JPS59179558A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:A composition that is composed of a soluble polyimide and a specific maleimide, thus being suitable for use as a laminating material or insulating material, because of its high flowability, processability, high mechanical strength and heat resistance. CONSTITUTION:A dimaleimide of formula I (R is a divalent group of 2 or more carbon atoms) and/or a polyvalent maleimide of formula II (m is a number larger than 0) is mixed with a soluble polyimide of formula III (Ar is divalent groups whose 0-50% are the recurring unit of formula IV, and the remaining is formula V or VI). The amount of the maleimide of formula I and II is 15- 85wt% in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition having excellent heat resistance and suitable for lamination materials, various molding materials, electrical insulation materials, and the like.

Conventionally, polyimide resin has been the most typical heat-resistant resin material, but in order to completely prevent the generation of voids due to condensation products during molding, polyimide resin is used to achieve a high molecular weight state through cyclization condensation, that is, complete imidization. Soluble polyimide resins that are soluble in organic solvents have also been developed and used (for example, US Pat. No. 3,787,367).

However, even in such a soluble polyimide resin, the problem of low fluidity and poor moldability due to the rigid main chain in its structure cannot be avoided.

On the other hand, in general, maleimide compounds have a low molecular weight, so they have high fluidity when melted in a bath, and they can be polymerized to give a cured product with excellent thermal properties, but their mechanical strength is low and the above-mentioned problems arise. It has a tendency to be impractical in terms of usage.

In view of this problem, the inventors conducted a large number of tests and research molds, and found that the above-mentioned problem could be solved by mixing a specific maleimide compound and polyimide resin. It has been completed.

That is, the present invention provides a simaleimide compound represented by (wherein R represents a divalent group containing at least 2 carbon atoms) or/and the general formula, (wherein m is a number greater than 0) with polyvalent maleimide compounds.

(B) A thermosetting resin composition obtained by mixing soluble polyimide represented by the general formula.

The above general formulas (I) and (I) used in this invention
Specifically, the simalide compound and polyvalent maleide compound represented by I) include N, N'-(methylenedi-p
-phenylene) simaleimide, N, N'-(,txy-p-phenylene) simaleimide, N, N'-(sulfone di-p-phenylene) simaleimide, N, N'-(sulfon di-m-phenylene) simaleimide, N ,N'
-2,4-tolylene dimaleimide, N,N'-2,6
-Dylene dimaleimide, N,N'-m-722 dimaleimide, N,N'-p-22 dimaleimide, N,N'-ethylene dimaleimide%, N',N'-
There are hexamethylene dimaleimide, etc., but these are 1
It can be used as a species or as a mixture of two or more types.

Next, as the soluble polyimide represented by the above general formula (2), 3.3', 4.4'- benzophenonetetracarpone yoshi dianhydride, 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate) (2,4
-isomer or 2,6-isomer or a mixture thereof) in a molar ratio of 0 to 30:100 to 70. It can also be obtained by a method of thermal dehydration condensation using the corresponding diamine.

A specific example of the soluble polyimide having the above composition ratio of 20:80 is polyimide 2080 (trade name, manufactured by Mitsubishi Chemical Industries, Ltd.), and it is appropriate to use all of these.

The mixing ratio of the maleimide compound and the polyimide compound is preferably such that the maleimide compound is in an amount of 15 to 85 liters based on the total amount of solids in the mixture.

This is because if the amount of the maleimide compound is less than 155 parts by weight, the fluidity of the assembled product becomes low and the processability is lowered, and if it exceeds 85% by weight, the mechanical strength decreases, both of which are undesirable.

The above-mentioned components may be mixed in a melt or solid powder state, but generally they are mixed using a solvent such as dimethylacetamide, dimethylformamide, or N-methyl-2-pyrrolidone. Then, the entire base material such as glass cloth or carbon fiber cloth is immersed in the obtained Resin M solution, or after the entire base material is coated with the grease-resistant solution, the bath agent is removed to obtain the entire prepreg. One example of use is a method of forming k M layers and molding them under heat and pressure to obtain a laminated molded product.

In the case of a molded article, the resin solution is poured into a large excess of water while stirring, and the precipitated resin is completely separated and dried, and the resulting resin powder is completely molded using a mold.

These molding conditions may vary depending on the composition of the resin, etc., but generally molding can be performed at 160 to 250°C.

The thermosetting resin composition of the present invention may be mixed with various known fillers, mold release agents, etc., depending on the usage conditions and applications.

The present invention will be explained in detail below with reference to Examples.

Example 1 Tolylene diin cyanate (2,4-isomeric Form 80q6.2,6-isomer 2
0%) 61.0 parts, 37.5 parts of 4,4'-diphenylmethane diincyane) were added, and the mixture was heated and stirred at 40°C for 2.5 hours, then the temperature was gradually raised, and the mixture was heated at 90°C for 2 hours.
Next, heat stirrable polyimide m at 130°C for 20 hours.
A liquid was prepared. Next, cool it to 60°C, N, N
'-(methylene di-p-)unishin) simaleimide 38
A uniform resin solution was obtained.

The entire resin solution obtained was applied onto an aminosila/treated glass cloth and dried by heating at 150° C. for 10 minutes to obtain a prepreg. These prepregs were appropriately stacked and preformed in a press heated to 170°C while degassing for 60 hours.
The temperature was raised to 200°C under a pressure of /m-, and pressure and heat molding was performed for 60 minutes to obtain a laminate, and the laminate was post-cured at 240°C.
Heat treated for 24 hours. The bending strength of the obtained laminate at 25°C is 47111f/yym', and 250°
In C it was 36 R.

The bending strength after further heating at 250°C for 1000 hours is 44 Ky/mrr? (25°C).

Example 2 161.1 parts of 3.3', 4.4'-benzophenone tetracarboxylic dianhydride and 10 parts of dimethylacetamide
2.4-)lylene diisocyanate 6 in a solution of 60 parts
9.7 parts and 25.0 parts of 4,41-diphenylmethane diisocyanate) were added and mixed with the polyimide solution. To this, 494 parts of N,N'-(methylenedi-p-phenylene) simaleimide was added, and the mixture was prepared as in Example 1. A uniform resin solution was obtained in the same manner.

A molded laminate was obtained using the obtained resin bath liquid in the same manner as in Example 1, but the bending strength of the laminate at 25°C was an initial value of 52 h/mrr? , 46Kf/mrr even after heating for 2500Cl000 hours? Met.

Next, the same resin solution was applied to an aluminum plate, and after drying with bath medium, the temperature was 200°.
The glass transition temperature of the coating film cured for 6 hours CI and then 4 hours at 250°C was 315°C.

Example 3 255 parts of the polyvalent maleimide compound represented by the general formula (m) and 1 part of the polyimide 2080 (trade name) described above
450 parts of 0Mjt% dimethylformamide bath solution were mixed together to form a uniform resin solution.

A molded laminate was obtained in the same manner as in Example 1 except that this resin bath solution was used, and the total bending strength at 25°C was measured to be 53K17mm m', and 36 Ky/m- at 250°C. I kept it.

Next, after heating this at 250°C for 1000 hours, the temperature remained at 45%.
Kg/mn? (25°C) was maintained.

Example 4 161.1 parts of 3.3', 4.4'-benzophenone tetracarboxylic dianhydride and 122 parts of dimethylacetamide
To 4 parts of the bath liquid, 87° 1 part of tolylene diisocyanate (80% 2,4-isomer, 20% 2,6-isomer) was added to obtain a polyimide solution, and to this was added N, N'-(methylene di-
A homogeneous resin solution was obtained in the same manner as in Example 1 by adding 204-2 parts of (p-phenylene) simaleimide.

The obtained resin solution was poured into a large amount of methanol with stirring, and the resulting powdery precipitate was separated and the remaining solvent was removed under reduced pressure.

The obtained powdered resin composition was placed in a mold and heated at 200℃50.
A molded article was obtained by heat curing (2 hours) under conditions of 9 parts m-, and this was further heat-treated at 240 DEG for 24 hours as post-curing. The bending strength of the molded product at 25°C is 12,3
Kf//m-, and the bending strength of 11.1 Kf/myn' (25°C) was maintained even after heating at 250°C for 1000 hours.

Agent Makoto Kuzuno - Commissioner of the Japan Patent Office 1, Indication of case: Patent Application No. 58-54144 2,
Name of the invention Thermosetting resin composition 3 Name of the person making the amendment (601,) Mitsubishi Electric Corporation Representative Hitoshi Katayama 4 Attorney 5 Claims of the specification to be amended and the invention Detailed Explanation Column 6 Contents of Amendment] 1) The scope of claims in the specification is corrected as shown in the attached sheet.

(2) ``It is appropriate'' on page 6, line 17, should be corrected to ``It is also possible.''

7 List of Attached Documents Revised Patent Claims 1 copy 2, Claims 11 + (4) general formula, (in the formula, R represents a divalent group containing at least 2 carbon atoms) or/and a polyvalent maleimide compound represented by the general formula, (wherein ITI is a number larger than 0); A thermosetting resin composition completely mixed with a soluble polyimide represented by CH3Hs.

The thermosetting resin composition according to claim 1, having 85 to 85 fluorocarbons.

Claims (2)

[Claims] (1) (A) A tumareimide compound represented by the general formula, (wherein R represents a divalent group containing at least 2 carbon atoms), or/and the general formula, (wherein m is greater than 0) A polyvalent maleimide compound represented by the following formula, and a thermosetting resin composition represented by the general formula (Bl). (2) The thermosetting resin composition according to claim 1, which contains 15 to 85% by weight of the simaleimide compound represented by the general formula II).