JPH02117913A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition suitable for semiconductor sealing and matrix of composite material, providing a cured material having excellent heat resistance, water resistance, toughness, etc., by blending a specific epoxy resin with a curing agent. CONSTITUTION:(A) an epoxy resin shown by formula I [A and B are group shown by formula II or III (R is H or lower alkyl; X is bifunctional group) and Anot equal to B; n is 0-10] is blended with (B) a curing agent (e.g., phenol novolak, phthalic anhydride or methylenedianiline) in a ratio of preferably 0.9-11 (molar ratio of functional group) to give the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition that provides a cured product, and more particularly to an epoxy resin composition that is suitably used for semiconductor encapsulation and as a composite material matrix.

[Prior Art] Epoxy resins are used in a wide range of industrial fields such as adhesives, paints, laminated materials, and electrical insulation materials due to their excellent heat resistance, mechanical strength, and insulation properties.

In recent years, especially with advances in the field of advanced materials, higher performance epoxy resins have been required. For example, epoxy resins used as composite matrix resins used in the aerospace industry are strongly required to have high toughness and high water resistance.
In the field of electronic materials, for example, in pace epoxy resins used as semiconductor sealing materials, crack resistance is strongly desired as semiconductor packages become larger in area and thinner.

By the way, conventionally known epoxy resins of this type include those obtained by curing bisphenol A type epoxy resin and phenol novolac type epoxy resin with phenol novolac, acid anhydride compounds, polyamine compounds, etc. Publication No. 1983-218.725, etc.).

However, the cured products of these epoxy resins all lack toughness, and especially those with increased crosslink density and heat resistance have extremely low toughness.

[Problems to be Solved by the Invention] Therefore, the present inventors have conducted intensive studies to maintain the heat resistance of cured epoxy resin products and improve their toughness. They have discovered an epoxy resin composition that provides a cured product with much higher toughness than conventional epoxy resins, and have arrived at the present invention.

[Means for Solving the Problems] That is, the present invention provides - Narrowing down (1) (wherein A and 8 are represented by the following formula (a) or (b), and A/ = 8, n is a rational number from 0.1 to 10) and a curing agent.

(However, R can be hydrogen or a low alkyl group) Formula (b)
-o-o-xQo-(b) (where, ) or (
b), but since A≠8, eight is (
When a), 8 is the formula (b), and when 8 is the formula (b), B is the formula (a). The former combination is preferred.

In formula (a), the substituent R is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

Furthermore, in formula (b), X is a divalent group, preferably -C112-1-C(CH3)2-1.

In general formula (1), n indicates the average degree of polymerization, and its value is in the range of 0.1 to 10.

The value of n greatly influences the melt viscosity and softening point of the composition according to the present invention, and is appropriately selected depending on the purpose and use to which the epoxy resin composition of the present invention is to be applied.

The epoxy resin represented by the general formula (1) of the present invention is synthesized, for example, by the following method.

That is, an epoxy compound (2) represented by the following formula (2) (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and an epoxy compound (2) represented by the following formula (3) % formula % (3) bisphenol compound and the molar ratio ((a)
/(b) ) 1 , 1 = 11 (DKe'JIJ
``'CaCa Chorus Reaction 6゜ At this time, in order to accelerate the reaction, it is necessary to use amine compounds, isidabures, organic bosphines, etc. as catalysts. 70 to 160'C is suitable as the reaction temperature. In addition, an appropriate solvent may be used during this reaction. Examples of this solvent include hydrocarbon solvents such as benzene, toluene, and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. is preferred.

Further, as the curing agent used in the present invention, any curing agent that is generally used as a curing agent for epoxy resins, such as polyhydric phenol type, acid anhydride type, and amine type, can be used. Examples of the polyhydric phenol curing agent include phenol novolak, polyvinylphenol, etc., and examples of the acid anhydride curing agent include phthalic anhydride, delahydrophthalic anhydride, hexahydrophthalic anhydride, and trimeritic anhydride. Examples of the curing agent include medilene dianiline, diaminodiphenyl ether, diaminodiphenyl sulfone, and the like.

The blending ratio of the above-mentioned epoxy resin and curing agent is such that the molar ratio of their functional groups is usually in the range of 0.7 to 1.3, preferably 0.9 to 1.3.
1.1.

In the epoxy resin composition of the present invention, 2
- Curing of imidazoles such as methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, and 2-phenylimidazole, amines, and organic bosphines represented by trinoenylphosphine, etc. Accelerators, various waxes, lubricants such as higher fatty acids or their calcium salts, surface treatment agents such as silane coupling agents, and inorganic fillers such as silica, alumina, glass fiber, and talc can be blended.

The epoxy resin composition of the present invention is prepared by blending the epoxy resin represented by the above-mentioned (1) with a predetermined curing agent in a predetermined ratio, and adding various additives as necessary to the coating. It is prepared by uniformly mixing and kneading using a mixer, roll, kneader, or other means.

[Examples] The present invention will be specifically described below based on Examples and Comparative Examples.

Example 1 4.4'-dihydroquine-3,3',5,5'-tetramethylbiphenyl diglycidyl ether 2409 and 9.
9-bis(4-hydroxyphenyl)fluorene 56g
Melt and mix at 150'C, add trinonylphos 7
In 1 gwo) Jtlt, 150'CT'3 hours reaction, epoxy resin 19. The epoxy equivalent of this epoxy resin was 317, and the softening point was 82°C.

100 g of the epoxy resin thus obtained, phenol novolak (phenol equivalent! 104, softening point 70°C)
)33g and triphenylphosphine 1°39 to 100g
The mixture was melt-kneaded at 150° C. for 14 minutes, pulverized, and then truncate-molded at 150° C. for 4 minutes to prepare a test piece. Using this test piece, the glass transition point, fracture toughness, and water absorption were measured. The results are shown in Table 1.

The glass transition point was measured using a thermomechanical analyzer at 7℃/
The temperature was measured at a temperature increase rate of min. In addition, fracture toughness is reported in Journal of Material Science, Vol. 21, No. 246.
It was measured according to the method described on page 2 (1986).

Furthermore, the water absorption rate is 100% in water vapor at 133°C and 3 atm.
It was determined by absorbing moisture for a period of time.

Example 2 4.4"-dihydroxy-3,3°,5.5'-tetramethylbiphenyl diglycidyl ether 2409.9
゜9-bis(4-hydroxyphenyl)fluorene 7
The reaction was carried out in the same manner as in Example 1 except that the epoxy resin was changed to 53 to obtain an epoxy resin having an epoxy weight of N384 and a softening point of 100°C.

Using phenol novolak (phenol equivalent: 104, softening point: 70°C) 279 as a curing agent for the epoxy resin 1009, test pieces were prepared in the same manner as in Example], and the glass transition point, fracture toughness, and water absorption were determined. The rate was measured. The results are shown in Table 1.

Example 3 240 g of 9.9-bis(4-hydroxyphenyl)fluorenedi glycidyl ether, 30y of 4,4°-dihydroxybiphenyl and 1.0g of trinoenylphosphine
was dissolved in 20 Od of methyl isobutyl ketone and reacted under heating and reflux for 6 hours, and then the solvent was distilled off under reduced pressure to obtain 1 q of epoxy resin. The epoxy equivalent of the 1q epoxy resin was 370, and the softening point was 123°C.

For 100g of epoxy resin obtained in this way,
Phenol novolac (phenol equivalent ω1) is used as a curing agent.
04, softening point 70° C.), a test piece was prepared in the same manner as in Example 1, and the glass transition point, fracture toughness, and water absorption were measured. The results are shown in Table 1.

Example 4 Bisphenol A diglycidyl ether 240J, 4.
Using 60 g of 4''-dihydroxybiphenyl and 1.C) g of triphenylphosphine, an epoxy resin was prepared by reacting in the same manner as in Example 3. The epoxy equivalent of the 1q epoxy resin was 477, and the softening point was is 79℃
Met.

For the epoxy resin 1007 obtained in this way,
Phenol novolac (phenol/m1) as a curing agent
A test piece was prepared in the same manner as in Example 1 above using 22 g of 04, softening point 70°C), and the glass transition point, fracture toughness, and water absorption were measured. The results are shown in Table 1.

Example 5 240 g of 4.4'-dihydroxy-3,3',5.5'-tetramethylbiphenyl diglycidyl ether and 4,
107 g of 4°-dihydroxydiphenyl sulfone was reacted in the same manner as in Example 3 to prepare epoxidized ff1405 and an epoxy resin having a softening point of 90°C.

Test specimens were prepared in the same manner as in Example 1 using 26 g of phenol novolac (phenol equivalent: 104, softening point: 70°C) as a hardening agent for 100 g of the epoxy resin prepared in this manner. The water absorption rate was measured. The results are shown in Table 1.

Comparative Example 1 Using bisphenol A diglycidyl ether as the epoxy resin and using phenol novolak (softening point 70°C) as the hardening agent, test pieces were prepared in the same manner as in Example 1, and the glass transition point, fracture toughness, and water absorption were measured. The rate was measured. The results are shown in Table 1.

Comparative Example 2 A test piece was prepared in the same manner as in Example 1, using Kotaresol Novolak epoxy (softening point 80°C) as the epoxy resin and phenol novolak (softening point 70°C) as the hardening agent. The glass transition point, fracture toughness and water absorption were measured. The results are shown in Table 1.

Comparative Example 3 4,4°-dihydroxy-3°3 as epoxy resin
', 5,5°-tetramethylbiphenyl diglycidyl ether and phenol novolak (
A test piece was prepared in the same manner as in Example 1, and the glass transition point, fracture toughness, and water absorption were measured.

The results are shown in Table 1.

Table 1 [Effects of the Invention] The epoxy resin composition of the present invention not only has excellent heat resistance and water resistance, but also provides a cured epoxy product with high toughness, and is useful in industrial applications. It is.

Claims (3)

[Claims] (1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, in the formula, A and B are represented by the following formula (a) or (b), and A≠B An epoxy resin composition prepared by blending a curing agent into an epoxy resin represented by the following formula (where n is a rational number from 0.1 to 10). Formula (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) (However, R represents hydrogen or a lower alkyl group) Formula (b)
▲There are mathematical formulas, chemical formulas, tables, etc.▼(b) (However, X indicates a divalent group) (2) The epoxy resin composition according to claim 1, wherein in general formula (1), A is represented by formula (a) and B is represented by formula (b). (3) The epoxy resin composition according to claim 1 or 2, wherein R in formula (a) is a methyl group, and X in formula (b) is ▲a numerical formula, a chemical formula, a table, etc. ▼.