KR101869704B1

KR101869704B1 - Thermosetting epoxy resin composition and optical semiconductor device

Info

Publication number: KR101869704B1
Application number: KR1020120125298A
Authority: KR
Inventors: 요시히로 츠츠미
Original assignee: 신에쓰 가가꾸 고교 가부시끼가이샤
Priority date: 2011-11-09
Filing date: 2012-11-07
Publication date: 2018-06-21
Also published as: JP2013100440A; KR20130051415A; CN103102643A; JP5650097B2; CN103102643B

Abstract

An object of the present invention is to provide a thermosetting epoxy resin composition having high strength and flexibility and a semiconductor device using the composition.
[Solution] In a thermosetting epoxy resin composition,
(A) a mixture containing (A-1) a triazine derivative epoxy resin and (A-2) an acid anhydride in a ratio of [epoxy equivalent weight / acid anhydride group equivalent] of 0.6 to 2.0 or a prepolymer ,
(B) a mixture containing (B-1) a triazine derivative epoxy resin and (B-2) a dicarboxylic acid represented by the following general formula (1) in a ratio of [epoxy equivalent / carboxyl equivalent] Or a prepolymer obtained by reacting the above mixture,
[Chemical Formula 1]

(C) a white pigment,
(D) an inorganic filler, and
(E) a curing catalyst.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting epoxy resin composition and a thermosetting epoxy resin composition,

The present invention relates to a thermosetting epoxy resin composition and a photosemiconductor device using the cured product of the composition as a reflector material.

2. Description of the Related Art Optical semiconductor devices such as LEDs (Light Emitting Diodes) are used as various indicators and light sources such as roadside displays, automobile lamps, residential lighting, and the like. Among them, white LEDs are rapidly developing products that are applied in various fields, with the keywords of reduction of carbon dioxide or energy saving.

BACKGROUND ART Polyphthalamide resin (PPA) is widely used as an optical reflector material as one of materials for semiconductor and electronic devices such as LEDs. The reflector material using PPA is excellent in that it has high strength and flexibility (bending property). In recent years, however, PPA is not suitable as a resin to be used in the vicinity of optical semiconductor elements because it causes deterioration such as discoloration and causes a decrease in light output One).

In the epoxy resin composition for encapsulating optical semiconductor in a B-stage state in which the encapsulating resin is composed of an epoxy resin, a curing agent and a curing accelerator, the epoxy resin composition is preferably a cured product of a resin composition in which the above- (Refer to Patent Document 2). In this case, bisphenol A type epoxy resin or bisphenol F type epoxy resin is mainly used as the epoxy resin, and it is also described that triglycidyl isocyanate and the like can be used.

Japanese Patent Application Laid-Open No. 2006-257314 Japanese Patent No. 2656336 Japanese Patent Application Laid-Open No. 2000-196151 Japanese Patent Application Laid-Open No. 2003-224305 Japanese Patent Application Laid-Open No. 2005-306952

However, a small amount of triglycidyl isocyanate is added to the bisphenol-type epoxy resin in the example of Patent Document 2. According to the studies of the present inventors, the epoxy resin composition for semiconductor encapsulation in the B-stage state has a high temperature and long time There is a problem that the yellowing occurs due to the neglect of the yellowing.

Furthermore, the use of triazine derivative epoxy resin in the epoxy resin composition for encapsulating a light-emitting element has not sufficiently solved the problem that yellowing occurs due to high temperatures and long-term exposure (Patent Documents 3 to 5).

In general, epoxy resins have high strength as compared with silicone resins and the like, but they are low in strength and low in flexure as compared with PPA, that is, lack toughness. As a result, imparting additional strength and flexibility to the epoxy resin is a very important problem also in the resin composition for encapsulating an LED element.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object thereof is to provide a thermosetting epoxy resin composition which provides a cured product having high strength and flexibility, and a semiconductor device using the composition.

In order to solve the above problems, in the present invention, in the thermosetting epoxy resin composition,

(A) an epoxy group equivalent in the component (A-1) / an acid anhydride group equivalent in the component (A-2)) of 0.6 to 2.0 , Or a prepolymer obtained by reacting the above mixture: 30 to 99 parts by mass,

(B-1) a triazine derivative epoxy resin and (B-2) a dicarboxylic acid represented by the following general formula (1) Of the total amount of the prepolymer and the component (A) obtained by reacting the mixture or the mixture containing the component (A) in a ratio of 0.6 to 4.0,

(In the general formula (1), m and n are independently integers satisfying 1? M? 10 and 1? N? 30.)

(C) a white pigment: 3 to 200 parts by mass,

(D) inorganic filler (except for (C) white pigment): 400 to 1000 parts by mass, and

(E) a curing catalyst: 0.01 to 10 parts by mass.

Such a thermosetting epoxy resin composition provides a cured product having high strength and flexibility. Further, by blending a mixture of the component (A) or a prepolymer as a resin component in the thermosetting epoxy resin composition, the yellowing of the cured product can be suppressed.

The triazine derivative epoxy resin of the component (A-1) and / or the component (B-1) is preferably a 1,3,5-triazine derivative epoxy resin.

Such a component (A-1) and / or component (B-1) provides a thermosetting epoxy resin composition that provides a cured product having superior light resistance and electrical insulation.

Further, the present invention provides a photosemiconductor device using the cured product of the thermosetting epoxy resin composition as a reflector material for forming an optical semiconductor element case.

Such an optical semiconductor device is sealed with a cured product having high strength and flexibility, and reliability is enhanced.

As described above, the thermosetting epoxy resin composition of the present invention provides a cured product having high strength and flexibility. Further, not only yellowing is suppressed but also deterioration with time is small, and a cured product having excellent light resistance and electrical insulation is obtained. The thermosetting epoxy resin composition of the present invention can be suitably used for encapsulating an optical element and other semiconductor elements. In particular, it can be used as a reflector material for forming an optical semiconductor element case such as an LED.

Hereinafter, the thermosetting epoxy resin composition and the semiconductor device of the present invention will be described in detail, but the present invention is not limited thereto. As described above, there has been a demand for a thermosetting epoxy resin composition which becomes a cured product having high strength and flexibility.

The inventors of the present invention have made intensive investigations in order to achieve the above object and as a result have found that a cured product of a thermosetting epoxy resin composition comprising the following components has high strength and flexibility and is useful as a reflector material for case- And the present invention has been completed. Hereinafter, the present invention will be described in detail.

[Component (A)]

The component (A) of the present invention is obtained by reacting (A-1) a triazine derivative epoxy resin and (A-2) acid anhydride in an amount equivalent to the epoxy equivalent in the component (A- Equivalent] of 0.6 to 2.0, or a prepolymer obtained by reacting the mixture. The component (A) is contained in an amount of 30 to 99 parts by mass. By blending a mixture or a prepolymer of the component (A) into the thermosetting epoxy resin composition as a resin component, it is possible not only to suppress the yellowing of the cured product of the thermosetting epoxy resin composition, but also to reduce deterioration with time.

(A-1) Triazine derivative epoxy resin

The component (A-1) is not particularly limited, but is preferably a 1,3,5-triazine derivative epoxy resin. Particularly, an epoxy resin having an isocyanurate ring is excellent in light resistance and electrical insulation, and is excellent in divalent or more (two or more), more preferably trivalent (three ) Epoxy group. Specific examples thereof include tris (2,3-epoxypropyl) isocyanurate, tris (? -Methyl glycidyl) isocyanurate, tris (1-methyl-2,3-epoxypropyl) isocyanurate Can be used. These triazine derivative epoxy resins may be used singly or in combination of two or more.

The softening point of the (A-1) triazine derivative epoxy resin used in the present invention is preferably 90 to 125 캜. On the other hand, in the present invention, the (A-1) triazine derivative epoxy resin does not include hydrogenated triazine rings.

(A-2) acid anhydride

The acid anhydride of the component (A-2) acts as a curing agent. Particularly, in order to impart light resistance, it is preferable that it is non-aromatic and has no carbon-carbon double bond. For example, trialkyltetrahydrophthalic acid such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and trimethyltetrahydrophthalic anhydride Phthalic anhydride, methylnadic anhydride and the like, among which methylhexahydrophthalic anhydride is preferable. These acid anhydrides may be used singly or in combination of two or more.

When the component (A) is a mixture comprising (A-1) a triazine derivative epoxy resin and (A-2) acid anhydride, the amount of the triazine derivative epoxy resin (A- The epoxy group is preferably used in an amount of 0.6 to 2.0 mol, preferably 1.0 to 2.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of the acid anhydride group in the acid anhydride (i.e., 1 mol of the acid anhydride corresponds to 2 equivalents) Is 1.2 to 1.6 moles. When the amount is less than 0.6 mol, defective curing may occur and reliability may be lowered. If the amount exceeds 2.0 mol, the unreacted curing agent (component (A-2)) may remain in the cured product to deteriorate the moisture resistance of the resulting cured product.

When the component (A) is a prepolymer obtained by previously reacting a mixture containing (A-1) a triazine derivative epoxy resin and (A-2) an acid anhydride, the triazine derivative epoxy The resin and the (A-2) acid anhydride are reacted in a molar ratio of [epoxy equivalent weight in component (A-1) / acid anhydride weight equivalent in component (A-2)] of 0.6 to 2.0. In the reaction, a solid product (that is, a prepolymer) obtained by the reaction in the presence of the same antioxidant as the component (G), the same curing catalyst as the component (E), and / or the curing accelerator, A) component. At this time, the solid product is preferably used in a fine powder state by pulverization or the like. The particle diameter of the fine powder is preferably in the range of 10 mu m to 3 mm. The molar ratio is preferably 1.2 to 1.6. If the molar ratio is less than 0.6, curing defects may occur and reliability may be lowered. On the other hand, if it exceeds 2.0, the acid anhydride (A-2) as an unreacted curing agent remains in the cured product, and the moisture resistance of the resulting cured product may be deteriorated. As the thermosetting epoxy resin composition of the present invention, it is preferable to use the component (A) as the solid phase prepolymer (particularly as a fine powder), because it can be used as a solid thermosetting resin having good workability.

When synthesizing the prepolymer, an epoxy resin other than the component (A-1) may be used in combination if necessary. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin or 4,4'-biphenol Phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthalene diol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenyl An epoxy resin obtained by hydrogenating an aromatic ring of an all ethane-type epoxy resin and a phenol dicyclopentadiene novolak-type epoxy resin, and an alicyclic epoxy resin. Among these epoxy resins, epoxy resins obtained by hydrogenating aromatic rings from the viewpoint of heat resistance and ultraviolet ray resistance and alicyclic epoxy resins are preferable. The other epoxy resin preferably has a softening point of 70 to 100 캜.

(A-1), (A-2) and (G) are preferably used as the components (A-1) Is reacted with the same antioxidant at 70 to 120 캜, preferably 80 to 110 캜 for 4 to 20 hours, preferably 6 to 15 hours. Alternatively, the same curing catalyst as that described below as the component (A-1), the component (A-2) and the component (E) And the same curing catalyst as that described below as the component (E) are previously reacted at 30 to 80 캜, preferably 40 to 60 캜, for 10 to 72 hours, preferably 36 to 60 hours. Thus, a prepolymer is obtained as a solid product having a softening point of 50 to 100 占 폚, preferably 60 to 90 占 폚. In order to incorporate it into the thermosetting epoxy resin composition of the present invention, it is preferable to make it finely powdered by pulverization or the like. If the softening point of the substance obtained by the reaction is less than 50 캜, it does not become a solid. If the temperature exceeds 100 캜, the fluidity required for molding as a composition may be too low.

Examples of the prepolymer include compounds represented by the following general formula (2).

(Wherein R is an acid anhydride residue and l is a number of 0 to 200)

[Component (B)]

The component (B) of the present invention is obtained by reacting a triazine derivative epoxy resin (B-1) and a dicarboxylic acid (B-2) represented by the following general formula (1) (B-2) component] of 0.6 to 4.0, or a prepolymer obtained by reacting the mixture. The component (B) is contained in an amount such that the total amount of the component (A) and the component (A) is 100 parts by mass. As described above, the mixture and the prepolymer of the component (B) can be incorporated into the thermosetting epoxy resin composition as a resin component to improve the strength and flexibility of the cured product of the thermosetting epoxy resin composition.

(B-1) triazine derivative epoxy resin

The component (B-1) is preferably a 1,3,5-triazine derivative epoxy resin similarly to the triazine derivative epoxy resin of the component (A-1). Particularly, an epoxy resin having an isocyanurate ring is excellent in light resistance and electrical insulation, and is excellent in divalent or more (two or more), more preferably trivalent (three ) Epoxy group. Specific examples thereof include tris (2,3-epoxypropyl) isocyanurate, tris (? -Methyl glycidyl) isocyanurate, tris (1-methyl-2,3-epoxypropyl) isocyanurate Can be used. These triazine derivative epoxy resins may be used singly or in combination of two or more.

The softening point of the (B-1) triazine derivative epoxy resin used in the present invention is preferably 90 to 125 캜. On the other hand, in the present invention, the (B-1) triazine derivative epoxy resin does not include hydrogenated triazine rings.

(B-2) Dicarboxylic acid

The dicarboxylic acid of the component (B-2) used in the present invention is represented by the following general formula (1). This dicarboxylic acid is used as a modifier such as a flexibility imparting agent, and when used in the present thermosetting epoxy resin composition, the strength and flexibility of the cured product can be improved. These dicarboxylic acids may be used singly or in combination of two or more kinds.

In the general formula (1), m and n are independently integers satisfying 1? M? 10 and 1? N? 30. m is preferably an integer satisfying 2? m? 8, more preferably 4? m? 6, and n is preferably an integer satisfying 2? n? 20, more preferably 3? to be.

When the component (B) is a mixture comprising (B-1) a triazine derivative epoxy resin and (B-2) dicarboxylic acid, the amount of the triazine derivative epoxy resin (B- The epoxy group is 0.6 to 4.0 mol, preferably 1.0 to 2.0 mol, and more preferably 1.2 to 1.6 mol, based on 1 mol of the carboxyl group of the (B-2) dicarboxylic acid. When the amount is less than 0.6 mol, defective curing may occur and reliability may be lowered. If the amount is more than 4.0 moles, the unreacted curing agent (component (B-2)) remains in the cured product to deteriorate the moisture resistance of the obtained cured product.

When the component (B) is a prepolymer obtained by previously reacting a mixture containing (B-1) a triazine derivative epoxy resin and (B-2) dicarboxylic acid, A mixture containing an epoxy resin and (B-2) dicarboxylic acid in a molar ratio of [epoxy group equivalent in component (B-1) / carboxyl group equivalent in component (B-2)] of 0.6 to 4.0 is reacted. In the reaction, the solid product (that is, the prepolymer) obtained by the reaction in the presence of the same antioxidant as the component (G), the same curing catalyst as described below as component (E) and / It may also be used as a component. At this time, the solid product is preferably used in a fine powder state by pulverization or the like. The particle diameter of the fine powder is preferably in the range of 10 mu m to 3 mm. The molar ratio is preferably 1.0 to 2.0 moles, and more preferably 1.2 to 1.6. If the molar ratio is less than 0.6, curing defects may occur and reliability may be lowered. On the other hand, if it exceeds 4.0, the dicarboxylic acid as an unreacted curing agent remains in the cured product and the moisture resistance of the resulting cured product may deteriorate. In the thermosetting epoxy resin composition of the present invention, the component (B) is preferably used as the solid-state prepolymer (particularly, in the form of a fine powder), because it can be used as a solid thermosetting resin with good workability.

(B-1) and (B-2) are preferably used as the components (B-1), (B-2) The same antioxidant as that described below is reacted at 70 to 120 ° C, preferably 80 to 110 ° C, for 1 to 20 hours, preferably 1.5 to 8 hours. (B-1), (B-2), (G), and (B), the same curing accelerator as that described below as the component And the same curing accelerator as that described below as the component (E) are previously reacted at 30 to 80 占 폚, preferably at 40 to 60 占 폚 for 10 to 72 hours, preferably 36 to 60 hours. Thus, a prepolymer is obtained as a solid product having a softening point of 30 to 100 캜, preferably 40 to 60 캜. In order to incorporate it into the composition of the present invention, it is preferable to carry out fine dispersion by pulverization or the like.

The component (B) is contained in an amount such that the total amount of the component (A) and the component (A) is 100 parts by mass. That is, when the total amount of the component (A) and the component (B) is 100 parts by mass, the mass ratio of the components (A) and (B) (A) / (B)? 50/50. (B) is less than 1% by mass (1 part by mass) of the sum of (A) and (B), the desirable strength and flexibility are not obtained and the ratio of (A) % (70 parts by mass), the curing is slowed.

[(C) White pigment]

(C) a white pigment is added to the thermosetting epoxy resin composition of the present invention in order to increase the degree of whiteness for use such as a reflector (reflector) of an optical semiconductor device. (C) The white pigment is not particularly limited, but it is possible to use one kind of the rare earth oxide represented by titanium dioxide, alumina, yttrium oxide, zinc sulfate, zinc oxide, magnesium oxide, etc., or two or more kinds of white pigments in combination have.

As the white pigment of the component (C), it is preferable to use titanium dioxide in order to further enhance the whiteness. The unit lattice of the titanium dioxide may be any of rutile type, anatase type and bourcite type. The average particle diameter and shape are not limited, but the average particle diameter is usually 0.05 to 5.0 占 퐉. The titanium dioxide can be surface-treated in advance with a hydroxide such as Al and Si in order to improve the compatibility with the resin or the inorganic filler and the dispersibility. On the other hand, the average particle diameter can be obtained as a cumulative mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser diffraction method.

The amount of the white pigment to be added is preferably 3 to 200 parts, and more preferably 5 to 150 parts per 100 parts by mass of the total of the components (A) and (B). When the amount is less than 3 parts by mass, sufficient whiteness may not be obtained. On the other hand, if it exceeds 200 parts by mass, not only the proportion of other components added for the purpose of improving the mechanical strength is decreased but also the moldability is remarkably lowered. On the other hand, the white pigment is preferably in the range of 1 to 50% by mass, more preferably 3 to 30% by mass based on the entire thermosetting silicone resin composition of the present invention in terms of optical properties such as high reflectance .

[(D) Inorganic filler]

In the thermosetting epoxy resin composition of the present invention, an inorganic filler other than the component (C) is further added as the component (D). The inorganic filler (D) is not particularly limited, but may be used in combination with an epoxy resin composition. For example, silica such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, antimony trioxide and the like can be mentioned, but the white pigment (white coloring agent) . The average particle diameter and shape of these inorganic fillers are not particularly limited, but the average particle diameter is usually 3 to 40 탆. On the other hand, the average particle diameter can be obtained from the cumulative mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser diffraction method.

Particularly, silica-based inorganic fillers such as fused silica and spherical silica are suitably used, and the particle diameter thereof is not particularly limited, but from the viewpoints of moldability and fluidity, the average particle diameter is preferably 4 to 40 μm, 7 to 35 mu m is preferable. It is preferable to use a combination of a fine region of 0.1 to 3 mu m, a medium-diameter region of 4 to 8 mu m, and a coarse region of 10 to 40 mu m in order to obtain the high permeability.

The inorganic filler (D) other than the component (C) is preferably a silane coupling agent, a silane coupling agent, a titanate (C), or a combination thereof, in order to strengthen the bonding strength between the resin component of the component (A) And a surface-treated with a coupling agent such as a coupling agent.

Examples of such a coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like Aminopropyltrimethoxysilane, N-phenyl- gamma -aminopropyltrimethoxysilane, and the like, such as epoxy functional alkoxysilane, N- (aminoethyl) - gamma -aminopropyltrimethoxysilane, Mercapto functional alkoxysilanes such as alkoxysilane and? -Mercaptopropyltrimethoxysilane, and the like are preferably used. On the other hand, the amount of the coupling agent to be used for the surface treatment and the surface treatment method are not particularly limited, but it is preferable that the treated filler (inorganic filler (D)) is not discolored when it is left at 150 占 폚 or more.

The amount of the inorganic filler (D) other than the component (C) is preferably 400 to 1,000 parts by mass, more preferably 600 to 950 parts by mass, per 100 parts by mass of the total of the components (A) and (B). If it is less than 400 parts by mass, there is a fear that sufficient strength can not be obtained. If it exceeds 1,000 parts by mass, poor filling or softness due to thickening (viscosity increase) is lost and defects such as peeling in the encapsulated device occur . On the other hand, it is preferable that the compounding amount of the inorganic filler (D) is in the range of 10 to 90 mass%, particularly 20 to 80 mass%, of the entire composition.

[(E) Curing Catalyst]

The curing catalyst of component (E) used in the present invention is a catalyst for curing thermosetting epoxy resin (component (A) and component (B)). As the catalyst, known catalysts can be used as the curing catalyst of the epoxy resin composition, and although not particularly limited, tertiary amines, imidazoles, organic carboxylic acid salts thereof, organic carboxylic acid metal salts, metal- Phosphorus-based curing catalysts such as compounds, aromatic sulfonium salts, organic phosphine compounds and phosphonium compounds, salts thereof, etc. may be used singly or in combination of two or more. Among them, imidazoles, phosphorus-based curing catalysts such as octylate of 2-ethyl-4-methylimidazole or methyl-tributylphosphonium-dimethylphosphate or tertiary amine are more preferable. Combination of an organic acid salt of a quaternary phosphonium bromide and an amine is also preferably used.

The curing catalyst is used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, particularly preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total of the components (A) and (B) . Outside of the above range, the balance between the heat resistance and the moisture resistance of the cured product of the thermosetting epoxy resin composition may deteriorate.

The thermosetting epoxy resin composition of the present invention may further contain various additives as required. Hereinafter, components that can be compounded are exemplified.

[(F) Release agent]

In the thermosetting epoxy resin composition of the present invention, (F) a release agent can be incorporated. The component (F) is blended so as to improve releasability in molding. In this case, (F) the release agent may include a component represented by the following general formula (3) and having a melting point in the range of 50 to 70 캜.

Wherein R ¹ , R ² and R ³ are any one of H, -OH, -OR ⁴ and -OCOC _a H _b , and at least one of them includes -OCOC _a H _b R ⁴ is C _s H _2s ₊₁ alkyl group (s is an integer of 1 to 30), a is an integer of 10 to 30, and b is an integer of 17 to 61)

(F) The release agent includes synthetic waxes including natural waxes such as carnauba wax, acid waxes, polyethylene waxes and fatty acid esters. Generally, under high temperature conditions or light irradiation, yellowing easily occurs, And thus the releasability is often lost.

Among them, the release agent of the formula (3) that can be contained in the thermosetting epoxy resin composition of the present invention maintains good releasability over a long period of time while suppressing sulfur denaturation even under high temperature or light irradiation.

In this case, at least one of R ¹ , R ² and R ³ in the general formula (3) must be -OCOC _a H _b . When all are -OH, sufficient releasability and heat resistance can not be obtained, but by including -OCOC _a H _b in the structure, it is possible to have good compatibility, heat resistance and releasability.

It is preferable that a and b included in -OCOC _a H _b are 10 _a 30, preferably 11 a 20. When a is less than 10, sufficient heat resistance sulfur change may not be obtained, and when a is more than 30, it is not sufficiently compatibilized and a good releasing effect may not be obtained.

_B is a saturated or unsaturated aliphatic hydrocarbon group with C _a H _b . In the case of an unsaturated aliphatic hydrocarbon group, it is preferable to have one or two unsaturated groups. Therefore, it is preferable that b = 2a + 1, 2a-1 or 2a-3, particularly b = 2a + 1, 2a-1. From this point, b is 17? B? 61, preferably 19? B? 61, more preferably 21? B? 41, particularly preferably 23? B?

Specific examples include glycerin monopalmitate, glycerin monostearate, glycerin mono 12-hydroxystearate, glycerin tri-12-hydroxystearate, glycerin monobehenate, propylene glycol monopalmitate, propylene glycol monostearate, propylene Glycol monobehenate, and the like.

However, the melting point and the volatile matter content at a high temperature (F) are important characteristics in the heat resistance characteristics of the release agent. The melting point is preferably 50 to 90 占 폚, and more preferably 65 to 85 占 폚. Furthermore, it is preferable that the volatile matter content at 250 ° C is 10 mass% or less. When the melting point is less than 50 캜, sufficient heat-resistant sulfur modification may not be obtained. When the melting point exceeds 90 캜, compatibility becomes insufficient and a good releasing effect may not be obtained. From the viewpoint of dispersibility and compatibility, glycerin monostearate having a melting point of 50 to 70 ° C is particularly preferable. A propylene glycol fatty acid ester is also preferable.

Further, in the thermosetting epoxy resin composition of the present invention, it is preferable to use the compound represented by the above general formula (3) and the carboxylic acid ester represented by the following general formula (4) in combination as the internal mold releasing agent.

(Wherein R ⁵ and R ⁶ are the same or different kinds of alkyl groups represented by C _t H _2t ₊₁ , and t is a number of 1 to 30, preferably 2 to 28, more preferably 5 to 25. )

The carboxylic acid ester of the general formula (4) also maintains excellent releasability over a long period of time while suppressing sulfur denaturation even under high temperature or light irradiation. In this case, the combined ratio of the carboxylic ester of the formula (4) and the compound of the formula (3) is 1: 5? (4) :( 3)? 10: 1, 4) :( 3)? 8: 1. If the amount of the carboxylic acid ester of the formula (4) is too small, the continuous formability may not be sufficient, while if too large, the adhesiveness may be deteriorated.

The amount of the releasing agent (F) added is preferably 0.5 to 7.0 parts by mass, particularly 1.0 to 5.0 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). When the addition amount is less than 0.5 parts by mass, sufficient releasability may not be obtained. When the addition amount exceeds 7.0 parts by mass, defects such as seepage and poor adhesion may occur.

[(G) antioxidant]

In the thermosetting epoxy resin composition of the present invention, an antioxidant (G) may be added as needed. As the antioxidant for the component (G), phenol-based, phosphorus-based, and sulfur-based antioxidants can be used. Specific examples of the antioxidant include the following antioxidants.

Examples of the phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di- 4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -1,3- 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. Of these, 2,6- desirable.

Examples of the phosphorus antioxidant include triphenyl phosphite, diphenyl alkyl phosphite, phenyldialkyl phosphite, phosphorus tri (nonylphenyl), phosphorus trilauryl, phosphorous trioctadecyl, triphenyl phosphite, distearyl pentaerythritol diphosphite, Tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, di (2,4-di-tert- butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite and Tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenyl diphosphonate, among which triphenyl phosphite is preferable.

Examples of the sulfur-based antioxidant include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, 2,4-bis- (n-octylthio) -6- (4- Dihydroxy-3,5-di-t-butyl anilino) -1,3,5-triazine, 2,4-bis- [(octylthio) methyl] -o-cresol and the like.

Each of these antioxidants may be used alone or in combination of two or more. The blending amount of the antioxidant is preferably 0.01 to 10 parts by mass, particularly 0.03 to 5 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). If the blending amount is too small, sufficient heat resistance can not be obtained and discoloration may occur. If too much, the curing may be inhibited and sufficient curability and strength may not be obtained.

[(H) coupling agent]

(H) couples such as a silane coupling agent and a titanate coupling agent are preferably added to the thermosetting epoxy resin composition of the present invention in order to strengthen the bonding strength between the thermosetting epoxy resin (A) and the inorganic filler (D) LINGER can be compounded.

Examples of such coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like Epoxy functional alkoxysilane, mercapto functional alkoxysilane such as? -Mercaptopropyltrimethoxysilane, and the like. On the other hand, the amount of the coupling agent to be used in the surface treatment and the surface treatment method are not particularly limited, but it is not so preferable that the amine-based silane coupling agent is discolored when it is left at 150 占 폚 or more.

(H) may be added in an amount of 0.1 to 8.0 parts by mass, preferably 0.5 to 6.0 parts by mass based on 100 parts by mass of the total of the components (A) and (B). If the amount is less than 0.1 part by mass, the effect of adhesion to the substrate is not sufficient, and if it exceeds 8.0 parts by mass, the viscosity may be excessively lowered, which may cause voids.

[Other additives]

In addition, additives such as a reinforcing material such as glass fiber, a silicone powder, a silicone oil, a thermoplastic resin, a thermoplastic elastomer, and an organic synthetic rubber may be added and mixed for the purpose of improving the properties of the thermosetting epoxy resin composition or the cured product.

[Process for producing thermosetting epoxy composition]

(C) a white pigment, (D) an inorganic filler, (E) a curing catalyst, and other additives in a predetermined composition ratio Kneader, extruder or the like, followed by cooling and solidification, followed by pulverization to an appropriate size to obtain a thermosetting epoxy resin composition (hereinafter referred to as " thermosetting epoxy resin composition " Can be used. At this time, from the viewpoint of handling, the component (A) and the component (B) are preferably used as a prepolymer as a solid product.

When not used for the preparation of the solid material (reactant), the component (E) and other additives, if necessary, are blended in a predetermined composition ratio, and the mixture is sufficiently uniformly mixed by a mixer or the like. Followed by melt-mixing treatment, followed by cooling and solidification, and then pulverized to an appropriate size to obtain a molding material for an epoxy resin composition.

[Reflector material]

The cured product of the thermosetting epoxy resin composition has high strength and flexibility and can be used as a reflector material for forming an optical semiconductor element case. The most common forming method of the reflector is a transfer molding method or a compression molding method. In the transfer molding method, molding is preferably performed at a molding pressure of 5 to 20 N / mm 2, a molding temperature of 120 to 190 ° C., a molding time of 30 to 500 seconds, particularly a molding temperature of 150 to 185 ° C. and a molding time of 30 to 180 seconds . In the compression molding method, it is preferable to use a compression molding machine at a molding temperature of 120 to 190 DEG C for a molding time of 30 to 600 seconds, particularly a molding temperature of 130 to 160 DEG C for a molding time of 120 to 300 seconds . Further, any molding method may be followed by post-curing at 150 to 185 ° C for 2 to 20 hours.

The thermosetting epoxy resin composition of the present invention may be used for encapsulating usual semiconductor encapsulants or various modules for vehicle use. At this time, carbon black or the like is used as the coloring agent. As the carbon black, any commercially available carbon black can be used, but it is preferable that the carbon black does not contain a large amount of an alkali metal or a halogen and has good purity.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The raw materials used in Examples and Comparative Examples are shown below.

(A-1) Triazine derivative epoxy resin:

Tris (2,3-epoxypropyl) isocyanurate (TEPIC-S: trade name, epoxy equivalent 100, manufactured by Nissan Chemical Industries, Ltd.)

(A-2) Acid anhydride:

Methyl hexahydrophthalic anhydride (RIKACID MH: trade name, manufactured by New Japan Chemical Co., Ltd.)

(B-1) triazine derivative epoxy resin:

Tris (2,3-epoxypropyl) isocyanurate (TEPIC-S: trade name, manufactured by Nissan Chemical Industries, Ltd.)

(B-2) dicarboxylic acid:

Dicarboxylic acid-1: dicarboxylic acid represented by the following structural formula (5)

Dicarboxylic acid-2: dicarboxylic acid represented by the following structural formula (6)

Dicarboxylic acid-3: dicarboxylic acid represented by the following structural formula (7)

(C) White pigment:

Titanium dioxide (rutile type) (CR-95; trade name, manufactured by Ishihara Sangyo Kaisha, Ltd., average particle diameter: 0.28 탆)

(D) Inorganic filler:

Silica: Fused spherical silica (CS-6103 53C2, trade name, manufactured by Tatsumori Ltd.)

(E) Curing catalyst:

(E-1) Phosphorous curing catalyst: Quaternary phosphonium bromide (U-CAT5003: trade name of San-Apro Ltd.)

(E-2) Amine curing catalyst: Special amine (U-CAT18X: trade name of San-Apro Ltd.)

(F) Release agent:

Propylene glycol monobehenate (PB-100; trade name, manufactured by Riken Vitamin Co., Ltd.)

(G) Antioxidant

Phosphite antioxidant: distearylpentaerythritol diphosphite (PEP-8; product of ADEKA Corporation)

(H) coupling agent

Silane coupling agent: 3-mercaptopropyltrimethoxysilane (KBM-803; trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Synthesis Example] Preparation of thermosetting epoxy resin prepolymer (component A and component B)

The prepolymer A as the component (A) was prepared by blending the (A-1) triazine derivative epoxy resin and the acid anhydride (A-2) shown in the following Table 1 in the indicated ratio (parts by mass) Were synthesized. Likewise, the prepolymers B to F as the component (B) were obtained by mixing the triazine derivative epoxy resin (B-1) shown in the following Table 1 with the (B-2) dicarboxylic acid and the other components in the indicated ratio (parts by mass) And the mixture was heated under a predetermined reaction condition.

[Examples 1 to 8 and Comparative Examples 1 to 3]

The materials (parts by mass) shown in Table 2 were mixed with Buss Ko-Kneader, cooled, and pulverized to obtain thermosetting epoxy resin compositions (Examples 1 to 8 and Comparative Examples 1 to 3).

The following properties of the thermosetting epoxy resin composition were measured. The results are shown in Table 2. Molding was carried out under the conditions of a transfer molding machine at a molding temperature of 175 캜, a molding pressure of 6.9 N / mm 2, and a molding time of 90 seconds.

[Spiral flow value]

Molding according to the EMMI standard was used under the conditions of a molding temperature of 175 캜, a molding pressure of 6.9 N / mm 2, and a molding time of 90 seconds.

[Bending strength at room temperature, bending elastic modulus, bending (flexibility)]

Molded under the conditions of a molding temperature of 175 DEG C, a molding pressure of 6.9 N / mm < 2 > and a molding time of 90 seconds using a mold conforming to the JIS-K6911 standard, and post-cured at 180 DEG C for 4 hours. The bending strength, flexural modulus and flexural strength (flexibility) of the post-cured test pieces were measured at room temperature (25 ° C).

[Light reflectance]

A cured product having a side length of 50 mm and a thickness of 0.35 mm was prepared under the conditions of a molding temperature of 175 캜, a molding pressure of 6.9 N / mm 2 and a molding time of 90 seconds, and a light reflectance of 450 nm was measured using SD XK- Respectively.

From Table 2, it can be seen that strength and flexibility are improved by using an epoxy resin in both the components (A) and (B). That is, toughness is improved. In addition, it is confirmed that a semiconductor device using a cured product of the composition as an LED reflector material is effective since the light reflectance shows a good value. Furthermore, the cured product of the composition according to the present invention showed no yellowing even when used at a temperature of 150 ° C for 2,500 hours.

On the other hand, the present invention is not limited to the above embodiment. The above embodiment is merely an example, and any technical equivalence of the technical idea described in the claims of the present invention is also included in the technical scope of the present invention.

Claims

In the thermosetting epoxy resin composition,
(A) a triazine derivative epoxy resin and (A-2) an acid anhydride, wherein the epoxy equivalent in the component (A-1) / the acid anhydride equivalent in the component (A- 2.0 or 30 to 99 parts by mass of a prepolymer obtained by reacting the mixture,
(B-1) a triazine derivative epoxy resin and (B-2) a dicarboxylic acid represented by the following general formula (1) ) Equivalent to carboxyl group in the component] of 0.6 to 4.0, or a prepolymer obtained by reacting the above mixture: a total amount of 100 parts by mass of the component (A)

[Chemical Formula 1]

(In the general formula (1), m and n are independently integers satisfying 1? M? 10 and 1? N? 30.)
(C) a white pigment: 3 to 200 parts by mass,
(D) an inorganic filler (excluding the above-mentioned (C) white pigment): 400 to 1000 parts by mass, and
(E) Curing catalyst: 0.01 to 10 parts by mass
Wherein the thermosetting epoxy resin composition is a thermosetting epoxy resin composition.

The method according to claim 1,
Wherein the triazine derivative epoxy resin of the component (A-1) and / or the component (B-1) is a 1,3,5-triazine derivative epoxy resin.

A optical semiconductor device characterized by using a cured product of the thermosetting epoxy resin composition according to claim 1 or 2 as a reflector material for forming an optical semiconductor element case.