JP2000063637A - Epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide injection molding materials which impart long-term storage stability to epoxy resin molding materials without damaging properties such as curability, mechanical properties, electrical characteristics and environmental resistance and are excellent in thermal stability in a cylinder. SOLUTION: Epoxy resin compositions comprise (A) a solid epoxy resin having two or more epoxy groups, (B) a solid novolak resin having two or more phenolic hydroxyl groups, (C) a hardening accelerator between the epoxy groups and phenolic hydroxyl groups such as 1,8-diazabicycloundecene, (D) a urea derivative such as N-(3,4-dicyclophenyl)-N',N'-dimethylurea, and (E) an inorganic filler.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition, and more particularly to long-term storage as an epoxy resin molding material without impairing properties such as curability, mechanical properties, electrical properties, and environmental resistance. The present invention relates to an epoxy resin composition that is a material for injection molding that can impart stability and is also excellent in thermal stability in a cylinder.

[0002]

2. Description of the Related Art Epoxy resins are used in various fields because of their excellent curability, mechanical properties, electrical properties and environmental resistance. However, the excellent curability of the resin means that it has high reactivity, and the premix type epoxy resin has a problem in that it can be stored at room temperature or for a long time. Further, when it is intended to be applied to applications such as injection molding materials, there is a problem in thermal stability in the cylinder. Therefore, in order to secure such thermal stability and secure necessary electrical characteristics and the like, urea compounds such as dicyandiamide (Japanese Patent Laid-Open Nos. 1-254731 and 5-14
8345) and a polymer-coated curing catalyst (JP-A-64-705)
23, JP-A-1-287131, JP-A-2-292324), metal chelate (JP-A-2-24318, JP-A-3-207713, JP-A-5-25225)
Although such catalysts have been studied so far, they have not yet reached the above-mentioned required properties.

[0003]

The object of the present invention is to provide a long-term storage stability to an epoxy resin composition, particularly an epoxy resin molding material, without impairing the properties such as curability, mechanical properties, electrical properties and environment resistance. And to obtain an epoxy resin molding material for injection molding which is excellent in thermal stability in the cylinder.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that as a specific catalyst for an epoxy resin, an amine-based catalyst, an imidazole-based catalyst, or a phosphorus-based catalyst and a urea-based catalyst are used. It was found that a resin composition having high resin performance and excellent heat stability can be obtained by combining with, and the present invention has been completed.

That is, the present invention provides (A) a solid epoxy compound having two or more epoxy groups in one molecule, (B) a solid phenolic compound having two or more phenolic hydroxyl groups in one molecule, ( An epoxy resin composition comprising C) a curing accelerator that promotes a curing reaction between an epoxy group and a phenolic hydroxyl group, (D) a urea derivative, and (E) an inorganic filler.

The present invention will be described in detail below.

The epoxy compound (A) used in the present invention may be a solid compound having two or more epoxy groups in one molecule. Examples of the solid epoxy compound include a bisphenol type epoxy resin, a novolac type epoxy resin, a triphenylmethane type epoxy resin, and a dicyclopentadiene type epoxy resin. Among them, a novolac type obtained by epoxidizing a hydroxyl group of a phenol novolac resin. Epoxy resins are preferred.

The (B) phenolic compound used in the present invention may be a solid compound having two or more phenolic hydroxyl groups in one molecule. Phenol novolac resin is suitable as the solid organic compound.

The curing accelerator (C) used in the present invention is
Epoxy compound (A) (novolak type epoxy resin)
As long as it accelerates the curing reaction between the epoxy group of (B) and the hydroxyl group of the phenolic compound (phenol novolac resin) of (B), an amine compound, an imidazole compound or a phosphorus compound having a softening point of 100 ° C. or higher is particularly preferable. Is. Specifically, for example, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, alphamethylbenzyldimethylamine, 1,8-diazabicycloundecene, etc. Amines, 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole and other imidazoles, triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine Phosphorus compounds such as fin, dibutylphenylphosphine, diphenylbutylphosphine, tris (paramethoxyphenyl) phosphine, tri (methacryl) phosphine, trinaphthylphosphine, and tris (2,6-dimethoxyphenyl) phosphine are listed. It is.

Further, these curing accelerators are preferably kneaded with a lubricant having a softening point of 100 ° C. or higher in advance, and then pulverized to be used as a surface coating type solid curing accelerator.

The urea derivative (D) used in the present invention is a substituted derivative of urea or a substituted derivative of a compound having two ureido groups in one molecule, and a urea compound having a softening point of 100 ° C. or higher is preferable. Specifically, as the derivative of the monourea compound, 3-phenyl-1,1-dimethylurea, 3- (parachlorophenyl) -1,1-dimethylurea,
3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3-
(Orthomethylphenyl) -1,1-dimethylurea, 3-
Examples include (paramethylphenyl) -1,1-dimethylurea, 3- (methoxyphenyl) -1,1-dimethylurea, 3- (nitrophenyl) -1,1-dimethylurea, etc., and derivatives of bisurea compounds. Are N, N-phenylene-bis (N ', N'-dimethylurea), N, N- (4-methyl-1,3-phenylene) -bis (N', N'-dimethylurea), 2 Examples thereof include dimethylamine adduct of 4,4-tolylene diisocyanate, dimethylamine adduct of 4,4 ′-(diphenylpropane) diisocyanate, trimethylamine adduct of triphenylmethane triisocyanate, and the like.

The compounding ratio of this (D) urea derivative is (C)
The weight ratio to the total amount of the curing accelerator and the (D) urea derivative is in the range of 0.8 to 0.2, that is, [D / (C + D)] = 0.
It is 8 to 0.2.

Examples of the inorganic filler (E) used in the present invention include crushed, spherical or intermediate fused silica, crystalline silica, and powdered silicon nitride,
Examples thereof include aluminum nitride, alumina, hydrated alumina, E glass short fibers, spherical glass powder and the like.

The epoxy resin composition of the present invention comprises the above-mentioned (A) epoxy compound, (B) phenolic compound,
Although (C) a curing accelerator, (D) a urea derivative and (E) an inorganic filler are essential components, they are, for example, natural waxes and synthetic waxes as long as they do not deviate from the object of the present invention and as necessary. , Metal salts of straight chain fatty acids, acid amides,
A release agent such as esters and paraffin, a flame retardant such as antimony trioxide, a coloring agent such as carbon black, a rubber-based or silicone-based low stress imparting agent, and the like can be appropriately added and blended.

[0015]

The epoxy resin composition of the present invention is a resin composition having high resin performance and excellent thermal stability obtained by combining an amine derivative, an imidazole catalyst or a phosphorus catalyst as a specific catalyst with a urea derivative. It was obtained. Moreover, the epoxy resin composition of the present invention exhibits a latent curing reaction. Due to this performance, various forms of molding epoxy resin composition capable of long-term storage, that is, powder,
Materials such as granules, tablets and sheets can be manufactured. Further, because of its thermal stability, it can be used as an epoxy resin molding material for injection molding.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, "part" means "part by weight".

Example 1 High Tg novolac type epoxy resin 10 having an epoxy equivalent of 215 10
Novolak type phenolic resin 40 with 0 part and hydroxyl equivalent 104
Part, 1,8-diazabicycloundecene phenol salt (softening point 120 ° C) 4 parts, N- (3,4-dichlorophenyl)-
8 parts of N ', N'-dimethylurea (melting point 157 ° C), 280 parts of crushed silica filler, 280 parts of spherical silica filler, 3 parts of wax, and 1 part of carbon black are mixed at room temperature and further kneaded at 90 to 100 ° C. After cooling, it was ground to produce an epoxy resin molding material.

Examples 2 to 14 With the formulations shown in Tables 1 and 2, in the same manner as in Example 1, epoxy resin molding materials were produced.

Comparative Examples 1 to 10 Epoxy resin molding materials were produced in the same manner as in Example 1 with the formulations shown in Tables 3 to 4.

Various tests were conducted on the resin compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 10. The results are shown in Tables 5 to 8. The excellent characteristics of the resin composition of the present invention could be confirmed.

The notes of the raw materials in Tables 1 to 4 are as follows. * 1: Epoxy equivalent 215 * 2: Epoxy equivalent 200 * 3: Epoxy equivalent 193 * 4: Hydroxyl equivalent 104 * 5: Hydroxyl equivalent 97 * 6: 1,8-Diazabicycloundecene phenol salt [softening point 120 ° C ] * 7: 2-methylimidazole [melting point: 130 ° C] * 8: Tris (2,6-dimethoxyphenyl) phosphine [melting point: 152 ° C] * 9: N- (3,4-dichlorophenyl) -N ', N ′ -Dimethylurea [melting point 157 ° C.] * 10: N, N- (4-methyl-1,3-phenylene) -bis (N ′, N′-dimethylurea) [melting point 143 ° C.] * 11: Zinc laurate Capsules coated with 2-methylimidazole [melting point 130 ℃] with [melting point 129 ℃] [softening point 84
° C].

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

[Table 4]

[0026]

[Table 5]

[0027]

[Table 6]

[0028]

[Table 7]

[0029]

[Table 8]

[0030]

EFFECTS OF THE INVENTION The present invention is based on the principle of invention that high resin performance and thermal stability can be obtained by combining an amine-based, imidazole-based or phosphorus-based catalyst and a urea-based catalyst as a specific catalyst for epoxy resin. Based on the above, the epoxy resin composition of the present invention can be applied to sealing and other insulating material applications of semiconductor elements, and in particular, the composition for molding material thereof can be stored at room temperature for a long time, Also, injection molding with a high degree of freedom in conditions is possible.

Continued front page    (72) Inventor Mitsuo Ito             5-14-25 Ryoke, Kawaguchi City, Saitama Prefecture             Mikaru Kawaguchi Factory (72) Inventor Akira Akira             5-14-25 Ryoke, Kawaguchi City, Saitama Prefecture             Mikaru Kawaguchi Factory (72) Inventor Tetsuo Uchikawa             6-2 Matsuyama-cho, Moka-shi, Tochigi Prefecture Toshiba reinforced plastic             Within Stick Co., Ltd. F-term (reference) 4J002 CC042 CD051 CD061 CD071                       CD181 DE148 DF018 DJ008                       DJ018 DL008 EN066 EN086                       ET017 EU116 EU136 EW146                       FA048 FA088 FB086 FD018                       FD142 FD156 FD207                 4J036 AC02 AE07 AF06 DC05 DC10                       DC13 DC25 DC41 DC46 DD07                       FA04 FA05 FB07 JA15

Claims (4)

[Claims] 1. A solid epoxy compound having (A) two or more epoxy groups in one molecule, (B) a solid phenolic compound having two or more phenolic hydroxyl groups in one molecule, and (C) an epoxy group. Curing accelerator, (D) urea derivative and (E), which accelerate the curing reaction of phenolic hydroxyl groups with
An epoxy resin composition comprising an inorganic filler. 2. (C) The curing accelerator that accelerates the curing reaction between the epoxy group and the phenolic hydroxyl group is an amine compound, an imidazole compound or a phosphorus compound and has a softening point of 100 ° C. or higher, (D) The urea derivative is a derivative of a compound having two or more ureido groups in one molecule and has a softening point of 100 ° C. or more, and the compounding ratio of the curing accelerator and the urea derivative [D / (C + D)] The epoxy resin composition according to claim 1, wherein the weight ratio is 0.8 to 0.2. 3. A solid epoxy compound having (A) two or more epoxy groups in one molecule is a novolac type epoxy resin obtained by epoxidizing a hydroxyl group of a phenol novolac resin, and (B) a phenolic hydroxyl group in one molecule. The epoxy resin composition according to claim 2, wherein the solid phenolic compound having two or more of them is a phenol novolac resin. 4. The (C) curing accelerator that accelerates the curing reaction between the epoxy group and the phenolic hydroxyl group has a softening point in advance.
The epoxy resin composition according to claim 1, which is a surface-coating type solid curing accelerator pulverized by heating and kneading with a lubricant having a temperature of 100 ° C or higher.