JP2014095051A - Thermosetting epoxy resin composition, reflector for led using the composition, and led device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition giving a set matter maintaining heat resistance and light resistance and having a reduced yellowing change, and also having high strength and high toughness using an epoxy resin and an acid anhydride setting agent, a reflector for LED formed with the composition, and an LED apparatus.SOLUTION: Provided is a thermosetting epoxy resin composition comprising: (A) an epoxy resin; (B) a setting agent; (C) a setting catalyst; and (D) an inorganic filler (wherein, the amount of the (D) component is 50 to 1,100 pts.mass to 100 pts.mass of the total of the (A) component and the (B) component), and, as the setting agent in the (B) component, acid anhydride represented by the general formula (1) is included.

Description

  The present invention relates to a thermosetting epoxy resin composition, a reflector for LED molded with a cured product of the composition, and an LED device.

  The reliability requirements for the sealing materials of semiconductor / electronic device devices are becoming more and more severe due to the increase in output as well as the reduction in thickness and size. As an example, semiconductor elements such as LEDs (light emitting diodes) and LDs (laser diodes) emit light with a small, efficient, and vivid color, and since they are semiconductor elements, they do not break the bulb, have excellent driving characteristics, and vibration. Strong against repeated ON / OFF lighting. Therefore, it is used as various indicators and various light sources.

  However, due to dramatic progress in today's optical semiconductor technology, the output power and wavelength of optical semiconductor devices have been remarkably reduced, and in optical semiconductor devices such as LEDs that emit high-energy light, especially as uncolored and white materials. In reflectors using conventional PPA (polyphthalamide) resin, deterioration due to discoloration and oxidation due to long-term use is remarkable, LED brightness deterioration, color unevenness, peeling from sealing resin, mechanical strength reduction, etc. Therefore, it was desired to solve such a problem effectively.

  Furthermore, in Patent Document 1, the sealing resin is a B-stage-shaped epoxy semiconductor composition for encapsulating an optical semiconductor containing an epoxy resin, a curing agent, and a curing accelerator as constituent components, and the constituent components are at the molecular level. An optical semiconductor device characterized in that it is composed of a cured body of a resin composition that is uniformly mixed 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.

Japanese Patent No. 2656336 JP 2000-196151 A JP 2003-224305 A JP 2005-306952 A

  However, triglycidyl isocyanate is used by adding a small amount to the bisphenol type epoxy resin in the example of Patent Document 1, and according to the study by the present inventors, this epoxy resin composition for B-stage semiconductor encapsulation is used. Has a problem of yellowing when left for a long time, particularly at high temperatures.

  Moreover, although there exists description in patent document 2-patent document 4 about use of the triazine derivative epoxy resin in the epoxy resin composition for light emitting element sealing, these all use triazine derivative epoxy resin and an acid anhydride. However, when used as a reflector for LED backlights such as recent flat-screen TVs, the reflector is very small and thin, so the strength and toughness are insufficient and the reflector is easily destroyed. Has been pointed out.

  The present invention has been made in order to solve the above-mentioned problems, and has heat resistance and light resistance over a long period of time, gives a cured product that is uniform and has little yellowing, and has high strength and high toughness. An object of the present invention is to provide a curable epoxy resin composition, a reflector for LED molded with a cured product of the composition, and an LED device.

（一般式（１）中、Ｒ_１、Ｒ_２は同一でも異なってもよく、水素原子または炭素数１〜１０のアルキル基もしくはアルケニル基である。) In order to solve the above-mentioned problems, in the present invention, a thermosetting epoxy resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a curing catalyst, and (D) an inorganic filler (provided that (D) component contains 50-1100 mass parts with respect to a total of 100 mass parts of (A) component and (B) component), and the following general formula (1) as a hardening | curing agent of the said (B) component. The thermosetting epoxy resin composition characterized by containing the acid anhydride shown by these.

(In general formula (1), R ₁ and R ₂ may be the same or different and are a hydrogen atom or an alkyl or alkenyl group having 1 to 10 carbon atoms.)

  A thermosetting epoxy resin composition containing such an epoxy resin and an acid anhydride curing agent having a specific structure is excellent in curability, heat resistance and light resistance, and has good strength and toughness. It will give things.

  Moreover, it is preferable that the content rate of the acid anhydride of the said General formula (1) is 5-100 mass% of the whole hardening | curing agent of the said (B) component.

  In this way, by containing the acid anhydride of the general formula (1) within the above range in the curing agent of the component (B), the cured product of the thermosetting epoxy resin composition has higher strength and high toughness. Can do.

  The epoxy resin as the component (A) is preferably an alicyclic epoxy resin.

  If it is such (A) component, it will become a thermosetting epoxy resin composition which gives the hardened | cured material which was further excellent in heat resistance and light resistance.

  Moreover, it is preferable that the thermosetting epoxy resin of the said (A) component is a triazine derivative epoxy resin.

  If it is such (A) component, it will become a thermosetting epoxy resin composition which gives the hardened | cured material which was further excellent by light resistance and was excellent in electrical insulation.

  Furthermore, what contains 1 type, or 2 or more types chosen from phenol type, phosphorus type, and sulfur type antioxidant as an antioxidant is preferable.

  By using such an antioxidant, discoloration of the composition can be further prevented.

  Moreover, it is preferable that the inorganic filler as the component (D) contains titanium dioxide.

  If it is such (D) component, the whiteness of hardened | cured material can be raised and the light which an LED element emits can be reflected efficiently.

  Furthermore, in the present invention, the thermosetting epoxy resin composition is cured and molded to provide a reflector for LED.

  Thus, the thermosetting epoxy resin composition can be cured and used as a reflector for high-brightness LEDs.

  Moreover, in this invention, the LED device which comprises the reflector for LED which consists of the said thermosetting epoxy resin composition, an LED element, the lead for connection, and an element electrode, and was sealed and protected with the transparent sealing material is provided.

  With such an LED device, heat resistance and light resistance are maintained, and it is uniform and less yellowing, and is highly reliable sealed with a cured product having high strength and high toughness.

  As explained above, the thermosetting epoxy resin composition of the present invention is a cured product having excellent curability and good strength and toughness. In addition, it retains heat resistance and light resistance over a long period of time, and gives a cured product that is uniform and has little yellowing. The reflector molded from the cured product of the composition of the present invention can be used for industrially particularly useful high-brightness LED devices.

It is the schematic regarding the measuring method of the fracture strength of a reflector. It is the schematic of a matrix type concave reflector. It is the figure of the reflector which diced the matrix type reflector board | substrate into pieces, (A) is a schematic top view, (B), (C) is a schematic sectional drawing.

Hereinafter, although the thermosetting epoxy resin composition of this invention, the reflector for LED shape | molded with the hardened | cured material of this composition, and an LED device are demonstrated in detail, this invention is not limited to these.
As described above, it has been desired to develop a thermosetting resin composition that retains heat resistance and light resistance for a long period of time, gives a cured product that is uniform and has little yellowing, and has high strength and high toughness. .

  Accordingly, as a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a heat comprising an epoxy resin, a curing agent containing an acid anhydride represented by the general formula (1), a curing catalyst, and an inorganic filler. It has been found that the curable epoxy resin composition can be a cured product having excellent curability, heat resistance and light resistance, and having good strength and toughness, and has led to the present invention. Hereinafter, the present invention will be described in detail.

(A) Component Epoxy Resin The component (A) of the present invention can be used with any epoxy resin as an epoxy resin, but preferably contains no aromatic ring from the viewpoint of heat resistance and light resistance. A formula epoxy resin or a triazine derivative epoxy resin is preferred.
Examples of the alicyclic epoxy resin include 1,2: 8,9-diepoxy limonene, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, (3,4-epoxycyclohexyl) methyl-3, 4-epoxycyclohexylcarboxylate, bis- (3,4-epoxycyclohexyl) adipate, bis- (3,4-epoxycyclohexylmethylene) adipate, bis- (2,3-epoxycyclopentyl) ether, (2,3-epoxy And compounds having at least one 4- to 7-membered cyclic aliphatic group in the molecule and at least one epoxy group in the molecule, such as -6-methylcyclohexylmethyl) adipate and dicyclopentadiene dioxide. It is done.

  In addition, when the component (A) used in the present invention is a triazine derivative epoxy resin, it is preferably a 1,3,5-triazine nucleus derivative epoxy resin. In particular, an epoxy resin having an isocyanurate ring is excellent in light resistance and electrical insulation, and desirably has a divalent, more preferably a trivalent epoxy group per one isocyanurate ring. Specifically, tris (2,3-epoxypropyl) isocyanurate, tris (α-methylglycidyl) isocyanurate, or the like can be used.

  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 is preferably one other than those obtained by hydrogenating the triazine ring.

  In the present invention, epoxy resins other than those described above can be used alone or in combination with the above epoxy resins. Examples of this 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 type epoxy resin. Biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenylol ethane type epoxy resin, And an epoxy resin obtained by hydrogenating an aromatic ring of a phenol dicyclopentadiene novolac type epoxy resin. The softening point of other epoxy resins is desirably 70 to 100 ° C.

（式(1)中、Ｒ_１、Ｒ_２は同一でも異なってもよく、水素原子または炭素数１〜１０のアルキル基もしくはアルケニル基である。)
ここで、Ｒ_１、Ｒ_２は、硬化物の高強度性、高靱性の点から、Ｒ_１、Ｒ_２のいずれか一方、特には両方が、炭素数１〜１０、特に、炭素数２〜１０のアルキル基もしくはアルケニル基であることが好ましく、炭素数２〜１０のアルキル基（例えば、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、オクチル基等）がより好ましい。 (B) Curing agent The acid anhydride represented by the general formula (1) contained in the component (B) used in the present invention gives high strength and high toughness to the cured product of the epoxy resin composition of the present invention. It is.

(In formula (1), R ₁ and R ₂ may be the same or different, and are a hydrogen atom or an alkyl or alkenyl group having 1 to 10 carbon atoms.)
Here, R ₁ and R ₂ are either one of R ₁ or R ₂ , particularly both having 1 to 10 carbon atoms, particularly 2 to 2 carbon atoms from the viewpoint of the high strength and toughness of the cured product. 10 alkyl group or alkenyl group, preferably an alkyl group having 2 to 10 carbon atoms (for example, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, A cyclohexyl group, an octyl group and the like are more preferable.

  It is preferable that the content rate of the acid anhydride of the said General formula (1) is 5-100 mass% of the whole (B) component.

  As a hardening | curing agent of the epoxy resin composition of this invention, you may use together the acid anhydride shown below in combination with the acid anhydride shown by General formula (1). Examples include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hydrogenated methylnadic acid anhydride, methylhymic anhydride, etc. Among these, methylhexahydrophthalic anhydride and hexahydro Phthalic anhydride is preferred. These acid anhydride-based curing agents are used alone or in combination of two or more in the range of 0 to 95% by weight, particularly 0 to 90% by weight, relative to the component (B). Also good.

  (B) As a compounding quantity of a component (another acid anhydride hardening | curing agent is included), the acid anhydride group in an acid anhydride type hardening | curing agent is 0.6 with respect to 1 equivalent of epoxy groups in an above-described epoxy resin. It is -2.0 equivalent, Preferably it is 1.0-2.0 equivalent, More preferably, it is 1.2-1.6 equivalent. If it is 0.6 equivalents or more, curing failure occurs, and there is no fear that the reliability is lowered. If it is 2.0 equivalents or less, the unreacted curing agent remains in the cured product, and the moisture resistance of the resulting cured product is reduced. This is preferable because there is no risk of deterioration. In addition, 1 mol of an acid anhydride group (— (C═O) ═O— (C═O) —) corresponds to 2 equivalents per 1 mol (1 equivalent) of an epoxy group.

(C) Curing catalyst As the curing catalyst of this component (C), any of those known as curing catalysts for epoxy resin compositions can be used, although not particularly limited, tertiary amines, imidazoles, those Use one or more of organic carboxylates, organic carboxylic acid metal salts, metal-organic chelate compounds, aromatic sulfonium salts, organic phosphine compounds, phosphorus-based curing catalysts such as phosphonium compounds, and salts thereof can do. Among these, imidazoles, phosphorus-based curing catalysts such as 2-ethyl-4-methylimidazole, methyl-tributylphosphonium-dimethyl phosphate, and quaternary phosphonium bromide are more preferable.

  It is preferable to mix the curing catalyst in an amount of 0.05 to 5% by mass, particularly 0.1 to 2% by mass of the entire composition. In the said range, since there exists no possibility that the balance of the heat resistance of the hardened | cured material of an epoxy resin composition and moisture resistance may worsen, it is preferable.

  In the present invention, the components (A) and (B) described above, preferably the components (A), (B) and (C), more preferably the components (A), (B) and (C) are described later. The antioxidant is reacted in advance at 70 to 120 ° C., preferably 80 to 110 ° C. for 4 to 20 hours, preferably 6 to 15 hours, and the softening point is 50 to 100 ° C., preferably 60 to 90 ° C. You may make it into a certain solid substance and pulverize and mix | blend this.

(D) Inorganic filler As the inorganic filler of component (D) to be blended in the epoxy resin composition of the present invention, those usually blended in epoxy resin compositions and silicone resin compositions can be used. For example, silica-based fine powders such as fused silica and crystalline silica, rare earth oxides such as alumina, magnesium oxide, aluminum hydroxide and lanthanum oxide, silicon nitride, aluminum nitride, boron nitride, hollow silica, glass fiber, walla Examples thereof include fibrous fillers such as stenite and antimony trioxide. These inorganic fillers may be used alone or in combination of two or more. Moreover, the average particle diameter and shape of a filler are not specifically limited.

  In particular, fused silica and fused spherical silica are preferably used, and the particle size is not particularly limited, but the average particle size is preferably 4 to 40 μm, particularly 7 to 35 μm from the viewpoint of moldability and fluidity. . Moreover, in order to obtain high fluidization, it is desirable to use a combination of a fine region of 3 μm or less, a medium particle size region of 4 to 8 μm, and a coarse region of 10 to 40 μm. When forming a premold package having a narrow portion or when using it as an underfill material, it is better to use an inorganic filler having an average particle size of 1/2 or less with respect to the thickness of the narrow portion. The average particle diameter can be measured, for example, as a cumulative mass average diameter D50 (or median diameter) in particle size distribution measurement by a laser light diffraction method.

  In order to increase the bond strength between the resin and the inorganic filler, the inorganic filler has a silane coupling agent (for example, alkenyl group, epoxy group, (meth) acryloxy group, amino group, mercapto group, ureido group, etc.). The alkoxysilane containing a monovalent hydrocarbon group substituted with a functional group and / or a partial hydrolysis-condensation product thereof) or a surface-treated one with a coupling agent such as a titanate coupling agent may be blended. 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.

  (D) The compounding quantity of the inorganic filler of a component is 50-1100 mass parts with respect to a total of 100 mass parts of (A) epoxy resin and (B) hardening | curing agent, especially 100-1000 mass parts, Furthermore, 200 -800 mass parts is preferable. If the amount is less than 50 parts by mass, sufficient strength may not be obtained. If the amount exceeds 1100 parts by mass, unfilled defects due to thickening and flexibility may be lost. In addition, it is preferable to contain this inorganic filler in 30-90 mass% of the whole composition, especially 60-90 mass%.

  Moreover, the epoxy resin composition of this invention can contain titanium dioxide as a part or all of the inorganic filler of (D) component. Titanium dioxide is added as a white colorant in order to efficiently reflect the light emitted from the LED element and to increase the whiteness of the cured product. The unit cell of titanium dioxide may be either a rutile type or an anatase type. Also, the average particle size and shape are not limited. The titanium dioxide can be surface-treated in advance with a hydrous oxide such as Al or Si in order to enhance the compatibility and dispersibility with a resin or an inorganic filler.

  The filling amount of titanium dioxide is preferably 2 to 30% by mass, particularly 5 to 20% by mass, based on the entire composition. Sufficient whiteness is obtained at 2% by mass or more, and 30% by mass or less is preferable because there is no possibility that moldability such as unfilling or voids is reduced.

Other components Further, an antioxidant as an optional component can be blended in the epoxy resin composition of the present invention as necessary. As the antioxidant, phenol-based, phosphorus-based and sulfur-based antioxidants can be used, and 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-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [ 5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, among which 2,6-di-t-butyl-p-cresol is preferable.

  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-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, di (2,4-di-tert-butylphenyl) pentaerythritol diphosphite , Tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenyl diphosphonate and the like, among which triphenyl phosphite is preferable.

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

  Each of these antioxidants can be used alone, but it is particularly preferable to use a phosphorus-based antioxidant alone or a combination of a phenol-based antioxidant and a phosphorus-based antioxidant. In this case, the use ratio of the phenolic antioxidant and the phosphorus antioxidant is, as a mass ratio, phenolic antioxidant: phosphorus antioxidant = 0: 100 to 70:30, particularly 0: 100 to 50: 50 is preferable.

  The blending amount of the antioxidant may be usually about 10 parts by mass or less (0 to 10 parts by mass) with respect to 100 parts by mass of the (A) epoxy resin. A) It is preferable to set it as 0.01-10 mass parts with respect to 100 mass parts of epoxy resins, especially 0.03-5 mass parts. If the blending amount is 0.01 parts by mass or more, sufficient heat resistance is obtained, and there is no fear of discoloration. If it is 10 parts by mass or less, curing inhibition is caused, and sufficient curability and strength cannot be obtained. No fear.

  Various additives can be further blended in the epoxy resin composition of the present invention as necessary. For example, various thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, silicone-based low stress agents, waxes, halogen trapping agents and other additives can be added and blended for the purpose of improving the properties of the resin.

Production method of thermosetting epoxy resin composition As the production method of the thermosetting epoxy resin composition of the present invention, the above-mentioned epoxy resin, curing agent, curing catalyst, inorganic filler, and other additives are added at a predetermined composition ratio. After blending and mixing it sufficiently uniformly with a mixer, etc., it is melt mixed with a hot roll, kneader, extruder, etc., then cooled and solidified, pulverized to an appropriate size and molded into an epoxy resin composition It can be.

Reflector for LED The present invention provides a reflector for LED, which is obtained by curing and molding the thermosetting epoxy resin described above.
Examples of the most common molding method for the thermosetting epoxy resin composition of the present invention include a low-pressure transfer molding method, an injection molding method, and a compression molding method. The epoxy resin composition of the present invention is desirably molded at 150 to 185 ° C. for 30 to 180 seconds. The post-curing may be performed at 150 to 185 ° C. for 2 to 20 hours. The reflectance of the cured product obtained by curing the thermosetting epoxy resin composition of the present invention with light having a wavelength of 380 nm to 750 nm is 70% or more at an initial value, and the reflectance after a deterioration test at 180 ° C. for 24 hours. Is preferably 70% or more of the initial value (that is, 49% or more). When the reflectance is 70% or less, the LED reflector has a problem that the luminance is lowered and a predetermined performance cannot be obtained.

LED Device Furthermore, the present invention provides an LED device comprising the above-described reflector for LED, LED element, connection lead, and element electrode, which is sealed and protected with a transparent sealing material.
A pre-molded package in which the present material is collectively sealed on a matrix array type metal substrate or organic substrate on which lead portions and pad portions are formed and only the LED element mounting portion is open also falls within the scope of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to these.

(Examples 1-7, Comparative Examples 1 and 2)
The following raw materials were blended in the proportions shown in Table 1, mixed with a Henschel mixer until sufficiently uniform, and melt-kneaded with a continuous biaxial kneader to produce a thermosetting epoxy resin composition. Kneading was performed under the conditions of a temperature control of 85 ° C., a screw rotation speed of 120 rpm, and a discharge amount of 205 ± kg / hr.
The following properties were measured for these compositions. The results are shown in Table 2.

[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.

[Bending strength]
Using a mold conforming to the EMMI standard, measurement was performed under the conditions of 175 ° C., 6.9 N / mm ² , molding time of 120 seconds, and post cure at 150 ° C. for 2 hours.

[Deflection]
Using a mold conforming to the EMMI standard, measurement was performed under the conditions of 175 ° C., 6.9 N / mm ² , molding time of 120 seconds, and post cure at 150 ° C. for 2 hours.

[Reflectance]
A disk with a thickness of 3 mm and a diameter of 50 mmφ was molded under the conditions of a molding temperature of 175 ° C., a molding pressure of 6.9 N / mm, and a molding time of 120 seconds, and 450 nm using S-DG 8200 The light reflectance was measured.

[Heat-resistant discoloration]
A disk having a diameter of 50 × 3 mm was molded under the conditions of 175 ° C., 6.9 N / mm ² , and molding time of 2 minutes, left at 180 ° C. for 24 hours, and yellowing was evaluated according to the following criteria.
◎ White ○ Slightly yellow △ Yellow × Tawny

The raw materials used in the examples are shown below.
(A) Epoxy resin triazine derivative epoxy resin (A1) Tris (2,3-epoxypropyl) isocyanate (TEPIC-S: trade name, manufactured by Nissan Chemical Co., Ltd., epoxy equivalent 100)
Alicyclic epoxy resin
(A2) 3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P: trade name, manufactured by Daicel Chemical Industries, epoxy equivalent 130)

(B) Curing agent (B1) 2,4-diethylpentanedioic anhydride (YH1120: trade name, manufactured by Mitsubishi Chemical Corporation)
(B2) Hexahydrophthalic anhydride (Licacid HH: trade name, manufactured by Shin Nippon Rika Co., Ltd.)
(B3) Methyltetrahydrophthalic anhydride (Ricacid MH: trade name, manufactured by Shin Nippon Rika Co., Ltd.)

(C) Curing catalyst
(C1) Phosphorus curing catalyst quaternary phosphonium bromide (U-CAT5003; trade name, manufactured by San Apro Co., Ltd.)
(C2) Phosphorus-based curing catalyst Methyl-tributylphosphonium-dimethyl phosphate (PX-4MP: product name manufactured by Nippon Chemical Co., Ltd.)
(C3) Imidazole catalyst 2-Ethyl-4-methylimidazole (2E4MZ: trade name, manufactured by Shikoku Kasei Co., Ltd.)

(D) Inorganic filler (D1) Titanium dioxide rutile type (R-45M: trade name manufactured by Sakai Chemical Industry Co., Ltd.)
(D2) Fused silica (trade name, manufactured by Tatsumori, CS-6103)

(E) Antioxidant
(E1) Phosphorous antioxidant Triphenyl phosphite (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
(E2) Phenolic antioxidant 2,6-di-t-butyl-p-cresol (BHT: trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
(F) Release agent carnauba wax (manufactured by Toa Kasei Co., Ltd.)
(G) Silane coupling agent
(KBM403: Shin-Etsu Chemical Co., Ltd.)

Production of Matrix Type Recessed Reflector and Blue LED Device The thermosetting epoxy resin composition produced in Examples 1, 2 and 5 was prepared using a copper lead frame 100 in which the matrix type recessed reflector 101 of FIG. It was produced by transfer molding under the following molding conditions.
The molding conditions are as follows.
Molding temperature: 170 ° C., molding pressure: 70 kg / cm ² , molding time: 3 minutes Further post-curing was performed at 170 ° C. for 2 hours.

  The molded reflector 101 had good adhesion between the lead and the resin, and the light reflectance of the reflector molded with any composition was 92%.

A blue LED device was assembled using the reflector described above.
As shown in FIG. 3, which is a diagram after separation, a blue LED element 105 is placed on the lead frame 102 exposed on the bottom of each concave shape of the molded matrix type reflector 101 with a silicone die bond agent (product name: LPS 8433, Shin-Etsu Chemical). The lead part 103 which connects an external electrode with the gold wire 104, and the blue LED element 105 were connected after hardening and mounting for 1 hour at 150 degreeC. Thereafter, silicone sealant 106 (LPS3419: manufactured by Shin-Etsu Chemical Co., Ltd.) was injected into each of the recess openings where the LED elements were placed, and cured and sealed at 120 ° C. for 1 hour and further at 150 ° C. for 1 hour. The sealed matrix type reflector 101 was diced into individual pieces. The thickness of the side surface of the separated reflector 101 was cut to 300 μm by dicing.
Similarly, for comparison, an LED device was assembled using the reflector molded with the resin composition of Comparative Example 1 and the other materials and the same conditions as above. Five each of these LED devices were used and left in an atmosphere of 25 ° C. and 80% for 48 hours, and then passed through a reflow furnace at 260 ° C. three times. Thereafter, adhesion failure between the reflector surface or the element surface and the sealing resin was examined. The thing using the reflector shape | molded with the composition of this invention did not produce a peeling defect at all.

Measuring method of the breaking strength of the reflector Next, the breaking strength of the reflector was measured by the following method, and a copper lead frame in which the epoxy resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were entirely plated was used, as shown in FIG. A matrix type concave reflector was produced by transfer molding under the following molding conditions.
The molding conditions are as follows.
Molding temperature: 170 ° C., molding pressure: 70 Kg / cm ² , molding time: 3 minutes Further post-curing was performed at 170 ° C. for 2 hours. The matrix type reflector was diced so as to have a side thickness of 300 μm.

Fracture strength was measured by fixing the bottom face of an unsealed individualized reflector manufactured with the compositions of Examples and Comparative Examples to the substrate with an adhesive, and pressing the side surface of the reflector with a push-pull gauge. The pressing speed was measured at 100 μm / second (see FIG. 1).

From Tables 2 and 3, the component (A) and the component (B) having the acid anhydride represented by the chemical formula (1), the component (C) and the component (D) [the sum of the components (A) and (B) It can be seen that by adding 50 to 1100 parts by mass with respect to 100 parts by mass, heat discoloration, reflectance, and breaking strength are improved. That is, it can be seen that the heat resistance, light resistance, strength and toughness have been improved.
Based on these results, the thermosetting epoxy resin of the present invention is used as a reflector material, which maintains heat resistance and light resistance, is uniform, has little yellowing, is useful as a reflector for LEDs with high strength and high toughness It was confirmed that. On the other hand, Comparative Example 1 that does not contain the B component of the present invention has a problem in strength and toughness, and Comparative Example 2 in which the blending amount of the D component is less than the amount specified in the present invention has a particularly high reflectance and strength. It was inferior and yellowed.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  100: Lead frame with a copper surface plated with silver, 101: Reflector, 102: Lead on which a light emitting element is mounted, 103: Lead portion connected to an external electrode, 104: Gold wire, 105: Blue LED element, 106: Sealed Stop material

Claims (8)

A thermosetting epoxy resin composition comprising:
(A) epoxy resin, (B) curing agent, (C) curing catalyst, and (D) inorganic filler (provided that (D) component is a total of 100 parts by mass of (A) component and (B) component) 50 to 1100 parts by mass), and a thermosetting epoxy resin containing an acid anhydride represented by the following general formula (1) as a curing agent for the component (B) Composition.

(In general formula (1), R ₁ and R ₂ may be the same or different and are a hydrogen atom or an alkyl or alkenyl group having 1 to 10 carbon atoms.)   2. The thermosetting epoxy resin composition according to claim 1, wherein the content of the acid anhydride of the general formula (1) is 5 to 100% by mass of the entire curing agent of the component (B).   The thermosetting epoxy resin composition according to claim 1 or 2, wherein the epoxy resin as the component (A) is an alicyclic epoxy resin.   The thermosetting epoxy resin composition according to claim 1 or 2, wherein the epoxy resin as the component (A) is a triazine derivative epoxy resin.   Furthermore, it contains 1 type, or 2 or more types chosen from phenol type, phosphorus type | system | group, and sulfur type antioxidant as antioxidant, The any one of Claim 1 thru | or 4 characterized by the above-mentioned. Thermosetting epoxy resin composition.   The thermosetting epoxy resin composition according to any one of claims 1 to 5, wherein the inorganic filler of the component (D) contains titanium dioxide.   A reflector for LED, wherein the epoxy resin composition according to any one of claims 1 to 6 is cured and molded. An LED device comprising the LED reflector according to claim 7, an LED element, a connection lead, and an element electrode, wherein the LED device is sealed and protected with a transparent sealing material.

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