JPS6136854B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an epoxy resin composition, and particularly to an epoxy resin composition capable of producing a cured product having a low modulus of elasticity, a low coefficient of expansion, and a high glass transition point. In recent years, in the field of electronic components, as the size and weight of electronic components have been reduced and reliability has increased, there has been a trend toward larger semiconductor element pellets and multifunctionality by combining active and passive elements. Therefore, there is a strong demand for resin materials for various device molds to have the property that the effect of stress on the insert is small even when directly molded. Conventionally, epoxy-based, silicone-based, phenol-based, diallyl phthalate-based materials, and the like have been used as molding resins for electronic components such as semiconductors and electrical equipment. Among these, epoxy resin compositions using phenol novolac resin as a curing agent are superior in that they have well-balanced adhesion to inserts, electrical properties, etc., and have become the mainstream resin for molding. However, if this type of resin composition is directly molded with the resin without applying a flexible protective coat to the element pellet, the ribbon cutting line that causes cracks in the element pellet will be cut, etc. Failures caused by stress are observed. As a countermeasure, it is important to reduce the stress exerted on the insert, and it is necessary to develop a molding resin that has a low modulus of elasticity, a low coefficient of expansion, and a high glass transition temperature. Addition of a flexibilizing agent may be considered as one means of lowering the modulus of elasticity of the molding resin. However, if this method is applied to epoxy resin compositions that use phenolic resin as a curing agent, the glass transition point of the cured resin will drop rapidly, and the electrical properties in high-temperature regions will decrease accordingly, resulting in a highly reliable mold. It is difficult to obtain the product. On the other hand, silicone-based materials have a low elastic modulus and a high glass transition temperature, and even when directly molded using silicone-based materials, no cracks occur in the element pellets. but,
This material has problems such as low insert adhesion and high transparency, and its molded products are unreliable in terms of moisture resistance. The present invention has been made in view of the current situation, and its purpose is to eliminate the drawbacks of the prior art,
An object of the present invention is to provide an epoxy resin composition capable of producing a cured product having a low modulus of elasticity, a low coefficient of expansion, and a high glass transition point. To summarize the present invention, the epoxy resin composition of the present invention comprises (a) a polyfunctional epoxy compound, (b) a butadiene-based low molecular weight polymer, and (c) an ethylenically unsaturated dicarboxylic acid or a reactive derivative thereof. It contains a reactant with a polyamine compound and (d) an inorganic filler, and the content of the inorganic filler is about 40 to 70% by volume based on the total volume of the above four components. . Examples of the polyfunctional epoxy compound (a) in the present invention include glycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexanecarboxylate, vinylcyclohexane dioxide, 4,4′-di(1,2
-Epoxyethyl) diphenyl ether, 2,2
-Bis-(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-
(2,3-epoxycyclopentyl)ether,
2-(3,4-epoxy)cyclohexane-5,
5-spiro(3,4-epoxy)cyclohexane-m-dioxane, bis-(3,4-epoxy-
6-methylcyclohexyl) adipate and N,
N′-m-phenylene bis-(4.5-epoxy-1.2
-Difunctional epoxy compounds such as cyclohexanedicarboximide, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3,5-tri(1,2-epoxyethyl)benzene, 2,2'4,4' - Tri- or higher-functional polyfunctional epoxy compounds such as tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde nopolac, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane. And mixtures of two or more of these can be applied. In addition, as the butadiene-based low molecular weight polymer b in the present invention, 1,2-polybutadiene, 1,3-polybutadiene and 1,4-polybutadiene having a molecular weight of about 300 to 10,000 are used.
-Polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, and furthermore, their polymers having carpoxyl groups, hydroxyl groups, amino groups, vinyl groups, etc. as reactive groups, etc. These are commercially available from Nippon Soda Co., Ltd., Ube Industries Co., Ltd., Mitsui Polychemical Co., Ltd., and others. In the present invention, the reaction product c of an ethylenically unsaturated dicarboxylic acid or its reactive derivative and a polyamine compound plays an important role in achieving the object of the present invention. As the ethylenically unsaturated dicarboxylic acid or its reactive derivative in the present invention, for example, maleic anhydride, various maleic acid esters, citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, etc. can be applied. Further, as the polyamine compound in the present invention, an aromatic or alicyclic polyamine compound is used. Examples of aromatic polyamine compounds include metaphenylenediamine, paraphenylenediamine, dianisidine, 2,6-diaminopyridine,
1,4-naphthylene diamine, 1,5-naphthylene diamine, 2,6-naphthylene diamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl thioether, 4,4'-diaminodiphenyl ketone, etc. are applied. It is also possible to use derivatives of these compounds in which the aromatic nucleus is substituted with alkyl. Furthermore, 1,2,3-triaminobenzene, 1,2,4-triaminobenzene, 1,
3,5-triaminobenzene, 1,2,3,4-
Aromatic polyamine compounds such as tetraaminobenzene, 1,2,3,5-tetraaminobenzene, 1,2,4,5-tetraaminobenzene, pentaaminobenzene, hexaaminobenzene, and the like can also be used. Among these polyamine compounds, compounds containing aromatic diamine as a main component are particularly desirable in terms of obtaining a cured product with excellent heat resistance. In addition, as alicyclic polyamine compounds such as polyamine compounds containing a cyclohexyl ring, for example, the general formula (In the formula, R is -CH ₂ -, -CH(CH ₃ ) ₂ , -C
(CH ₃ ) ₂ -, -S-, -O-, etc.) can be applied, and specific examples thereof include 4,4'-diaminocyclohexylmethane, 4, Examples include 4'-diaminodicyclohexylpropane and 4,4'-diaminodicyclohexyl ether. In the present invention, the reaction product of the polyamine compound and the ethylenically unsaturated dicarboxylic acid or its reactive derivative is blended in a ratio within the range of about 0.05 to 0.5 carboxyl group of the latter to one amino group of the former, It is obtained by a melt reaction at about 90 to 200°C for about 10 to 60 minutes. If the amount of ethylenically unsaturated dicarboxylic acid exceeds this range, the melting point of the reactant will be relatively high, which will be disadvantageous in terms of workability and fluidity of the resin composition, and if it is less than the above range, the properties of the cured product will deteriorate. Degraded and undesirable. The blending ratio of the three components, the polyfunctional epoxy compound (a), the butadiene-based low molecular weight polymer b, and the melt reaction product (c) of the ethylenically unsaturated dicarboxylic acid or its reactive derivative and the polyamine compound, is (a) )component
It is appropriate that the amount of component (b) is about 1 to 50 parts by weight and the amount of component (c) is about 20 to 70 parts by weight per 100 parts by weight. When the blending ratio of component (b) to component (a) exceeds about 50 parts by weight, the curability of the resin composition is lost;
Moreover, even when curing, it becomes difficult to impart the desired good heat resistance. Moreover, if it is less than about 1 part by weight, the effect of lowering the elastic modulus is almost lost. Also, regarding the blending ratio of components (a) and (b), for example,
When using a mixture of novolac type epoxy resin and bisphenol A type epoxy resin as component (a), approximately 20% of the novolac type epoxy resin as component (a) is used.
It is suitable that the blending ratio is about 90 parts by weight, about 5 to 40 parts by weight of the bisphenol A type epoxy resin, and about 5 to 40 parts by weight of component (b). On the other hand, the blending ratio of component (c) to component (a) is (a)
The amount can be changed appropriately so that one proton of the amino group of the polyamine compound (c) is equivalent to one epoxy group of the epoxy compound (component), and in normal cases, the amount of component (a) 100 It is suitable to range from about 20 to 70 parts by weight, but there is no particular limitation to this amount. Inorganic filler (d) which is an essential component in the present invention
Examples include zircon oxide, silica, fused silica glass, clay, alumina, aluminum hydroxide, calcium carbonate, quartz glass, glass, asbestos, whisker, gypsum, magnesite, mica, kaolin, talc, graphite, cement, iron. Examples include carbonyl, ferrite, lead compounds such as lead dioxide, molybdenum disulfide, zinc white, titanium white, carbon black, silica sand, and wollastonite, and two or more of these can be used in combination. Component (d) is blended in a proportion of about 40 to 70% by volume based on the total volume of the four components (a), (b), (c) and (d). If this is less than about 40% by volume, the coefficient of linear expansion becomes large, causing resin cracks and pellet cracks. If it exceeds about 75% by volume, the fluidity of the resin composition will be significantly reduced, causing problems in molding elements, inserts, etc. Further, in the present invention, various catalysts can be added for the purpose of promoting the curing reaction of the polyfunctional epoxy compound, and examples of the catalyst include triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, Tertiary amines such as tetramethylhexanediamine, triethylenediamine and dimethylaniline, oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol, and amines such as tris(dimethylaminomethyl)phenol and methylmorpholine can be applied. can. For the same purpose, as a catalyst, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzylmethylpalmitylammonium chloride, allyldodecyltrimethylammonium bromide , benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride and benzyldimethyltetradecylammonium acetate, and further quaternary ammonium salts such as 2-undecylimidazole, 2-methylimidazole, 2-ethylimidazole can be applied. , 2-heptadecylimidazole, 2-
Methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole,
1-cyanoethyl-2-methylimidazole, 1
-cyanoethyl-2-undecylimidazole,
1-cyanoethyl-2-phenylimidazole,
Imidazole compounds such as 1-azine-2-methylimidazole and 1-azine-2-undecylimidazole, or triphenylphosphine tetraphenylborate, triethylaminetetraphenylborate, N-methylmorpholinetetraphenylborate, pyridinetetra Tetraphenylboron salts such as phenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and 2-ethyl-1.4dimethylimidazole tetraphenylborate are useful. Two or more of the above catalysts can be used in combination. In addition, in the present invention, depending on the use and purpose of use, mold release agents such as fatty acids and waxes, known coupling agents such as epoxysilane, vinylsilane, borane compounds and alkoxy titanate compounds, and further, Known flame retardants such as antimony, phosphorus compounds and halogens and halogen-containing compounds can be used. Each of the above ingredients is heated (70 to 80
°C) It is blended by kneading. Furthermore, if all the components are solid, a dry blending method may be employed in which the components are pulverized and then mixed. The epoxy resin composition of the present invention has a low flexural modulus (approximately 2.0 × 10 ⁵ Kg/cm ² or less at room temperature), a low linear expansion coefficient (approximately 3.0 × 1.0 ^-5 °C ^or less), and a high A cured resin product having a glass transition point (approximately 150° C. or higher) can be provided. EXAMPLES Hereinafter, the present invention and its effects will be explained with reference to Examples, but the present invention is not limited to these in any way. Examples 1 to 13 and Comparative Examples 1 to 4 (i) Preparation of component (c) 4,4'-diaminodiphenylmethane (hereinafter referred to as
A predetermined amount of DDM (abbreviated as DDM) is heated and melted at 100 to 130°C, and maleic anhydride (hereinafter abbreviated as MA) is added to this in the proportion (molar ratio) shown in Table 1 below.
were added and reacted with stirring. Foaming begins soon, and the temperature of the reaction system is 160-200℃.
reached. The reaction was allowed to proceed for more than 30 minutes, and when foaming was substantially completed, the mixture was allowed to cool to obtain four types of DDM-MA molten reaction products. Note that all of the obtained reaction products were transparent. The properties of the reactants are shown in Table 1 below.

[Table] (ii) Preparation of epoxy resin composition As the epoxy resin for the component (a), novolak type epoxy resin (manufactured by Ciba Corporation, ECN 1273, epoxy equivalent: 179 and DEN, manufactured by Dow Chemical Company) were used.
438, epoxy equivalent: 179) and bisphenol A type epoxy resin (manufactured by Ciel, _EP
1002, epoxy equivalent: 650), as the butadiene-based low molecular weight polymer of component (b), butadiene-
Acrylonitrile copolymer (BF/Goodrich
Co., Ltd., CTBN 1800×8, viscosity 1250 poise, molecular weight 3500), and as the inorganic filler of component (d), quartz glass powder was blended in a predetermined ratio shown in Table 2 below. In addition to these, 1 part by weight of a higher fatty acid ester (manufactured by Hoechst Japan Co., Ltd., Hoechst Wax-E) as a mold release agent, and an epoxy silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-
403) 1 part by weight, colorant carbon black 1
Parts by weight were added to each system, and the DDM-MA melt reactants A to D as component (c) were added to each system at predetermined ratios shown in Table 2 below.
These formulations were kneaded for 10 minutes at 70 to 80°C, and then ground to obtain 17 types of epoxy resin compositions (4 of these were compositions outside the scope of the present invention, and these were used in Comparative Examples 1 to 1). 4) was prepared. (iii) Preparation of cured product and its characteristic test Each of the above epoxy resin compositions was cured at 180°C and 70°C.
Cured products (test pieces) were prepared by transfer molding at Kg/cm ² for 2 to 3 minutes, and their various properties were tested. The results obtained are shown in Table 2 below.

【table】

[Table] As is clear from Table 2, all of the cured products obtained from the epoxy resin composition of the present invention have good properties, but the epoxy resin compositions that are outside the range of the blending ratio according to the present invention The properties of the cured products obtained were unsatisfactory. Examples 14-25 As the epoxy resin of component (a), the epoxy resin of Example 1 above was used.
In addition to ECN1273, bisphenol A type epoxy resin (manufactured by Ciel, E _P 1001, epoxy equivalent
475) and hydantoin type epoxy resin (Ciba・
Using XB-2818 (manufactured by Geigy, epoxy equivalent: 163), and using various compounds shown in Table 3 below as the butadiene-based low molecular weight polymer of component (b),
In addition, as the reactant of component (c), DDM of Example 1
-Using MA molten reactant B, and further using fused quartz powder and silica powder as the inorganic filler of component (d),
They were blended in the proportions shown in Table 3 below. Additionally, 2 parts by weight of stearic acid and an epoxysilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.,
1 part by weight of KBM-403) and 1 part by weight of carbon black as a coloring agent were added. These blends were kneaded and ground in the same manner as in Example 1 to give 12
A variety of epoxy resin products were prepared and cured to prepare test pieces, and various properties were tested. The results obtained are shown in Table 3 below.

[Table] As is clear from Table 3, all of the molded products (cured products) made from the resin composition of the present invention have good properties, including glass transition point, flexural modulus, and Bacall hardness. The standard value of 150℃
The above shows values that fully satisfy 0.8×10 ⁵ Kg/cm ² or less and 35 or more. As explained above, according to the present invention, it is possible to provide an epoxy resin composition capable of producing a cured product having a low elastic modulus, a low expansion coefficient, and a high glass transition point.

Claims (1)

[Scope of Claims] 1 (a) a polyfunctional epoxy compound, (b) a butadiene-based low molecular weight polymer, (c) a reaction product of an ethylenically unsaturated dicarboxylic acid or a reactive derivative thereof and a polyamine compound, and (d) ) An epoxy resin composition containing an inorganic filler, wherein the content of the inorganic filler is about 40 to 75% by volume based on the total volume of the four components. 2 From about 20 to 90 parts by weight of a novolak type epoxy resin, about 5 to 40 parts by weight of a bisphenol A type epoxy resin, and about 5 to 40 parts by weight of a butadiene-based low molecular weight polymer (b) as a polyfunctional epoxy compound (a). An epoxy resin composition as claimed in claim 1. 3 The reaction product (c) of ethylenically unsaturated dicarboxylic acid or its reactive derivative and polyamine compound is about 0.05 to 100% maleic anhydride per mole of aromatic diamine.
The epoxy resin composition according to claim 1 or 2, which is a reaction product obtained by melting and reacting both in a ratio of 0.5 mole.