WO2013105425A1 - Epoxy resin composition, cured product of same, and optical semiconductor device - Google Patents

Abstract

The present invention is an epoxy resin composition which contains an epoxy resin and a curing agent. The epoxy resin contains an epoxy compound that is represented by general formula (1). (In general formula (1), each of X¹, X² and X³ independently represents a substituent represented by general formula (2).) (In general formula (2), m represents an integer of 1-10, and each of Y¹, Y², Y³ and Y⁴ represents a hydrogen atom or the like.)

Description

Epoxy resin composition, cured product thereof, and optical semiconductor device

The present invention relates to an epoxy resin composition, a cured product thereof, and an optical semiconductor device.

The reliability required for the sealing material and package material of semiconductor / electronic equipment is becoming higher as the device becomes thinner, smaller, and higher in output. As an example, an optical semiconductor element such as an LED or an LD (laser diode) emits light of a bright color with a small size and efficiency. Further, since the optical semiconductor element is a semiconductor element, it has a long life, excellent driving characteristics, and high durability against repeated vibration and ON / OFF lighting. Therefore, the said optical semiconductor element is utilized as various indicators and various light sources.
A polyphthalamide resin (PPA resin) is currently widely used as one of package materials for housing such optical semiconductor elements such as LEDs.

However, with the rapid progress of today's optical semiconductor technology, the optical semiconductor device has a remarkable increase in output and wavelength. Therefore, in an optical semiconductor device such as a photocoupler that can emit or receive high-energy light, the conventional optical semiconductor element sealing material and package using PPA resin are significantly deteriorated due to long-term use. Coloring, color unevenness, sealing resin peeling, mechanical strength reduction, etc. are likely to occur. For this reason, it is desired to effectively solve such a problem.

In relation to the above, Patent Document 1 below proposes a resin composition for an optical semiconductor element package containing a triazine derivative epoxy resin, and this resin composition is said to be excellent in heat resistance and light resistance. Yes. Patent Document 1 below exemplifies 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6-trione as a triazine derivative epoxy resin. .

International Publication No. 2007/015426

However, it is a cured product of a resin composition containing an epoxy resin composed of 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6-trione as described above. Even in such a case, it may be difficult to say that sufficient performance is obtained in terms of light resistance.

An object of the present invention is to provide an epoxy resin composition capable of forming a cured product excellent in light resistance, a cured product thereof, and an optical semiconductor device.

As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by using a specific epoxy compound having a triazine skeleton as the epoxy resin contained in the epoxy resin composition. As a result, the present invention has been completed.

（上記一般式（１）中、Ｘ^１、Ｘ^２及びＸ^３はそれぞれ独立に下記一般式（２）で表される置換基である。）

（上記一般式（２）中、ｍは１～１０の整数であり、Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４はそれぞれ独立に、水素原子、ハロゲン基、置換若しくは無置換の炭素数１～１０の直鎖状脂肪族炭化水素基、置換若しくは無置換の炭素数３～１０の分岐鎖状脂肪族炭化水素基、置換若しくは無置換の炭素数３～１０の脂環式脂肪族炭化水素基又は置換若しくは無置換の芳香族炭化水素基を示す。） That is, this invention is an epoxy resin composition containing an epoxy resin and a hardening | curing agent, and the said epoxy resin contains the epoxy compound represented by following General formula (1).

(In the general formula (1), X ¹ , X ² and X ³ are each independently a substituent represented by the following general formula (2).)

(In the general formula (2), m is an integer of 1 to 10, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted carbon number of 1 to 10 linear aliphatic hydrocarbon groups, substituted or unsubstituted branched aliphatic hydrocarbon groups having 3 to 10 carbon atoms, substituted or unsubstituted alicyclic aliphatic hydrocarbon groups having 3 to 10 carbon atoms Or a substituted or unsubstituted aromatic hydrocarbon group.)

According to the epoxy resin composition of the present invention, a cured product having excellent light resistance can be formed by thermally curing the epoxy resin composition. Therefore, the epoxy resin composition of the present invention is extremely useful for forming an optical semiconductor element package that is exposed to light emitted from the optical semiconductor element.

In the above epoxy resin composition, in the general formula ^(2), it is preferable Y ^1, Y 2, ^{Y 3} and ^{Y 4} are hydrogen atoms.

In this case, the viscosity of the epoxy compound represented by the general formula (1) is lower than in the case where Y ¹ , Y ² , Y ³ and Y ⁴ in the general formula (2) are other than hydrogen atoms. Therefore, the epoxy resin composition is easy to handle.

In the epoxy resin composition, m is preferably 1 in the general formula (2).

In this case, the epoxy compound represented by the general formula (1) can obtain more excellent thermal responsiveness than when m is larger than 1 in the general formula (2). Therefore, the epoxy resin composition has better thermal response.

Moreover, in the said epoxy resin composition, it is preferable that the content rate of the epoxy compound represented by the said General formula (1) in the said epoxy resin is 90.0 mass% or more.

In this case, compared with the case where the content rate of the epoxy compound represented by the general formula (1) in the epoxy resin is less than 90.0% by mass, the epoxy resin composition has more excellent light resistance. A cured product can be formed.

Further, the present invention is a cured product obtained by thermosetting the above epoxy resin composition.

The cured product of the present invention can have excellent light resistance.

Further, the present invention is an optical semiconductor device comprising an optical semiconductor element and an optical semiconductor element package for fixing the optical semiconductor element, wherein the optical semiconductor element package includes the cured product.

According to the optical semiconductor device of the present invention, even if light emitted from the optical semiconductor element is irradiated onto the optical semiconductor element package, the optical semiconductor element package contains a cured product having excellent light resistance. The service life of the device can be extended.

In the present invention, the “cured product” means a material having a melt viscosity larger than the melt viscosity of the epoxy resin composition used for the formation.

According to the present invention, it is possible to provide an epoxy resin composition capable of forming a cured product having excellent light resistance, a cured product thereof, and an optical semiconductor device.

It is sectional drawing which shows one Embodiment of the optical semiconductor device of this invention.

Hereinafter, the present invention will be described in detail.

（上記一般式（１）中、Ｘ^１、Ｘ^２及びＸ^３はそれぞれ独立に下記一般式（２）で表される置換基である。）

（上記一般式（２）中、ｍは１～１０の整数であり、Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４はそれぞれ独立に、水素原子、ハロゲン基、置換若しくは無置換の炭素数１～１０の直鎖状脂肪族炭化水素基、置換若しくは無置換の炭素数３～１０の分岐鎖状脂肪族炭化水素基、置換若しくは無置換の炭素数３～１０の脂環式脂肪族炭化水素基又は置換若しくは無置換の芳香族炭化水素基を示す。） <Epoxy resin composition>
The epoxy resin composition of the present invention contains an epoxy resin and a curing agent, and the epoxy resin contains an epoxy compound represented by the following general formula (1) (hereinafter simply referred to as “epoxy compound”).

(In the general formula (1), X ¹ , X ² and X ³ are each independently a substituent represented by the following general formula (2).)

(In the general formula (2), m is an integer of 1 to 10, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted carbon number of 1 to 10 linear aliphatic hydrocarbon groups, substituted or unsubstituted branched aliphatic hydrocarbon groups having 3 to 10 carbon atoms, substituted or unsubstituted alicyclic aliphatic hydrocarbon groups having 3 to 10 carbon atoms Or a substituted or unsubstituted aromatic hydrocarbon group.)

According to the epoxy resin composition of the present invention, a cured product having excellent light resistance can be formed by thermally curing the epoxy resin composition. Therefore, the epoxy resin composition of the present invention is extremely useful for forming an optical semiconductor element package that is exposed to light emitted from the optical semiconductor element.

The present inventors presume the reason why the epoxy resin composition of the present invention can form a cured product having excellent light resistance as follows.
That is, the epoxy resin composition includes an epoxy compound having a triazine skeleton, and the compound having a triazine skeleton functions as an ultraviolet absorber that absorbs ultraviolet rays and converts them into heat. Therefore, the epoxy resin composition can sufficiently suppress yellowing due to light irradiation from the optical semiconductor element in a cured product obtained by thermosetting the epoxy resin composition. Therefore, as described above, the present inventors presume that the epoxy resin composition of the present invention can form a cured product having excellent light resistance.

Moreover, the epoxy resin composition of the present invention can incorporate a triazine skeleton functioning as an ultraviolet absorber in a polymer chain in a cured product obtained by curing. For this reason, the epoxy resin composition of the present invention is different from the epoxy resin composition containing a low molecular weight UV absorber having a triazine skeleton as an additive, and the cured product obtained by the curing contains a component having a triazine skeleton. No bleed out on the surface of the cured product. That is, the epoxy resin composition of the present invention can make it difficult to reduce the light reflectance on the surface of the cured product. For this reason, the epoxy resin composition of the present invention is useful for forming an optical semiconductor element package of an optical semiconductor device that can suppress a decrease in luminance by suppressing a decrease in light reflectance.

Further, the epoxy resin composition of the present invention is a general epoxy resin (for example, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6- Curing can be initiated at a sufficiently lower temperature than when trione or 3,4-epoxycyclohexylmethyl (3, p) 4-epoxy) cyclohexanecarboxylate) is used. Specifically, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6-trione and 3,4-epoxycyclohexylmethyl (3, p) 4 -Epoxy) Curing can be initiated at a temperature 20-30 ° C. lower than the curing initiation temperature of the epoxy resin composition containing cyclohexanecarboxylate. For this reason, according to the resin composition for optical semiconductor packages of this invention, hardened | cured material can be manufactured efficiently.

Hereinafter, the epoxy resin composition will be described in detail.

(Epoxy resin)
As described above, the resin composition for an optical semiconductor element of the present invention contains the epoxy compound.

Examples of the halogen group represented by Y ¹ , Y ² , Y ³ and Y ^{4 in the} general formula (2) include —F group, —Cl group, —Br group and —I group.

Examples of the linear aliphatic hydrocarbon group represented by Y ¹ , Y ² , Y ³ and Y ^{4 in the} general formula (2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, Examples include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

Examples of the branched aliphatic hydrocarbon group represented by Y ¹ , Y ² , Y ³ and Y ^{4 in the} general formula (2) include, for example, isopropyl group, isobutyl group, s-butyl group, t-butyl group, Isopentyl group, s-pentyl group, t-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, isohexyl group, s-hexyl group, t-hexyl group, neohexyl group 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, isoheptyl group, s-heptyl group, t-heptyl group, neoheptyl group, cycloheptyl group, n- Octyl group, isooctyl group, s-octyl group, t-octyl group, neooctyl group, 2-ethylhexyl group, isononyl group, s-nonyl group, t-nonyl group, neo Group, isodecyl group, s- decyl, t-decyl group, and the like neodecyl group

Examples of the alicyclic aliphatic hydrocarbon group represented by Y ¹ , Y ² , Y ³ and Y ^{4 in the} general formula (2) include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a decalyl. Group, norbornyl group, adamantyl group and the like.

Examples of the aromatic hydrocarbon group represented by Y ¹ , Y ² , Y ³ and Y ^{4 in the} general formula (2) include a phenyl group, a naphthyl group, and an anthracyl group.

In addition, the linear aliphatic hydrocarbon group, branched aliphatic hydrocarbon group, alicyclic aliphatic hydrocarbon group, and aromatic represented by Y ¹ , Y ² , Y ^3, and Y ^{4 in the} general formula (2) Examples of the substituent of the group hydrocarbon group include halogen groups such as —F group, —Cl group, —Br group and —I group, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, carbon Examples thereof include alkylthio groups of 1 to 10.

In the general formula (2), Y ¹ , Y ² , Y ³ and Y ⁴ are preferably hydrogen atoms.

In this case, the viscosity of the epoxy compound is lower than in the case where Y ¹ , Y ² , Y ³ and Y ⁴ in the general formula (2) are other than hydrogen atoms. Therefore, the epoxy resin composition is easy to handle.

As described above, in the general formula (2), m is an integer of 1 to 10. When m is an integer larger than 10, the thermal responsiveness of the epoxy compound is insufficient. Therefore, in this case, the thermal responsiveness of the epoxy resin composition is insufficient.

In the above general formula (2), m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and particularly preferably 1.

When m is 1, the epoxy compound represented by the general formula (1) can obtain more excellent thermal responsiveness than when m is an integer greater than 1. Therefore, the epoxy resin composition has better thermal response.

In the general formula (2), Y ¹ , Y ² , Y ³ and Y ⁴ are hydrogen atoms and m is 1, that is, the epoxy compound represented by the general formula (1) is Particularly preferred is 2,4,6-tri (glycidyloxy) -1,3,5-triazine represented by the following formula (3).

In this case, the epoxy compound represented by the above formula (3) has a low viscosity and particularly excellent thermal response. Therefore, the epoxy resin composition containing this epoxy compound can be easily handled and has a particularly excellent thermal response.

The epoxy resin may contain an epoxy resin other than the epoxy compound.
Examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, alicyclic epoxy resins, and hydantoin type epoxy resins. And hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, biphenyl type epoxy resin, dicyclocyclic type epoxy resin, naphthalene type epoxy resin and the like.
These resins may be used alone or in combination of two or more.

The content of the epoxy compound in the epoxy resin is preferably 30.0% by mass or more, more preferably 60.0% by mass or more.

The content of the epoxy compound in the epoxy resin is more preferably 90.0% by mass or more.

In this case, the epoxy resin composition can form a cured product having more excellent light resistance as compared with the case where the content of the epoxy compound in the epoxy resin is less than 90.0% by mass.

(Curing agent)
As described above, the epoxy resin composition of the present invention contains a curing agent. The curing agent is not particularly limited as long as it can form a cured product by reacting with an epoxy resin, and can be appropriately selected from commonly used curing agents. For example, in addition to a novolak-type phenol resin obtained by condensation reaction of acid anhydride, phenol, cresol, xylenol, resorcin and the like with formaldehyde, polymercapto resin such as liquid polymercaptan and polysulfide, amide, amine type curing agent, Acrylate, carbonate, isocyanate and the like can be used. Among these, from the viewpoint of light resistance, a compound that is non-aromatic and does not have an ethylenically unsaturated bond is preferable. Specific examples include acid anhydride curing agents such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and hydrogenated methylnadic acid anhydride. Among these acid anhydride curing agents, methylhexahydrophthalic anhydride is more preferable. One type of curing agent may be used alone, or two or more types may be used in combination.

The content of the curing agent is, for example, a content in which the number of moles of reactive groups such as acid anhydride groups and active hydrogen is 0.4 mol to 2.0 mol with respect to 1 mol of the epoxy group of the epoxy compound. can do. The number of moles of the reactive group is preferably 0.6 mol to 2.0 mol, more preferably 0.8 mol to 1.6 mol. By setting the number of moles to 0.4 moles or more, good curability is obtained, and reliability is improved. Moreover, it can suppress that an unreacted hardening | curing agent remains in hardened | cured material by making the said mole number into 2.0 mol or less, and the moisture resistance of the hardened | cured material obtained improves more.

Moreover, the epoxy resin composition of the present invention may further contain at least one of a curing accelerator, an inorganic filler, a surface conditioner, and an antioxidant as necessary.

(Curing accelerator)
As said hardening accelerator, the compound normally used as a hardening accelerator of an epoxy resin can be especially used without a restriction | limiting. Specific examples include imidazoles, quaternary ammonium salts, phosphorus compounds, amines, phosphines, phosphonium salts, bicyclic amidines, and salts thereof. These may be used alone or in combination of two or more.

More specifically, imidazoles such as 2-methylimidazole and 2-phenyl-4-imidazole, imidazole salts such as 2-phenylimidazole and isocyanuric acid adducts, 1,8-diazabicyclo [5,4,0] undecene-7, etc. When using bicyclic amidines of 1,8-diazabicyclo [5,4,0] undecene-7 octylate and other bicyclic amidine carboxylates, and tetraphenylphosphonium bromide phosphonium salts It is more preferable because it is excellent in properties and coloring is suppressed. The addition amount of the curing accelerator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy compound.

(Inorganic filler)
The shape of the inorganic filler is not particularly limited, and may be fibrous, plate-like, or powdery.
Examples of the fibrous inorganic filler include glass fiber, asbestos fiber, silica fiber, silica / aluminum fiber, alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, and potassium titanate fiber.
In addition, powdered inorganic fillers include silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, wollastonite and other silicates, iron oxide, titanium oxide, Metal oxides such as zinc oxide, antimony trioxide, alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other ferrites, silicon carbide, silicon nitride, boron nitride And aluminum nitride.
Examples of the plate-like inorganic filler include mica and glass flakes. These inorganic fillers may be used alone or in combination of two or more.

The color of the inorganic filler is not particularly limited, but is preferably a white inorganic filler from the viewpoint of light resistance and high reflectance. For example, examples of the white inorganic filler include titanium oxide, zinc oxide, silica, quartz powder, talc, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, mica, and alumina.

Among these, the inorganic filler is more preferably at least one selected from the group consisting of titanium oxide, silica and alumina.

The volume average particle diameter of the inorganic filler is not particularly limited. From the viewpoint of moldability and fluidity of the epoxy resin composition, the volume average particle size is preferably 0.5 μm to 40 μm, and particularly preferably 1 μm to 35 μm. Further, particles having a volume average particle size in a fine region of less than 1 μm, particles in a medium particle size region of not less than 1 μm and less than 10 μm so as to be highly fluidized when potting or underfilling the epoxy resin composition, and It is also preferred to use a combination of particles in the coarse region of 10-40 μm.
In addition, the volume average particle diameter of an inorganic filler can be measured using a laser diffraction scattering particle size distribution measuring apparatus.

The content of the inorganic filler contained in the epoxy resin composition can be appropriately selected according to the purpose. From the viewpoint of light resistance and high reflectance, the content of the inorganic filler is preferably 97% by mass to 50% by mass, and 95% by mass to 75% by mass with respect to the total mass of the epoxy resin composition. It is more preferable.

(Surface conditioner)
When the epoxy resin composition of the present invention contains a surface conditioner such as a silane coupling agent, the interfacial adhesive force between the epoxy resin and the inorganic filler is improved, and the cured product obtained by curing the epoxy resin composition. The mechanical strength of is improved.
For example, silane coupling agents include epoxy functional alkoxy such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Amino-functional alkoxysilanes such as silane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyl And mercapto-functional alkoxysilanes such as trimethoxysilane. The surface conditioner may be used for the surface treatment of the inorganic filler.

(Antioxidant)
As said antioxidant, a phenolic antioxidant, phosphorus antioxidant, and sulfur type antioxidant can be used. Specific examples of the antioxidant include the following antioxidants.

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-t-butyl- 4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol, 4,4′-butylenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1 -Dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

Phosphorus antioxidants include triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tri (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, triphenyl phosphite Distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tri Examples include stearyl sorbitol triphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenyl diphosphonate.

Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate.

These antioxidants can be used singly or in combination of two or more.

The content of the antioxidant is preferably 0.01% by mass to 10% by mass in the epoxy resin composition, and particularly preferably 0.03% by mass to 5% by mass. When the content of the antioxidant is 0.01% by mass or more, better heat resistance is obtained and discoloration tends to be more effectively suppressed. Further, when the content of the antioxidant is 10% by mass or less, inhibition of curing is suppressed and sufficient curability and strength tend to be obtained.

In addition, the epoxy resin composition may contain a thermosetting resin other than the epoxy resin, if necessary, for the purpose of modifying the characteristics. Examples of such thermosetting resins include cyanate ester resins, phenol resins, polyimide resins, urethane resins, bismaleimide resins, and the like.

(Other additives)
Moreover, the epoxy resin composition of this invention may contain various additives, such as a discoloration prevention agent, a deterioration prevention agent, a mold release agent, a plasticizer, and a diluent, as needed.

<Method for producing epoxy resin composition>
The manufacturing method of an epoxy resin composition is not specifically limited, It can select from the manufacturing method normally used as a manufacturing method of an epoxy resin composition, and can use it suitably. Specifically, for example, the above epoxy resin is dissolved in an organic solvent, a curing agent, and if necessary, a curing accelerator is added to the organic solvent. It can be manufactured by adding and mixing a functional resin.

Also, after thoroughly mixing the epoxy resin, curing agent, and curing accelerator, inorganic filler, etc. added as necessary, using a mixer, etc., melt mixing with a hot roll, kneader, extruder, etc. An epoxy resin composition can also be produced by performing the treatment, then cooling and solidifying the obtained mixture, and pulverizing to an appropriate size.

<Hardened product>
The cured product of the present invention is obtained by thermosetting the above-described epoxy resin composition.
According to the cured product of the present invention, it is possible to have excellent light resistance.

<Optical semiconductor device>
The optical semiconductor device of the present invention includes an optical semiconductor element and an optical semiconductor element package for fixing the optical semiconductor element, and the optical semiconductor element package includes the cured product described above.
According to the optical semiconductor device of the present invention, even if the light emitted from the optical semiconductor element is irradiated onto the optical semiconductor element package, the optical semiconductor element package contains the cured product having excellent light resistance. The lifetime of the semiconductor device can be extended.

(Optical semiconductor device)
An optical semiconductor element is an element constituted by a stacked body of semiconductor layers in which positive and negative electrodes are formed on the same surface or different surfaces. Examples of the optical semiconductor element include a light emitting element, a light emitting diode, a laser diode, a phototransistor, and a photodiode.

(Optical semiconductor device package)
An optical semiconductor element package is for fixing an optical semiconductor element. The optical semiconductor element package has at least a member for supporting and fixing the optical semiconductor element. The optical semiconductor element package may further include a member for protecting the optical semiconductor element and a member for reflecting light emitted from the optical semiconductor element.
The shape of the optical semiconductor element package is not particularly limited, and may be a shape having a recess for mounting the optical semiconductor element, a flat plate shape, or a ring shape.

Here, an embodiment of the optical semiconductor device of the present invention will be specifically described with reference to FIG. FIG. 1 is a cross-sectional view showing an embodiment of an optical semiconductor device of the present invention.

As shown in FIG. 1, the optical semiconductor device 100 includes an optical semiconductor element 10 and an optical semiconductor element package 20 that fixes the optical semiconductor element 10.
In the present embodiment, the optical semiconductor element package 20 includes an element mounting portion 30 that has the concave portion 30 a and mounts the optical semiconductor element 10, and a sealing portion 40 that fills the concave portion 30 a of the element mounting portion 30. The element mounting part 30 is provided on the element fixing part 31 for supporting and fixing the optical semiconductor element 10, and surrounds the optical semiconductor element 10 and reflects light emitted from the optical semiconductor element 10. The light reflection part 32 is comprised. The element fixing portion 31 includes a first lead 31a connected to one of the two electrodes included in the optical semiconductor element 10 and a bonding wire connected to the other electrode of the two electrodes included in the optical semiconductor element 10. The second lead 31b connected via the conductive member 50, etc., and the insulating portion 31c that insulates the first lead 31a and the second lead 31b. The concave portion 30 a is formed by the element fixing portion 31 and the inner peripheral surface of the light reflecting portion 32.

In the optical semiconductor device 100, at least one of the light reflecting portion 32, the insulating portion 31 c, and the sealing portion 40 of the optical semiconductor element package 20 is configured by a cured product obtained by thermosetting the epoxy resin composition. The Here, it is preferable that at least the light reflecting portion 32 is composed of a cured product obtained by thermosetting the epoxy resin composition. This is due to the following reason. That is, the inner peripheral surface of the light reflecting portion 32 reflects light emitted from the optical semiconductor element 10, and the reflectance of light on the inner peripheral surface affects the luminance of the optical semiconductor device 100. In that respect, when the light reflection part 32 is comprised with the hardened | cured material obtained by thermosetting an epoxy resin composition, since the light reflection part 32 is excellent in light resistance, it maintains a high light reflectance in an internal peripheral surface. can do. Therefore, a decrease in luminance of the optical semiconductor device 100 can be sufficiently suppressed.

<Method for Manufacturing Optical Semiconductor Device>
The optical semiconductor device can be obtained by fixing the optical semiconductor element package to the optical semiconductor element.
The optical semiconductor element package can be obtained using a molding method. A method for molding the optical semiconductor element package can be appropriately selected from conventionally used molding methods. For example, a method of obtaining an optical semiconductor element package by injection-molding or transfer-molding the epoxy resin composition and curing it by heating and pressurizing is preferably used. The conditions for the heat treatment and the pressure treatment are not particularly limited, and can be appropriately selected according to the configuration of the epoxy resin composition. For example, the conditions for the heat treatment and the pressure treatment are as follows: the temperature is 100 ° C. to 200 ° C., the pressure at the time of pressurization is 0.1 MPa to 10 MPa, and the time required for the heat and pressure treatment is 0.5 minutes to 30 minutes. It can be a condition that there is. The epoxy resin composition of the present invention can be cured at a temperature of 150 ° C. to 200 ° C., preferably 170 ° C. to 190 ° C., for example.
The epoxy resin composition can be formed by various methods as described above and then post-cured (aftercured) as necessary.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass”.

(Synthesis of 2,4,6-tri (glycidyloxy) -1,3,5-triazine)
To a 2,000 mL three-necked flask equipped with a stirrer, a thermometer and a dropping funnel was charged 110 g of cyanuric chloride (Aldrich) and 600 mL of chloroform as a solvent, and 222 g of glycidol (Kanto Chemical Co., Ltd.) was added while maintaining the temperature at 3 ° C. It was. Thereafter, the reaction temperature was set to 10 ° C., and 176 g of a 50% aqueous sodium hydroxide solution was added dropwise over 6 hours, and the reaction was further performed for 1 hour. 400 mL of water was added to the reaction product to remove excess sodium hydroxide, and the organic matter was dehydrated with magnesium sulfate. Magnesium sulfate was filtered off and concentrated under reduced pressure to obtain a white solid. This was washed twice with 400 mL of cold methanol to obtain 120 g (yield 68%, epoxy equivalent 100 g / eq) of 2,4,6-tri (glycidyloxy) -1,3,5-triazine. The epoxy equivalent was determined according to JIS K-7236.

(Examples 1 to 3 and Comparative Examples 1 to 4)
The following epoxy resin, curing agent, curing accelerator, and inorganic filler were blended so as to have the composition shown in Table 1, followed by roll kneading at 50 ° C. to 60 ° C. for 10 minutes. 3 and Comparative Examples 1 to 4 were obtained. In addition, the unit of the numerical value described in the resin composition of Table 1 is a mass part.
<Epoxy resin>
TGC [2,4,6-tri (glycidyloxy) -1,3,5-triazine, the above synthetic product]
・ TEPIC [1,3,5-Tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6-trione, manufactured by Nissan Chemical Co., Ltd.]
Celoxide 2021P [3,4-epoxycyclohexylmethyl (3, p) 4-epoxy) cyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd.]
<Curing agent>
Methylhexahydrophthalic anhydride [Licacid MH, manufactured by Shin Nippon Chemical Co., Ltd.]
<Curing accelerator>
1,8-diazabicyclo [5.4.0] undecene-7, [hisilicone PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.]
<Inorganic filler>
Alumina [AO-802, manufactured by Admatechs, average particle size 0.7 μm]
Silica A [FB-304, manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 6 μm]
Silica B [HS-202, manufactured by Micron, average particle diameter of 16 μm]
・ Titanium oxide [CR-90-2, manufactured by Ishihara Sangyo Co., Ltd., average particle size 0.3 μm]
・ Borosilicate glass [Glass Bubbles S60HS, manufactured by Sumitomo 3M, average particle size of 30 μm]

※表１において、「－」は、配合量が０質量部であることを示す。

* In Table 1, “-” indicates that the blending amount is 0 parts by mass.

(Characteristic evaluation)
<Curing start temperature>
The curing start temperature of the epoxy resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4 was set as the heat generation starting temperature in differential scanning calorimetry (DSC3100SA Bruker AEX). The results are shown in Table 1.

<Light resistance>
The epoxy resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were heated and pressurized at a mold temperature of 180 ° C., a pressure of 0.16 MPa and a curing time of 2 minutes, and the thickness of the cured product was 1 mm. A plate-shaped test piece was prepared. The melt viscosity of the plate-like test pieces of Examples 1 to 3 and Comparative Examples 1 to 4 was 100 to 100,000 times the melt viscosity of the epoxy resin composition used as the raw material.
And about each test piece, the light reflectance in wavelength 460nm of each test piece was measured using the spectrophotometer (U4000 type, Hitachi Ltd. make).
Next, for each test piece, using a light resistance tester (Metal Weather KW-R5TP-A, manufactured by Daipura Wintes Co., Ltd.) under an irradiation intensity of 850 W / cm ² , a temperature of 83 ° C., a humidity of 20% RH and no condensation. 100, 150, 200, 250 hours. Then, about each test piece, the light reflectivity in wavelength 460nm was measured like the above.
Table 1 shows the results of the light reflectance. The light reflectance of each test piece is a relative value with the light reflectance of polytetrafluoroethylene being 100%. Table 1 shows the results of the light reflectance based on the following criteria.

(Evaluation criteria)
A: Light reflectance is 90% or more B: Light reflectance is 80% or more and less than 90% C: Light reflectance is 70% or more and less than 80% D: Light reflectance is less than 70%
Here, when the result of the light reflectance of the test piece after 250 hours test is A, the light reflectance is acceptable, and when the light reflectance is B, C or D, the light resistance is unacceptable. It was.

From the results shown in Table 1, it can be seen that the epoxy resin composition of the present invention can form a cured product capable of maintaining a high light reflectance even after the light resistance test. That is, it turns out that the epoxy resin composition of this invention can form the hardened | cured material which is excellent in light resistance.

DESCRIPTION OF SYMBOLS 10 ... Optical semiconductor element 20 ... Optical semiconductor element package 100 ... Optical semiconductor device

Claims (6)

Epoxy resin,
Containing a curing agent,
The epoxy resin composition in which the epoxy resin contains an epoxy compound represented by the following general formula (1).

(In the general formula (1), X ¹ , X ² and X ³ are each independently a substituent represented by the following general formula (2).)

(In the general formula (2), m is an integer of 1 to 10, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted carbon number of 1 to 10 linear aliphatic hydrocarbon groups, substituted or unsubstituted branched aliphatic hydrocarbon groups having 3 to 10 carbon atoms, substituted or unsubstituted alicyclic aliphatic hydrocarbon groups having 3 to 10 carbon atoms Or a substituted or unsubstituted aromatic hydrocarbon group.) The epoxy resin composition according to claim ¹ , wherein in the general formula (2), Y ¹ , Y ² , Y ³ and Y ⁴ are hydrogen atoms. The epoxy resin composition according to claim 1, wherein m is 1 in the general formula (2). The epoxy resin composition according to any one of claims 1 to 3, wherein the content of the epoxy compound represented by the general formula (1) in the epoxy resin is 90.0 mass% or more. A cured product obtained by thermosetting the epoxy resin composition according to any one of claims 1 to 4. An optical semiconductor element;
An optical semiconductor element package for fixing the optical semiconductor element;
The optical semiconductor element package is
An optical semiconductor device comprising the cured product according to claim 5.

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