JPH089655B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a thermosetting resin composition which, when cured, gives a cured product having good heat resistance.

[Prior Art] It has been conventionally known that a cured product can be obtained from a triallyl isocyanurate monomer or a triallyl isocyanurate prepolymer, and these cured products have good stability, so that a molding material or resin modification Used as an agent,
In addition, the obtained cured product is particularly excellent in heat resistance and is therefore used in various electric parts such as connectors, switches, plugs, magnet cores, and printed wiring boards.

[Problems to be Solved by the Invention] However, although these cured products have the above-mentioned characteristics, they have the drawback of being extremely brittle, and on the other hand result in limited use conditions. .

The present invention is a thermosetting resin suitable for applications such as impregnation, casting, lamination, molding and adhesion, which has improved reliability without observing defects such as voids and cracks in a cured product under these circumstances. It is intended to provide a composition.

[Means for Solving the Problems] As a result of intensive studies for solving the above problems, the present inventors have found that triallyl isocyanurate prepolymers and / or triallyl isocyanurate monomers, polyepoxy compounds and allylphenol The inventors have found that a cured product free from cracking can be obtained by using a composition containing a reaction product and, if necessary, an organic peroxide, and reached the present invention.

That is, the present invention comprises (a) 30 to 70 parts by weight of a triallyl isocyanurate prepolymer and / or triallyl isocyanurate monomer, (b) 70 to 30 parts by weight of a reaction product of a polyepoxy compound and allylphenol,
(C) A thermosetting resin composition comprising 0 to 5 parts by weight of an organic peroxide.

As described in JP-A-64-62311, triallyl isocyanurate prepolymer which is one of the components (a) used in the present invention is a triallyl isocyanurate in the presence of molecular oxygen at 100 ° C. or higher. It is obtained by heating to the temperature of and causing a polymerization reaction. This reaction is carried out under normal pressure or under pressure. As the molecular oxygen, oxygen gas or an oxygen-containing gas such as air is used. The supply amount of molecular oxygen varies depending on its form, supply method, and polymerization temperature and cannot be uniformly limited. The point is that it is arbitrarily selected within a range in which the polymerization temperature can be controlled.

The polymerization temperature is required to be 100 ° C. or higher, and at a temperature lower than 100 ° C., the polymerization reaction does not substantially proceed even in the presence of a molecule. The upper limit of the polymerization temperature is not particularly limited,
At a temperature of 180 ° C. or higher, the signal of the polymerization reaction is fast and it becomes difficult to control the polymerization rate. Normally 100-110 ° C
A range of degrees is preferred.

The molecular weight of the triallyl isocyanurate prepolymer used in the present invention is 1,000 to 100,000.

The triallyl isocyanurate monomer, which is the other component (a) used in the present invention, is a colorless, low-viscosity liquid at room temperature.

The polyepoxy compound constituting the component (b) used in the present invention is a bisphenol compound such as bisphenol A or bisphenol F, phenol, a novolac resin obtained by the reaction of cresol and formaldehyde, aminophenol, 4,4′- A general polyglycidyl compound which is a reaction product of an amino compound such as diaminophenylmethane and epichlorohydrin is used.

The component (b) can be easily obtained by reacting these epoxy compounds and allylphenol with the presence of an epoxy curing catalyst such as a tertiary amine or an organic phosphine compound.

The amount ratio of the component (a) and the component (b) is 30 to 70/70 to 30 (parts by weight). When the amount of the component (a) exceeds 70 parts by weight, the effect of improving the brittleness of the cured resin is small, and when it is less than 30 parts by weight, the triallyl isocyanurate cured product has an unfavorable effect on the conventional excellent heat resistance. give.

Examples of the organic peroxide that is the component (c) include t-butylperoxyisopropyl carbonate, di-t-butylperoxyphthalate, t-butylperoxyacetate, and 2,5-dimethyl-2,5-di (benzoyl). Peroxy)
Hexane, t-butyl peroxylaurate, t-butyl peroxymaleic acid, t-butyl peroxybenzoate, methyl ethyl ketone peroxide,
Dicumyl peroxide, silohexanone peroxide, t-butyl dicumyl peroxide and the like can be mentioned.

Two or more kinds of these organic peroxides may be mixed and used. The addition amount of these is 0 to 5 parts by weight, preferably 1 to 3 parts by weight, based on the resin composition. In the present invention, the purpose can be sufficiently achieved without using an organic peroxide, but when an organic peroxide is used, it can be cured at a low temperature, and by selecting an organic peroxide, the curing temperature is Can be set arbitrarily. For example,
By selecting dicumyl peroxide as the organic peroxide, it is possible to obtain a cured product that is sufficiently cured by heating at 120 ° C. for 3 hours, 150 ° C. time, and 180 ° C. for 3 hours and does not cause cracking.

An inorganic or organic fibrous reinforcing material, a granular filler, a release agent, a coloring agent, an antistatic agent and the like can be added to the resin composition of the present invention.

The resin composition of the present invention can be easily subjected to operations such as impregnation, casting, lamination, molding and adhesion.

Since the resin composition of the present invention has good solubility, it can be easily impregnated into the reinforcing base material in a solution state. Further, it can be impregnated with or without a solvent by adjusting the viscosity.

Examples of the impregnating solvent include acetone, ketone type solvents such as methyl ethyl ketone, tetrahydrofuran, cyclic ether type solvents such as dioxane, methylene chloride,
A halogen-based solvent such as chloroform can be used, but a solvent having a low boiling point is preferable in consideration of easy drying after impregnation.

The reinforcing base material includes paper, cloth, glass, fiber, aramid fiber, carbon fiber, etc., and is selected depending on the application.

The prepreg thus obtained is easy to handle at room temperature.

The cured product obtained from the resin composition of the present invention is suitable for the fields of electronics, electric parts, aircraft, automobiles, construction and the like.

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Examples 1-2 Triallyl isocyanurate prepolymer and / or triallyl isocyanurate monomer (manufactured by Nippon Kasei Co., Ltd.),
The resin composition of the present invention shown in Table 1 was prepared using a reaction product of diglycidyl ether of bisphenol A (manufactured by E-828 Yuka Shell Co., Ltd.) and o-allylphenol and an organic peroxide. These compositions were dissolved in THF, impregnated with carbon fiber (Torayca T300 Toray Co., Ltd.), and dried prepreg was subjected to thermocompression molding (120 ° C. for 3 hours + 150 ° C. for 3 hours) + 180 ° C. for 3 hours according to a conventional method. Laminates were manufactured. The obtained laminate was a good laminate without voids.

Comparative Example 1 As a comparative example, a prepreg was manufactured with the resin composition shown in Table 1 by the same manufacturing method as in the example, and thermocompression molding (3 at 100 ° C.
Time + 120 ° C. for 3 hours + 150 ° C. for 3 hours) to produce a laminate. The resulting laminate had no voids but had cracks along the fiber axis.

[Effects of the Invention] As described above, the thermosetting resin composition of the present invention can be obtained as a good cured product with improved brittleness and no defects such as voids and cracks.

Claims (1)

[Claims] (1) 30 to 70 parts by weight of a (a) trial isocyanurate prepolymer and / or triallyl isocyanurate monomer, (b) 70 to 30 parts by weight of a reaction product of a polyepoxy compound and allylphenol, (c) A thermosetting resin composition comprising 0 to 5 parts by weight of an organic peroxide.