JPS6055025A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in rapid curability and suitable for sealing electronic parts, prepared by dispersing an organopolysiloxane in a curable epoxy resin composition containing a combination of an organic acid dihydrazide compound with an organic tert, phosphine compound. CONSTITUTION:A dispersion is formed by mixing 100pts.wt. epoxy resin (e.g., bisphenol A-derived epoxy resin) with 10-80pts.wt. phenolic resin (epoxy resin curing agent, e.g., phenol novolak resin), 0.1-20pts.wt. organic acid dihydrazide (a cure accelerator, e.g., adipic acid dihydrazide), 0.1-20pts.wt. organopolysiloxane of degree of polymerization >=3 (e.g., polydimethylsiloxane), and 0.01- 20pts.wt. organic tert. phosphine compound (e.g., trimethylphosphine).

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to an epoxy resin composition]-1 More specifically,
The present invention relates to an epoxy resin composition that is excellent in heat resistance, crack resistance, moisture resistance, and electrical properties in a well-balanced manner and has fast curing properties.

[Technical background of the invention and its problems]

In recent years, cured resin products made of epoxy resin compositions have come to be widely used in various technical fields because they have excellent electrical properties. In particular, as a sealing material for electronic components that are becoming smaller, thinner, and more dense, it is a material that has a good balance of properties such as heat resistance, crack resistance, moisture resistance, and electrical properties. At the same time, for the purpose of improving industrial productivity, there has been a strong demand in the art for a material that exhibits excellent rapid curing properties without impairing the above-mentioned properties.

BACKGROUND ART Epoxy resin compositions using phenol novolak resin as a curing agent have been popular as encapsulating materials for electronic components such as semiconductors.

In order to improve the crack resistance of the cured product, such resin compositions contain various sintering agents such as polysulfide polymer, polyoxyalkylene ether glycol, polyoxyalkylene glycidyl ether, etc.
However, on the other hand, there was a problem that properties such as the glass transition point, water resistance, and heat resistance of the cured product deteriorated. Furthermore, when a silicone compound is added as a curing accelerator, it is difficult to improve the crack resistance without deteriorating the electrical properties such as high temperature volume resistivity of the cured product.

Furthermore, when adding and blending a curing accelerator such as amines, ibadazole, boron trifluoride-azon complexes, etc., it is possible to increase the quick curing property without reducing the electrical properties of the cured product as described above. It was difficult to improve.

Therefore, regarding epoxy resin compositions, a resin composition that simultaneously has the above-mentioned properties in a well-balanced manner has not yet been obtained.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned problems and to provide an epoxy resin composition that has excellent heat resistance, crack resistance, moisture resistance, and electrical properties in a well-balanced manner, and has excellent fast curing properties. It is in.

[Summary of the invention]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, they have developed an organic acid dihydrazide compound and an organic tertiary hydrazide compound.
We have discovered that the above object can be achieved by dispersing or dispersing co-crosslinking organopolysiloxane in a curable epoxy resin composition using a combination of phosphine compounds,
The present invention has been completed.

That is, the epoxy resin composition of the present invention contains, in parts by weight,
100 parts of epoxy resin; 10 to 80 parts of phenolic resin;
It is characterized by consisting of 1 to 20 parts of organic acid dihydrazide O, 70.1 to 20 parts of organopolysiloxa having a degree of polymerization of 3 or more; and 0.01 to 20 parts of an organic tertiary phosphine compound.

The epoxy resin used in the present invention has 2
Any compound having at least 1 oxirane ring can be used.

Such epoxy resins include, for example, bisphenol A type epoxy resin; bisphenol F type epoxy resin; phenol novolac type epoxy resin; cresol novolac type epoxy resin; alicyclic epoxy resin; triglycidyl isocyanurate, hydantoin epoxy, etc. Complex m-r-poxy resin; hydrogenated bisphenol A type epoxy resin; aliphatic epoxy resin such as propylene glycol-diglycidyl ether, pentaerythritol-polyglycidyl ether; aromatic, aliphatic or alicyclic carboxylic acid; Ebi Kurorhi)” IJ 7 (
! :) Glycidyl ester fJl obtained by reaction
x boxy resin i spiro ring-containing epoxy resin; glycidyl ether type epoxy resin which is the reaction product of an 0-allyl-phenol novolac compound and epichlorohydrin; Examples include glycidyl ether type epoxy resins which are reaction products of bisphenol compounds and epichlorohydrin, as well as those in which these resins are substituted with halogen atoms.

In the present invention, one or more selected epoxy resins from the group consisting of the epoxy resins listed in - are used.

The phenolic resin used in the present invention has two or more phenolic hydroxyl groups in one molecule and is used as a curing agent for epoxy resins. Specific examples of such phenolic resins include novolak-type phenolic resins such as phenol novolak resin, orncresol novolak resin, metacresol novolak resin, tert-butylphenol novolak resin, and nonylphenol novolak resin, resol-type phenolic resins, and the like. , and 1 selected from the group consisting of
A species or two or more species may be used.

The blending amount of the above phenol resin is 10 epoxy resins.
It is preferably io to 80 parts by weight, more preferably 20 to 60 parts by weight, relative to 0 parts by weight. If the amount is less than 10 parts by weight or more than 80 parts by weight, heat resistance, moisture resistance and electrical properties will deteriorate at the same time.

The organic acid dihydrazide used in the present invention is a curing accelerator for a curable epoxy resin using a phenol resin. Such organic dihydrazide compounds include:
Any compound that is normally used as a curing accelerator may be used, such as adipic acid dihydrazide, conolilic acid dihydrazide, fumaric acid dihydrazide,
dimer acid dihydrazide, sepatic acid dihydrazide, azelaic acid dihydrazide, isophthalic acid dihydrazide,
Terephthalic acid dihydrazide, dodecanoic acid dihydrazide, eicozanniic acid dihydrazide, and hexadecanoic acid dihydrazide are praised, and those selected from the group consisting of lal or 2's or more are used.〇The above-mentioned organic acid dihydrazide The blending JiX of the compound is 0.1 to 2 for 1 m part of epoxy resin 1001f.
It is preferably 0 parts by weight, more preferably 0.5 parts by weight.
~5 parts by weight. If the amount is less than 1 part by weight, the curing speed will decrease, while if it exceeds 20 parts by weight,
Heat resistance, moisture resistance, and electrical properties deteriorate. ``The organopolysiloxane used in the present invention is added to improve the cracking resistance and cracking resistance of the cured resin product. Any commonly used organopolysiloxane may be used, such as polydimethylsiloxane, α,ω-dihydroxyboridimethylsiloxane, α,ω-dimethoxyborosiloxane, etc. dimethylsiloxane, polymethylphenylsiloxane,
α,ω-dihydroxypolymethylphenylsiloxane,
α,ω-dimethoxypolymethylphenylsiloxane, dimethylsiloxane/methylvinylsiloxane copolymer,
Dimethylsiloxane/diphenylsiloxane copolymer,
Hydroxy at both ends (dimethylsiloxane/diphenylsiloxane copolymer), methoxy at both ends (dimethylsiloxane/diphenylsiloxane copolymer), polymethylhydrogensiloxane, hydrogen atoms bonded to silicon atoms in polymethylhydrogensiloxane are γ- Examples include polyorganosiloxanes having a +n4 epoxy group substituted with a glycidoxyprobyl group or a 2-(3',4'-epoxycyclohexyl)ethyl group, and one selected from the group consisting of these. Or two or more species are used.

The amount of the organopolysiloxane described above is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than 1 part by weight, the effect of improving crack resistance will be small, while if it exceeds 20 parts by weight, heat resistance, moisture resistance, and electrical properties will deteriorate. The degree of polymerization of the merganoborisiloxane is 3 or more. When the degree of polymerization is less than 3, it is difficult to impart sufficient crack resistance to the resulting cured resin product.

The organic tertiary phosphine compound used in the present invention is a curing accelerator for a post-curable epoxy resin using a phenol resin. The organic phosphine compound may be any compound that is normally used as a curing accelerator, such as trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, )IJ (p-methyl phenyl)
Phosphine, tri(nonylphenyl)phosphine, methyldiphenylphosphine, dibutylphenylphosphine, tricyclohexylphosphine% 112-Bis(diphenylphosphine)ethane, bis(diphenylphosphine)methane, etc., selected from the group consisting of fl, 几One or more types may be used.

The amount of the organic phosphine compound compounded is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than 0.01 parts by weight, the curing speed will decrease, while if it exceeds 20 parts by weight, heat resistance, moisture resistance, and frost characteristics will deteriorate.

In the present invention, if necessary, inorganic fillers, pigments, mold release agents, colorants, flame retardants, coupling agents, rubber plasticizers, thermoplastic resins, glass fibers, anti-aging agents, etc. , may be added and blended as appropriate.

The method for producing the resin composition of the present invention is obtained by applying a commonly used method such as dry kneading, melt kneading or solution kneading using a continuous mixer with a roll, kneader or screw set.

The resin composition of the present invention can be used as a molding compound for compression, transfer, injection, etc. coating materials such as liquid or solution powder,
It can be used in a wide range of molding methods and applications such as botting materials.

EXAMPLES Below, Examples and Comparative Examples of the present invention will be listed and explained in more detail.

[Embodiments of the invention]

Examples 1 to 6 EOCN-102 (manufactured by Nippon Kayaku Co., Ltd., cresol novolak type epoxy resin) was used as the epoxy resin, BRM-558 (manufactured by Showa Union Co., Ltd., phenol novolac resin) was used as the phenol resin, Adipic acid dihydrazide and isophthalic acid dihydrazide were used as organic acid dihydrazide compounds, and T8F-451-50M (manufactured by Toshiba Silicone Corporation, polydimethylsiloxane) and XF-40 were used as organopolysiloxanes.
-1015 (manufactured by Toshiba Silicone Corporation, α,ω-dihydroxypolydimethylsiloxane) and XF-42-21
7 (manufactured by Toshiba Silicone Co., Ltd., dimethylsiloxane 2
-(3',4'-epoxycyclohexyl)ethylmethylsiloxane copolymer), triphenylphosphine was used as the organic tertiary hostuin compound, and the blending amount (parts by weight) shown in the table was 6. Various epoxy resin compositions were prepared. In addition, fused silica glass powder is used as an inorganic filler and carbon black is used as a coloring agent.
H@xist E (manufactured by Hoechst Javan Co., Ltd.) was used as a coupling agent, and A-187 (manufactured by Nippon Unicar Co., Ltd.) was used as a mold release agent, which were further added and blended.

The time (seconds) for gelatinization of the resin composition was measured by a 180° C. hot plate method.

These resin compositions were heated at 175°C for 2 minutes and then further heated at 175°C for 4 hours to obtain cured resins.

The coefficient of linear expansion of the thus obtained cured resin was measured using a thermal dilatometer (DL-1500, manufactured by Shinku Riko Co., Ltd.), and the glass transition point was measured from the bending point. Using a high insulation resistance tester (manufactured by Yokotsutsu Co., Ltd., 4329A),
Volume resistivity was measured at 0°C. Using a thermal shock testing device (one elevator type), a thermal cycle test was conducted in the range of -55 to 150° C., and the number of cycles until a defective rate of 50 pieces was measured. Pressure cutter (Hirata Seisakusho Co., Ltd.)
The water absorption rate was measured after 500 hours at 121° C.

Their pulp is shown in the table along with the blending amount.

Comparative Examples 1 to 4 The organic acid dihydrazide compound, organopolysiloxane, and organic tertiary hostuin compound were not used.
In the same manner as in the example, four types of epoxy resin compositions were
I made an egg.

For these epoxy resin compositions, the curing time, glass transition point, volume resistivity, thermal cycle test, and water absorption were measured in the same manner as in the examples.

The blending amounts and results of the ingredients are shown in the table together with Examples.

〔Effect of the invention〕

As described above, the epoxy resin composition of the present invention has excellent heat resistance, crack resistance, moisture resistance, and electrical properties in a well-balanced manner, and also has excellent rapid curing properties. The value is great.

Claims (1)

[Claims] By weight, 100 parts of epoxy resin + 10 to 80 parts of phenol resin, 0.1 to 20 parts of organic acid dihydrazide, and organopolysiloxane () with a degree of polymerization of 3 or more, 1 to 201 parts by weight.
An epoxy resin composition comprising 0.01 to 20 parts of 1N and an organic tertiary phosphine compound.