JP2012167225A - Thermosetting epoxy resin composition, reflective member for optical semiconductor device, and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting epoxy resin composition giving a cured product which has a high initial reflectance and good shielding properties, retains reflexivity, heat resistance and light resistance for a long period, is uniform and hardly turns yellow.SOLUTION: The thermosetting epoxy resin composition contains, as essential components: (A) a triazine derivative epoxy resin; (B) a curing agent; (C) an antioxidant; (D) an internal release agent having a melting point in the range of 50-80°C; (E) a reflection improver having a lead content of <10 ppm on a mass basis; (F) an auxiliary flame retardant; (G) an inorganic filler; and (H) a curing catalyst; wherein with respect to 100 parts in total of (A) and (B), (C), (D), (E), (F), (G) and (H) are contained in amounts of 0.02-5.0 parts, 0.2-10.0 parts, 50-1,000 parts, 2.0-100 parts, 50-1,000 parts and 0.05-5.0 parts, respectively, and wherein the molar ratio of epoxy groups of the epoxy resin of (A) to reactive groups of epoxy groups contained in the curing agent of (B) fulfills (epoxy groups)/(reactive groups of epoxy groups)≥1.0.

Description

  The present invention provides a cured product that has excellent releasability, fluidity, reliability at high temperature storage and good light resistance, suppresses discoloration due to heat, particularly yellowing, and has excellent reflectivity and shielding properties. The present invention relates to a thermosetting epoxy resin composition to be applied, a reflecting member for an optical semiconductor device using a light emitting element, a light receiving element and other optical semiconductor elements, and an optical semiconductor device having the reflecting member.

  In recent years, the requirements for the reliability of the sealing material and the reflecting member of the optical semiconductor / electronic device are becoming more and more severe as the device is made thinner and smaller and the output is increased. As an example, a reflecting member that reflects light from a light emitting element toward a light receiving element is used for an optical semiconductor device such as a photocoupler and an optical semiconductor element such as a light emitting diode (LED).

Epoxy resins, silicone resins, and the like are currently widely used as sealing materials for such optical semiconductor / electronic device devices.
Also, a resin composition obtained by adding titanium oxide to a polyamide-based resin is often used as a reflecting member of an optical semiconductor / electronic device.

  However, due to the dramatic progress of today's optical semiconductor technology, the output power and the shortening of the wavelength of the optical semiconductor device are remarkable, and the optical semiconductor device such as a photocoupler capable of emitting or receiving high energy light is used for a long time. Deterioration due to the above is remarkable, and color unevenness, peeling, and mechanical strength are likely to decrease. For this reason, it has been desired to effectively solve such problems.

  More specifically, in Japanese Patent No. 2656336 (Patent Document 1), a B-stage epoxy resin composition for encapsulating an optical semiconductor, in which the sealing resin comprises an epoxy resin, a curing agent and a curing accelerator as constituent components. An optical semiconductor device characterized in that it is composed of a cured body of a resin composition in which the constituent components are uniformly mixed at a molecular level is described. In this case, as the epoxy resin, bisphenol A type epoxy resin or bisphenol F type epoxy resin is mainly used, and it is also described that triglycidyl isocyanate or the like can be used, but triglycidyl isocyanate is a bisphenol type in Examples. A small amount is added to the epoxy resin, and according to the study by the present inventors, this epoxy resin composition for B-stage semiconductor encapsulation has a problem that it turns yellow particularly when left at high temperature for a long time. is there.

Japanese Patent No. 2656336

  The present invention has been made in view of the above circumstances, and is thermosetting that retains reflectivity (that is, whiteness), heat resistance, and light resistance over a long period of time and gives a cured product that is uniform and has little yellowing. An object of the present invention is to provide an epoxy resin composition, a reflecting member made of a cured product of the composition, and an optical semiconductor device having the reflecting member.

The epoxy resin composition of the present invention is
(A) a triazine derivative epoxy resin,
(B) a curing agent,
(C) an antioxidant,
(D) an internal release agent having a melting point in the range of 50 to 80 ° C.,
(E) a reflection improver whose lead content is less than 10 ppm on a mass basis;
(F) flame retardant aid,
(G) inorganic filler,
(H) a curing catalyst,
Is an essential ingredient,
For a total of 100 parts by mass of the component (A) and the component (B),
0.02 to 5.0 parts by mass of the component (C),
0.2 to 10.0 parts by mass of the component (D),
50 to 1000 parts by mass of the component (E),
2.0 to 100 parts by mass of the component (F),
50 to 1000 parts by mass of the component (G),
0.05 to 5.0 parts by mass of the component (H),
Including
The molar ratio of the epoxy group of the epoxy resin of the component (A) and the reactive group of the epoxy group contained in the curing agent of the component (B) is
It is a thermosetting epoxy resin composition in which the epoxy group / reactive group with the epoxy group ≧ 1.0.

According to the thermosetting epoxy resin composition of the present invention, it is possible to maintain a whiteness, heat resistance, and light resistance for a long period of time, to provide a cured product that is uniform and has little yellowing, and is excellent. Formability, particularly mold release properties can be obtained.

The thermosetting epoxy resin composition of the present invention is useful as a reflecting member for use in an optical semiconductor device because the resulting cured product has high whiteness and is excellent in light reflectivity.

  Moreover, the optical semiconductor device of this invention is equipped with the reflection member which consists of hardened | cured material of the said thermosetting epoxy resin composition, and an optical semiconductor element. Furthermore, an electronic apparatus device according to the present invention includes the optical semiconductor device according to the present invention.

The thermosetting epoxy resin composition of the present invention is excellent in fluidity, reflow resistance, reliability at high temperature storage, releasability, and maintains light resistance for a long period of time, uniform and yellowing. It gives less cured product.
In addition, the cured product of the composition is excellent in mechanical strength, hardly discolored by light, and has good light reflectivity after reflow, and therefore is suitable for a reflective member such as a photocoupler or a premolded package.

It is sectional drawing which shows one example of the photocoupler using the thermosetting epoxy resin composition of this invention.

As described above, the thermosetting epoxy resin composition of the present invention includes components (A) to (H) as essential components. Hereinafter, first, each component will be described in detail.
(A) Triazine derivative epoxy resin The epoxy resin of component (A) used in the present invention is preferably a triazine derivative epoxy resin from the viewpoint of heat resistance and weather resistance. The thermosetting epoxy resin composition of the present invention contains the curing agent of the component (A) and the component (B) at a specific ratio, so that the cured product of the thermosetting epoxy resin composition can be yellowed. An optical semiconductor device that is suppressed and has little deterioration with time is realized. The triazine derivative epoxy resin is preferably a 1,3,5-triazine nucleus derivative epoxy resin (eg, isocyanurate ring-containing epoxy resin, cyanurate ring-containing epoxy resin). In particular, an epoxy resin having an isocyanurate ring is excellent in light resistance and electrical insulation, and is divalent (that is, two), more preferably trivalent (three) with respect to one isocyanurate ring. It is desirable to have an epoxy group). Specifically, tris (2,3-epoxypropyl) isocyanurate, tris (γ-glycidoxypropyl) isocyanurate, tris (α-methylglycidyl) isocyanurate, or the like can be used. Moreover, these may be used individually by 1 type or may use 2 or more types together.

  The softening point of the triazine derivative epoxy resin used in the present invention is preferably 90 to 125 ° C. In the present invention, the triazine derivative epoxy resin does not include a hydrogenated triazine ring.

(B) Curing agent The curing agent of the component (B) is not particularly limited, and is an epoxy having at least 2, preferably 3 or more functional groups that can react with the epoxy group in the component (A). What is necessary is just what is normally used as a hardening | curing agent of resin, for example, although a well-known thing is mentioned, such as a phenol resin hardening | curing agent, an amine hardening | curing agent, and an acid anhydride hardening | curing agent, Then, a phenol resin-based curing agent is preferably used.

In this case, as the phenol resin-based curing agent, a phenol resin having at least 2, preferably 3 or more phenolic hydroxyl groups in one molecule is used. Specific examples of such curing agents include novolak-type phenol resins such as phenol novolak resins, cresol novolak resins, and naphthol novolak resins, paraxylylene-modified novolak resins, metaxylylene-modified novolak resins, orthoxylylene-modified novolak resins, and bisphenol A. Bisphenol type resins such as bisphenol F, biphenyl type phenol resins, resol type phenol resins, phenol aralkyl resins, biphenyl skeleton-containing aralkyl type phenol resins, triphenol alkane type resins and their polymers, phenol resins, naphthalene ring-containing phenol resins , Dicyclopentadiene modified phenolic resin, terpene modified phenolic resin, alicyclic phenolic resin, heterocyclic phenolic resin, etc. Phenol resin can also be used. Moreover, these may be used individually by 1 type, or may use 2 or more types together.

In addition, as for these phenol resin type hardening | curing agents, the thing whose softening point is 60-150 degreeC, especially 70-130 degreeC is preferable. Moreover, as a hydroxyl equivalent, the thing of 90-250 is preferable. Further, when such a phenol resin-based curing agent is used for semiconductor encapsulation, the content of sodium and potassium is preferably 10 ppm or less, and the semiconductor device is encapsulated with a content exceeding 10 ppm for a long time. When a semiconductor device is left under high temperature and high humidity, deterioration of moisture resistance may be promoted.

Examples of amine-based curing agents include aliphatic polyamines such as diethylenetriamine, triethylenetetraamine, and tetraethylenepentamine; aromatic amines such as metaphenylenediamine and diaminodiphenylmethane, and one or more of these may be used. Can be used.

Examples of acid anhydride curing agents include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydro. Phthalic anhydride, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic acid An acid anhydride, a methylnorbornane-2,3-dicarboxylic acid anhydride, a methylcyclohexene dicarboxylic acid anhydride, etc. can be mentioned, These 1 type (s) or 2 or more types can be used.

(B) Although the compounding quantity of a component is not restrict | limited in particular, It is an effective quantity which hardens | cures an epoxy resin, Preferably, with respect to 1 mol of epoxy groups contained in the epoxy resin of (A) component from a heat resistant surface, ( B) molar ratio of epoxy group reactive group (for example, phenolic hydroxyl group, carboxyl group (or carboxylic acid anhydride group 1/2 equivalent), amino group) contained in the curing agent of component (epoxy group / The reactive group with the epoxy group) is preferably 1.0 or more, particularly 1.0 to 2.0, more preferably 1.2 to 1.8.

(C) Antioxidant Antioxidant is mix | blended with the thermosetting epoxy resin composition of this invention as (C) component.

Although it does not specifically limit as antioxidant of (C) component, For example, following General formula (1):

(In the formula, R is an alkyl group represented by C _n H _{2n + 1} , and n is a number from 1 to 10.)
It is preferable to use 1 type (s) or 2 or more types of hindered phenol type antioxidant shown by these. Specific examples of the antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxy) in that the cured product of the resulting composition is excellent in heat resistance and strength. Phenyl) propionate] is preferred.

  The amount of component (C) is 0.02 to 5.0 parts by weight, particularly 0.1 to 4.0 parts by weight, based on 100 parts by weight of the total of components (A) and (B). preferable. When the blending amount of the component (C) is less than 0.02 parts by mass, sufficient heat resistance cannot be obtained and discoloration may easily occur. When the amount is more than 5.0 parts by mass, curing of the composition is inhibited. Sufficient curability and strength may not be obtained.

(D) Internal mold release agent having a melting point in the range of 50 to 80 ° C. The thermosetting epoxy resin composition of the present invention has a melting point of 50 to 80 ° C., particularly 50 to 70 ° C. as the component (D). An internal mold release agent in the range of is added. The internal mold release agent of the component (D) is preliminarily blended with the resin raw material and has a function of improving the mold release property so that the molded product can be easily peeled from the mold.

［式中、Ｒ¹、Ｒ²、Ｒ³は、独立に、Ｈ、−ＯＨ、−ＯＲ、又は−ＯＣＯＣ_aＨ_bであり、Ｒ¹、Ｒ²、Ｒ³の少なくとも１つは−ＯＣＯＣ_aＨ_bである。ＲはＣ_nＨ_2n+1のアルキル基（ｎは１〜３０の整数である。）、ａは１０〜３０の整数、ｂは１７〜６１の整数である。］
で示される化合物が好ましく、融点が５０〜８０℃、特には、５０〜７０℃の範囲であるグリセリンモノステアレート化合物の１種又は２種以上を含むことが好ましい。 In this case, as the internal mold release agent of the component (D), the following general formula (2):

[Wherein, R ¹ , R ² , R ³ are independently H, —OH, —OR, or —OCOC _a H _b , and at least one of R ¹ , R ² , R ³ is —OCOC _{a Hb} . R is an alkyl group of C _n H _{2n + 1} (n is an integer of 1 to 30), a is an integer of 10 to 30, and b is an integer of 17 to 61. ]
The compound shown by these is preferable, and it is preferable to contain 1 type, or 2 or more types of the glycerol monostearate compound whose melting | fusing point is 50-80 degreeC, especially 50-70 degreeC.

  Conventionally, natural waxes such as carnauba wax, acid waxes, polyethylene waxes, and synthetic waxes such as fatty acid esters are known as internal mold release agents. Below, there are many that easily turn yellow or lose their releasability due to deterioration over time. On the other hand, the compound represented by the general formula (2) has a low yellowing property even when left at high temperature or under light irradiation, and continuously maintains good releasability over a long period of time. .

It is essential that at least one of R ¹ , R ² and R ^{3 in} the general formula (2) is —OCOC _a H _b . When all are —OH, sufficient releasability and heat resistance cannot be obtained, but by including —OCOC _a H _b in the structure, good compatibility with other components, particularly the above prepolymer, cured product Good heat resistance and releasability can be obtained.

A contained in —OCOC _a H _b is an integer of 10-30, preferably 11-20. If a is less than 10, sufficient heat-resistant yellowing may not be obtained, and if a exceeds 30, it may not be sufficiently compatible with other components and a good release effect may not be obtained.

C _a H _b is a saturated or unsaturated aliphatic hydrocarbon group. In the case of unsaturation, those having one or two unsaturated bonds are preferred, and therefore b = 2a + 1, 2a-1 or 2a-3 is preferred, and in particular b = 2a + 1 or 2a-1. It is preferable. From this point, b is an integer of 17 to 61, preferably an integer of 19 to 41, more preferably 21 to 41, and particularly preferably an integer of 23 to 41.

  Specifically, as the internal mold release agent of component (D), glycerol monopalmitate, glycerol monostearate, glycerol mono12-hydroxystearate, glycerol tri12-hydroxystearate, glycerol monobehenate, propylene glycol mono Examples include palmitate, propylene glycol monostearate, propylene glycol monobehenate, propylene glycol monobehenate, stearyl stearate and the like.

  However, the melting point and volatile content at high temperature are also important factors affecting the heat resistance. (D) It is preferable that melting | fusing point of the internal mold release agent of a component is 50-80 degreeC, More preferably, it is 65-80 degreeC, More preferably, it is 65-70 degreeC. Moreover, a volatile matter at 250 ° C. is preferably 10% by mass or less. If the melting point of the internal release agent is less than 50 ° C, sufficient heat-resistant yellowing may not be obtained. If it exceeds 80 ° C, the compatibility with other components becomes insufficient, and a good release effect is obtained. It may not be possible. In particular, glycerin monostearate and propylene glycol fatty acid ester (specifically, propylene glycol monobehenate) having a melting point of 50 to 70 ° C. are preferable from the viewpoint of dispersibility in the composition and compatibility with other components.

The internal mold release agent of component (D) preferably contains the compound represented by the formula (2) in a ratio of 20 to 100% by mass, particularly 50 to 100% by mass, in all the internal mold release agents. .
As the internal mold release agent for the component (D), when other compounds are used in combination with the compound of the general formula (2), the following general formula (3):

R ⁴ —COO—R ⁵ (3)
(In the formula, R ⁴ and R ⁵ are the same or different alkyl groups represented by C _n H _{2n + 1} , and n is an integer of 1-30, preferably 2-28, more preferably 5-25. .)
It is preferable to use together with the carboxylic acid ester shown by. As other mold release agents, the above-mentioned natural wax, acid wax, other synthetic waxes and the like can be used.

  The carboxylic acid ester of the general formula (3) is also low in yellowing even when left at high temperature or under light irradiation, and continuously maintains good releasability over a long period of time. In this case, the ratio of the carboxylic acid ester of the formula (3) and the compound of the formula (2) is, on a mass basis, the ester of the general formula (3): the compound of the general formula (2), preferably 1: 5 10: 1, more preferably 1: 4 to 8: 1. In addition, when there are too many carboxylate ester of Formula (3), the adhesiveness with a metal frame and the mechanical strength of hardened | cured material may fall.

  (D) The compounding quantity of a component is 0.2-10.0 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and 0.5-5.0 mass parts is preferable. When the blending amount of the component (D) is less than 0.2 parts by mass, sufficient releasability may not be obtained, and when it exceeds 10.0 parts by mass, poor curing, poor adhesion to the metal frame, etc. May happen.

(E) Reflection improver A reflection improver is mix | blended with the epoxy resin composition of this invention as (E) component. The (E) component reflection enhancer is added as a white colorant to enhance the light reflectivity on the surface of the cured product by increasing the whiteness of the cured product. In the present invention, in particular, The lead content is less than 10 ppm on a mass basis. That is, when the lead content in the reflection improver is 10 ppm or more, it is found that the reflectance (under initial conditions and heat resistance) of the cured epoxy resin is unexpectedly deteriorated. As the component (E) of the present invention, those having a lead content of less than 10 ppm, preferably 5 ppm or less, particularly preferably 2 ppm or less on a mass basis are used.

  (E) As a reflection improving agent, a white pigment is preferable, and titanium dioxide is particularly preferable, and titanium dioxide having a rutile structure is particularly preferable in terms of weather resistance. Examples of white pigments other than titanium dioxide include potassium titanate, zircon oxide, zinc sulfide, zinc oxide, and magnesium oxide. These can be used singly or in combination of two or more. White materials other than titanium dioxide are preferably used in combination with titanium dioxide.

Although not particularly limited, the average particle size of the white pigment is usually 0.05 to 5.0 μm. Here, the average particle diameter of the white pigment can be obtained as a cumulative mass average value D ₅₀ (or median diameter) in particle size distribution measurement by a laser light diffraction method.

  Starting with the titanium dioxide, these white pigments were pre-treated with an inorganic substance such as sodium aluminate or an organic substance such as trimethylolpropane in order to improve the mixing, dispersibility and weather resistance with the resin component and inorganic filler. In particular, it is preferable to treat with Al, Si or polyol.

  Moreover, it is preferable to use titanium dioxide with a low lead content for the component (E) of the present invention. In terms of environmental measures, lead may be restricted in use if its content is large, and surprisingly it may adversely affect the light reflectivity of the cured epoxy resin. The content of lead contained in the component (E) is less than 10 ppm (that is, less than 0 to 10 ppm) on a mass basis, preferably 5 ppm or less (0 to 5 ppm), more preferably 2 ppm or less, Furthermore, 1 ppm or less is preferable, and 0 ppm is particularly preferable. Specific examples of such component (E) include rutile titanium dioxide CR-95 (trade name, lead content 1 ppm) manufactured by Ishihara Sangyo Co., Ltd., but are not particularly limited.

  (E) The compounding quantity of a component is 50-1000 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and 80-800 mass parts is preferable. When the blending amount of the component (E) is less than 50 parts by mass, sufficient whiteness is difficult to obtain, and when it exceeds 1000 parts by mass, unfilling and voids are likely to occur, and the moldability tends to decrease.

The component (F) in the thermosetting epoxy resin composition of the present invention is a flame retardant auxiliary (a flame retardant improver) different from the component (E), specifically, an inorganic filler. Zinc molybdate supported on is preferably exemplified.

  In order to impart a sufficient flame retardant effect to the thermosetting epoxy resin composition of the present invention, it is preferable to uniformly disperse zinc molybdate in the epoxy resin composition, in order to improve dispersibility, It is optimal to use zinc molybdate previously supported on an inorganic filler such as silica or talc.

Examples of the inorganic filler for supporting zinc molybdate include silicas such as fused silica and crystalline silica, talc, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, zinc oxide, and glass fiber. In this case, the average particle size of the inorganic filler is preferably 0.1 to 40 μm, and particularly preferably 0.5 to 15 μm. Moreover, it is preferable that the specific surface area of this inorganic filler is 0.5-50 m < ² > / g, and it is preferable that it is especially 0.7-10 m < ² > / g.

  In the present invention, the average particle diameter of the inorganic filler can be determined, for example, as a cumulative mass average value (or median diameter) by a laser light diffraction method or the like, and the specific surface area is determined by, for example, a BET adsorption method. be able to.

  The content of zinc molybdate in the zinc molybdate supported on the inorganic filler is preferably 5 to 40% by mass, particularly 10 to 30% by mass. If the content of zinc molybdate is less than 5% by mass, a sufficient flame retardant effect may not be obtained, and if it is more than 40% by mass, fluidity and curability may be deteriorated.

  As a commercial example of the zinc molybdate carry | supported by the inorganic filler, KEGGARD1260, 1261, 911B, 911C by SHERWIN-WILLIAMS, etc. are mentioned, for example.

  (F) The compounding quantity of a component is 2.0-100 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 5-40 mass parts, More preferably, it is 10-10 mass parts. 30 parts by mass. When the blending amount of the component (F) is less than 2.0 parts by mass, a sufficient flame retardant effect may not be obtained, and when it exceeds 100 parts by mass, fluidity and curability may be deteriorated. In addition, as for the quantity of zinc molybdate itself, 3-30 mass parts is preferable with respect to a total of 100 mass parts of (A) component and (B) component, and 5-20 mass parts is especially preferable. If the amount of zinc molybdate is less than 3 parts by mass, a sufficient flame retardant effect may not be obtained, and if it exceeds 30 parts by mass, fluidity and curability may be lowered.

(G) Inorganic filler In the thermosetting epoxy resin composition of this invention, inorganic fillers other than the said (E) and (F) component are further mix | blended as a (G) component. As the inorganic filler of the component (G) to be blended, what is usually blended into the epoxy resin composition can be used. Examples thereof include silicas such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, glass fiber, antimony trioxide, and the like. The white pigment used as the component (E) and ( F) Flame retardant aids such as inorganic filler-supported zinc molybdate used as component are excluded.

Although the average particle diameter and shape of these (G) inorganic fillers are not particularly limited, the average particle diameter is usually 5 to 40 μm. Here, the average particle diameter of (G) inorganic filler can be determined as the cumulative mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser light diffraction method.

  The (G) inorganic filler may have been surface-treated in advance with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to increase the bond strength between the resin component and the inorganic filler.

  Examples of such a coupling agent include epoxy functions such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Functional alkoxysilanes such as N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercapto It is preferable to use a mercapto functional alkoxysilane such as propyltrimethoxysilane. The amount of coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

  (G) The compounding quantity of a component is 50-1000 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and 80-800 mass parts is preferable. When the blending amount of the component (G) is less than 50 parts by mass, the strength of the cured product may be insufficient, and when it exceeds 1000 parts by mass, due to the thickening of the composition of the present invention, poor filling or cured product Loss of flexibility may cause defects such as peeling of the reflecting member formed of the present composition in the semiconductor device.

(H) Curing catalyst The curing catalyst for the component (H) may be any known curing catalyst for the epoxy resin composition, and is not particularly limited. For example, tertiary amines; imidazoles; Examples thereof include phosphorus-based curing catalysts such as acid salts; organic carboxylic acid metal salts; metal-organic chelate compounds; aromatic sulfonium salts, organic phosphine compounds, phosphonium compounds, and salts of these phosphorus compounds. These can be used singly or in combination of two or more. Among these, imidazoles (for example, 2-ethyl-4-methylimidazole) and phosphorus-based curing catalysts (for example, quaternary phosphonium bromide) are preferable.

  (H) The usage-amount of a component is 0.05-5.0 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and is in the range of 0.1-3.0 mass parts It is preferable to mix with. If it is out of the above range, the balance between the heat resistance and moisture resistance of the cured product of the epoxy resin composition may be deteriorated.

  In the thermosetting epoxy resin composition of the present invention, various components can be added and blended as necessary within a range not impairing the effects of the present invention. For example, low stress such as epoxy resins other than the component (A), various thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, hydrogenated epoxy resins, etc. for the purpose of improving the properties of the composition of the present invention or the cured product thereof. And additives such as an agent and a halogen trapping agent.

  In the thermosetting epoxy resin composition of the present invention, the epoxy resin other than the component (A), which is blended as necessary, is a certain amount or less (particularly the component (A) and ( B) 0 to 40 parts by mass, particularly 5 to 20 parts by mass with respect to a total of 100 parts by mass of the components.

  Examples of the epoxy resin other than the component (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol type epoxy resin, 4,4 '-Biphenol type epoxy resin such as biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin and other novolak type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type Examples thereof include epoxy resins, tetrakisphenylolethane type epoxy resins, and epoxy resins obtained by hydrogenating aromatic rings of phenol dicyclopentadiene novolac type epoxy resins. The softening point of these epoxy resins is preferably 70 to 100 ° C.

The thermosetting epoxy resin composition of the present invention can be obtained in a wide variety of forms such as liquid, solid, and powder. For example, the components (A) to (H) and various components to be blended as necessary are blended at the predetermined composition ratio described above, and after sufficiently mixing them with a mixer or the like, a heat roll, a kneader Then, a melt-mixing process using an extruder or the like is performed, followed by cooling and solidification, and pulverization to an appropriate size, whereby a powdery molding material can be obtained.

In the case of molding using the thermosetting epoxy resin composition of the present invention, transfer molding, injection molding, compression molding and the like can be mentioned, and the most common method is a low pressure transfer molding method. In addition, as for the molding temperature of the thermosetting epoxy resin composition of this invention, 150-185 degreeC is desirable, and time may be 30-180 second normally. If necessary, post-curing may be performed. In this case, the temperature is preferably 150 to 185 ° C., and the time may be 2 to 20 hours.

  FIG. 1 is a cross-sectional view showing an example of a photocoupler using the thermosetting epoxy resin composition of the present invention. The photocoupler shown in FIG. 1 includes opposing lead frames 2 and 5, a semiconductor element (light emitting element) 1 connected to the lead frame 2, and a semiconductor element (light receiving element) 4 connected to the lead frame 5. ing. The light emitting element 1 and the lead frame 2 are connected by a bonding wire 3, and the light receiving element 4 and the lead frame 5 are connected by a bonding wire 6. The light emitting element 1 and the light receiving element 4 are sealed with a transparent sealing resin 7, and the periphery of the transparent sealing resin 7 is covered with a cured product 8 of the thermosetting epoxy resin composition of the present invention. Yes. The light signal generated from the light emitting element 1 is reflected by the cured product 8 through the transparent sealing resin 7 and enters the detection surface of the light receiving element 4, and the light generated from the light emitting element 1 is converted into the light receiving element 4. Detect with. The cured product 8 which is a reflecting member according to the present invention has a high reflectance with respect to the light emitted from the light emitting element 4.

  As a typical optical semiconductor device using a reflective member formed of the thermosetting epoxy resin composition of the present invention, a photocoupler, a premold package, and the like can be given. As a reflecting member formed with the thermosetting epoxy resin composition of this invention, if it is a member which wants to provide light reflectivity, it will be mentioned without a restriction | limiting in particular. For example, in the case of a light emitting element such as an LED element, a member that covers the periphery of a sealing body made of a transparent resin, a base substrate, a submount, etc. so that light is emitted only in a specific direction (for example, upward) Examples thereof include a film-like member that covers at least a part of the surface of another constituent member.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
The raw materials used in the following examples and comparative examples are shown below.

(A) Epoxy resin (A-1) Triazine derivative epoxy resin: Tris (2,3-epoxypropyl) isocyanurate (trade name: TEPIC-S, manufactured by Nissan Chemical Industries, epoxy equivalent 100)
(A-2) Novolac type epoxy resin (trade name: EOCN-1020-55, Nippon Kayaku Co., Ltd., epoxy equivalent 200)
(B) Curing agent Novolak type phenolic resin (trade name: TD-2131, manufactured by DIC)
(C) Antioxidant Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: ADK STAB AO-60; manufactured by ADEKA)
(D) Internal mold release agent (D-1) Propylene glycol monobehenate (trade name: Riquemar PB-100; manufactured by Riken Vitamin) Melting point: 57 ° C
(D-2) Stearyl stearate (trade name: Riquemar SL-900A; manufactured by Riken Vitamin Co., Ltd.) Melting point 55 ° C.
(D-3) Carnauba wax (trade name: Carnauba wax NS-1P; manufactured by Nikko Rica) Melting point: about 83 ° C
(E) Reflection improver (E-1) Chlorine method titanium dioxide (trade name: CR-95, manufactured by Ishihara Sangyo Co., Ltd., rutile lead content 1 ppm)
(E-2) Sulfuric acid method titanium dioxide (trade name: R-45M, manufactured by Sakai Chemical Co., Ltd., lead content: 10 ppm)
(F) Flame retardant auxiliary zinc molybdate (trade name: KEMGARD911B; manufactured by SHERWIN-WILLIAMS)
(G) Inorganic filler: spherical fused silica (manufactured by Tatsumori)
(H) Curing catalyst: Quaternary phosphonium bromide (trade name: U-CAT5003: manufactured by San Apro)

[Examples 1 to 3, Comparative Examples 1 to 6]
Each component was mix | blended with the composition ratio of Table 1, and it melt-mixed uniformly with the heat | fever 2 roll mill, cooled and grind | pulverized, and obtained the white epoxy resin composition.
The following properties were measured for these compositions. The results are shown in Table 1. In Table 1, the molar ratio is (B) the molar ratio of the epoxy group in the epoxy resin (epoxy group / phenolic hydroxyl group) to the reactive group (phenolic hydroxyl group) with the epoxy group contained in the curing agent. ).

《Flame resistance test》
Based on UL-94 standard, 1/8 inch thick plate is molded under the conditions of temperature 175 ° C, molding pressure 6.9N / mm ² , molding time 120 seconds, post-cured at 150 ° C for 4 hours, flame retardant I examined the sex.

<Spiral flow value>
Measurement was performed under the conditions of 175 ° C., 6.9 N / mm ² and a molding time of 120 seconds using a mold conforming to the EMMI standard.

《Light reflectivity》
A disk (cured product) having a diameter of 50 mm and a thickness of 3 mm was molded under the conditions of 175 ° C., 6.9 N / mm ² and a molding time of 120 seconds. The obtained cured product was measured for light reflectance at a wavelength of 450 nm immediately after molding and after storage at 150 ° C. for 4 hours using a spectrocolorimeter (trade name: X-rite 8200, manufactured by SDG Corporation).

<Light transmittance>
A cured product having a thickness of 0.35 mm was molded under the conditions of 175 ° C., 6.9 N / mm ² and a molding time of 120 seconds. About the obtained hardened | cured material, the light transmittance in wavelength 450nm was measured using the spectrocolorimeter (brand name: X-rite 8200, SDG company make) immediately after shaping | molding.

As shown in Table 1, Comparative Example 1 having a molar ratio of less than 1.0, Comparative Example 3 in which no antioxidant is added, and Comparative Example 4 in which carnauba wax is used as an internal mold release agent have poor heat resistance. As a result, although the initial reflectance was good, the light reflectance under heat-resistant conditions (after storage at 150 ° C. for 4 hours) was significantly deteriorated. Moreover, regarding the comparative example 6 which does not add a flame retardant adjuvant, both heat resistance and flame retardance were bad. Further, Comparative Example 2 in which the epoxy resin was changed to a novolak type and Comparative Example 5 in which the titanium oxide was changed to sulfuric acid-based titanium dioxide (lead content: 10 ppm) had poor reflectivity at the initial stage and after heat resistance. It turned out that the hardened | cured material (Examples 1-3) obtained from the thermosetting epoxy resin composition of invention has high initial reflectance, and the light reflectance after 150 degreeC 4h storage is also excellent.

  The thermosetting epoxy resin composition of the present invention is useful for forming a reflective member of an optical semiconductor device.

1 Semiconductor element (light emitting element)
2 Lead frame 3 Bonding wire 4 Semiconductor element (light receiving element)
5 Lead frame 6 Bonding wire 7 Transparent encapsulating resin 8 Cured product of thermosetting epoxy resin composition

Claims (9)

(A) a triazine derivative epoxy resin,
(B) a curing agent,
(C) an antioxidant,
(D) an internal release agent having a melting point in the range of 50 to 80 ° C.,
(E) a reflection improver whose lead content is less than 10 ppm on a mass basis;
(F) flame retardant aid,
(G) inorganic filler,
(H) a curing catalyst,
Is an essential ingredient,
For a total of 100 parts by mass of the component (A) and the component (B),
0.02 to 5.0 parts by mass of the component (C),
0.2 to 10.0 parts by mass of the component (D),
50 to 1000 parts by mass of the component (E),
2.0 to 100 parts by mass of the component (F),
50 to 1000 parts by mass of the component (G),
0.05 to 5.0 parts by mass of the component (H),
Including
The molar ratio of the epoxy group of the epoxy resin of the component (A) and the reactive group of the epoxy group contained in the curing agent of the component (B) is
Thermosetting epoxy resin composition wherein the epoxy group / reactive group with the epoxy group ≧ 1.0.   The thermosetting epoxy resin according to claim 1, wherein the internal mold release agent of the component (D) contains glycerin monostearate or propylene glycol fatty acid ester having a melting point in the range of 50 to 80 ° C. Composition.   The thermosetting epoxy resin composition according to claim 1, wherein the reflection improver of the component (E) is titanium dioxide.   The thermosetting epoxy resin composition according to claim 1 or 2, wherein the reflection enhancer of the component (E) is titanium dioxide having a rutile structure.   The thermosetting epoxy resin composition according to any one of claims 1 to 4, wherein the flame retardant auxiliary of the component (F) is zinc molybdate.   The reflection member for optical semiconductor devices formed by hardening | curing the thermosetting epoxy resin composition of any one of Claims 1-5.   An optical semiconductor device comprising the reflecting member for an optical semiconductor device according to claim 6.   7. An optical semiconductor device, wherein the reflecting member for an optical semiconductor device according to claim 6 is a film that covers at least a part of a surface of another constituent member of the optical semiconductor device. An electronic apparatus device on which the optical semiconductor device according to claim 7 or 8 is mounted.

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