TW201402635A - Curable epoxy resin composition - Google Patents

Abstract

The purpose of this invention is to provide a curable epoxy resin composition, which can form a cured article having high heat resistance, high light resistance, and high thermal-shock resistance, especially having excellent hygroscopicity-reflow resistance. The curable epoxy resin composition of this invention is characterized in that comprises alicyclic epoxy compounds (A), monoallyl diglycidyl isocyanurate compounds (B) represented by the following formula (1), and glass fillers (C). The curable epoxy resin composition wherein the alicyclic epoxy compound (A) is a compound which is preferable to have a cyclohexene oxide group. [In the formula, R 1and R2 are identical with or different from each other, representing a hydrogen atom or an alkyl group of 1 to 8 of carbon numbers.]

Description

Curable epoxy resin composition

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

In recent years, optical semiconductor devices have been increasing in power, and high heat resistance and light resistance are required for coating resins (packaging materials) of optical semiconductor devices in such optical semiconductor devices. The encapsulating agent for forming a high heat-resistant sealing material is, for example, a composition containing a monopropenyl diglycidyl trimeric isocyanate and a bisphenol A type epoxy resin (see Patent Document 1). However, the composition is used for high power blue. In the case of a white photo-semiconductor encapsulant, the light emitted from the optical semiconductor element causes coloring of the encapsulant to absorb light that should be output, and as a result, the luminosity of the output light of the photo-semiconductor decreases.

An encapsulant capable of forming a cured product (packaging material) having high heat resistance and light resistance and not easily yellowing, and 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane is known. a carboxylate, an adduct of 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate and ε-caprolactone, and 1,2,8,9-di Liquid alicyclic epoxy having an alicyclic skeleton such as epoxy oxime Resin. However, the cured products of the alicyclic epoxy resins are weak against various stresses, and if a thermal shock such as a thermal cycle (periodical heating and cooling is applied), cracking may occur (crack; crack cracking). And other issues.

Further, an optical semiconductor device (for example, a surface-adhesive optical semiconductor device) generally undergoes a reflow step of bonding an electrode of an optical semiconductor device to a wiring substrate by soldering. In recent years, the solder used for the bonding material is mostly a high-melting lead-free solder, and the heat treatment in the reflow step is higher (for example, the maximum temperature is 240 to 260 ° C). In such a case, in the conventional optical semiconductor device, the heat treatment in which the reflow step occurs causes deterioration of the package material from the lead frame of the optical semiconductor device and cracking of the package material.

For this reason, in addition to high heat resistance and light resistance, the package of the optical semiconductor device is required to have a property of not easily generating cracks even when a thermal shock is applied (also referred to as "thermal shock resistance"), and it is difficult to heat-treat in the reflow step. Produces the characteristics of cracking or peeling. Especially in recent years, from the viewpoint of ensuring high reliability of packaging materials, it is required to place the optical semiconductor device under high humidity conditions for a certain period of time (for example, 30 ° C, 168 hours under 70% RH conditions; 60 ° C, 60% RH conditions) After the moisture absorption in the next 40 hours, etc., the heat treatment in the reflow step is also less likely to cause cracking or peeling as described above (this property is also referred to as "water absorption reflow resistance").

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2000-344867

Accordingly, an object of the present invention is to provide a curable epoxy resin composition which can form a cured product having high heat resistance, light resistance, and thermal shock resistance, particularly excellent moisture absorption reflow resistance.

Further, another object of the present invention is to provide a cured product which has high heat resistance, light resistance and thermal shock resistance, and particularly excellent moisture absorption reflow resistance.

Moreover, another object of the present invention is to provide an optical semiconductor device capable of suppressing deterioration such as reduction in luminosity, and in particular, it is possible to suppress deterioration such as reduction in illuminance during heat treatment in a reflow step after storage in a high-humidity condition.

As a result of a positive review of the problem, the present inventors have found that a curable epoxy resin composition containing an alicyclic epoxy compound and a monopropylene diepoxypropyl trimer isocyanate compound and a glass filler can be formed to have high heat resistance. The present invention has been completed in terms of properties, light resistance and thermal shock resistance, particularly a cured product excellent in moisture absorption reflow resistance.

In other words, the present invention provides a curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A) and a monopropenyldioxypropyltrimeric isocyanate compound represented by the following formula (1) (B) ) with glass filler (C),

[wherein R ¹ and R ^{2 are the} same or different from each other to represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

Further, a curable epoxy resin composition as described above is provided, wherein the alicyclic epoxy compound (A) is a compound having an epoxycyclohexane group.

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

Further, a curable epoxy resin composition as described above is provided, which comprises a decane derivative having two or more epoxy groups in its molecule.

Further, a curable epoxy resin composition as described above is provided, which contains an alicyclic polyester resin.

Further, a curable epoxy resin composition as described above is provided, which contains rubber particles.

Further, a curable epoxy resin composition as described above is provided, which contains a curing agent (D) and a curing accelerator (E).

Further, a curable epoxy resin composition as described above is provided, which contains a curing catalyst (F).

Further, the present invention provides a cured product obtained by hardening a curable epoxy resin composition as described above.

Further, a curable epoxy resin composition as described above is provided, which is a resin composition for optical semiconductor encapsulation.

Further, the present invention provides an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of the above-described curable epoxy resin composition.

Since the curable epoxy resin composition of the present invention has the above-described configuration, the resin composition can be cured to have high heat resistance, light resistance, and thermal shock resistance, and particularly excellent in moisture absorption reflow resistance. Things. Therefore, when the curable epoxy resin composition of the present invention is used as a resin composition for photo-semiconductor encapsulation, particularly after storage under high-humidity conditions, heat treatment in the reflow step can also cause deterioration such as luminosity reduction. A high-quality optical semiconductor device with high durability.

100‧‧‧Reflective layer (resin composition for light reflection)

101‧‧‧Metal wiring

102‧‧‧Optical semiconductor components

103‧‧‧bonding line

104‧‧‧ hardened materials (packaging materials)

Fig. 1 is a schematic view showing an embodiment of an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of the curable epoxy resin composition of the present invention. The left side view (a) is a perspective view, and the right side view (b) is a cross-sectional view.

Fig. 2 is a view showing an example of the tendency of the surface temperature of the optical semiconductor device (the temperature tendency of one of the heat treatments of the two heat treatments) in the solder heat resistance test of the example.

Embodiment of the invention <Curable epoxy resin composition>

The curable epoxy resin composition of the present invention contains at least an alicyclic epoxy compound (A) and a monopropenyldioxypropyltrimeric isocyanate compound (B) represented by the following formula (1) and a glass filled Resin composition of material (C),

[wherein R ¹ and R ^{2 are the} same or different from each other to represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

[Cycloaliphatic epoxy compound (A)]

In the curable epoxy resin composition of the present invention, the alicyclic epoxy compound (A) is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in the molecule (in one molecule). Specific examples of the alicyclic epoxy compound (A) include (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom constituting the alicyclic ring, and (ii) a compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond or the like. However, the alicyclic epoxy compound (A) does not contain a halogenated alkane derivative having two or more epoxy groups in the molecule to be described later.

The above (i) has a compound having an epoxy group (alicyclic epoxy group) constituting an adjacent two carbon atoms and an oxygen atom of the alicyclic ring, and can be arbitrarily selected from known or customary compounds. Among them, the alicyclic epoxy group is preferably an epoxycyclohexane group.

The above (i) has a compound consisting of an epoxy group (alicyclic epoxy group) constituting two adjacent carbon atoms and an oxygen atom of the alicyclic ring, and is transparent. From the viewpoint of the properties and heat resistance, a compound having an epoxycyclohexane group is preferred, and a compound represented by the following formula (I) (alicyclic epoxy compound) is particularly preferred.

In the formula (I), X represents a single bond or a linking group (having a divalent group of one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine group, and a group obtained by linking a plurality of these groups.

In the formula (I), the alicyclic epoxy compound wherein X is a single bond may, for example, be 3,4,3',4'-dicyclooxybicyclohexane.

Examples of the divalent hydrocarbon group include a linear or branched alkyl group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. The linear or branched alkylene group having 1 to 18 carbon atoms may, for example, be a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group or a trimethylene group. The divalent alicyclic hydrocarbon group may, for example, be a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, or a divalent cycloalkylene group (including a cycloalkylene group) such as a 4-cyclohexylene group or a cyclohexylene group.

The linking group X is particularly preferably a linking group containing an oxygen atom, and specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-; from a plurality of such groups a group to be linked; a group obtained by linking one or two or more such groups to one or two or more divalent hydrocarbon groups. The divalent hydrocarbon group can be exemplified above.

Representative examples of the alicyclic epoxy compound represented by the formula (I) include compounds represented by the following formulas (I-1) to (I-10). In addition, In the following formulae (I-5) and (I-7), l and m each represent an integer of 1 to 30. In the following formula (I-5), R is an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an exoethyl group, a propyl group, an isopropyl group, a butyl group, an exobutyl group, and a stretching group. A straight or branched chain alkyl group such as a second butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. Further, these are preferably a linear or branched alkyl group having 1 to 3 carbon atoms such as a methylene group, an ethyl group, a propyl group and an isopropyl group. In the following formulas (I-9) and (I-10), n1 to n6 each represent an integer of 1 to 30.

The compound (ii) wherein the epoxy group is directly bonded to the alicyclic ring by a single bond may, for example, be a compound represented by the following formula (II).

In the formula (II), R' is a p-valent alcohol to remove p-OH groups, and p and n represent natural numbers. The p-valent alcohol [R'-(OH) _p ] may, for example, be a polyvalent alcohol such as 2,2-di(hydroxymethyl)-1-butanol or the like (an alcohol having 1 to 15 carbon atoms). p is preferably from 1 to 6, and n is preferably from 1 to 30. When p is 2 or more, the n of each of the groups (in the arc of the arc) may be the same or different. Specific examples of the above compound include 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, and commercial products. Name "EHPE3150" (manufactured by Daicel, Inc.).

In the curable epoxy resin composition of the present invention, the alicyclic epoxy compound (A) may be used alone or in combination of two or more. In addition, as the alicyclic epoxy compound (A), for example, commercially available products such as "CELLOXIDE 2021P" and "CELLOXIDE 2081" (manufactured by Daicel Co., Ltd.) can be used.

The alicyclic epoxy compound (A) is particularly preferably a 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate represented by the formula (I-1). , the product name "CELLOXIDE 2021P" (manufactured by Daicel, Inc.).

In the curable epoxy resin composition of the present invention, the content (doping amount) of the alicyclic epoxy compound (A) is not particularly limited, but the curable epoxy resin composition of the present invention contains a hardener (D). The amount of the curable epoxy resin composition (100% by weight) is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, still more preferably 20 to 70% by weight. On the other hand, when the curable epoxy resin composition of the present invention contains a curing catalyst (F) as an essential component, the amount (content) of the alicyclic epoxy compound (A) is compared with that of the curable epoxy resin. The content (100% by weight) is preferably 25 to 95% by weight, more preferably 30 to 90% by weight, still more preferably 35 to 90% by weight.

The content (mixing amount) of the alicyclic epoxy compound (A) is not particularly limited with respect to the total amount (all epoxy compounds) (100% by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. However, it is preferably 20 to 95% by weight, more preferably 30 to 92% by weight, still more preferably 40 to 90% by weight. When the content of the alicyclic epoxy compound (A) is less than 20% by weight, the cured product may have heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance.

[monopropenyldioxypropyltrimeric isocyanate compound (B)]

In the curable epoxy resin composition of the present invention, the monopropenyldioxypropyltrimeric isocyanate compound (B) is a compound represented by the following formula (1). Monopropenyldioxypropyltrimeric isocyanate compound (B) The role played is to improve the toughness, thermal shock resistance and moisture reflow resistance of the hardened material in particular (especially the crack resistance (characteristic of cracking) which is heat-treated in the post-moisture reflow step).

In the formula (1), each of R ¹ and R ² (identical or different) represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may, for example, be a straight chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. Branched chain alkyl. Further, it is preferably a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group. In the formula (1), R ¹ and R ^{2 are} particularly preferably a hydrogen atom.

Representative examples of the monopropenyldioxypropyltrimeric isocyanate compound (B) include monopropenyldioxypropyltrimeric isocyanate and 1-propenyl-3,5-di(2-methylepoxy). Propyl)trimeric isocyanate, 1-(2-methylpropenyl)-3,5-diepoxypropyl trimer isocyanate, 1-(2-methylpropenyl)-3,5-di(2- Methyl epoxypropyl) isocyanurate or the like. In addition, the monopropenyl digoxypropyl trimeric isocyanate compound (B) may be used alone or in combination of two or more.

Further, the monopropenyldioxypropyltrimeric isocyanate compound (B) may be previously modified by adding a compound reactive with an epoxy group such as an alcohol or an acid anhydride.

The content (doping amount) of the monopropenyl diglycidyl trimeric isocyanate compound (B) is not particularly limited, but is relative to the curable epoxy resin. The total amount (100% by weight) of the epoxy group-containing compound contained in the composition is preferably 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight. If the content of the monopropenyldioxypropyltrimeric isocyanate compound (B) is more than 60% by weight, the solubility of the monopropenyldioxypropyltrimeric isocyanate compound (B) in the curable epoxy resin composition will be Reduced, but has a negative impact on the physical properties of hardened materials. On the other hand, when the content of the monopropenyldioxypropyltrimeric isocyanate compound (B) is less than 5% by weight, the thermal shock resistance and the moisture reflow resistance of the cured product may be lowered.

Further, the monopropenyldioxypropyltrimeric isocyanate compound is based on the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monopropenyldioxypropyltrimeric isocyanate compound (B). The content (the amount of blending) of (B) is not particularly limited, but is preferably 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight. If the content of the monopropenyldioxypropyltrimeric isocyanate compound (B) is more than 60% by weight, the solubility of the monopropenyldioxypropyltrimeric isocyanate compound (B) in the curable epoxy resin composition will be Reduced, but has a negative impact on the physical properties of hardened materials. On the other hand, when the content of the monopropenyldioxypropyltrimeric isocyanate compound (B) is less than 5% by weight, the thermal shock resistance and the moisture reflow resistance of the cured product may be lowered.

[Glass Filler (C)]

In the curable epoxy resin composition of the present invention, a glass filler (C) may be a known or customary glass filler, and is not particularly limited, and examples thereof include glass beads, glass flakes, glass powder, and grit. Glass, fiberglass and fiberglass cloth (eg glass cloth and glass non-woven fabric, etc.) Wait. Among them, glass beads, glass flakes, and glass frits are preferred from the viewpoints of easy improvement of the filling ratio and easy improvement of moisture absorption reflow resistance and thermal shock resistance.

The type of the glass constituting the glass filler (C) is not particularly limited, and examples thereof include T glass, E glass, C glass, A glass, S glass, L glass, D glass, NE glass, quartz glass, and low dielectric constant glass. , high dielectric constant glass, etc. Among them, E glass, T glass, and NE glass are preferable from the viewpoint that the ionic impurities are small and the heat resistance and electrical insulation are excellent. Further, in the curable epoxy resin composition of the present invention, the glass filler (C) may be used alone or in combination of two or more.

The refractive index of the sodium D line (light of a wavelength of 589.29 nm) of the glass filler (C) is not particularly limited, but is preferably 1.40 to 2.10, more preferably 1.45 to 1.60. When the refractive index exceeds this range, the transparency of the cured product tends to be remarkably lowered. Further, the sodium D-line refractive index of the glass filler (C) can be measured using, for example, an Abbe refractometer (measurement temperature: 25 ° C).

When glass frit or glass frit is used for the glass filler (C), the average particle diameter is not particularly limited, but is preferably 0.5 to 200 μm, more preferably 1 to 100 μm. When the average particle diameter of the glass filler (C) is less than 0.5 μm, the glass fillers may aggregate with each other when the resin is mixed, and the dispersibility may be lowered. On the other hand, when the average particle diameter of the glass filler (C) is more than 200 μm, the transparency of the cured product tends to be remarkably lowered. Further, the average particle diameter of the glass filler (C) can be calculated by, for example, a laser diffraction/scattering particle size distribution measuring apparatus, by calculating the average particle diameter of the glass filler (glass beads, glass filler, etc.). And ask for it.

When a glass fiber cloth such as glass cloth is used as the glass filler (C), the fiber weaving method is not particularly limited, and examples thereof include plain weave, square weave, satin weave, and twill weave. The thickness of the glass cloth (including the glass nonwoven fabric) is not particularly limited, but is preferably 20 to 200 μm, more preferably 30 to 180 μm, still more preferably 40 to 150 μm. The glass fiber cloth (including the glass non-woven fabric) may be used alone or in combination of a plurality of sheets.

The glass filler (C) can be surface-treated by various known or conventional surface treatment agents. The surface treatment agent may, for example, be a decane coupling agent such as γ-aminopropyltriethoxysilane or γ-glycidoxypropyltriethoxysilane, a surfactant, or an inorganic acid. By this surface treatment, the wettability, affinity, and adhesion of the interface between the glass filler (C) and other components (for example, a compound having an epoxy group) can be improved.

The glass filler (C) can be produced by a known or customary method. In addition, a commercially available product may be used as the glass filler (C), and the product name "glass beads CF0018WB15C" (manufactured by Nippon Frit Co., Ltd.), "glass beads CF0018WB15" (manufactured by Nippon Frit Co., Ltd.), and " Glass powder L-BSL7" (manufactured by OHARA Co., Ltd.) or the like.

The content (doping amount) of the glass filler (C) is not particularly limited, but is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 50 parts by weight, based on the total amount of the epoxy compound contained in the curable epoxy resin composition. Preferably, it is 1 to 30 parts by weight, and further preferably 3 to 15 parts by weight. When the content of the glass filler (C) is less than 0.5 part by weight, the cured product may not exhibit sufficient moisture reflow resistance and thermal shock resistance. On the other hand, when the content of the glass filler (C) is more than 50 parts by weight, the transparency of the cured product may be lowered.

[hardener (D)]

The curable epoxy resin composition of the present invention may further contain a hardener (D). The hardener (D) is a compound which contributes to hardening an epoxy compound. As the hardener (D), a hardener which is known or conventionally used as a hardener for an epoxy resin can be used. Among them, the hardener (D) is preferably a liquid acid anhydride at 25 ° C, and examples thereof include methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, and methylene. Methyltetrahydrophthalic anhydride or the like. Further, for example, anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic anhydride are solid anhydrides at room temperature (25 ° C), and can also be dissolved at room temperature (25 ° C). It is used as a liquid mixture in the form of a liquid acid anhydride, and is preferably used as the curing agent (D) of the present invention. Further, the curing agent (D) may be used alone or in combination of two or more. As described above, the curing agent (D) is preferably a saturated monocyclic hydrocarbon dicarboxylic anhydride (including a substituent such as a ring-bonded alkyl group) from the viewpoint of heat resistance, light resistance, and crack resistance of the cured product.

In the present invention, the hardener (D) can also be used under the trade name "RIKACID MH-700" (manufactured by Shin-Nippon Chemical Co., Ltd.) and the trade name "RIKACID MH-700F" (manufactured by Shin-Nippon Chemical Co., Ltd.). Commercial product such as "HN-5500" (made by Hitachi Chemical Co., Ltd.).

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

[hardening accelerator (E)]

The curable epoxy resin composition of the present invention may further contain a curing accelerator (E). The hardening accelerator (E) is a compound which has a function of promoting the curing speed when the compound having an epoxy group is cured by the curing agent (D). As the hardening accelerator (E), a known or conventional hardening accelerator may be used, and examples thereof include 1,8-difluorenebicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (for example, a phenate or an octoate). , p-toluenesulfonate, formic acid salt and tetraphenyl borate); 1,5-dioxabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (eg phenate, octoate, p -tosylate, formic acid salt and tetraphenyl borate); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylcyclohexylamine a third-grade amine; an imidazole such as 2-ethyl-4-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole; a phosphine such as a phosphate ester or a triphenylphosphine; An anthracene compound such as (p-tolyl)borate; an organic metal salt such as zinc octylate or tin octylate; a metal chelate compound or the like. The curing accelerator (E) may be used alone or in combination of two or more.

Further, in the present invention, the hardening accelerator (E) may be a trade name of "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", or "12XD" ( Development product) (The above is manufactured by San-Apro Co., Ltd.); trade names "TPP-K" and "TPP-MK" (above, manufactured by Kitakatsu Chemical Industry Co., Ltd.); trade name "PX-4ET" (Nippon Chemical Co., Ltd.) Commercial products such as Industrial Co., Ltd.).

The content (doping amount) of the hardening accelerator (E) is not particularly limited, but is preferably 0.05 to 5 based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. The weight fraction is more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight. When the content of the hardening accelerator (E) is less than 0.05 part by weight, the hardening promoting effect may be insufficient. On the other hand, when the content of the hardening accelerator (E) is more than 5 parts by weight, the cured product may be colored to deteriorate the hue.

[hardening catalyst (F)]

The curable epoxy resin composition of the present invention may further contain a curing catalyst (F). The hardening catalyst (F) is a compound having a function of initiating and/or promoting a hardening reaction of a compound having an epoxy group. The curing catalyst (F) is not particularly limited, and examples thereof include a cationic catalyst (cationic polymerization initiator) which initiates polymerization by generating a cationic substance by ultraviolet irradiation or heat treatment. Further, the curing catalyst (F) may be used alone or in combination of two or more.

The cationic catalyst which generates a cationic substance by ultraviolet irradiation may, for example, be hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate or hexafluoroarsenate. For the cation catalyst, for example, the product name "UVACURE 1590" (manufactured by Daicel-Cytec Co., Ltd.); trade names "CD-1010", "CD-1011", and "CD-1012" (above, Sartomer, USA) can be suitably used. The product name is "IRGACURE 264" (manufactured by Ciba Japan Co., Ltd.); and the product name "CIT-1682" (made by Nippon Soda Co., Ltd.).

The cationic catalyst which generates a cationic substance by heat treatment may, for example, be an aryl diazonium salt, an aryl sulfonium salt, an aryl sulfonium salt or a heavy olefin-ion complex, and the product name "PP-" may be suitably used. 33", the product name "CP-66" and the product name "CP-77" (made by ADEKA Co., Ltd.); the product name "FC-509" (made by 3M); the product name "UVE1014" (made by GE); "SAN-AID SI-60L", trade name "SAN-AID SI-80L", trade name "SAN-AID SI-100L", trade name "SAN-AID SI-110L", and trade name "SAN-AID SI-" 150L" (made by Sanshin Chemical Industry Co., Ltd.); a commercial item such as "CG-24-61" (made by Ciba Japan). Further, it may be a compound of a metal such as aluminum or titanium, a chelating compound of acetonitrile or a diketone, and a sterol such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and acetonitrile or a diketone. A compound of a chelating compound and a phenol such as bisphenol S.

The content of the hardening catalyst (F) (the amount of blending) is not particularly limited, but is preferably 0.01 to 15 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. More preferably, it is 0.01 to 12 parts by weight, further preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight. By using the curing catalyst (F) in the above range, a cured product excellent in heat resistance, light resistance, and transparency can be obtained.

[Cycloester type polyester resin]

The curable epoxy resin composition of the present invention preferably further contains an alicyclic polyester resin. By containing the alicyclic polyester resin, the heat resistance and light resistance of the cured product can be improved, and the optosity of the optical semiconductor device can be more suppressed. The alicyclic polyester resin is a polyester resin having at least an alicyclic structure (aliphatic ring structure). especially The alicyclic polyester resin is preferably an alicyclic polyester resin having an alicyclic ring (alicyclic structure) in its main chain from the viewpoint of improving heat resistance and light resistance of the cured product.

The alicyclic structure of the alicyclic polyester resin is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure or a crosslinked cyclic hydrocarbon structure (for example, a bicyclic hydrocarbon). Among them, a saturated monocyclic hydrocarbon structure or a saturated crosslinked hydrocarbon structure in which an alicyclic skeleton (carbon-carbon bond) is composed of a carbon-carbon single bond is particularly preferable. Moreover, the alicyclic structure of the alicyclic polyester resin can be introduced into either one of the constituent unit derived from the dicarboxylic acid and the constituent unit derived from the diol, and can be introduced into both of them simultaneously, and is not particularly limited.

The alicyclic polyester resin has a constituent unit derived from a monomer component having an alicyclic structure. The monomer having an alicyclic structure may be exemplified or conventionally used as a diol or a dicarboxylic acid having an alicyclic structure, and is not particularly limited, and examples thereof include 1,2-cyclohexanedicarboxylic acid and a 1,3-ring. Hexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, norbornene dicarboxylic acid, 1,4-decahydronaphthalene dicarboxylic acid a dicarboxylic acid having an alicyclic structure such as 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid or 2,7-decahydronaphthalene dicarboxylic acid (including a derivative such as an acid anhydride) Etc.; 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, bis(hydroxymethyl)tricyclic [5.2.1.0] 5-membered ring diol such as decane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexane 6-membered cyclic diol such as alkyl dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 2,2-bis-(4-hydroxycyclohexyl)propane, hydrogenated bisphenol A, etc. A diol having an alicyclic structure (including such derivatives) and the like.

The alicyclic polyester resin may also have a constituent unit derived from a monomer component having no alicyclic structure. Examples of the monomer having no alicyclic structure include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid (including derivatives such as acid anhydrides); adipic acid; , an aliphatic dicarboxylic acid such as azelaic acid, sebacic acid, succinic acid, fumaric acid, maleic acid (including derivatives such as acid anhydride); ethylene glycol, propylene glycol, 1,2-propanediol , 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane Alcohol, diethylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl- a diol such as 2-ethyl-1,3-propanediol, benzenedimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A (including such derivatives) . Further, a suitable substituent (for example, an alkyl group, an alkoxy group, a halogen atom or the like) bonded to a dicarboxylic acid or a diol having no alicyclic structure is also contained in a monomer having no alicyclic structure. in.

The ratio of the monomer unit having an alicyclic ring is not particularly limited, but is preferably 10 mol% or more, based on all the monomer units (all monomer components) (100 mol%) constituting the alicyclic polyester resin. For example, 10 to 80 mol%), more preferably 25 to 70 mol%, and even more preferably 40 to 60 mol%. When the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, thermal shock resistance, and moisture repellency reflow resistance of the cured product may be lowered.

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

Wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two of them selected from R ⁴ to R ⁷ may be bonded to form a ring. ]

Wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two of them selected from R ⁴ to R ⁷ may be bonded to form a ring. ]

Wherein R ³ represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two of them selected from R ⁴ to R ⁷ may be bonded to form a ring. ]

Preferred examples of the constituent units represented by the formulas (2) to (4) include 4-methyl-1,2-cyclohexanedicarboxylic acid represented by the following formula (5) and from B. a constituent unit of a diol. The alicyclic polyester resin having these constituent units can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride with ethylene glycol.

In addition, as another preferable example of the structural unit represented by the formula (2) to (4), for example, 1,4-cyclohexanedicarboxylic acid represented by the following formula (6) and from the novel The constituent unit of alcohol. The alicyclic polyester resin having such a constituent unit can be obtained, for example, by polycondensing 1,4-cyclohexanedicarboxylic acid with neopentyl glycol.

When the alicyclic polyester resin has a constituent unit represented by the formulas (2) to (4), the total amount of the constituent unit contents (the total content; all the monomer units constituting the constituent unit) is not particularly limited. However, it is preferably 20 mol% or more (for example, 20 to 100 mol%) based on all constituent units (100 mol%; all monomer units constituting the alicyclic polyester resin) of the alicyclic polyester resin. More preferably 50~100% by mole, further better 80~100% by mole. When the content of the constituent unit represented by the formulas (2) to (4) is less than 20 mol%, the cured product heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance may be lowered.

The number average molecular weight of the alicyclic polyester resin is not particularly limited, but is preferably from 300 to 100,000, more preferably from 300 to 30,000. When the number average molecular weight of the alicyclic polyester resin is less than 300, the toughness and toughness of the cured product are insufficient, and the thermal shock resistance and the moisture reflow resistance are lowered. On the other hand, when the number average molecular weight of the alicyclic polyester resin is more than 100,000, the compatibility with the curing agent (D) is lowered, and the transparency of the cured product is lowered. Further, the number average molecular weight of the alicyclic polyester resin can be determined by a value of a standard polystyrene by, for example, GPC (gel permeation chromatography).

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

The alicyclic polyester resin is not particularly limited and can be produced by a known or customary method. More specifically, it can be obtained, for example, by polycondensing the alicyclic polyester resin with the above dicarboxylic acid and a diol by a usual method, and also with the above dicarboxylic acid derivative (anhydride, ester, acid halide). And the like) is obtained by polycondensation with a diol in a usual manner.

In the curable epoxy resin composition of the present invention, the alicyclic polyester resin content (doping amount) is not particularly limited, but when the curable resin composition contains the curing agent (D), it is relative to the alicyclic type. The total amount (100% by weight) of the polyester resin and the hardener (D) is preferably from 1 to 60% by weight, more preferably from 5 to 30% by weight. When the content of the alicyclic polyester resin is less than 1% by weight, the cured product may have insufficient thermal shock resistance and moisture reflow resistance. another On the other hand, when the content of the alicyclic polyester resin is more than 60% by weight, the transparency and heat resistance of the cured product may be lowered.

Further, the alicyclic polyester resin content (doping amount) is not particularly limited, and is preferably 5 to 50 parts by weight, more preferably 10 to 45, based on 100 parts by weight of the alicyclic epoxy compound (A). The weight is further preferably 15 to 40 parts by weight. When the content of the alicyclic polyester resin is less than 5 parts by weight, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be insufficient. On the other hand, when the content of the alicyclic polyester resin is more than 50 parts by weight, the thermal shock resistance and moisture absorption reflow resistance of the cured product may be lowered.

[a oxane derivative having two or more epoxy groups in the molecule]

The curable epoxy resin composition of the present invention preferably further contains a pyrithione derivative having two or more epoxy groups in a molecule (in one molecule). By containing a decane derivative having two or more epoxy groups in the molecule, the heat resistance and light resistance of the cured product can be improved to a higher level.

In the oxoxane derivative having two or more epoxy groups in the molecule, the siloxane skeleton (Si-O-Si skeleton) is not particularly limited, and examples thereof include a cyclic oxirane skeleton; and a linear polyfluorene skeleton; An alkane or a polyoxane skeleton such as a cage or ladder-like polysulfonate. In particular, the siloxane skeleton is preferably a cyclic siloxane chain or a linear polyoxyalkylene skeleton from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the decrease in luminosity. In other words, a cyclodecane derivative having two or more epoxy groups in the molecule is preferably a cyclic siloxane having two or more epoxy groups in the molecule, and a linear polycondensation having two or more epoxy groups in the molecule. Oxane. In addition, intramolecular The decane derivative having two or more epoxy groups may be used alone or in combination of two or more.

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

The weight average molecular weight of the decane derivative having two or more epoxy groups in the molecule is not particularly limited, but is preferably from 100 to 3,000, more preferably from the viewpoint of improving heat resistance and light resistance of the cured product. ~2000.

The amount of the epoxy group in one molecule of the oxoxane derivative having two or more epoxy groups in the molecule is not particularly limited as long as it is two or more. However, from the viewpoint of improving heat resistance and light resistance of the cured product, Good for 2~4 (2, 3 or 4).

The epoxy equivalent of the decane derivative having two or more epoxy groups in the molecule (in accordance with JIS K7236) is not particularly limited, but from the viewpoint of improving heat resistance and light resistance of the cured product, it is preferably from 180 to 400. More preferably, it is 240 to 400, and further preferably 240 to 350.

The epoxy group in the cyclooxyl derivative having two or more epoxy groups in the molecule is not particularly limited, but from the viewpoint of improving heat resistance and light resistance of the cured product, it is preferred to form a phase constituting the aliphatic ring. An epoxy group (alicyclic epoxy group) composed of an adjacent 2 carbon atom and an oxygen atom, and particularly preferably an epoxycyclohexane group.

The oxoxane derivative having two or more epoxy groups in the molecule, and specific examples thereof include 2,4-bis[2-(3-{oxybicyclo[4.1.0]heptyl})ethyl] -2,4,6,6,8,8-hexamethyl-cyclotetraoxane, 4,8-bis[2-(3-{oxybicyclo[4.1.0]heptyl})ethyl] -2,2,4,6,6,8-hexamethyl-cyclotetraoxane, 2,4-bis[2-(3-{oxybicyclo[4.1.0]heptyl})ethyl] -6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 4,8-bis[2-(3-{oxybicyclo[4.1.0]heptyl} Ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,8-tris[2-(3-{oxybicyclo[4.1] .0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetraoxane, 2,4,8-tri[2-(3-{oxybicyclo[4.1] .0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,6,8-tetra[2-(3-{ Oxybicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetraoxane, sesquioxalic acid having two or more epoxy groups in the molecule, etc. . More specifically, for example, a cyclic oxirane having two or more epoxy groups in the molecule represented by the following formula may be mentioned.

In addition, the oxirane derivative having two or more epoxy groups in the molecule may be, for example, an alicyclic epoxy group-containing polyfluorene oxide resin described in JP-A-2008-248169, or a special issue in Japan. In the publication No. 2008-19422, an organopolysilsesquioxane resin having at least two epoxy functional groups in the molecule is described.

For example, a commercially available cyclooxygenane having two or more epoxy groups in the molecule may be used under the trade name "X-40-2678" (Shin-Etsu Chemical Industry). A product of the company name, "X-40-2670" (manufactured by Shin-Etsu Chemical Co., Ltd.), and the product name "X-40-2720" (manufactured by Shin-Etsu Chemical Co., Ltd.).

The content (doping amount) of the oxoxane derivative having two or more epoxy groups in the molecule is not particularly limited, but the total amount of the compound having an epoxy group contained in the curable epoxy resin composition (100 weight) %), preferably 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight. When the content of the decane derivative having two or more epoxy groups in the molecule is less than 5% by weight, the heat resistance and light resistance of the cured product may be insufficient. On the other hand, when the content of the decane derivative having two or more epoxy groups in the molecule is more than 60% by weight, the thermal shock resistance and moisture repellency of the cured product may be lowered.

In addition, the content (mixing amount) of the decane derivative having two or more epoxy groups in the molecule is not particularly limited, and is preferably from 10 to 200, based on 100 parts by weight of the alicyclic epoxy compound (A). The weight is preferably 20 to 180 parts by weight, and further preferably 30 to 150 parts by weight, particularly preferably 35~145 weight points. When the content of the decane derivative having two or more epoxy groups in the molecule is less than 10 parts by weight, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be insufficient. On the other hand, when the content of the decane derivative having two or more epoxy groups in the molecule is more than 200 parts by weight, the thermal shock resistance and moisture repellency of the cured product may be lowered.

[Rubber particles]

The curable epoxy resin composition of the present invention may further contain rubber particles. Examples of the rubber particles include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). The rubber particles are preferably rubber particles having a multilayer structure (core shell structure) composed of a core portion having rubber elasticity and a shell layer covering at least one layer of the core portion. The rubber particles are particularly preferably a polymer having a (meth) acrylate as an essential monomer component, and have a functional group of a hydroxyl group and/or a carboxyl group (either one or both of a hydroxyl group and a carboxyl group) on the surface. A rubber particle which reacts with a compound having an epoxy group such as an alicyclic epoxy compound (A). If the surface of the rubber particle does not have a hydroxyl group and/or a carboxyl group, thermal shock such as a heat cycle may cause the cured product to be cloudy and the transparency may be lowered.

The polymer constituting the rubber-elastic core portion of the rubber particles is not particularly limited, but is preferably methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate (methyl group). Acrylate as an essential monomer component. The polymer constituting the core portion having rubber elasticity may contain other aromatic B such as styrene or α-methylstyrene Alkene; a nitrile such as acrylonitrile or methacrylonitrile; a conjugated diene such as butadiene or isoprene; or a monomer component such as ethylene, propylene or isobutylene.

Here, the polymer constituting the elastic core portion preferably contains a (meth) acrylate and a combination of one selected from the group consisting of aromatic vinyl, nitrile and conjugated diene. Two or more types are used as a monomer component. In other words, the polymer constituting the core portion may, for example, be a binary copolymer such as (meth) acrylate/aromatic ethylene or (meth) acrylate/conjugated diene; (meth) acrylate/aromatic ethylene; a terpolymer such as a conjugated diene or the like. Further, the polymer constituting the core portion may contain polyoxyalkylene or polycarbamate such as polydimethyl siloxane or polyphenylmethyl siloxane.

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

The core portion of the rubber particles, wherein from the viewpoint of easy adjustment of the refractive index of the rubber particles, a binary copolymer of (meth) acrylate/aromatic ethylene (particularly butyl acrylate/styrene) is preferred. The core part of the composition.

The core portion of the rubber particles can be produced by a usual method, and for example, the monomer can be produced by an emulsion polymerization method or the like. In the emulsion polymerization method, the monomer may be charged into the polymerization at a time, or the monomer may be partially polymerized, and then the remaining monomers may be continuously or intermittently added to the polymerization. Further, seed particles may be used. The polymerization method.

The polymer constituting the shell layer of the rubber particles is preferably a polymer different from the polymer constituting the core portion. Further, as described above, the shell layer preferably has a functional group having a hydroxyl group and/or a carboxyl group, and can be reacted with a compound having an epoxy group such as an alicyclic epoxy compound (A). Thereby, the bondability with the interface of the alicyclic epoxy compound (A) can be particularly improved, and the cured product obtained by hardening the curable epoxy resin composition containing the rubber particles having the shell layer can be It can make it excellent in crack resistance. Further, it is also possible to prevent the glass transition temperature of the cured product from decreasing.

The polymer constituting the shell layer preferably contains a (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate as an essential monomer component. For example, when (meth) acrylate is used as the butyl acrylate in the core portion, the monomer component of the polymer constituting the shell layer is preferably a (meth) acrylate other than butyl acrylate (for example, (methyl) ) Methyl acrylate, ethyl (meth) acrylate, butyl methacrylate, etc.). Examples of the monomer component which may be contained in the (meth) acrylate include aromatic vinyl such as styrene or α-methylstyrene; and nitriles such as acrylonitrile and methacrylonitrile. In the rubber particles, it is preferable to contain a (meth) acrylate and to combine the monomer alone or in combination of two or more kinds thereof as a monomer component constituting the shell layer, from the viewpoint of easily adjusting the refractive index of the rubber particle. In view, it is particularly preferable to contain at least aromatic vinyl.

Further, the polymer constituting the shell layer is a functional group which forms a hydroxyl group and/or a carboxyl group which can react with a compound having an epoxy group such as an alicyclic epoxy compound (A), and preferably contains a hydroxyl group-containing monomer. (for example, hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth)acrylate) or a carboxyl group-containing monomer (for example, α,β-unsaturated acid such as (meth)acrylic acid, maleic anhydride, etc. As a monomer component, α,β-unsaturated acid anhydride or the like.

The polymer constituting the shell layer of the rubber particles preferably contains one or more selected from the above monomers as a monomer component, in addition to the (meth) acrylate. In other words, the shell layer is preferably, for example, (meth) acrylate/aromatic ethylene/hydroxyalkyl (meth) acrylate and (meth) acrylate/aromatic ethylene/α,β-unsaturated acid, etc. a shell composed of a meta-copolymer or the like.

Further, the polymer constituting the shell layer is the same as the core portion, and may contain other monomer components in addition to the above monomers, such as divinylbenzene, allyl (meth)acrylate, and ethylene di(meth)acrylate. One monomer (one molecule) such as an ester, diallyl maleate, triallyl cyanurate, diallyl phthalate or butylene diacrylate has two or more reactive functions a reactive cross-linking monomer.

The rubber particles (rubber particles having a core-shell structure) can be obtained by coating the core portion with a shell layer. The method of coating the core portion with a shell layer, for example, a method of coating a surface of a core portion having a rubber elasticity obtained by the above method and coating a shell layer to form a shell layer; A method in which a rubber elastic core portion is used as a main component, and each component constituting the shell layer is grafted and polymerized as a branch component.

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

The refractive index of the rubber particles is not particularly limited, but is preferably 1.40 to 1.60, more preferably 1.42 to 1.58. Further, the refractive index of the rubber particles and the refractive index of the cured product obtained by curing the curable epoxy resin composition (the curable epoxy resin composition of the present invention) containing the rubber particles are preferably ± Within 0.03. When the refractive index difference is more than 0.03, the transparency of the cured product is lowered, and the opacity of the optical semiconductor device tends to be reduced, and the optical semiconductor device loses its function.

The refractive index of the rubber particles can be obtained by, for example, injecting 1 g of rubber particles into a mold, and compression-molding at 210 ° C and 4 MPa to obtain a flat plate having a thickness of 1 mm, and then cutting a test piece having a length of 20 mm and a width of 6 mm from the obtained flat plate, and using Using a multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by ATAGO Co., Ltd.), the sodium brominated naphthalene was used as an intermediate liquid to make the sodium D line at 20 ° C in close contact with the test piece. The refractive index is obtained.

The cured product of the curable epoxy resin composition of the present invention can be cut into a length of 20 mm, a width of 6 mm, and a thickness of 1 mm by, for example, a cured product obtained by a heat curing method described in the following optical semiconductor device. In the test piece, bismuth bromide was used as an intermediate liquid, and the ruthenium was brought into close contact with the test piece, and sodium at 20 ° C was measured using a multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by ATAGO Co., Ltd.). The refractive index of the D line is obtained.

In the curable epoxy resin composition of the present invention, the rubber particle content (doping amount) is not particularly limited, but is relative to the curable epoxy tree. The total amount (100 parts by weight) of the epoxy group-containing compound contained in the lipid composition is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the rubber particle content is less than 0.5 part by weight, the crack resistance of the cured product tends to decrease. On the other hand, when the rubber particle content is more than 30 parts by weight, the heat resistance of the cured product tends to decrease.

[additive]

The curable epoxy resin composition of the present invention may contain various additives in addition to the above, without departing from the effects of the present invention. When the additive contains a hydroxyl group-containing compound such as ethylene glycol, diethylene glycol, propylene glycol or glycerin, the reaction can be progressed slowly. Others can also use polyfluorene-based or fluorine-based defoamers, leveling agents, γ-glycidoxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxy in the range of non-destructive viscosity or transparency. A decane coupling agent such as a decane, a surfactant, an inorganic filler such as cerium oxide or aluminum oxide, a flame retardant, a colorant, an antioxidant, an ultraviolet absorber, an ion absorbing body, a pigment, a phosphor, a release agent, etc. Conventional additives.

<Method for Producing Curable Epoxy Resin Composition>

The curable epoxy resin composition of the present invention may contain at least the above-mentioned alicyclic epoxy compound (A), a monopropenyl digoxypropyl trimer isocyanate compound (B), and a glass filler (C). The production method (preparation method) is not particularly limited. Specifically, for example, the components can be stirred at a predetermined ratio. It is prepared by mixing and defoaming under vacuum, and may also be an epoxy group-containing compound such as an alicyclic epoxy compound (A) or a monopropenyl digoxypropyl trimer isocyanate compound (B). a composition contained as an essential component (also known as "epoxy resin"), and hardened The epoxy resin and epoxy hardener are prepared after the preparation of the composition (D) and the curing accelerator (E) or the curing catalyst (F) as essential components (also referred to as "epoxy hardener"). Stir at a predetermined ratio. Mix and prepare as needed to defoam under vacuum. In addition, in this case, the glass filler (C) may be blended in advance as a constituent component of the epoxy resin and/or the epoxy hardener, or when the epoxy resin is mixed with the epoxy hardener. The epoxy resin and the epoxy hardener are blended as components.

The epoxy resin is stirred during preparation. The mixing temperature is not particularly limited, but is preferably from 30 to 150 ° C, more preferably from 35 to 130 ° C. Also, the epoxy hardener is stirred during preparation. The mixing temperature is not particularly limited, but is preferably from 30 to 100 ° C, more preferably from 35 to 80 ° C. Stir. A known device such as a self-rotating mixer, a planetary mixer, a kneader, a dissolver, or the like can be used for the mixing.

In particular, when the curable epoxy resin composition of the present invention contains a hardener (D) and the alicyclic polyester resin as an essential component, it is preferred from the viewpoint of obtaining a relatively uniform composition. The alicyclic polyester resin and the hardener (D) are premixed to obtain a mixture of the alicyclic polyester resin and the hardener (D), and the mixture is blended with the hardening accelerator (E) and An epoxy hardener is prepared by using other additives, and then the epoxy hardener is prepared by mixing with an epoxy resin prepared separately. The temperature at which the alicyclic polyester resin is mixed with the curing agent (D) is not particularly limited, but is preferably 60 to 130 ° C, more preferably 90 to 120 ° C. The mixing time is not particularly limited, but is preferably from 30 to 100 minutes, more preferably from 45 to 80 minutes. The mixing is not particularly limited, but it is preferably carried out under a nitrogen gas atmosphere. Further, the above-mentioned known device can be used for mixing.

The alicyclic polyester resin is not particularly limited as long as it is mixed with the curing agent (D), but it is preferred to further carry out a suitable chemical treatment (for example, hydrogenation or terminal modification of an alicyclic polyester resin). Further, in the mixture of the alicyclic polyester resin and the hardener (D), a part of the hardener (D) may be reacted with the alicyclic polyester resin (for example, a hydroxyl group of the alicyclic polyester resin).

For the mixture of the alicyclic polyester resin and the hardener (D), for example, the trade name "HN-7200" (manufactured by Hitachi Chemical Co., Ltd.) and the trade name "HN-5700" (Hitachi Chemical Industry Co., Ltd.) can be used. Commercial products such as company system).

<hardened matter>

By curing the curable epoxy resin composition of the present invention, it is possible to obtain a cured product which is excellent in heat resistance, light resistance and thermal shock resistance, and particularly excellent in moisture absorption reflow resistance. The heating temperature (hardening temperature) at the time of hardening is not particularly limited, but is preferably 45 to 200 ° C, more preferably 100 to 190 ° C, still more preferably 100 to 180 ° C. Further, the heating time (hardening time) at the time of curing is not particularly limited, but is preferably from 30 to 600 minutes, more preferably from 45 to 540 minutes, still more preferably from 60 to 480 minutes. When the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening will be insufficient, and if the upper limit is higher than the above range, the resin component will be decomposed, which is not preferable. The hardening conditions can be appropriately adjusted according to various conditions, such as increasing the hardening temperature to reduce the hardening time, and lowering the hardening temperature to extend the hardening time.

<Resin composition for optical semiconductor encapsulation>

The curable epoxy resin composition of the present invention is preferably used as a resin composition for optical semiconductor encapsulation. By the foregoing as an optical semiconductor package When the resin composition is used, it is possible to obtain an optical semiconductor device comprising a cured product having high heat resistance, light resistance, and thermal shock resistance, particularly, a moisture-resistant reflow resistance. In the optical semiconductor device, even when an optical semiconductor device having high power and high luminance is provided, the illuminance is less likely to decrease over time, and particularly after storage under high-humidity conditions, deterioration in luminosity or the like is less likely to occur during heating in the reflow step.

<Optical semiconductor device>

The optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of the curable epoxy resin composition (resin composition for optical semiconductor encapsulation) of the present invention. In the encapsulation of the optical semiconductor element, the curable epoxy resin composition prepared by the above method is injected into a predetermined forming module and heat-hardened under predetermined conditions. Thereby, an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of a curable epoxy resin composition can be obtained. The hardening temperature and the hardening time can be set to the same range as when the cured product is prepared.

The curable epoxy resin composition of the present invention is not limited to the sealing application of the optical semiconductor element, and may be used, for example, as an adhesive, an electrical insulating material, a laminate, a coating film, an ink, a paint, or a sealant. , photoresist, composite material, transparent substrate, transparent sheet, transparent film, optical component, optical lens, optical component, photocuring stereoscopic shape, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory Body and other uses.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

Manufacturing example 1 (Manufacture of rubber particles)

Into a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were added, and the mixture was stirred under a nitrogen gas stream and heated to 80 °C. Here, a single-body mixture consisting of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene was added in an amount of about 5% by weight of the amount required to form the core portion, and stirred for 20 minutes. After emulsification, 9.5 mg of potassium peroxodisulfate was added, and the mixture was stirred for 1 hour to carry out the first polymerization. Next, 180.5 mg of potassium peroxodisulfate was added, and the mixture was stirred for 5 minutes. Here, 0.95 g of dioctylsulfosuccinate was dissolved in 180.5 g of butyl acrylate, 48.89 g of styrene, and 7.33 g of divinylbenzene in the amount required to form the core portion (about 95% by weight). The monolithic mixture was continuously added over 2 hours, and the second polymerization was carried out, followed by aging for 1 hour to obtain a core portion.

Next, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, 0.3 g of dioctylsulfosuccinate was dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid, and 0.3 g of allyl methacrylate. The monolithic mixture was continuously added over a period of 30 minutes to carry out seed polymerization. Thereafter, it was aged for 1 hour to form a shell layer covering the core portion.

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

Further, the average particle diameter and maximum particle diameter of the rubber particles, based by dynamic light scattering method as measurement principle in the form of the "Nanotrac ^TM" nanotrack particle size distribution measuring apparatus (trade name "UPA-EX150" manufactured by Nikkiso Co. Shares In the particle size distribution curve obtained by the company, the particle size (cumulative mean diameter) when the cumulative curve is 50% is the average particle diameter, and the maximum frequency when the frequency (%) of the particle size distribution measurement result exceeds 0.00% The particle size is the largest particle size. In addition, this sample was used by dispersing a rubber particle-dispersed epoxy compound obtained in the following Production Example 2 in a weight ratio of 20 parts by weight to tetrahydrofuran.

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

10 parts by weight of the rubber particles obtained in Production Example 1 was heated to 60 ° C under a nitrogen gas flow, and dispersed in a product name "CELLOXIDE 2021P" (3,4-epoxycyclohexyl group) using a dissolver (1000 rpm, 60 minutes). Methyl (3,4-epoxy)cyclohexanecarboxylate, manufactured by Daicel Co., Ltd.), 90 parts by weight, vacuum defoaming to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C: 542 mPa·s) .

Further, the rubber particle-dispersed epoxy compound obtained in Production Example 2 (10 mass parts of rubber particles dispersed in 90 parts by weight of CELLOXIDE 2021P) was measured by a digital viscometer (trade name "DVU-EII type", manufactured by TOKIMEC Co., Ltd.). .

Manufacturing Example 3 (Manufacture of epoxy hardener)

According to the blending ratio shown in Table 1 and Table 2 (unit: weight), the trade name "RIKACID MH-700" (hardener, new Japanese Co., Ltd.), the trade name "HN-7200", "HN-5700" (all are a mixture of hardener and alicyclic polyester resin, manufactured by Hitachi Chemical Co., Ltd.), and the trade name "U-CAT 18X" (hardening accelerator, manufactured by San-Apro Co., Ltd.), ethylene glycol (additive, manufactured by Wako Pure Chemical Industries, Ltd.), using a self-revolving stirring device (manufactured by THINKY, THINKY MIXERAR-250) The epoxy hardener (also known as the K agent) is obtained by mixing and defoaming. In addition, "-" in Tables 1 to 4 means that the ingredients are not blended, and the same applies hereinafter.

Manufacturing Example 4 (Manufacture of alicyclic polyester resin)

172 parts by weight of 1,4-cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and neopentyl glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser. 208 parts by weight and tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.) were 0.1 parts by weight, heated to 160 ° C, and further heated from 160 ° C to 250 ° C for 4 hours. Subsequently, the pressure was reduced to 5 mmHg over 1 hour, and the pressure was reduced to 0.3 mmHg or less, and then reacted at 250 ° C for 1 hour to obtain an alicyclic polyester resin.

Further, the obtained alicyclic polyester resin had a number average molecular weight of 5,300. Further, the number average molecular weight of the alicyclic polyester resin is determined by gel permeation chromatography (GPC) to determine the residence time (retention capacity), and the polystyrene residence time of the known molecular weight is determined by the same conditions (retention) Capacity), and the value obtained by converting the polystyrene molecular weight. Specifically, the gel permeation chromatography apparatus uses "HLC-8220GPC" (trade name, manufactured by TOSOH Co., Ltd.), and the column uses "TSKgel G2000H _HR ", "TSKgel G1000H _HR " and "protection column TSKgel H". _HR- L" (trade name, all manufactured by TOSOH Co., Ltd.) was used in total, and the detector was measured using a differential refractometer, a mobile phase: tetrahydrofuran, a measurement temperature of 40 ° C, and a flow rate of 1 mL/min.

Example 1

First, according to the blending ratio (unit: weight fraction) shown in Table 1, the trade name "CELLOXIDE 2021P" (alicyclic epoxy compound, manufactured by Daicel Co., Ltd.), monopropenyldioxypropyltrimer trimer Isocyanate (MA-DGIC, Shikoku Chemical Industry Co., Ltd.) and trade name "glass beads CF0018WB15C" (glass filler, manufactured by Nippon Frit Co., Ltd., refractive index 1.52), using a self-revolving stirring device (THINKY , THINKY MIXERAR-250) uniformly mixes and defoams to make epoxy resin. Further, in order to dissolve the MA-DGIC, the mixing was carried out by stirring at 80 ° C for 1 hour.

Then, according to the blending ratio (unit: weight fraction) shown in Table 1, the epoxy resin obtained in the above and the epoxy hardener obtained in Production Example 3 were used in a self-revolving stirring apparatus (manufactured by THINKY, THINKY). MIXERAR-250) uniformly mixes and defoams to obtain a hardenable epoxy resin composition.

Further, the curable epoxy resin composition obtained as described above was injected into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of the optical semiconductor shown in Fig. 1, and then heated in an oven (resin hardened oven) at 120 ° C for 5 hours. An optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of the curable epoxy resin composition is obtained. In addition, in Fig. 1, 100 indicates a reflective layer (resin composition for light reflection), 101 indicates metal wiring, and 102 indicates In the light-emitting semiconductor element, 103 denotes a bonding wire, and 104 denotes a cured material (packaging material).

Examples 2 to 13 and Comparative Examples 1 to 9

A curable epoxy resin composition was prepared in the same manner as in Example 1 except that the composition of the curable epoxy resin composition was changed to the compositions shown in Tables 1 and 2. Further, in Example 13, the rubber particle-dispersed epoxy resin obtained in Production Example 2 was used as the constituent component of the epoxy resin.

Further, an optical semiconductor device was produced in the same manner as in the first embodiment.

Example 14

First, according to the blending ratio (unit: weight fraction) shown in Table 3, the trade name "CELLOXIDE 2021P" (alicyclic epoxy compound, manufactured by Daicel Co., Ltd.), monopropenyldioxypropyltrimer trimer Isocyanate (MA-DGIC, Shikoku Chemical Industry Co., Ltd.) and trade name "glass beads CF0018WB15C" (glass filler, manufactured by Nippon Frit Co., Ltd., refractive index 1.52), using a self-revolving stirring device (THINKY , THINKY MIXERAR-250) uniformly mixes and defoams to make epoxy resin. Further, in order to dissolve the MA-DGIC, the mixing was carried out by stirring at 80 ° C for 1 hour.

Then, according to the blending ratio (unit: weight fraction) shown in Table 3, the epoxy resin obtained above and the trade name "SAN-AID SI-100L" (hardening catalyst, manufactured by Sanshin Chemical Industry Co., Ltd.) were used. A curable epoxy resin composition was obtained by uniformly mixing and defoaming using a self-rotating stirring device (manufactured by THINKY, THINKY MIXERAR-250).

Further, the curable epoxy resin composition obtained as described above was injected into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of the optical semiconductor shown in Fig. 1, and then heated in an oven (resin hardened oven) at 120 ° C for 5 hours. An optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of the curable epoxy resin composition is obtained.

Examples 15 to 25 and Comparative Examples 10 to 18

A curable epoxy resin composition was prepared in the same manner as in Example 14 except that the composition of the curable epoxy resin composition was changed to the compositions shown in Tables 3 and 4. Further, as shown in Table 3, the alicyclic polyester resins obtained in Production Example 4 were further blended in Examples 20 and 23.

Further, an optical semiconductor device was produced in the same manner as in Example 14.

<evaluation>

The following evaluation tests were carried out on the optical semiconductor devices obtained in the examples and the comparative examples.

[Power-on test (high-temperature power-on test)]

The total beam of the optical semiconductor device obtained in the examples and the comparative examples was measured by a total beam measuring machine to obtain a "total light beam of 0 hours". Further, a current of 30 mA was applied to the optical semiconductor device in a constant temperature bath at 85 ° C for 100 hours, and then the total light beam was measured, which was the "full beam after 100 hours". Thereafter, the luminosity retention ratio was calculated from the following formula. The results are shown in the column "Photos retention rate [%]" in Tables 1 to 4.

{Photometric retention rate (%)}={100 hours after full beam (lm)}/{0 hour full beam (lm)}×100

[Welding heat resistance test]

The optical semiconductor device (two for each curable epoxy resin composition) obtained in the examples and the comparative examples was allowed to stand at 30 ° C and 70% RH for 192 hours to carry out moisture absorption treatment. Next, the optical semiconductor device was placed in a reflow furnace and heat-treated under the following heating conditions. Thereafter, the optical semiconductor device was taken out to room temperature and allowed to cool, and then placed in a reflow furnace again to be heat-treated under the same conditions. In other words, in the solder heat resistance test, the secondary semiconductor heat history was applied to the optical semiconductor device under the following heating conditions.

[heating conditions (surface temperature reference of optical semiconductor device)]

(1) Preheating: 60~120 seconds at 150~190°C

(2) Formal heating after preheating: 217°C for 60~150 seconds, maximum temperature 260°C

However, when transferring from preheating to main heating, the temperature increase rate is controlled to a maximum of 3 ° C / sec.

Fig. 2 is a view showing an example of a trend of the surface temperature of the optical semiconductor device when heated by the reflow furnace (temperature tendency of one of the heat treatments of the two heat treatments).

Then, the optical semiconductor device was observed using a digital microscope (trade name "VHX-900", manufactured by KEYENCE Co., Ltd.) to evaluate whether or not the cured product was cracked with a length of 90 μm or more, and whether or not electrode peeling occurred (the cured product was peeled off from the electrode surface). ). In the two optical semiconductor devices, the number of optical semiconductor devices in which the cured material has a crack length of 90 μm or more is shown in the "welding heat resistance test [crack number]" table in Tables 1 to 4, and the number of optical semiconductor devices in which electrode peeling occurs is shown. The "welding heat resistance test [electrode peeling number]" column shown in Tables 1 to 4 is shown.

[thermal shock test]

The optical semiconductor device obtained in the examples and the comparative examples (two for each curable epoxy resin composition) was exposed to a -40 ° C environment for 30 minutes, and then exposed to a temperature of 120 ° C for 30 minutes for 1 cycle of heat. Impact, 200 cycles were applied using a thermal shock tester. Then, the crack length of the cured product in the optical semiconductor device was observed using a digital microscope (trade name "VHX-900", manufactured by KEYENCE Co., Ltd.), and cracks of 90 μm or more in the cured product were measured in the two optical semiconductor devices. The number of optical semiconductor devices. The results are shown in the "thermal shock test [crack number]" column of Tables 1 to 4.

[Comprehensive judgment]

As a result of each test, if each of the following (1) to (4) is satisfied, it is judged as ○ (good). On the other hand, if any one of the following (1) to (4) cannot be satisfied, it is judged as × (bad).

(1) Power-on test: luminosity retention rate is above 90%

(2) Solder heat resistance test: The number of optical semiconductor devices with a cracked length of 90 μm or more is 0.

(3) Solder heat resistance test: the number of optical semiconductor devices in which electrode peeling occurs is 0

(4) Thermal shock test: the number of optical semiconductor devices with a cracked length of 90 μm or more is 0.

The results are shown in the "Comprehensive Judgment" column of Tables 1 to 4.

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

(epoxy resin)

CEL2021P (CELLOXIDE 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, manufactured by Daicel Co., Ltd.

MA-DGIC: monopropenyldioxypropyltrimeric isocyanate, manufactured by Shikoku Chemical Industry Co., Ltd.

Glass filler: glass beads CF0018WB15C (surface-treated (3-methacryloxypropyltriethoxydecane), refractive index 1.52, average particle diameter (average particle diameter) 20 μm, manufactured by Nippon Frit Co., Ltd.)

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

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

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

YD-128: bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd.

(K agent)

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

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

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

U-CAT 18X: Hardening accelerator, manufactured by San-Apro Co., Ltd.

Ethylene glycol: manufactured by Wako Pure Chemical Co., Ltd.

(hardening catalyst)

SAN-AID SI-100L: Hardening Catalyst, manufactured by Sanshin Chemical Industry Co., Ltd.

Test machine

. Resin hardened oven

GPHH-201 manufactured by ESPEC Co., Ltd.

. Thermostat

ESPEC Co., Ltd. small high temperature box ST-120B1

. Full beam measuring machine

Optronic Laboratories Multi-Spectrophotometric System OL771

. Thermal shock test machine

ESPEC Co., Ltd. small thermal shock device TSE-11-A

. Reflow furnace

NIPPON ANTOM Co., Ltd., UNI-5016F

Industrial use possibility

The curable epoxy resin composition of the present invention can be suitably used as a resin composition for optical semiconductor encapsulation. Also, the hardening of the present invention The epoxy resin composition can also be used, for example, as an adhesive, an electrical insulating material, a laminate, a coating film, an ink, a coating, an encapsulant, a photoresist, a composite material, a transparent substrate, a transparent sheet, a transparent film, an optical element. , optical lenses, optical components, photo-curing stereoscopic shapes, electronic paper, touch panels, solar cell substrates, optical waveguides, light guides, holographic memory, etc.

Claims (11)

A curable epoxy resin composition comprising an alicyclic epoxy compound (A) and a monopropenyl epoxypropyl trimeric isocyanate compound (B) represented by the following formula (1) and a glass filler (C), [wherein R ¹ and R ^{2 are the} same or different from each other to represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. The curable epoxy resin composition of claim 1, wherein the alicyclic epoxy compound (A) is a compound having an epoxycyclohexane group. The curable epoxy resin composition according to claim 1 or 2, wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (I-1), The curable epoxy resin composition according to any one of claims 1 to 3, further comprising a decyl alkane derivative having two or more epoxy groups in the molecule. The curable epoxy resin composition according to any one of claims 1 to 4, which further contains an alicyclic polyester resin. The curable epoxy resin composition according to any one of claims 1 to 5, further comprising rubber particles. The curable epoxy resin composition according to any one of claims 1 to 6, which further contains a hardener (D) and a hardening accelerator (E). The curable epoxy resin composition according to any one of claims 1 to 6, which further contains a hardening catalyst (F). A cured product obtained by hardening a curable epoxy resin composition according to any one of claims 1 to 8. The curable epoxy resin composition according to any one of claims 1 to 8, which is a resin composition for optical semiconductor encapsulation. An optical semiconductor device in which an optical semiconductor element is packaged by a cured product of the curable epoxy resin composition of claim 10.