JPH0618830B2 - Thermosetting resin composition - Google Patents

Description

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 various electrical insulating materials, structural materials, etc. as casting, impregnating, laminating, and molding materials. In recent years, the usage conditions of materials have tended to be severe in each of these applications, and the heat resistance of materials has become an important characteristic.

Conventionally, a thermosetting polyimide resin has been used for this purpose, but in terms of workability, heating at a high temperature for a long time is required.

Further, although the epoxy resin having improved heat resistance is excellent in processability, its high heat resistance such as mechanical properties at high temperature, electrical properties, and long-term heat deterioration resistance is insufficient.

One of the alternative materials is, for example, Japanese Patent Publication Sho 58.
As disclosed in JP-A-27806 and JP-B-59-15126, a thermosetting resin containing a monomer having a double bond and a maleimide compound has been proposed. However, in these, since the molecular weight of the above-mentioned monomer is low, it is necessary to pre-polymerize before heat-curing, and when directly heat-curing without pre-polymerization, a part of the monomer is There was a problem of evaporation during curing. Further, regarding a monomer having only one double bond in the molecule, the crosslink density in the cured product is limited, and the heat resistance was insufficient.

For other materials, for example, a thermosetting mixture containing polyimide and alkenylphenol and / or alkenylphenol ether (JP-A-52-99).
4), a heat-resistant resin composition containing a maleimide compound, a polyallylated phenolic compound and an epoxy resin (Japanese Patent Laid-Open No. 58-134099) and the like have been proposed. However, the polyallylated phenolic compound used here has a structure in which a phenolic hydroxyl group is generated by the Claisen transition during heat curing, because it is a compound obtained by subjecting the polyallyl ether compound to the Claisen transition.
There is a problem that the dielectric constant of the cured product is high, and the water resistance is inferior.Furthermore, in the case of a novolak type, in particular, the nucleus-substituted allyl group and the hydroxyl group or ether group are located at the ortho position of the same aromatic ring, Even after curing, it was likely to remain unreacted, and there was a problem with cured physical properties at high temperatures.

From such a background, as a result of diligent studies by the present inventors on a resin composition having excellent heat resistance and excellent processability,
The inventors have found that a resin composition containing the following specific compound and a maleimide compound is suitable for the above purpose, and completed the present invention.

That is, the present invention comprises an S-triazine compound having at least two or more alkenyl-substituted aryloxy groups in the molecule and a polymaleimide compound having at least two maleimide groups in the molecule. The present invention relates to a thermosetting resin composition.

The alkenyl group-substituted phenoxy group-containing S-triazine compound, which is one of the constituents of the present invention, has the following general formula:
It mainly contains the compound represented by (1).

Wherein X- represents an alkenyl group _CH 2 = CH
-, CH ₂ = CHCH ₂ - , CH ₃ CH = CH- and the like. Y is above However, other alkyl groups, alkoxy groups, halogen atoms, alkyl group-substituted or unsubstituted amino groups, aryl groups, aryloxy groups, hydroxyl groups, CH ₂ = CHCH ₂ O-, and the like. Also In the aromatic ring of, a substituent other than X may be substituted.

Further, the S-triazine compound of the present invention may include a compound having a structure in which two or more S-triazine groups are bonded.

Regarding the method for producing the S-triazine compound of the present invention, for example, 2 mol of alkenylphenol is added to 1 mol of the compound represented by (Z is a halogen atom and Y is the same as in the formula (1)).
Obtained by reacting in the presence of a base. For the base,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Examples include potassium carbonate, sodium methylate, sodium ethylate, triethylamine, diethylaniline, pyridine and the like. When Y is also a phenoxy group substituted with an alkenyl group, It is obtained by reacting 1 mol of the compound represented by (Z is a halogen atom) with 8 mol of alkenylphenol in the presence of a base. However, the method is not limited to this.

The polymaleimide which is the other component of the present invention is a compound containing two or more maleimide groups represented by the general formula (2) in the molecule.

(In the formula, R ₁ represents a hydrogen atom or a lower alkyl group.) Specific examples thereof include N, N′-diphenylmethane bismaleimide, N, N′-phenylene bismaleimide,
N, N'-diphenyl ether bismaleimide, N,
N'-diphenylsulfone bismaleimide, N, N'-
Dicyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'-tolylene bismaleimide, N, N'-benzophenone bismaleimide, N,
N'-diphenylpropane bismaleimide, N, N'-
Diphenyl sulfide bismaleimide, N, N'-xylylene bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N'-dichloro-diphenylmethane bismaleimide, N, N'-diphenylmethane bismethylmaleimide, N, N ' -Diphenyl ether bismethylmaleimide, N, N'-diphenylsulfone bismethylmaleimide (including isomers), N, N '
-Ethylene bismaleimide, N, N'-hexamethylenebismaleimide, N, N'-hexamethylenebismethylmaleimide, N, N'-oxypropylene bismaleimide, and these N, N'-bismaleimide compounds and diamines Prepolymer having N, N'-bismaleimide bone nucleus at the end obtained by addition, and aminophenyl-1,3,3-trimethyl-aminoindane, bisaminophenoxybenzene, 2,2-bisaminophenoxyphenylpropane , 4,4'-bisaminophenoxydiphenyl sulfone (each including isomers), maleimide compound or methylmaleimide compound of aniline / formalin polycondensation, and the like.

The compounding ratio of the S-triazine compound and the polymaleimide compound of the present invention can be in a wide range, but a particularly preferable range is 0.4 to 3 equivalents of maleimide group to 1 equivalent of alkenyl group. If either the S-triazine compound or the polymaleimide compound is extremely abundant, the curability, heat resistance, etc. will decrease.

Regarding the method of heat curing, it is possible to easily perform heat curing without a catalyst, and it is also possible to perform heat curing using a radical polymerization initiator such as an organic peroxide or an azo compound in combination. Examples of such radical polymerization initiators include benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide. , Azobisisobutyronitrile and the like. Other tertiary amines such as tributylamine, triethylamine and triamylamine, benzyltriethylammonium chloride,
It is also possible to use a quaternary ammonium salt such as benzyltrimethylammonium hydroxide, an imidazole, a boron trifluoride complex, a transition metal acetylacetonate, etc. in combination. The curing temperature is preferably 50 to 300 ° C.

Also, a known polymerization inhibitor may be used in combination in order to adjust the curing speed. For example, 2,6-di-t
-Butyl-4-methylphenol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,
Phenols such as 4'-methylenebin (2,6-di-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), hydroquinone monomethyl ether, hydroquinone, catechol, p-t
-Polyphenols such as -butylcatechol, 2,5-di-t-butylhydroquinone, methylhydroquinone, t-butylhydroquinone pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine, acetamidophenothiazine, N-nitrosodiphenylamine, N- There are N-nitrosamine-based compounds such as nitrosodimethylamine.

Thus, the resin composition of the present invention exhibits excellent properties in processability, heat resistance, mechanical properties, and electrical properties.

In the composition of the present invention, if necessary, a filler, a filler, a reinforcing agent, a pigment or the like is used in combination. For example, silica, calcium carbonate, antimony trioxide, kaolin, titanium dioxide, zinc oxide, mica, barite, carbon black, polyethylene powder, polypropylene powder, aluminum powder, iron powder, copper powder, glass fiber, carbon fiber, alumina fiber, asbestos. Fibers and the like are used and provided for molding, lamination, adhesives, composite materials and the like. Further, other known thermosetting resins such as alkenyl group-containing resin or triazine group-containing resin other than the present invention, unsaturated polyester resin, epoxy resin, silicone resin, phenol resin and the like may be added depending on the purpose.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 Cyanuric chloride 25.8 g (0.14 mol), m-isopropenylphenol 56.4 g (0.42 mol) and acetone 140 were placed in a four-necked flask equipped with a stirrer, a thermometer and a dropping funnel.
g was added and dissolved. Thereafter, while maintaining the temperature at room temperature, 176 g (0.441 mol) of 10% aqueous NaOH solution was added dropwise over 1 hour. After dripping and keeping the same temperature for 1 hour,
The product was taken out, washed with water and dried to obtain the following compound.

The obtained compound had a melting point of 129 to 131 ° C., elemental analysis was carbon 75.8%, hydrogen 5.65%, nitrogen 8.84%, and FD
-In combination with the analysis results of MS and NMR, tris (m-
Isopropenylphenoxy) -S-triazine (IPT
And)).

Synthesis Example 2 The following compound was obtained by performing the same operation as in Synthesis Example 1 except that m-isopropenylphenol of Synthesis Example 1 was changed to o-allylphenol.

The obtained compound has a melting point of 108 to 110 ° C., elemental analysis is carbon 75.6%, hydrogen 5.73%, nitrogen 8.70%, FD
-Tris (o-
Allylphenoxy) -S-triazine (APT)
Identified.

Examples and Comparative Examples Compounds obtained in Synthesis Examples 1 and 2, 2,2 'for comparison
-Using diallyl bisphenol A, N, N'-4,
A cured product was obtained under the conditions shown in Table 1 in combination with 4'-diphenylmethane bismaleimide [a product of Mitsui Toatsu (BMI)]. The physical properties of the cured product are also shown in Table 1. It can be seen that the composition of the present invention has a good balance of curability, heat resistance and mechanical properties.

Claims (2)

[Claims] 1. An S-triazine compound having at least two or more alkenyl-substituted aryloxy groups in the molecule, and a polymaleimide compound having at least two maleimide groups in the molecule. , A thermosetting resin composition. 2. The thermosetting resin composition according to claim 1, wherein the alkenyl group is an isopropenyl group or an allyl group.