JPH0315821B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a resin-sealed semiconductor device that provides a colorless or light-colored transparent cured product, and in which light scattering from the element spreads uniformly over the entire resin. [Technical background of the invention and its problems] In recent years, light emitting devices such as light emitting diodes (LEDs), which have been put into practical use for various displays, are manufactured by resin sealing. Conventionally, liquid low-viscosity epoxy resin and the like have been used as the sealing resin used here. However, the commonly used epoxy resin sealing has the drawback that light from the element is not scattered and the light is not spread uniformly throughout the resin. One way to solve this problem is to use silica-based fillers as dispersants, but adding a small amount increases the epoxy resin's viscosity, makes it easy to separate, and its scattering properties are insufficient. There was a problem. [Purpose of the Invention] As a result of intensive research aimed at achieving the above problems, the inventors have developed a semiconductor and/or component using an epoxy resin composition to which polymethylsilsesquioxane is added as a light scattering agent. It was discovered that a resin-sealed semiconductor device with good transmittance and uniform light scattering can be obtained by sealing the semiconductor device. The present invention has been made based on these findings, and provides a resin-sealed semiconductor device in which a semiconductor or the like is sealed with a low-viscosity epoxy resin composition that has good transmittance and light scattering properties. The purpose is to [Structure of the Invention] That is, the present invention provides an epoxy resin composition that provides a transparent cured product consisting of (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, and (D) polymethylsilsesquioxane. The present invention relates to a resin-sealed semiconductor device characterized by encapsulating a semiconductor and/or a component. As the epoxy resin (A) used in the present invention, a colorless or light-colored transparent liquid or solid epoxy resin is used because it is necessary to obtain a transparent cured epoxy resin. Furthermore, in the present invention, it is particularly effective to use known epoxy resins having an epoxy equivalent of 1000 or less. Such epoxy resins include bisphenol type epoxy resins obtained from bisphenol A and epichlorohydrin, diglycidyl esters of hexahydrophthalic acid and tetrahydrophthalic acid; polyorthocresol formaldehyde poly(2,3-epoxypropyl); Epoxy novolacs such as ether, polyphenol formaldehyde poly(2,3-epoxypropyl) ether, and alicyclic epoxy resins are commercially available.Commercial products of these epoxy resins include Epon 827, manufactured by Ciel Chemical Co., Ltd.;
Epon 828, Epon 834, Epon 1001, Epon
1004; Product name: Araldite manufactured by Ciba Geigy
Examples include CY183, CY182, CY175; trade names DEN431 and DEN438 manufactured by Dow Chemical; trade names Chitsonox 221 and Chitsonox 289 manufactured by Chitsuso Corporation; and trade name Adeka Resin EP-4080 manufactured by Asahi Denka Kogyo Co., Ltd. Ru. Further, in the present invention, bisphenol F type epoxy resin is preferred as an epoxy resin that has low stress, heat resistance, and low viscosity. Commercial products of this bisphenol F type epoxy resin include Epicote 807 (trade name manufactured by Ciel Chemical Co., Ltd.),
Examples include YDF-170 (trade name manufactured by Toto Kasei Co., Ltd.) and R114 (trade name manufactured by Mitsui Epoxy Co., Ltd.). These epoxy resins may be used alone or in combination of two or more. (B) is a curing agent for the epoxy resin of (A), and is used singly or in combination of two or more polybasic carboxylic anhydrides. Such curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6 endomethylenetetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, maleic anhydride, azelaic anhydride, and pyromellitic anhydride. Examples include acid dianhydrides. In addition, it is desirable to use these curing agents that are sufficiently purified and have little coloring, and the amount thereof is preferably 0.5 to 1.2 equivalents per equivalent of the epoxy resin (A). be. As the curing accelerator (C) used in the present invention,
Tertiary amines, imidazoles, carboxylic acid metal salts, quaternary ammonium salts, quaternary phosphates,
Examples include diazabicycloalkenes and their salts. Examples of these compounds include benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, triamylammonium phenolate, and sodium hexanetriolate. The amount of these curing accelerators added is preferably (A)
The amount is 0.05 to 10 parts by weight based on 100 parts by weight of the total amount of the epoxy resin (B) and the curing agent (B). The polymethylsilsesquioxane (D) used in the present invention scatters the light from the light emitting element so as to spread throughout the resin, and is the most characteristic feature of the present invention. This powder has a lower specific gravity in the composition compared to other silica-based powders of similar average particle size, such as ground quartz and diatomaceous earth, and compared to fumed and wet silicas. There is little increase in viscosity when made into a composition. Furthermore, in any case, the problem of sedimentation during long-term storage is significantly less compared to other powders. Therefore, a large amount can be filled. As polymethylsilsesquioxane,
The products obtained by hydrolyzing and condensing methyltrialkoxysilane or its hydrolysis/condensation products in an aqueous solution of ammonia or amines have almost no impurities such as chlorine atoms, alkaline earth metals, and alkali metals, and are spherical. It is preferred because it has excellent free-flowing properties. The average particle diameter of polymethylsilsesquioxane is 0.1 to 100 μm, preferably 0.1 to 100 μm.
It is 20 μm. Items smaller than 0.1μm are difficult to manufacture;
Moreover, if it exceeds 100 μm, it will not be uniformly dispersed in the resin, making it impossible to emit uniform light. In addition, the blending amount is (A) 100
It is preferably 0.1 to 50 parts by weight. This is because if it is less than 0.1 part by weight, it is difficult to obtain uniform light emission, and if it exceeds 50 parts by weight, the light transmittance may deteriorate. In addition to the above-mentioned components, additives such as antioxidants and dyes can be added to the epoxy resin composition of the present invention, if necessary. The epoxy resin composition obtained in this way can be used to create light emitting devices.
The method for sealing the light receiving element and/or components is performed as follows. For example, as shown in FIG. 1a, an epoxy resin composition 2 is injected into a plastic mold 1 for a light emitting diode coated with a mold release agent, and a gallium-
A frame 4 on which chips 3 of arsenic-phosphorus (G-As-P) emitting yellow color are mounted is attached using a fixing jig 5, and cured by heating at a temperature of 140° C. for 16 hours. The thus sealed light emitting diode can be removed from the fixing jig 5 to obtain a light emitting device 6 sealed with the epoxy resin composition. The resin-sealed semiconductor device removed from mold 1 is
Shown in Figure b. [Examples of the Invention] Next, the present invention will be explained using Examples and Reference Examples, but the present invention is not limited thereto. In the Examples and Reference Examples, all parts indicate parts by weight. Reference Example 1 (Production of polymethylsilsesquioxane) A four-necked flask equipped with a thermometer, reflux device, and stirrer was charged with the amount of water shown in Table 1 and an ammonia aqueous solution with a concentration of 28%. 200 parts of methyltrimethoxysilane was gradually added dropwise to the ammonia aqueous solution over about 40 minutes while stirring. The reaction temperature started at 10°C and reached 30°C at the end of the dropwise addition. Next, the mixture was heated with a mantle heater to reflux at 84°C, and stirring was continued at this temperature for about 1 hour. After cooling, the precipitated product in the flask is circulated, washed with water, dried, and then pulverized to produce powdered polymethylsilsesquioxane (F-1 to F- 2) was obtained.

[Table] Reference Example 2 (Production of polymethylsilsesquioxane) 9 parts of water was added to 178 parts of methyltriethoxysilane containing 1% by weight of chlorine atoms, and the mixture was partially hydrated by heating at 80°C for about 2 hours. A decomposed condensate was obtained. This was dropped into 500 parts of a 3% by weight aqueous solution of ethylenediamine and hydrolyzed and condensed under the same conditions as in Reference Example 1. As a result, powdered polymethylsilsesquioxane (F-3 )was gotten. Example 1 100 g of Epon 807 (epoxy resin trade name manufactured by Ciel Chemical Co., Ltd.), 100 g of hexahydrophthalic anhydride,
2.0 g of VCAT SA102 [2-ethylhexanoate of 1,8-diazabicyclo(5,4,0) undecene 7 manufactured by Sun Apot] and 1 part of polymethylsilsesquioxane of F-1 were mixed and stirred to make a homogeneous mixture. were mixed to obtain an epoxy resin composition. The obtained resin composition was poured into a plastic mold for a light emitting diode coated with a mold release agent, and a frame mounted with a gallium-arsenic-phosphorus (Ga-As-P) chip with a yellow luminescent color was placed using a jig. Installation, 140℃
Heat cure for 16 hours and remove from the jig.
The resin-sealed light-emitting devices were obtained by cutting into individual pieces. Examples 2 to 7 LEDs were sealed using the resin compositions shown in Table 2 in the same manner as in Example 1 to obtain resin-sealed light emitting devices. Comparative Examples 1 to 2 LEDs were sealed using the resin compositions shown in Table 2 in the same manner as in Example 1 to obtain resin-sealed light emitting devices. Comparative Example 1 is a system that does not contain polymethylsilsesquioxane as in Example 1, and Comparative Example 2 is a system that does not contain polymethylsilsesquioxane.
It uses 5μm wet silica. Next, the brightness of this device was measured using a dedicated device. Next, connect each LED to 25mA, 2.2V
After energizing for 168 hours at room temperature under the conditions of
The brightness of the LED was measured and changes in brightness were investigated. The measurement was performed using 20 LEDs, and the average of the residual brightness rates was taken as the residual brightness rate for that time. In addition, two high-pressure mercury lamps with an output of 2 kW were used as light sources, and irradiation was performed at a distance of 10 cm from the light source, and the presence or absence of light scattering was observed. Furthermore, the compositions of Examples 1 to 7 and Comparative Example 2 were placed in 500 ml glass bottles, left to stand for one month, and the presence or absence of filler sedimentation was observed. The results are shown in Table 2.

[Table] As is clear from Table 2, the resin-sealed semiconductor device using the epoxy resin composition of the present invention was confirmed to have uniform light scattering properties. [Effects of the Invention] As explained above, by sealing with an epoxy resin composition consisting of an epoxy resin, a curing agent, a curing accelerator, and polymethylsilsesquioxane, luminance efficiency with uniform light scattering property can be achieved. A resin-sealed semiconductor device with good heat resistance and heat resistance could be obtained.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of the resin-sealed semiconductor device of the present invention during casting, and FIG. 2 shows the semiconductor device after resin-sealing. 1... Plastic mold, 2... Epoxy resin composition, 3... LED chip, 4... Frame, 5
...Fixing jig, 6...Resin-sealed semiconductor device.

Claims (1)

[Claims] 1. Semiconductor and/or Or a resin-sealed semiconductor device characterized by being formed by sealing components. 2. The semiconductor device according to claim 1, wherein the epoxy resin (A) is a bisphenol F type epoxy resin. 3. The semiconductor device according to claim 1, wherein the amount of the curing agent (B) is equivalent to 0.5 to 1.2 equivalents per equivalent of the epoxy resin (A). 4 The amount of curing accelerator in (C) is the epoxy resin of (A) and the amount of curing accelerator in (B)
2. The semiconductor device according to claim 1, wherein the amount of the curing agent is 0.05 to 10 parts by weight based on 100 parts by weight of the total amount of the curing agent. 5 The amount of polymethylsilsesquioxane in (D) is (A)
The semiconductor device according to claim 1, wherein the amount is 0.1 to 50 parts by weight based on 100 parts by weight of the epoxy resin. 6. The semiconductor device according to claim 1, wherein (D) is polymethylsilsesquioxane having an average particle diameter of 0.1 to 100 μm. 7. Claim 1, wherein (D) is polymethylsilsesquioxane obtained by hydrolyzing and condensing methyltrialkoxysilane or its hydrolyzed and condensed product in an aqueous solution of ammonia or amines, The semiconductor device according to any one of Items 5 to 6. 8. The semiconductor device according to any one of claims 1, 5, 6 and 7, wherein the average particle diameter of (D) is 0.1 to 20 μm.