JPH02123123A - Epoxy resin composition and use thereof - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for coating and sealing semiconductor devices, providing cured molded articles having excellent heat resistance, flexibility and adhesivity, containing a polyfunctional epoxy compound, hydroxy- vinyl-quinoline, etc. CONSTITUTION:The aimed composition containing (A) a polyfunctional epoxy compound (e.g., diglycidyl ether of bisphenol A) and (B) 8-hydroxy-vinyl-quinoline shown by formula I, etc., and/or a quinaldine derivative shown by formula II, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition capable of providing a cured molded product with excellent heat resistance, flexibility, and adhesiveness.

[Conventional technology]

In the field of electronic components, semiconductor element pellets are becoming larger as they become smaller, lighter, and more reliable.

Multifunctionality is being sought 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.

(Japanese Unexamined Patent Publication No. 62-292828) Among the epoxy, silicone, phenol, and allyl ester resins that have been conventionally used for molding electronic parts such as semiconductors and electrical equipment, phenol novolac resin is The epoxy resin composition used as a curing agent is
It has the advantage of being well-balanced in adhesion to inserts and electrical properties, so it has become the mainstream resin for molding.

However, when this type of resin composition is used for molding into an element pellet 1 that is not provided with a flexible protective coat, cracks in the pellet, cutting of bonding wires, etc. occur in the insert 1 of the mold resin. corrosion of the aluminum electrodes and bonding glands due to moisture entering from the bonding interface due to failure due to stress on metal inserts 1 to 1, or due to insufficient adhesion to the metal inserts It also has the disadvantage of causing wire breakage.

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.

[Problem to be solved by the invention]

Addition of a flexibilizing agent can be considered as one means of improving the density and lowering the elastic modulus of the resin. However, this method usually lowers the glass transition point of the cured resin, making it difficult to obtain a highly reliable molded product, and has not yet achieved results that meet the requirements.

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 30 to 180 seconds and can greatly contribute to streamlining production.

[Means to solve the problem]

The resin composition of the present invention is characterized in that it contains at least a polyfunctional epoxy compound (A), 8-hydroxy-5-vinyl-quinoline, and/or a quinaldine derivative (B).

In the present invention, the polyfunctional epoxy compound (A) is, for example, diglycidyl ether of bisphenol A, butadiene dieboxide, 3,4-epoxycyclohexylmethyl-
(3,4-epoxy)cyclohexane-1
-, vinylcyclohexane dioxide, 4,4'-di(
], ]2-epoxyethyl diphenyl ether, 4.4
' −(],.

]2-epoxyethylbiphenyl, 2,2-bis(3,
4-Epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,3-epoxycyglobentyl)ether, 2-(3,4epoxy)cyclohexane -5,5-
Suhiro (3,4-epoxy)-cyclohexane-In-
Trifunctional epoxy compounds such as dioxane, bis-C3,4-epoxy-6-methylcyclohexyl)adipate, N,N'-m phenylenebis(4,5-epoxy-1,2-cyclohexane)dicarboximide, para-amino 1-liglycidyl ether of phenol, polyallyl glycidyl ether, l,3,5-tri(1,2-
epoxyethyl)benzene, 2,2',4,4'-te1helagrin1-xybenzophenone, tetraglycidoxyte1-raphenylethane, polyglycidyl ether of zenol formaldehyde novolac, triglycidyl ether of glycerin ,]-Tri- or higher-functional epoxy compounds such as triglycidyl ether of trimethylolpropane are used.

Next, examples of 8-hydroxy-5-vinyl-quinoline and quinaldine derivatives include those shown below.

H H Quinoline Quinoline polymer (MackromoL, ChemJ4g, 19 (19
There are quinaldine derivatives such as 71)). Furthermore, copolymers of these with, for example, epoxy resins, phenol resins, polyurethane resins, diallyl phthalate resins, 1-lylylisocyanurate resins, polystyrene, polyacrylate-1, etc. can also be used.

Furthermore, a conventionally known curing agent can also be used in combination with the epoxy resin composition of the present invention. They are: Hiroshi Kakiuchi: Epoxy Resin (published September 1970), pages 109-149, Lee, Neville: EpoxyItesi
ns(Me Graw-11i11 Book Com
pany Inc: New York, published in 1957)
63-14], Page, P.E.

Written by Brunis: Epoxy Re5ins Tech
nology(Interscie-nce Publ.
ishers, New York, 1968) 4
Compounds described on pages 5 to 111, for example,
Aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, carboxylic acid anhydrides, aliphatic and aromatic polyamide oligomers and polymers, trilinear boron-amine complexes, phenols resins, synthetic resin initial condensates such as melamine resins, urea resins, and urethane resins, as well as dicyandiamide, carboxylic acid hydrazides, polyaminomaleimides, and poly-P-vinylphenols.

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

[Effect]

Furthermore, depending on the purpose and use, a metal chelate compound or a metal alcoholate compound can be used in combination with the composition of the present invention. For example, a metal consisting of at least one metal selected from aluminum, titanium, tin, zinc, lead, and zirconium, and a ligand selected from β-dikelones and β-keto acid esters. Chelating compounds are used. For example, tris(2,4-pentanedionate)aluminum(2,4-pentanedionate)
1-) Bis(ethyl acetoacetate 1-)aluminum, 1-lis(ethyl acetate 1-acetate)aluminum, bis(ethylacet I/acetate 1-) titanium, tetrakis(2,4-pentanediona-1-)titanium, diptylbis (2,4-pentanediona-1-)tin, dimethylbis(ethylacetoacetate)tin, bis(2,4-pentanedionato)zinc, bis(ethylacetoacetate-1-) button, tetrakis(ethylacetoacetate-1-) acetate) zirconium, etc. Also, aluminum, titanium,
An alcohol-1-based compound of at least one metal selected from tin, zinc, lead and zirconium.

Used as an ingredient. Such alcoholate compounds include, for example, aluminum methyl 1-, aluminum ethylene 1-, aluminum propylate, aluminum lobutyrate, mono-5eC-butoxyaluminum, di-mie propylate, ethylaluminum, Diethylate, ethylaluminum, di-j-propylate, titanium, tetra-j-propylene-1-1tin, tetra-1-propylate, zinc, di-j-propylate.

Button, Jimmy Proville 1~, Zirconium, Tetra
There are 1-propylates and the like, and they can be used alone or in combination of two or more, and some or all of them may be used as a prepolymer polycondensed.

Furthermore, in the present invention, various catalysts can be added for the purpose of promoting the curing reaction of the composition, and these catalysts include, for example, triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, and tetramethylhexanediamine. , triethylenediamine, and tertiary amines such as dimethylaniline, oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol, and tris(dimethylaminomethyl)
Phenol and amines such as methylmorpholine can be used.

In addition, for the same purpose, as a catalyst, for example, cetyltrimethylammonium promy 1-, cetyl 1-helimethylammonium chloride, dodecyltrimethylammonium iodide, 1-limethyltodecylammonium glolite, benzyldimethylteI-radecylammonium Quaternary ammonium salts such as chloride, pencilmethyl palmitylammonium chlorite, allyldodecyltrimethylammonium bromide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride, and benzyldimethyltetradecylammonium acetate can be applied. Furthermore, 2-undecylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, ], -butylimidazole, 1-propyl-2-
Methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,
1-cyanoethyl-2-undecylimidazole, 1-
Cyanoethyl-2-phenylimidazole.

1-Azine-2-methylimidazole and 1-azine-
imidazole compounds such as 2-undecylimidazole,
Alternatively, triphenylphosphite 1~roughenylborate, triethylaminetetraphenylborate, N
-Methylmorpholinetetraphenylborate 1-, pyridinete-raphenylborate 2-ethyl-4-methylimidazoletetraphenylborate, and 2-ethyl-1,4dimethylimidazoletetraphenylborate 1
Tetraphenylboron salts such as those of He et al. are useful.

Two or more of these catalysts can also be used in combination, and the amount used may be in the range of 0.01 to 20 in weight ratio to the polyfunctional epoxy compound (A) lOO.

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, copper, and iron, fatty acids, mold release agents such as waxes, epoxy silane, vinyl silane, borane compounds, and
Camping agents such as alkyl titanate-1 compounds, as well as flame retardants such as antimony and phosphorus compounds and halogen-containing compounds can be added.

The resin composition of the present invention is prepared by kneading these components by heating (about 70 to 80°C) using a roll, a kneader, a co-kneader, a Henschel mixer, or the like. Prepared by two. Furthermore, when the component compounds are solid, they can also be blended by a tri-blend method in which they are pulverized and then mixed. 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> Epoxy resin E CN1273 (manufactured by Ciba Co., Ltd., epoxy equivalent weight 225), phenol-formaldehyde novolac type resin (manufactured by Hitachi Chemical Co., Ltd. HP-607N)
) 60 parts by weight, a predetermined amount of 8-hydroxy-5-vinyl-quinoline, 3 parts by weight of triethylaminete 1-raphenylbore-1- (abbreviation 1'E A-K) as a catalyst, 2 stearic acid as a mold release agent. Parts by weight, 1 part by weight of epoxy silane KI3M-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and 1 part by weight of carbon blank as a coloring agent were blended, and after roll kneading at 70 to 80°C,
The target resin composition was obtained by coarse pulverization.

The cured resin specimens obtained by molding this material at 180° C. for 2 minutes + 70 kg/7 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 period of time. Moisture resistance of the resin samples was evaluated from the volume resistivity after standing and the waveform of the insulation resistance test. In addition, semiconductor M
The O3LSI 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. 4
50 to 550), and to this, phenol formaldehyde novolac resin HP-607N, 8-hydroxy-5-vinyl-quinoline polymer (number average molecular weight: 32
00) and quinaldine derivatives were blended in the prescribed amounts shown in Table 2 to prepare different formulations. 2 parts by weight of stearic acid as a mold release agent and KBM-303 ((
A resin composition was prepared in the same manner as in Example 1 except that 1 part by weight (manufactured by Goetsu Kagaku Co., Ltd.) of carbon black was added as a coloring agent.

Using these types of compositions, a MO5LSI semiconductor element was molded under the conditions of 180'C, 2 minutes, and 70 kg/crJ, and PCT was performed. I measured it. The results are shown in Table 2. For comparison, 8-hi-1- was added to the composition of Example 4.
In the example in which Roxy-5-vinyl-quinoline was not added, the semiconductor function became defective after 500 hours of PCT.

<Examples 123 to 15> To 100 parts by weight of epoxy resin DEN438 (manufactured by Dow Corning, epoxy equivalent weight 176 to 181), 50 parts by weight of p-alkyl substituted phenol/formaldehyde novolasic type resin Hytanol 5500 (Hitachi Chemical Co., Ltd.? J,) was added. ．．
60.80 parts by weight, 10 parts by weight of polyvinyl butyral,
3 parts by weight of hexamethylenetetramine as a catalyst and T E
A-K ], , 5 parts by weight As a filler, fused silica glass powder (RD-8, manufactured by Ryumori) was added to the resin system,
60% by volume, 1 part by weight of an alkoxy titanate compound as a coupling agent, and 2 parts by weight of carbon black as a coloring agent.
Add 30 parts by weight of 1-roxy-5-vinylquinoline polymer (number average molecular number: 1500) and heat at 50 to 60°C.
After roll kneading for 10 minutes, the mixture was coarsely ground to obtain the desired resin composition.

Using the above composition, heat the MO5LSI for calculators at 180°C.
, molded for 1.5 minutes at 70r/d, and then
A molded product was obtained.

Table 3 shows the results of PCT.

Table 3 This can be said to be a major feature of the epoxy resin composition of the present invention, which has excellent adhesion to inserts such as semiconductor chips and lead wires. In other words, this effect is thought to be due to the ability of the curing agent to form chelates with metals, and L
Not limited to SI encapsulant.

It has the effect of improving performance in a wide range of fields such as adhesives, paints, and Cu lamination.

〔Effect of the invention〕

Claims (3)

[Claims] 1. An epoxy resin composition containing a polyfunctional epoxy compound, 8-hydroxy-5-vinyl-quinoline and/or a quinaldine derivative. 2. A semiconductor device coated and/or sealed with the resin composition according to claim 1. 3. A multilayer wiring board comprising the resin composition according to claim 1.