JPS6211716A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition containing a partially allyl etherified substituted phenol novolak resin and an N, N'-bismaleimide compound and having improved processability and heat resistance. CONSTITUTION:A composition containing (A) a partially allyl etherified substituted phenol novolak resin and (B) an N, N'-bismaleimide compound, e.g. N, N'-diphenylmethanebismaleimide. The resin (A) is obtained by condensing a substituted phenol with formaldehyde, etc., and reacting the resultant novolak resin with an allyl halide, e.g. allyl chloride, in the presence of an alkali.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition having excellent processability and heat resistance.

Thermosetting resins are used as materials for casting, impregnation, lamination, and molding, as well as for various electrically conductive insulating materials, structural materials, adhesives, and the like. In recent years, the conditions for using materials in each of these applications have tended to become stricter, and in particular, the heat resistance of materials has become an important characteristic.

Thermosetting polyimide resins have conventionally been used for such purposes, but in terms of processability, they require heating at high temperatures for long periods of time.

In addition, although epoxy resins with improved heat resistance have excellent processability, they are insufficient in high heat resistance performance such as mechanical properties and electrical properties at high temperatures and long-term heat deterioration resistance.

As an alternative material, for example, a thermosetting mixture containing polyimide and alkenylphenol and/or alkenylphenol ether (Japanese Patent Application Laid-Open No. 1983-1983-1)
994), a heat-resistant resin composition containing a maleimide compound, a polyallylated phenol compound, and an epoxy resin (Japanese Unexamined Patent Publication No. 184099/1983), etc. have been proposed. However, the polyaryl) I/chemically engineered enol-based compound used here is a polyallyl ether compound subjected to Claisen rearrangement, or because it has a structure in which phenolic hydroxyl groups are generated through Claisen rearrangement during heat curing, the nucleus Substituted allyl groups and hydroxyl or ether groups are located in the ortho position of the same aromatic ring, and especially in the case of novolac types, they tend to remain unreacted even after curing, causing problems in cured properties at high temperatures, heat deterioration resistance, etc. there were.

Against this background, the present inventors conducted extensive studies on resin compositions with excellent heat resistance and processability.
A resin composition containing a specific resin and a maleimide compound is
The present inventors have found that the above object can be achieved and have completed the present invention.

The present inventors have previously discovered a heat-resistant thermosetting resin composition containing an allyl etherified substituted phenol novolak that does not substantially contain phenolic hydroxyl groups and an N,N'-bismaleimide compound. After that, as a result of intensive studies, it was found that a heat-resistant thermosetting resin composition containing a substituted phenolic novolac whose moiety (J'J is allyl etherified) and an N,N'-bismaleimide compound also has heat-resistant properties. This is what we found to be excellent.

That is, the present invention provides (a) a partially allyl etherified substituted phenolic novolac resin, and (b) N , N
A thermosetting resin composition containing a '-bismaleimide compound is provided.

The present invention will be explained in detail below.

The partially allyl etherified substituted phenolic novolak resin used in the present invention refers to phenols substituted with alkyl groups, alkenyl groups, aryl groups, aralkyl groups, or halogen atoms, specifically cresol, ethyl Phenol, isopropylphenol, butylphenol, octylphenol, nonylphenol,
One or more substituted phenols such as vinylphenol, isopropenylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, xylenol, and methylbutylphenol (including isomers of each) and aldehydes such as formaldehyde, furfural, and acrolein. Novolak resin, which usually has an average number of nuclei of 2 to 15, obtained by condensation reaction of It will be done.

Here, the alkali used is equivalent to the equivalent of the portion of the phenolic hydroxyl group desired to be allyl etherified.

Further, the amount of allyl halide used is an amount equivalent to or more with respect to the alkali.

In the present invention, since the substituted phenol novolak is used as a raw material, the formation of phenol hydroxyl groups by Claisen rearrangement hardly occurs, and the major feature is that the allyl ether group and the hydroxyl group are present in separate aromatic rings.

Examples of the N,N'-bismaleimide compounds used in the present invention include N,N'-diphenyl memaleimide, N,N'-dicyclohexylmethane bismaleimide, N,N'-xylene bismaleimide, N,
N'-tolylene bismaleimide, N IN'-xylylene bismaleimide, N, N'-diphenylcyclohexane bismaleimide (each including isomer), N, N'
- Ethylene bismaleimide, N,N'-hexamethylene bismaleimide, and prepolymers having N,N'-bismaleimide bone cores at the ends obtained by adding these N,N'-bismaleimide compounds and diamines, etc. can be exemplified.

In the resin composition of the present invention, the quantitative ratio of the partially allyl etherified substituted phenolic novolak resin and the N,N'-bismaleimide compound is such that the ratio of the double bonds of the former to the double bonds of the latter is 2 or less. It is preferable to choose as follows.

If it exceeds 2, the content of unreacted allyl groups in the cured product increases, which is not preferable.

Here, the N,N'-bismaleimide compound can be reacted with the allyl group in advance to such an extent that gelation does not occur.

The resin composition of the present invention can be easily cured by heat. In this case, curing is promoted by adding ionic catalysts such as imidazoles, 8th class amines, quaternary ammonium salts, and triborated boron amine salts, and radical polymerization initiators such as azo compounds and organic peroxides. You can also.

The resin composition of the present invention can be processed in a mixer or kneader at a relatively low temperature.
It is possible to prepare a casting or molding material by blending fillers and reinforcing materials of each type using a roll, etc. Furthermore, it is possible to prepare a casting or molding material by blending fillers and reinforcing materials of each type using a roll, etc. Furthermore, it is possible to dissolve each type of filler and reinforcing material in a solvent and make it into various plate reinforcing fibers such as glass fiber, carbon a miscellaneous, etc. It can also be applied to laminated materials. Depending on the purpose, other known thermosetting resins such as other allyl #l resins, epoxy resins, unsaturated polyester resins, phenol resins, silicone resins, triazine resins, etc. may be added.

Thus, the resin composition of the present invention is useful as a thermosetting resin composition with excellent processability and heat resistance as a material for casting, impregnation, lamination, and molding.

Next, reference examples and examples will be shown to explain the present invention in detail, but the present invention is not limited thereto. In the examples, parts indicate weight units.

Reference Example 1 In a reactor equipped with a thermometer, stirrer, dropping port and reflux condenser, 118 parts (1 equivalent) of 0-cresol novolak resin with a softening point of 100°C and 15 parts of acetone as a reaction solvent were added.
After completely dissolving the resin, add 102 parts (0.84 parts) of allyl bromide and stir well. While maintaining the temperature of the reaction system at 60"C, 114 parts of a 28% caustic soda aqueous solution (0.8%) was added dropwise over 2 hours, and then the temperature was raised to 60"C.
and hold at the same temperature for 8 hours. Next, the aqueous layer is removed by fractionation, and after distilling off acetone and unreacted allyl bromide, 155 parts of toluene is charged to dissolve the resin.

Then, after removing the inorganic salts of the microya by washing with water and filtration,
By concentrating, the allylation rate is 80% and the OH equivalent is 750.
142 parts of a yellow-orange viscous liquid resin of f/eq was obtained.

<AlN-1) Reference Example 2 Allyl bromide 76 parts (0.68 equivalents), 86 parts of 28% caustic soda aqueous solution (0.6 equivalents, 1) Allylation rate was determined in the same manner as in Reference Example 1 except that 0.6 equivalents were used. 60%, OH equivalent 855 g/e
185 parts of a yellow-orange semi-solid resin of q was obtained. (ALN-2
Example 1 ALN-1 and ALN-2 as allyl compounds, diallylbisphenol A (abbreviated as ABPA) synthesized by the method described in JP-A-52-994 as a comparative sample, and the method described in JP-A-58-184099 O-allylphenol novolac (APN) synthesized by N,
N as an N'-bismaleimide compound.

Using N'-4,4'-diphenylmethane bismaleimide [manufactured by Mitsui Toatsu Co., Ltd. (referred to as BMI)], a resin composition was obtained by mixing the double bond equivalent ratio of BMI to each allyl compound at a predetermined value. , after B stage at 180°C 2
After press molding at 00℃ for 1 hour at 50 Ky/d, 28
A cured product was obtained by post-curing at 0''C for 5 hours.

Table 1 shows the physical properties of each cured product. It can be seen that the composition of the present invention provides a cured product with superior heat resistance properties compared to other allyl compound systems.

Claims (1)

Claims: A thermosetting resin composition comprising (a) a partially allyl etherified substituted phenolic novolac resin, and (b) an N,N-bismaleimide compound.