JPS6222812A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in processability and heat resistance and useful as a material for casting, impregnation, lamination or molding, comprising an OH group-free, allyl-etherified substituted phenol novolak resin and N,N'-bismaleimide compound at a specified mixing ratio. CONSTITUTION:An OH group-free, allyl-etherified substituted phenol novolak resin (A) is obtained by reacting a novolak resin of the average number of nuclei of 2-15, obtained by condensing at least one phenol substituted with an alkyl, alkenyl, aryl, aralkyl or halogen group with an aldehyde such as HCHO. Component A is mixed with an N,N'-bismaleimide compound (B) (e.g., N,N'-diphenyl ether bismaleimide) so that the ratio of the number of the double bonds of component A to that of the double bonds of component B may be 1-3.

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, and in various electrical insulation materials, structural materials, and the like.

In recent years, the conditions for using materials in each of these applications have tended to become stricter, and the heat resistance of materials has become an especially important characteristic. Conventionally, thermosetting polyimide resins have been used for these purposes. However, in terms of processability, it required heating at high temperatures for long periods of time◇ Also, although epoxy resins with improved heat resistance have excellent processability, they have poor mechanical properties at high temperatures, electrical properties, and long-term durability. High heat resistance performance such as heat deterioration resistance was insufficient ◇ As an alternative material, for example, a thermosetting mixture containing polyimide and alkeni diN phenol and/or 7-keniμ phenol ether (specially Kaisho 52-9
94), a heat-resistant resin composition containing a maleimide compound, a polyallylated phenol compound, and an epoxy resin (
Japanese Unexamined Patent Publication No. 5FLL-184099) and the like have been proposed.

However, the polyallylated phenol compound used here is either a polyallyl ether compound subjected to Claisen rearrangement, or has a structure in which diphenolic hydroxyl groups are generated through Claisen rearrangement during heat curing, resulting in nuclear substitution. In particular, in the case of borac type, where the aryl group and the hydroxyl group or ether group are located in the ortho position of the same aromatic ring,
It also tends to remain unreacted in the curing machine, and there are problems with cured physical properties at high temperatures, heat deterioration resistance, etc.

Against this background, the present inventors have conducted extensive studies on resin compositions that have excellent heat resistance and processability.
The present invention has been completed by discovering that a resin composition containing a specific resin and a maleimide compound is suitable for the above-mentioned purpose◇ That is, the present invention is directed to an ali-ether-substituted phenol containing substantially no hydroxyl group. Novohook resin and N, N'
- To provide a thermosetting resin composition containing a bismaleimide compound in a quantitative ratio such that the ratio of the former double bond to the latter double bond is more than 1 and 8 or less. The present inventors previously discovered that the double bond ratio is preferably 1 or less, an allyl etherified substituted phenol μ-class novolac resin, and N , N
We have discovered a thermosetting resin composition containing '-bismaleimide, and we have found that the quantitative ratio of the present invention not only satisfies the above objectives, but also slightly improves toughness. The present invention will be explained in detail below.

The arylated substituted phenolic resin used in the present invention refers to a phenolic resin substituted with an alkyl group, an alkenyl group, an aryl group, an afulkyl group, or a halogen atom, specifically, Freezee, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol
, isozolobenylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, xylenol, methibutypphenol/L/ (each including isomers) and one or more substituted phenols and formaldehyde, A novolac resin which usually has an average nuclear number of 2 to 15 and is obtained by condensing aldehydes such as furfural and acrolein by a known method, and an allyl halide such as allium chloride μ, allium bromide μ, and allium iodide ρ. It is a resin substantially free of phenolic hydroxyl groups obtained by reacting the above in the presence of an alkali, and in particular, allyl etherified cresol novolac resins can be preferably used.

N,N'-bismaleimide compounds used in the present invention include N,N'-diphenylmethane bismaleimide, N,N-7enylene bismaleimide, N,N'-
Diphenyl ether bismaleimide, N,N'-diphenylsulfone bismaleimide, N,N'-synchrohexylmethane bismaleimide, N,N'-xylene bismanimide, N,N'-tolylene bismaleimide, N.

N-xylylene bismaleimide, N,N'-diphenylcyclohexane bismaleimide (each containing isomers),
N,N'-ethylene bismaleimide F, N,N-hexamethylene bismaleimide, and the terminal obtained by adding diamines to these N,N'-bismaleimide compounds are N,N'-bismaleimide bone cores. Examples include greborimer and the like.

In the resin composition of the present invention, a) a reetherified substituted phenol novolac resin; and N.

X-bismalenom)/l- is selected such that the ratio of the former double bond to the double bond of the martyrdom obi 1 spring soup-hakuo exceeds 1 and is 3 or less, preferably 2 or less. This is not preferable because the heat resistance decreases.

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, add radical polymerization initiators such as azo compounds and organic peroxides, ion catalysts such as tertiary amines, quaternary ammonium salts, imidazo-V, boron trifluoride, and amine salts, etc. It can also accelerate curing.

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 various fillers and reinforcing shafts using a roll, etc. Furthermore, it can be dissolved in a solvent and applied to various reinforcing fibers such as glass fibers and carbon fibers. Depending on the bond type, other known thermosetting resins such as other allyl resins, EVO! e resin, unsaturated polyefthene/
V resin, fluorine resin, silicone resin, and triazine resin 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, M8, and molding. Reference examples and! j! Examples will be shown, but the present invention is not limited to these examples. In the examples, parts indicate weight units.

Reference Example 1 In a reactor equipped with a thermometer, a stirrer, a dropping pouch and a reflux condenser, 118 parts (1 equivalent #) of an O-ri Vsol novolak resin with a softening point of 100C and 15 parts of acetone as a reaction solvent were added.
After completely dissolving the resin, add bromide μ
Add 88 parts (1.1 equivalents) of m and stir well.

While keeping the temperature of the reaction system at 60°C, 28g6 157 parts of caustic soda aqueous solution (1,1 addition i) was added dropwise over 2 hours.
The temperature was raised to 0 ut and kept at the same temperature for 8 hours. Next, the aqueous layer was removed by separation, and acetone and unreacted alibrobromide were removed.
After distilling off, 155 parts of toluene was added to dissolve the resin. Next, trace amounts of inorganic salts were removed by water washing and phosphorus filtration, and the mixture was concentrated to obtain 154 parts of a pale yellow viscous liquid resin with an υ conversion rate of 1024 and an OH content of 0.2%.

Example 1 Resin obtained in Reference Example 1 (referred to as ALN), JP-A-58-1
O-allylphenol novolak (for comparison) synthesized (by the method described in 84099) and N,N'-4,4'-
Diphenylmethanebia, maleimide [Mitsui Toatsu product (B)
A resin composition was obtained by mixing the double bond equivalent ratio of each allyl compound with respect to the BMI shown in Table 1, and the mixture was B-staged at 180°C and then heated at 50V at 200°C.
The cured products were obtained by press molding at - for 1 hour and post-curing at 280° C. for 5 hours. Table 1 shows the cured products. The composition of the present invention comprises:
It can be seen that the balance of strength and toughness is compromised in the 111d class.

By flTMA method Rice! 816℃×7 days later US s Compliant with JISK6911

Claims (1)

[Claims] A quantitative ratio of an allyl etherified substituted phenolic novolak resin substantially free of hydroxyl groups and an N,N'-bismaleimide compound such that the ratio of the double bonds of the former to the double bonds of the latter exceeds 1 and is 3 or less. A thermosetting resin composition containing.