JPS5819325A - Heat-resistant epoxy resin composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in electrical, mechanical and thermal properties, consisting of a specified heat-resistant epoxy resin, an acid anhydride, a phenolic resin and an aromatic amine. CONSTITUTION:A heat-resistant epoxy resin of the formula, wherein X is a 2-8C alkyl and m and n are each 2-4, is prepared by esterifying at least four carboxyl groups of a polycarboxyl compound having a trimellitic acid skeleton bonded to its terminal alkyl groups, which is prepared by a ring-opening addition reaction of at least two trimellitic anhydride molecules to a polyhydric alcohol, with the aid of epichlorohydrin, an alkali and a quat. ammonium salt catalyst to obtain a glycidyl ester. Then this epoxy resin is mixed with an acid anhydride, a phenol resin and an aromatic amine as curing agents. EFFECT:It is possible to obtain cured products having a heat distortion temperature >=150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel heat-resistant epoxy resin composition with excellent electrical, mechanical, and thermal properties, and to the production of the heat-resistant epoxy resin that is the main component thereof. .

Epoxy resins generally have good electrical properties, mechanical properties, and adhesive properties, and are widely used, for example, as structural materials or insulating materials for electrical equipment.

In recent years, resin encapsulation methods in which electronic circuit components such as semiconductor elements, resistors, mounters, and coils are encapsulated using epoxy resin molding materials have been widely adopted, and have greatly contributed to the development of industry in this field.

Conventional epoxy resin molding materials such as bisphenol A type epoxy resin, alicyclic type epoxy resin, novolak type epoxy resin, etc. are added with a curing agent such as acid anhydride, phenol resin, amine or metal complex, and tertiary resin is added as necessary. Amine, imidazole, etc. are added to speed up curing.

However, due to recent developments in electronic and electrical equipment,
Materials used in such devices are required to have increasingly higher properties.

In particular, due to miniaturization, high density, high integration, etc., epoxy resin compositions with high heat resistance are particularly required.

This invention was made with the objective of developing and providing an epoxy resin composition with excellent heat resistance in response to the above-mentioned demands.

As a result of repeated research, the present inventors found that in order to improve the characteristics of epoxy resin, by using a heat-resistant epoxy resin represented by the general formula, which is an epoxy resin with a high crosslinking density,
High glass transition point (with a composition of 60-80% filler)
We have now invented a tIfM epoxy resin composition (Tgl 50-200'C).

The heat-resistant epoxy resin in the present invention is produced by ring-opening addition of trimellitic anhydride, which is inexpensively available as a raw material for heat-resistant polyamide resins, polyamideimide resins, etc., to a polyhydric alcohol such as ethylene glycol without a solvent or in an organic solvent. , a trimellitic acid bone core is attached to the end of the alkyl group to obtain a polyvalent carboxyl compound.

Furthermore, according to the conventional epoxy resin manufacturing method, 4
This is an alkylpolyol polytrimellitate polyglycidyl ester that can be obtained easily and inexpensively by glycidyl esterifying a carboxyl group of 1 or more using epichlorohydrin, an alkali, and a catalyst (quaternary ammonium salt).

If shown in the reaction formula, (1) (1) ... Reaction formula 2 However, X is a C2 to C8 alkyl group, n = 2 to 4, m = 2
~4.

Specific examples of the polyhydric alcohol (X(OH)m) used in the present invention include ethylene glycol, globylene glycol, phethylene gelicol, neopentyl glycol, trimethylolpropane, chrycerin, and pentaerythritol.

Next, reaction formula 1 and reaction formula 2 will be explained in more detail. The reaction between polyhydric alcohol and trimellitic anhydride shown in reaction formula 1 of the present invention can be carried out regardless of whether the amount of polyhydric alcohol used relative to trimellitic anhydride is in excess or in shortage of the stoichiometric amount. A particularly heat-resistant compound is obtained.

In addition, the reaction between compound (1) shown in Reaction Formula 2 and epichlorohydrin can be performed by changing the equivalent ratio of the carboxyl group equivalent of compound (1) and the epoxy equivalent of epichlorohydrin to produce heat-resistant epoxy resins with different average molecular weights. can be obtained.

To the heat-resistant epoxy resin thus obtained, acid anhydrides, phenolic resins, aromatic amines, etc. are added as curing agents, and if necessary, tertiary amines, imidazole, etc. are added as curing accelerators. The cured product obtained by curing had an HDT of 150°C or higher, and was a heat-resistant epoxy resin composition characterized by a high glass transition temperature.

The present invention will be specifically explained below by giving examples.

Example 1 884 g of trimellitic anhydride and 62 g of ethylene glycol
f and catalyst tetramethylammonium chloride 11/
are reacted in a solvent dioxane at 90 to 110°C for 1 to 10 hours, and after the reaction is completed, the solvent dioxane is distilled off to obtain 446 g of ethylene glycol bistrimelitate. Further, 647f to 925 g of epichlorohydrin and 2 g of tetramethylammonium chloride as a catalyst are added and reacted by heating.

The resulting talolhydrin, which is easily esterified at 100-110°C, is reacted with NaOH161-2Of to dehalogenate and glycidylate, and the generated NaCl is removed by filtration or washing with water, and excess epichlorohydrin is distilled off. The Na+ and C1- ions were purified and removed by washing with water to obtain 637 g of a resin containing ethylene glycol bistrimelitate tetraglycidyl ester as a main component.

(Yield 95%, WPE 175-21.5) Example 2 The above components were stirred and mixed at 70-90°C for 5-10 minutes to prepare an epoxy resin composition.

The resulting composition was cured at 110°C to 120°C for 5 minutes and post-cured at 150°C to 170°C for 15 hours, and the cured product had a heat distortion temperature HDT of 150°C to 160°C.

As described above, the epoxy resin composition according to the present invention, which uses the epoxy resin produced by the method according to the present invention, has excellent heat resistance and is a heat-resistant epoxy resin composition that can be produced at low cost. It is.

Procedural amendment August 7, 1980 Haruki Shimada, Commissioner of the Patent Office Heat-resistant epoxy resin composition 3, relationship with the case of the person making the amendment Patent applicant 4, agent address: 2- Junkeimachi-dori, Minami-ku, Osaka-shi In Column 6 of the Detailed Description of the Invention in the Specification 20, and lines 16 and 17 on page 2 of the Description of the Amendment, ... is added as a curing speed, and ... is a curing accelerator. Toshi 251

Claims (2)

[Claims] (1) General formula, where X is a 02-C8 alkyl group, n2-4, m
= A heat-resistant epoxy resin composition obtained from a heat-resistant epoxy resin represented by 2 to 4, and an acid anhydride, a phenol resin, and an aromatic amine as a curing agent. (2) Heat resistance shown by the above general formula obtained by ring-opening addition of two or more trimellitic anhydrides to a polyhydric alcohol, followed by glycidylation by reaction with four or more carboxyl groups, epichlorohydrin, and an alkali using a catalyst. Manufacturing method of epoxy resin.