JPH02102219A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To form an epoxy resin compsn. tightly adhered to an insert without giving a bad influence caused by an internal stress and having a high glass transition temp. by compounding a polyfunctional epoxy compd. with 1-0- tolylbiguanide as a curing agent. CONSTITUTION:This epoxy resin compsn. contains a polyfunctional epoxy compd. and 1-0-tolylbiguanide. Well-known curing agent, catalyst for acceleration of curing, filler, coupling agent, flame-retardant, etc., can be incorporated in this resin compsn. which can be prepd. by kneading said raw material components at about 70-80 deg.C and can be cured at about 150-200 deg.C in a short time.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition that can be rapidly cured at a temperature of 200° C. or lower to a resin having excellent heat resistance and flexibility.

[Conventional technology]

In the field of electronic components, as the size and weight of electronic components are reduced and reliability increases, efforts are being made to increase the size of semiconductor element pellets and to increase their functionality by combining active elements and passive elements. Therefore, there is a strong demand for materials that have a small effect of stress on inserts such as elements even when the elements are directly molded.

Among the epoxy-based, silicone-based, phenol-based, and allyl ester-based resins that have been conventionally used in molds of electronic parts and electrical equipment such as semiconductors, epoxy resin compositions using phenol novolak resin as a curing agent are
It has the advantage of being well-balanced in adhesion to inserts and electrical properties, making it the mainstream resin for molding.

However, when this type of resin composition is used in the molding of device pellets that do not have a flexible protective coating, it can cause cracking of the pellets, cutting of bonding wires, etc. due to stress on the mold resin insert. The drawback is that aluminum electrodes and bonding wires may be corroded or disconnected due to moisture entering through the adhesive interface due to insufficient adhesion to the metal inserts. be.

[Problem to be solved by the invention]

Therefore, it is necessary to reduce the stress acting on the insert and to make the bond between the insert and the mold resin tight and strong. Specifically, a molding resin that strongly adheres to metals such as gold, aluminum, silver, nickel, and cobalt, and that can be converted into a cured product that has a low modulus of elasticity, a low coefficient of expansion, and a high glass transition temperature. A composition is needed.

[Means to solve the problem]

Addition of a flexibilizing agent may be considered as one means of improving the adhesion of the resin and lowering the elastic modulus. However, this method usually lowers the glass transition point of the cured resin, making it difficult to obtain molded products with high reliability, and has not yet achieved results that meet the demands.

An object of the present invention is to provide a molding material that tightly adheres to inserts without adverse effects caused by internal stress and has a high glass transition temperature. The object of the present invention is to provide a resin composition that can be cured in a short time of ~180 seconds and can greatly contribute to streamlining production.

[Function] The resin composition of the present invention is characterized by containing at least a polyfunctional epoxy compound (A), 1-0-tolylbiguanide m-p 140 to 144°C (manufactured by Irinai Shinko Kagaku Co., Ltd.), a rubber with a molecular weight of 191, and a flowable rubber. It is a composition.

In the present invention, polyfunctional epoxy compounds include, for example, diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,
4-epoxy) cyclohexane carboxylate, 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 resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,3-epoxycyclobentyl,) ether, 2-(3,4- epoxy)cyclohexane-5
, 5-Shilo(3°4-epoxy)-cyclohexane-m-dioxane, bis-(3,4-epoxy-6-methylcyclohexyl)adipate, N,N'-m-phenylenebis(4,5-epoxy) trifunctional epoxy compounds such as -1,2-cyclohexane)dicarboximide, triglycidyl ether of para-aminophenol,
Polyallyl glycidyl ether, 1.3.5-tri(1
,2-epoxyethyl)benzene, 2.2', 4.4
Tri- or higher functional epoxy compounds are used, such as -tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of tzenol formaldehyde novolak, triglycidyl ether of glycerin, triglycidyl ether of 1-limethylolpropane, etc. It will be done.

Next, the resin composition of the present invention includes the above-mentioned 1-0-tolylbiguanide and, for example, epoxy resin, phenol resin,
Copolymers with polyurethane resins, diallyl phthalate resins, triallyl isocyanurate resins, etc. can also be used.

Further, a conventionally known curing agent can also be used in combination with the epoxy resin composition of the present invention. They are: Hiki Kakiuchi: Epoxy Resin (published September 1970), pages 109-149, Lee, Neville: EpoxyResin
s (MCGraw-Hill Book Compa
ny Inc: NevYork, published in 1957)
Pages 63-141, P, E.

Written by Brunis: Epoxy Re5ins Tec
hnology (Interscience Pub
lishers, New York, 1968), pages 45 to 111, such as aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, and carboxylic acid anhydrides. , aliphatic and aromatic boamide oligomers and polymers, trilinear boron-amine complexes, synthetic resin initial condensates such as phenolic resin, melamine resin, urea resin, urethane resin, etc., dicyandiamide, carboxylic acid hydrazide, polyamino There are maleimides, etc.

One or more types of these curing agents can be used depending on the use and purpose.

Furthermore, in the present invention, various catalysts can be added to promote the curing reaction of the composition containing these three components, and examples of the catalyst include triethanolamine, triethanolamine,
Tertiary amines such as tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine and dimethylaniline, oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol, and tris(dimethylaminomethyl)phenol; , methylmorpholine, and other amines can be applied.

For the same purpose, as a catalyst, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium bromide, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzylmethylbalmitylammonium chloride, allyldodecyltrimethylammonium bromide,
benzyldimethylstearylammonium bromide,
Quaternary ammonium salts such as stearyltrimethylammonium chloride and benzyldimethyltetradecylammonium acetate can be applied, and 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
- Imidazole compounds such as phenylimidazole, 1-azine-2-methylimidazole and 1-azine-2-undecylimidazole, or triphenylphosphine tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholinetetraphenylborate, pyridine Tetraphenylboron salts such as tetraphenylborate 2-ethyl-4-methylimidazole tetraphenylborate and 2-ethyl-1,4-dimethylimidazole tetraphenylborate are useful.

Two or more of the above catalysts can also be used in combination, and the amount thereof is as follows:
It may be used in a weight ratio of 0.01 to 20.

The epoxy resin composition of the present invention may also include, for example, calcium carbonate, silica, alumina, titania, aluminum hydroxide, aluminum silicate, zirconium silicate, zircon, glass, talc,
Powders and short fibrous fillers such as mica, graphite, aluminum, steel, and iron, fatty acids, mold release agents such as waxes, epoxy silane, vinyl silane, borane compounds, and
Coupling agents such as alkyl rapeseed-1-based compounds and flame retardants such as antimony and phosphorus compounds and halogen-containing compounds can be added.

The resin composition of the present invention can be produced by heating (
It is prepared by kneading (about 70-80°C). In addition, if the component compound is solid, after pulverizing it,
They can also be blended by a triblend method of mixing. The resulting composition can be cured in a short period of time at temperatures of about 150-200°C.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

<Examples 1 to 3> To 100 parts by weight of epoxy resin ECN1273 (manufactured by Ciba Corporation, epoxy equivalent weight 225), phenol-formaldehyde novolac type resin (manufactured by Hitachi Chemical Co., Ltd. HP-607N) 6
0 parts by weight of 1-0-tolylbicuanide, 3 parts by weight of triethylaminete) raphenylbore-1- (abbreviation TEA-K) as a catalyst, 2 parts by weight of stearic acid as a mold release agent, cup 1 part by weight of epoxy silane KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a ring agent and 1 part by weight of carbon black as a coloring agent were blended, roll-kneaded at 70 to 80°C for 7 minutes, and then coarsely ground to obtain the desired product. A resin composition was obtained.

This material was molded at 180° C. for 2 minutes at 70 kg/a# (71 conditions), and the cured resin specimens were tested for heat resistance, moisture resistance, etc. The results are shown in Table 1. Moisture resistance test (PCT) The sample was left in superheated steam at 120°C and 2 atm for a predetermined time.For the resin sample, the moisture resistance was evaluated based on the volume resistivity after leaving and the waveform of the insulation resistance test. M
The O8LSI sealed sample was evaluated based on the PCT time that elapsed until its function became malfunctioning. The time also serves as a measure of the adhesion between the resin and the insert.

Table 1 <Examples 4 to 12> As the epoxy resin, ECN1273 or EPl
ool (bisphenol A epoxy equivalent manufactured by Shell Co., Ltd., 450-55o), and phenol formaldehyde novolac resin HP = 607 N, 1-0
- Tolylbiguanide was blended in the prescribed amounts shown in Table 2, and different formulations were applied.

To each of these formulations, 2 parts by weight of stearic acid as a mold release agent, 1 part by weight of a coupling agent KBM-303 (manufactured by Shin-Etsu Chemical Co., Ltd.), and carbon black as a coloring agent were added, and a resin composition was prepared in the same manner as in Example 1. I prepared something.

Using these compositions, a MO8LSI semiconductor device was molded at 180° C. for 2 minutes at 70 kg/d, PCT was performed, and the PCT time until the semiconductor function was impaired was measured. The results are shown in Table 2. For comparison, in an example in which no polysulfide polymer was added, the semiconductor function deteriorated after 50 hours of PCT.6 [Effects of the Invention] According to the present invention, 1-Q was used as a curing agent for epoxy compounds.
- A new epoxy composition employing tolylbiguanide and capable of producing a cured product with excellent heat resistance, moisture resistance, and corrosion resistance was obtained.

Claims (1)

[Claims] 1. An epoxy resin composition containing a polyfunctional epoxy compound and 1-0-tolyl biguanide.