JPS5941455B2 - thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition having excellent heat resistance, fast curing properties, and solubility in solvents.

BACKGROUND ART In recent years, insulating materials with excellent heat resistance have been required as electrical and electronic devices have become larger in capacity, smaller and lighter, and more reliable. Hitherto, as flame-resistant resins, heterocyclic polymers typified by polyimide, silicone resins, and the like have been known.

However, many of the heterocyclic polymers are condensation type and have various drawbacks, such as producing volatile components during curing, making them difficult to mold, making them difficult to mold, being expensive, and only being able to use certain polar solvents in applications such as varnishes. There are restrictions, especially in the fields of molding materials, laminated materials, and powder materials. On the other hand, silicone resin has low mechanical strength at high temperatures, poor adhesion, and high moisture permeability, so its uses are also limited.

To improve these shortcomings, addition-type imide (bismaleimide) was developed by Lorne Boulin (France).
It is known to use a combination of epoxy compounds, unsaturated polyesters, etc.

However, even in this case, there are problems in providing fast curing properties, solubility in various solvents, and material cost, which has been a major obstacle to commercialization for applications such as molding materials, prepregs, powder coatings, and adhesives. The present invention has been made in view of the above, and it can be used at a relatively low temperature (150 to 2000C) and for a short period of time (1
The object of the present invention is to provide a thermosetting resin composition that can be converted into a cured product with excellent high-temperature strength just by heating (~30 minutes), and the resin composition before curing has excellent solubility in a solvent.

The gist is that the reaction product of N-substituted maleimide and epichlorohydrin is ^ / [2>N-R-0-CH2CH-buH2 (auto), \ [wherein R is 1 (CH2)].

- (n is O or an integer greater than or equal to 1) or 1 (ΣXi.H
This is a resin composition containing as essential components condensed UB obtained by reacting phenols and aldihydes. In the present invention, a polyfunctional epoxy compound (C) is preferably further a constituent component. According to the present invention, a conventional bismaleimide and amine compound or/or
It has remarkable effects on resin compositions containing acid anhydrides and/or epoxy compounds as essential components in terms of solubility in solvents and rapid curing.

N-substituted maleimide, which is an important essential component constituting the present invention, is mainly N-(HydrOxy, Hydroxy
alkyl, Hydroxyaryl)Maleimi
de, for example, N-hydroxymaleimide, N(
2-hydroxyethyl)maleimide, N(2-hydroxyethyl)2,3-dimethylmaleimide, N-hydroxymethylmaleimide, N(hydroxymethyl)2,3dimethylmaleimide, N-(0-hydroxyphenyl)maleimide, N -(p-hydroxyphenyl)maleimide, N[p-[(2-hydroxyethino(ha)sulfonyl]maleimide), and the like.

In the present invention, a phenol and novolak resin condensate obtained by reacting a phenol and an aldehyde is used. Examples of the phenol include phenol, cresol, xylenol, resorcinol, chlorophenol, phenylphenol, and bisphenol. A, etc., or a mixture of two or more of these are used, and as the aldehyde, for example, one or more of formaldehyde (formalin), acetaldehyde, or butyraldehyde is used.

In the present invention, the intended purpose can be achieved even when two or more of these phenolic resins are used in combination. In the present invention, the epoxy compound refers to a compound having an oxirane ring in the molecule, such as diglycidyl ether of bisphenol A, butadiene diepoxide,
, 4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexanecarboxylate, vinylcyclohexene dioxide, 4,41-di(1,2-epoxyethyl)diphenyl ether, 4,41-di(1,2
-Epoxyethino(ha)biphenyl, 2,21-bis(
3,4-epoxycyclohexyl)propane, diglycidyl ether of resorcin, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglycin [
-ter, bis(2,3-epoxycyclobentyl)ether, 2-(3,4-epoxy)cyclohexane-5,
5/-spiro(3,4-epoxy)cyclohexane 1 m
-dioxane, bis-(3,4-epoxy-6-methylcyclohexyl)adipate, N,m-phenylenebis(4,5-epoxy-1,2-cyclohexanedicarboximide), hydantoin diepoxide, hydantointris epoxide, triglycidyl compound of para-aminophenol, polyallyl glycidyl ether,
1,3,5-tri(1,2-epoxyethyl)benzene, 2,2(4,1-tetraglycidoxybenzophenone, tetraglycidoxytetraphenyl urethane, polyglycidyl ether of phenol formaldehyde novolak), Triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, polyfunctional hydantoin epoxy compounds, halogenated epoxy compounds, etc. are used.

Among these epoxy compounds, the most common diglycidyl ether of bisphenol A and the polyglycidyl ether of phenol formaldehyde novolak are useful. Furthermore, one or more of the following various materials may be used in combination with the composition of the present invention, depending on various uses and purposes.

For example, considering the use as a molding material, zircon, silica, fused silica glass, clay, alumina hydroxide, calcium carbonate, quartz glass, glass, asbestos, whisker, gypsum, magnesite, mica, kaolin, and talc. , inorganic fillers such as graphite, cement, carbon iron, barium, ferrite, lead compounds, molybdenum disulfide, zinc white, white titanium, carbon black, silica sand, and wollastonite, or mold release agents such as fatty acids and waxes; Coupling agents such as epoxysilane, vinylsilane, borane compounds, and alkoxytitanate compounds can be used.

Further, if necessary, a known flame retardant material such as antimony or phosphorus, or a flexibilizing agent can be used. Furthermore, so-called solvents can be used for applications such as varnishes. For example, as organic polar solvents, N-methyl-2-pyrrolidone, N,N-tmethylacetoand, N,N-dimethylformamide, N,N-diethylformamide, N-
Methylformamide, dimethylsulfoxide, N,N
-diethylacetamide, N,N-dimethylmethoxyacetamide, hexamethylphosphoramide, pitodine, dimethylsulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, etc., and the phenolic solvent group includes phene, ol, cresol, There are xylenol and other ketones such as methyl ethyl ketone and acetone.

The above substances may be used alone or in combination of two or more.

In addition, a non-solvent such as toluene, xylene, petroleum naphtha, etc. can be used in combination if the amount thereof is small.

Examples 1-3 113 parts of hydroxymaleimide, 9 parts of epichlorohydrin
2.5 parts were reacted using 44 parts of caustic soda as a catalyst to obtain a reaction product (A-1).

The following three types of blended compositions were made using the reactant (A-1). Add the above blended composition to 8I da 2 at 60/700C.
Roll kneading was carried out for 10 minutes using this roll to obtain the desired resin composition.

The obtained resin composition was molded for 18"Cl3 minutes using a 130 x 10 x 1.3 t sample mold.

After heating and deteriorating these molded and cured products at 200°C for a long time, the bending strength (Atl8O°C) was measured. The bending strength of the molded product after being left at 200° C. for 40 days did not decrease compared to the initial value, and its heat resistance was excellent.

Examples 4-6 125 parts of hydroxymaleimide, 1 part of epichlorohydrin
02 parts were reacted using 44 parts of caustic soda as a catalyst to obtain a reaction product (A-2).

The following three types of blended compositions were made using the reactant (A-2). These blended compositions include N-methylpyrrolidone,
Not only polar solvents such as dimethyl sulfoxide, but also ketones such as methyl ethyl ketone and acetone, etc.
It has a solubility of 70 or higher.

Examples 7-9 113 parts of hydroxymaleimide, 1 part of epichlorohydrin
20 parts were reacted using 44 parts of caustic soda as a catalyst to obtain a reaction product (A-1).

The above blended composition was roll-kneaded for 10 minutes using two rolls of 8I/2 at 60/70°C to obtain the desired resin composition. The three molding material compositions mentioned above have a hot hardness of 50 (Bacall hardness Taki 935) or more after molding for 170' Cll.

Claims (1)

[Claims] 1 Reactant of N-substituted maleimide and epichlorohydrin (A) ▲ Numerical formula, chemical formula, table, etc. ▼ (A) [In the formula, R is -(CH_2)_n-, (n is 0 or A thermosetting resin composition consisting of a condensate (B) obtained by reacting a phenol and an aldihyde.