product is in heat resistance. In addition, if the reflectance retention after heating at 120 ° C. for 250 hours is 90% or more, it can be said that the material is particularly excellent in heat resistance as a light reflecting material.

[Reflectance retention before and after UV aging]
Using a test piece (cured product: length 30 mm × width 30 mm × 3 mm thickness) on which the initial reflectance was evaluated, the test piece was irradiated with ultraviolet light having an intensity of 10 mW / cm ² for 250 hours (light resistance test) ), The reflectance of light having a wavelength of 450 nm was measured in the same manner as the initial reflectance. And the reflectance retention (before and after ultraviolet ray aging) was computed by the following formula. The results are shown in Tables 1 to 3.
[Reflectance retention (before and after ultraviolet aging)] = ([Reflectance after ultraviolet aging] / [Initial reflectance]) × 100
It is suggested that the higher the reflectance retention, the more excellent the light resistance of the cured product. In addition, when the intensity retention is 10 mW / cm ² and the reflectance retention after irradiation for 250 hours is 90% or more, it can be said that it is particularly excellent in light resistance as a light reflecting material.

[Evaluation of presence or absence of cracks during cutting (toughness evaluation)]
The cured products obtained in the examples and comparative examples were cut to prepare test pieces having a width of 5 mm, a length of 5 mm, and a thickness of 3 mm. For cutting of the cured product, a micro cutting machine (trade name “BS-300CL”, manufactured by Meiwa Forsys Co., Ltd.) was used, and whether or not cracks occurred in the cured product during the cutting process. This was observed and confirmed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation). In Tables 1 to 3, ten test pieces are prepared for each sample, and the number of test pieces in which cracks are confirmed [pieces / 10 pieces] is shown as an evaluation result.

[Evaluation of crack presence during reflow (toughness evaluation)]
Using a reflow furnace (trade name “UNI-5016F”, manufactured by Nippon Antom Co., Ltd.), the maximum temperature of 260 ° C. is applied to the test piece (width 5 mm × length 5 mm × thickness 3 mm) obtained by the above cutting process. The reflow treatment was performed at a temperature of 5 seconds and a total reflow time of 90 seconds. Thereafter, whether or not the test piece was cracked by the reflow treatment was observed and confirmed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation). Tables 1 to 3 show the number of test pieces [pieces / 10 pieces] in which the occurrence of cracks was confirmed among 10 test pieces per sample as evaluation results.

[Comprehensive judgment]
As a result of each test, a sample satisfying all of the following (1) to (5) was judged as ◯ (good). On the other hand, when any of the following (1) to (5) was not satisfied, it was determined as x (defective).
(1) Initial reflectance: light reflectance is 95% or more (2) Reflectivity retention ratio before and after heating aging: Reflectivity retention ratio is 90% or more (3) Reflectivity retention ratio before and after ultraviolet aging: Reflectance retention ratio 90% or more (4) Evaluation of presence or absence of cracks during cutting: 0 number of cracks generated (5) Evaluation of presence or absence of cracks during reflow: 0 number of cracks generated It is shown in the “determination” column.

The components shown in Tables 1 to 3 will be described below.
(Rubber particle dispersed epoxy compound)
Rubber particle-dispersed epoxy compound (epoxy compound) obtained in Production Example 2
Celoxide 2021P: Trade name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate), manufactured by Daicel Corporation EHPE3150: Trade name “EHPE3150” (2,2-bis (hydroxymethyl) ) -1-Butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct), manufactured by Daicel Corporation (isocyanuric acid derivative)
TEPIC: Trade name “TEPIC” [triglycidyl isocyanurate], manufactured by Nissan Chemical Industries, Ltd. MA-DGIC: Trade name “MA-DGIC” [monoallyl diglycidyl isocyanurate], Shikoku Kasei Kogyo DA- MGIC: Trade name “DA-MGIC” [diallyl monoglycidyl isocyanurate], manufactured by Shikoku Chemicals Co., Ltd. (siloxane derivative)
X-40-2678: Trade name “X-40-2678” (siloxane derivative having two epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd. X-40-2720: Trade name “X-40-2720” "(Siloxane derivative having three epoxy groups in the molecule), X-40-2670 manufactured by Shin-Etsu Chemical Co., Ltd .: trade name" X-40-2670 "(siloxane derivative having four epoxy groups in the molecule) , Shin-Etsu Chemical Co., Ltd. (curing agent composition)
MH-700: Trade name “Licacid MH-700” (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride), manufactured by Shin Nippon Rika Co., Ltd. 18X: Trade name “U-CAT 18X” (curing accelerator) , San Apro Co., Ltd. (additive)
Ethylene glycol: Trade name “Ethylene glycol”, Wako Pure Chemical Industries, Ltd. (curing catalyst)
Sun-Aid SI-100L: Trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd. (white pigment)
DCF-T-17050: Trade name “DCF-T-17050” (titanium oxide, average particle size 0.3 μm, maximum particle size 1 μm or less), manufactured by Resino Color Industry Co., Ltd. (inorganic filler)
FB-970FD: Trade name “FB-970FD” (silica, no surface treatment, average particle size 16.7 μm, maximum particle size 70 μm), manufactured by Denka Corp. DAW-1025: Trade name “DAW-1025” (alumina, (Average particle size 7.9 μm, maximum particle size 32 μm), manufactured by Denka Co., Ltd. HF-05: trade name “HF-05” (alumina nitride, average particle size 5 μm, maximum particle size 5 μm), manufactured by Denka Co., Ltd.

Since the curable resin composition of the present invention has the above-described configuration, it can form a cured product having high light reflectivity, excellent heat resistance and light resistance, and light reflectivity hardly decreasing over time. Especially, when the cured product is formed by compression molding, the above-mentioned effect is remarkably exhibited. Therefore, it is possible to provide a highly reliable optical semiconductor device in which the luminance of light hardly decreases over time.

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

Claims (9)

Alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), isocyanuric acid derivative (H) having one or more oxirane rings in the molecule, and in the molecule It contains a siloxane derivative (I) having two or more epoxy groups, and further contains a curing agent (E) and a curing accelerator (F) or a curing catalyst (G), and is liquid at 25 ° C. A curable resin composition for light reflection characterized by the above. The rubber particles (B) are composed of a polymer having (meth) acrylic acid ester as an essential monomer component, have a hydroxyl group and / or a carboxy group on the surface, and the rubber particles (B) have an average particle diameter. The curable resin composition for light reflection according to claim 1, which has a particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm. The alicyclic epoxy compound (A) is represented by the following formula (I-1)

The curable resin composition for light reflection of Claim 1 or 2 containing the compound represented by these. The isocyanuric acid derivative (H) is represented by the following formula (III-1)

[In 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 3, which is a compound represented by the formula: The white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate;
The light reflecting material according to any one of claims 1 to 4, wherein the inorganic filler (D) is at least one selected from the group consisting of silica, alumina, silicon nitride, aluminum nitride, and boron nitride. Curable resin composition. 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 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 made of a cured product of the light reflecting curable resin composition according to claim 8.

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