JPS621609B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an epoxy resin composition that provides 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 towards increasing the size of semiconductor element pellets and increasing their functionality by combining active and passive elements. Therefore, coating materials and molding materials for semiconductor devices are required to have well-balanced properties such as heat resistance, flexibility (crack resistance), and moisture resistance. At the same time, there is a strong demand for a material that causes less stress on the insert even when directly molded onto an element. Conventionally, materials such as epoxy-based, silicone-based, phenol-based, and diallyl phthalate-based materials 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 adhesiveness to inserts, electrical properties, etc. are relatively balanced, and have become the mainstream resin for molding. However, if this type of resin composition is directly molded with the resin without applying a highly flexible protective coat to the element pellet, the element pellet may crack or the bonding wires may be cut. Failures caused by stress on the mold resin inserts are observed. Furthermore, when a flexibilizing agent or the like is added to the resin as a countermeasure to this problem, it is difficult to meet the targets of heat resistance and moisture resistance required for a semiconductor element molding material. That is, when a flexibilizing agent is added to an epoxy resin composition using a phenol resin as a curing agent, the glass transition point of the cured resin drops rapidly, and the electrical properties in a high temperature region are accordingly reduced. It is difficult to obtain highly reliable semiconductor molded products. On the other hand, silicone-based materials have a low elastic modulus and a high glass transition temperature, and even if they are directly molded, no cracks will occur in the element pellets. However, this material has problems such as low adhesion to metal inserts (frame parts, etc.) and high moisture permeability, and the molded product lacks reliability in terms of moisture resistance. The present invention was made in view of the above-mentioned circumstances, and its objectives are to provide a material with a low elastic modulus, a low coefficient of linear expansion, and a high glass transition point, specifically,
2.0×10 ⁵ Kg/cm ² (room temperature), 3.0×10 ^-5 (℃ ^-1 ), and cures to a resin with properties of 150℃ or higher, with an excellent balance of heat resistance, crack resistance, and moisture resistance. An object of the present invention is to provide an epoxy resin composition. The features of the present invention are as follows: [A] A polyfunctional epoxy compound [B] (a) A reaction product of an ethylenically unsaturated dicarboxylic acid anhydride or its functional derivative, (b) a polyamine, and [C] A silicone compound, preferably an organopolysiloxane compound [D] contains an inorganic filler, the content volume % of the inorganic filler [D] is 100D/A+
B+C+D is in the range of 40-75. Next, in the present invention, as the polyfunctional epoxy compound (B), for example, diglycidyl ether of bisphenol A, butadiene diepoxide, 3-4-
Epoxycyclohexylmethyl-(3,4-epoxy)cyclohexanecarboxylate, vinylcyclohexane dioxide, 4,4'-di(1,2
-epoxyethyl)diphenyl ether, 4.
4′-(1,2-epoxyethyl)biphenyl,
2,2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcin, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,3-epoxycyclohentyl) ether, 2 -(3,4-epoxy)cyclohexane-
5,5-spiro(3,4-epoxy)-cyclohexane-m-dioxane, bis-(3,4-epoxy-6-methylcyclohexyl)adipate,
Bifunctional epoxy compounds such as N・N'-m-phenylenebis(4,5-epoxy-1,2-cyclohexane)dicarboximide, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3,5- Tori (1・2
-epoxyethyl)benvin, 2, 2', 4, 4'-
Tri- or higher functional epoxy compounds are used, such as tetraglycidoxybenzophenone, tetraglycidquin tetraphenylethane, polyglycidyl ether of phenol formaldehyde novolac, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane. In the present invention, the reaction product of ethylenically unsaturated dicarboxylic acid anhydride or its functional derivative and polyamine plays an important role in achieving the purpose of generation. Examples of the ethylenically unsaturated dicarboxylic anhydride or its functional derivative include maleic anhydride, various maleic esters, citraconic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride. In addition, in the present invention, the polyamine includes:
For example, metaphenylenediamine, paraphenylenediamine, dianisidine, 2,6-diaminopyridine, 1,4-naphthylenediamine, 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, 2,2'-bis[4-(4- aminophenoxy)phenyl]propane, 2,2'-bis[3
-Methyl-4-(4-aminophenoxy)phenyl]propane, 1.1.1.3.3.3-hexafluoro-2.2-bis[4-(4-aminophenoxy)phenyl]propane, 1.1. 1・3・
3,3-hexafluoro-2,2-bis[3,5
Examples thereof include -dibromo-4-(4-aminophenoxy)phenyl]propane and derivatives thereof alkylated to an aromatic nucleus. In addition, as an example of an amine compound containing a cyclohexylene ring, the following general formula [Wherein, R is _-CH2- , -CH( _CH3 )-, -C
(CH ₃ ) ₂ -, -S-, -O-, etc.). Specific examples of such diamine compounds include 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, and 4,4'-diaminodicyclohexyl ether. Also, 1,2,3-triaminobenzene, 1.
2,4-triaminobenzene, 1,3,5-triaminobenzene, 1,2,3,4-tetraaminobenzene, 1,2,3,5-tetraaminobenzene, 1,2,4,5- Examples include tetraaminobenzene, pentaaminobenzene, and hexaaminobenzene. Among the above-mentioned polyamines, it is preferable to use aromatic diamine as the main component in order to obtain a cured product with an excellent balance between heat resistance and flexibility, which are the effects of the present invention. The molten reactant, which plays an important role in achieving the object of the present invention, is a mixture of the above-mentioned amine compound and ethylenically unsaturated dicarboxylic acid anhydride in an amount of less than 0.6 mole of the latter per 1 mole of the former. 90~250
Obtained by melt reaction at ℃ for 10-60 minutes. If the amount of the ethylenically unsaturated dicarboxylic acid anhydride is larger than the above, the melted reaction product will have a relatively high melting point, which will be disadvantageous in terms of workability and fluidity of compositions using this melted reaction product as a raw material. , is not preferable from the viewpoint of imparting heat resistance to the cured product of the present invention. Regarding the blending ratio of the three components described above, [A] polyfunctional epoxy compound, [B] reaction product of ethylenically unsaturated dicarboxylic acid anhydride and polyamine, and [C] silicone compound, 100 weight of component [A] parts, [B] component 20 to 70 parts by weight, [C] component 1 to 60 parts by weight.
It may be used by changing the weight part as appropriate.
If the ratio of component [C] to component [A] exceeds 60 parts by weight, the composition may become uncurable, or even if it is cured, it will be difficult to impart the desired heat resistance. Furthermore, if it is added in an amount of 1 part by weight or less, there is almost no effect of lowering the elastic modulus. On the other hand, the amount of component [B] added to component [A] is as follows:
The amount can be changed as appropriate depending on the purpose and use so that one proton of the amino group of the above-mentioned molten reactant is equivalent, and in normal cases, it is within the range of 20 to 70 parts by weight, but depending on the time and case. It is not particularly limited. In addition, as the silicone compound which is an essential component of the present invention, for example, for one silicon atom,
The ratio of this to the organic group bonded to it is R/Si (where R is a substituted or unsubstituted monovalent hydrocarbon group)
is 1.0 to 1.7, and the content of hydroxyl groups bonded to silicon atoms is at least 0.2% by weight, and the siloxane units constituting this siloxane resin are:
_{CH3SiO15 , C2H5SiO15 , C6H5SiO15 , _ _}
C ₈ H ₇ SiO ₁₅ , Cl ₂ C ₆ H ₃ SiO ₁₅ ,
Examples include CF ₃ CH ₂ CH ₂ CH ₂ SiO ₁₅ , but R/
As long _as the Si ratio is in the range of 1.0 _to 1.7, its components include ( _CH3 ) _2SiO , ( _C2H5 ) _2SiO , ( _C6H5 ) _2SiO ,
CH ₃ (CH ₂ =CH)SiO, CH ₃ (C ₆ H ₅ )SiO, C ₆ H ₅
( _CH2 =CH)SiO, _C6H5 ( _{C2H5 ) SiO} , _CH3
(CF ₃ CH ₂ CH ₂ H ₂ ) May contain a structural unit exemplified by SiO. Furthermore, it may contain an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. bonded to a silicon atom. Organopolysiloxane resins having such structural units can be produced by selectively blending the corresponding organohalosilanes and alkoxysilanes so that the R/Si ratio is 1.0 to 1.7, and subjecting them to hydrolysis and condensation reactions. It is obtained as having hydroxyl groups fused to a certain amount of silicon atoms. If the content of hydroxyl groups bonded to silicon atoms is too small, curing will be insufficient, so it is necessary to contain at least 0.2% by weight of hydroxyl groups. There is no reason to limit the number of organopolysiloxane resins used to one type, and a mixture of two or more types may be used. By the way, examples of the inorganic filler [D] that plays an important role in achieving the object of the present invention include zircon, silica, fused silica glass, clay,
Alumina, calcium carbonate, quartz glass, glass, asbestos, whiskers, gypsum, magnesite, mica, kaolin, talc, graphite, cement, carbonyl iron, ferrite, lead compounds, molybdenum disulfide, zinc white, titanium white, carbon black , silica sand, wollastonite, glass fiber, glass beads, hydrated alumina, chalk powder, aluminum silicate, titanium oxide, etc., and one or more of these can be used in combination. In the composition of the present invention, the [D] component has the following formula: 100×[D]/[A]+[B]+[C]+[D]=40
~
Contains 75% by volume. If it is less than 40% by volume, the coefficient of linear expansion (α) becomes large and the difference in α from the metal insert becomes large, which is one of the causes of resin cracks and element pellet cracks. Also,
When the amount is more than 75% by volume, the fluidity of the material decreases significantly, making it difficult to mold elements, inserts, etc. Further, a catalyst can be added to the resin composition of the present invention for the purpose of promoting the curing reaction. Such catalysts include, for example, tertiary amines such as triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine, dimethylaniline, dimethylaminoethanol,
Examples include oxyalkylamines such as dimethylaminopentanol, amines such as tris(dimethylaminomethyl)phenol, and N-methylmorpholine. Also, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzylmethylpalmitylammonium chloride, allyldodecyltrimethylammonium bromide, benzyldimethylstearylammonium bromide , stearyltrimethylammonium chloride, benzyldimethyltetradecylammonium acetate, and other quaternary ammonium salts. Furthermore, 2-undecylimidazole, 2-methylimidazole, 2-ethylimidazole, 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, 1-azine- 2
There are imidazoles such as -methylimidazole and 1-azine-2-undecylimidazole. Also, triphenylphosphine tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholinetetraphenylborate, pyridinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, 2-ethyl-1. Kalibol salts such as 4-dimethylimidazole tetraphenylborate are useful. One or more of the above-mentioned catalysts can also be used in combination. In addition, if necessary, known flexibilizers, such as polybutadiene, acrylonitrile rubber, butadiene-acrylonitrile copolymers, styrene rubber, polyvinyl acetals, phenoxy resins, may be used in combination with component [C] of the present invention. , diglycidyl ether of dimer acid, etc. can be used. In addition, depending on the use and purpose, fatty acids such as stearic acid, calcium stearate, zinc stearate, and aluminum stearate, waxes, mold release agents such as silicone oil, epoxy silane, vinyl silane, borane compounds,
Already known coupling agents such as alkoxy titanate compounds, antimony, phosphorus compounds,
Known flame retardants such as halogens and halogen-containing compounds can be used. Examples 1 to 9 4,4'-diaminodiphenylmethane (hereinafter
100 parts by weight of DDM (abbreviated as DDM) were separately collected into six reaction vessels, and heated to 90 to 130°C to melt. Maleic anhydride (hereinafter abbreviated as MA) having the molar ratio shown in Table 1 was added to this mixture while stirring. A yellow reaction insoluble material was immediately produced, but when heating was continued for about 30 minutes at 130 to 200°C, the insoluble material gradually dissolved and a transparent brown reaction material was obtained. Next, using predetermined amounts of these reactants, epoxy novolac (manufactured by Ciba Geigy, ECN1273,
Epoxy equivalent 225; hereinafter abbreviated as ECN1273),
Bisphenol A type epoxy (manufactured by Ciel, E _P
1001, epoxy equivalent 475; hereinafter abbreviated as E1001), silicone compound mold release agent (manufactured by Hoechst, Hexist Wax.E, hereinafter abbreviated as Hexist Wax E), coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., epoxy silane KBM403, (hereinafter abbreviated as KBM403),
After blending the filler (fused silica glass powder) and colorant (carbon black) in the prescribed amounts shown in Table 2, the mixture was heated at 70 to 80°C using two rolls with an outer diameter of 8 inches.
The mixture was mixed for 5 minutes to prepare a molding material composition.

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Claims (1)

[Scope of Claims] 1 [A] Polyfunctional epoxy compound [B] (a) A reaction product of an ethylenically unsaturated dicarboxylic acid anhydride or its functional derivative, (b) a polyamine, and [C] Origano A polysiloxane compound, [D] contains an inorganic filler, the content volume % of the [D] inorganic filler, 100D/A+
An epoxy resin composition characterized in that B+C+D is in the range of 40 to 75. 2. The epoxy resin composition according to claim 1, wherein the component [ B ] is a reaction product obtained by subjecting 1 mol of aromatic diamine to a reaction product of maleic anhydride in a ratio of less than 0.6 mol by heating.