JPS6112724A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved heat resistance, crack resistance, electrical characteristics in good balance, obtained by blending an epoxy resin with a phenolic resin, an organic acid dihydrazide, an organopolysiloxane, a salt of diaza-bicycloundecene, etc. CONSTITUTION:(A) 100pts.wt. epoxy resin is blended with (B) 10-80pts.wt. phenolic resin, (C) 0.1-20pts.wt. organic acid dihydrazide, (D) 0.1-20pts.wt. organopolysiloxane having >=3 polymerization degree, (E) 0.1-10pts.wt. compound selected from a group consisting of 1,8-diaza-bicyclo(5.4.0)undecene-7, its salt, an imidazolin, an imidazole, a secondary and a tertiary amines.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition with excellent heat resistance and crack resistance.

[Technical background of the invention and its problems] In recent years, cured resins made of epoxy resin compositions,
1. It has come to be widely used in various technical fields because of its electrical properties. In particular, as encapsulating materials for electronic components, which are trending toward smaller size, thinner layers, and higher density, it is important to develop materials that have a good balance of properties such as heat resistance, crack resistance, moisture resistance, and electrical properties. It was strongly requested in the industry.

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.

Such resin compositions are used with various flexibilizing agents, such as liquid rubber, for the purpose of improving the crack resistance of the cured product.

Elastomers such as polysulfide polymers.

Polyoxydiallylkylene glycidyl ether and the like are added and blended, but on the other hand, there is a problem in that properties such as the glass transition point, water resistance, or heat resistance of the cured product are reduced. In addition, when adding and blending silicone compounds,
It has been difficult to reduce stress and improve crack resistance without reducing mechanical properties such as bending strength of the cured product.

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.

[Object 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 and crack resistance in a well-balanced manner.

[Summary of the Invention] As a result of extensive studies to solve the above-mentioned problems, the present inventors have discovered an organic acid dihydrazide compound, 1,8-diaza-bicyclo(54,0)undecene-7 or its salts, and imidazoline. By dispersing or dispersing co-crosslinking the organopolysiloxane in a phenol-curable epoxy resin composition using a combination of at least one compound selected from the group consisting of amines, imidazoles, and secondary to tertiary amines, the above-mentioned The inventors discovered that the object can be achieved and completed the present invention.

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;
01 to 20 parts of organic acid dihydrazide; 0.1 to 20 parts of organopolysiloxane with a degree of polymerization of 3 or more; i.8-diaza-
At least one selected from the group consisting of bicyclo(5.4.0) undecene-7 or its salts, imidazolines, imidazoles, and secondary to tertiary amines.
It is characterized in that it consists of 0.1 to 10 parts of a seed 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; heterocyclic epoxy resin; hydrogenated bisphenol A5 epoxy Resin; aliphatic epoxy resin, nigericidyl ester type epoxy resin, spiro-embedded epoxy resin, glycidyl ether type epoxy resin, etc., and also those in which these resins are substituted with halogen atoms are also included. In the present invention, One or more epoxy resins selected from the group consisting of the above-mentioned epoxy resins are used, and particularly preferred representative examples include phenol novolac type epoxy resins and cresol novolac type epoxy resins.

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, orthocresol novolak resin, metacresol novolak resin, fert-butylphenol novolak resin, and nonylphenol novolac resin, resol-type phenolic resin, etc. 1 selected from the group consisting of these
A species or two or more species may be used.

The amount of phenol resin mentioned above is 1 epoxy resin.
It is preferably 10 to 80 parts by weight, more preferably 20 to 60 parts by weight, based on 00N parts. If the blending amount is less than 10 parts by weight or 80 parts by weight,
Heat resistance, moisture resistance and electrical properties deteriorate at the same time.

The organic acid dihydrazide used in the present invention is a flexible curing agent based on a curable epoxy resin using a phenolic resin. Such an organic acid dihydrazide compound may be any compound that is normally used as a curing accelerator, such as adipic acid dihydrazide, succinic acid dihydrazide, fumaric acid dihydrazide, dimer acid dihydrazide, and cepatic acid dihydrazide. , azelaic acid dihydrazide, in7tal acid dihydrazide,
Examples include terephthalic acid dihydrazide, and one or more selected from these may be used.

The amount of the organic acid dihydrazide compound described above is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than 0.1 parts by weight, mechanical properties such as strength and crankability will deteriorate, while if it exceeds 20 parts by weight, heat resistance, moisture resistance, and electrical retention will deteriorate.

The organopolysiloxane used in the present invention is
It is added to improve the crack resistance of cured resin products. Such organopolysiloxane may be any commonly used organopolysiloxane, such as polydimethylsiloxane, α, ω, etc.
-dihydroxypolydimethylsiloxane, α,ω-dimethoxypolydimethylsiloxane, polymethylphenylsiloxane, α,ω-dihydroxypolymethylphenylsiloxane, α,ω-dimethoxypolymethylphenylsiloxane, dimethylsiloxane/methylvinylsiloxane copolymer, Dimethylsiloxane/ginenylsiloxane copolymer 1 Hydroxy at both ends (dimethylsiloxane/diphenylsiloxane copolymer) 9 Methoxy at both ends (dimethylsiloxane/diphenylsiloxane copolymer), polymethylhydrodiene siloxane, polymethylno 1
The hydrogen atom bonded to the silicon atom of hydrodiene siloxane is a γ-glycidoxyprobyl group or 2-(3:4'-
Examples include polyorganosiloxanes having epoxy groups substituted with epoxycyclohexyl)ethyl groups, and one or more than 12 types selected from the group consisting of these are used.

The amount of the organopolysiloxane to be blended is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the epoxy resin. If the blending amount is less than 0.1 part by weight, the effect of improving crack resistance will be slightly less than -i, and if it exceeds 2°,
Heat resistance, moisture resistance, and electrical properties deteriorate. Further, the degree of polymerization of the organosiloxane 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.

1,8-diaza-bicyclo(
5.4.0) Undecene-7 (hereinafter referred to as DBU) or its salts, imidazolines, imidazoles, and secondary to tertiary amines can accelerate the curing of curable epoxy resin systems using phenolic resins. Examples of the salts of 0DBU, which are both a curing accelerator and a curing accelerator for the organic acid dihydrazide used in the present invention, include phenol salts, 2
-Ethylhexanoate, carbonate, etc. are preferably used. As the imidazolines, 2-phenylimidazoline, 2-phenylimidazoline,
2-undecylimidazoline, 2-heptadecyl imidazoline, 2-ethylimidazoline.

Examples include 2-isopropylimidazoline, 2,4-dimethylimidazoline, and 2-phenyl-4-methylimidazoline.

In addition, as imidazoles, 2-methylimitasole, 2-phenylimitasol, 2-heptadecyl imidazole, 2-undecylimidazole, 2-ethyl-
4-Methylimidazole.

2-ethyl-4-methylimidazole, 2-phenyl-
Examples include 4-methylimidazole.

In addition, examples of secondary amines include diptylamine, jetanolamine, piperidine, dibenzylamine, and pyrrolidine, and examples of tertiary amines include tributylamine, morpholine, N,N'-dimethylallylamine,
Examples include N,N'-dimethylgropanolamine, N-methylpiperidine, and 2,4,6-dorisdimetelaminomethylphenol.

Combination of the above-mentioned curing accelerator f! Niha, epoxy resin 10
It is preferable that the amount is 0.1 to 10 parts by weight relative to 0 parts by weight (<, more preferably 02 to 5 parts by weight). If more than 10 overlapping parts are used, heat generation during curing becomes too intense, resulting in poor crack resistance, moisture resistance, and electrical properties of the cured product.

The present invention further includes an inorganic filler, an organic filler, a pigment, a mold release agent, a coloring agent, a flame retardant, a coupling agent, a thermoplastic resin, and a glass fiber, if necessary.

There is no problem in adding an anti-aging agent or the like 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, solution, powder, etc.
It can be used in a wide range of molding methods and applications such as botting materials.

[Examples of the Invention] Below, Examples and Comparative Examples of the present invention are listed and explained in more detail.

Examples 1 to 5 EOCN-102 (manufactured by Nippon Kayaku ■, cresol novolac type epoxy resin) was used as the epoxy resin, and BRM-558 (phenol novolac resin, manufactured by FF[0 Union Co., Ltd.) was used as the phenol resin. Adipic acid dihydrazide was used as the organic acid dihydrazide compound, and T8F- was used as the organopolysiloxane.
451-105 (manufactured by Toshiba Silicone ■, α.

W-dihydro n-xypolydimethylsiloxane) and XF-
42-217 (manufactured by Toshiba Silicone ■, dimethylsiloxane/2-(a:4'-epoxycyclohexyl)ethylmethylsiloxane polymer), and as a curing accelerator: 1) BU, 2-phenylimidazoline.

2-Methylimidazole, phenylethylamine.

Using tri-n-butylamine, five types of epoxy resin compositions were prepared in the amounts (parts by weight) shown in the table.

In addition, fused silica glass powder is used as the inorganic filler.
Carbon black was used as a coloring agent, Hexist B (manufactured by Hoechst Japan Co., Ltd.) was used as a mold release agent, and A-187 (manufactured by Nippon Unicar Co., Ltd.) was used as a coupling agent, and these were further added and blended.

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 pure expansion coefficient of the cured resin product thus obtained was measured using a thermal dilatometer (manufactured by Shinku Riko ■, DL-1500), and the glass transition point was measured from this bending point. -55 to 200 using a thermal shock test device (elevator method)
A heating and cooling cycle test was conducted in the range of 0.degree. C., and the number of cycles until 50% defective rate was measured.The results are shown in the table together with the blending amount.

Comparative Examples 1 to 3 Three types of epoxy resin compositions were prepared in the same manner as in Examples, except that the organic acid dihydrazide compound and organopolysiloxane were not used.

Regarding these epoxy resin compositions, the glass transition point and number of cooling/heating cycles were measured in the same manner as in the examples.

Their blending amounts and results are shown in the table together with Examples.

Margins below [Effects of the Invention] As detailed above, the epoxy resin composition of the present invention has excellent heat resistance and crack resistance at the same time in a well-balanced manner, and its industrial value is great.

Claims (1)

[Claims] 1. By weight, 100 parts of epoxy resin; 10 to 80 parts of phenolic resin; 0.1 to 20 parts of organic acid dihydrazide; 0.1 to 20 parts of organopolysiloxane with a degree of polymerization of 3 or more;
1,8-diaza-bicyclo(5.4.0) undecene-
7 or its salts, imidazolines, imidazoles, and secondary to tertiary amines.