JPS58134141A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:A composition, consisting of a prepolymer of triallyl isocyanurate and diallyl phthalate, bis(4-cyanatophenyl)propane, biamaleimide compound and amine, having class H heat resistance, and useful for electrical insulating materials. CONSTITUTION:A composition consisting of (A) preferably 95-50wt% copolymeric prepolymer of triallyl isocyanurate and diallyl phthalate, usually containing 20-80mol% triallyl isocyanurate, and having 5,000-15,000 number-average molecular weight with (B) preferably 0.2-28wt% 2,2-bis(4-cyanatophenyl)propane or a prepolymer thereof, preferably having 800-4,000 weight-average molecular weight, (C) preferably 0.3-22wt% bismaleimide compound expressed by the formulaI(X is formula II, III or IV) or a prepolymer thereof and (D) preferably 0.5-25wt%, based on the total composition, amine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel heat-resistant resin composition. - In recent years, so-called electrical insulating materials such as electrical parts and electronic parts have been required to have excellent properties9, and resins with particularly good heat resistance, mechanical properties, and electrical properties have been developed. Moreover, its application fields are wide-ranging, including molding materials, laminates, and insulation panels. Diaryl phthalate resin has been known as a heat-resistant electrical insulating material, and a prepolymer of diallyl ortho-7-talate or diallyl sipthalate has been used. Molded products made by curing these prepolymers have excellent electrical properties and heat resistance, as well as chemical resistance and
It also has excellent mechanical properties and is used in a moderate number of electrical parts.

However, for example, in fields where high heat resistance is desired,
Diallyl 7-thalerate resin cannot be used in fields that require H class (ito C) in the heat resistance category of electrical insulating materials.

The present inventor has proposed a method for producing a copolymer prepolymer of triallyl isocyanurate and diallyl phthalate and a method for producing a copolymerized prepolymer of triallyl isocyanurate and diallyl phthalate as an alternative to these diallyl phthalate prepolymers, which satisfies the field in which such heat resistance is required. A patent application has been filed for a curable resin composition containing a coalesced prepolymer as a main component.

(4$ Gansho!j-/4t)! 7θko, Tokugan Shoj Goo 13
Core 0j1 Patent Application 1f9-43603) The molded product obtained by curing this resin composition has performance equivalent to class I in the heat resistance classification of insulating materials, and has excellent electrical and mechanical properties. The time characteristics are also satisfied. .

However, these cured products are somewhat brittle and have poor adhesion to glass, so when applied to laminates of molded + glass woven fabrics using short glass fibers as fillers, their bending strength and impact strength are low. There is a disadvantage.

As a result of subsequent intensive studies, the present inventor discovered that a copolymer prepolymer of triallyl isocyanurate and 'diallyl phthalate obtained by the method related to the earlier application of the present inventor and λ, --bis(tercyanatophenyl) propane,
It has been found that a resin composition containing a bismaleimide compound and an amine solves the above drawbacks while maintaining the heat resistance of Hfi in the heat resistance category of electrical insulating materials, thereby providing a resin composition.

That is, the present invention provides: (a) a copolymerized prepolymer of triallyl isocyanurate and diallyl phthalate; (b) 2. Bis represented by λ-bis(tercyanatophenyl)propane or its prepolymer and!・It is based on a heat-resistant resin composition containing a reimide compound or its prepolymer, and (d) an amine.

A copolymer prepolymer of triallyl isocyanurate and diallyl phthalate used in the present invention (hereinafter sometimes simply referred to as a copolymer prepolymer).
Although any ratio of each component can be used, usually 10 to 10 moles of triallyl isocyanurate is preferably used. The number average molecular weight of the skeleton copolymerized prepolymer is 5ooo~/j 000. from the molding surface. And the melting point is 30-. A temperature of 200°C is preferred.

In addition, the 2,λ-bis(4I-cyanato, phenyl)propane used in the present invention may be mixed with a mineral acid, a Lewis acid, or a charcoal salt.
Alternatively, it can be obtained by polymerization in the presence of a catalyst such as a phosphate ester such as tributylphosphine. This prepolymer aX* has an average molecular weight of too-tiooo and a softening point of 3.
A temperature of 0 to 70°C is preferably used.

The bismaleimide compound used in the present invention is coated with:

A-body Ka
Al with bismaleimide.

These can be obtained by dehydrating and cyclizing bismaleamic acid, which is usually obtained by the reaction of maleic anhydride and the corresponding diamines, by a method of cyclization. These bismaleimide compounds may be substituted with monomers such as metaphenylenediamine, s, cubisaminophenylmethane, μ, μ′-, and suaminophenyl sulfone, p, 4
It can also be used in the form of a prepolymer with diamines such as I'-bisaminophenyl ether. In this case, the blending ratio of the bismaleimide compound and diamine is not limited, and the bismaleimide is 1.0 mol. In contrast, a ratio of 0 mol of diamine O0j~/0 is particularly suitable.

The resin composition of the present invention can contain amines such as diamines, if necessary.

These amines include meta-phenylene diamine, ≠, ri'-bimeaminophenylmethane, ≠, v'-bis-aminophenyl sulfone, ≠, 3'-bis-aminophenyl ether, meta-xylene diamine, para-xylene diamine,
Co, λ-bi□varnish (guaminophenyl) diamide such as propane, λ-methyl\:1゜imidazole, coethyl≠-methylimidazole,
Imidazoles such as l-propyl-2-methylimidazole can be used. These amines can be present in the composition in free form or in the form of prepolymers with bismaleimides as described above. The co-polymer prepolymer in the resin composition of the present invention, which can also be used, and λ, --
The mixing ratio of bis(cucyanatophenyl)propane or its prepolymer and the bismaleimide compound -S
It is appropriate to use ``co, -monobis(≠-cyanatophenyl)propane in an amount of 00λ~co'' and a bismaleimide compound in a range of 0.3 to 2.2 weight% based on the weight of O. .Also, amines include O, S-2, jl in the resin composition.
It is preferable to add so that i: fiqb.
.

The composition of the present invention is air-cured by heating at high temperatures, and in order to accelerate curing, one organic peroxide, such as benzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide,
It is preferable to add a small amount of dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc. Considering the curing speed and physical properties of the cured product, the amount added is 10% of the mixed resin, ON
A suitable range of 2 to 5 parts by weight of Q to N is appropriate.

The curing treatment m& of the composition of the present invention is not particularly limited, but is preferably ioo to 300°C.

The composition of the present invention may optionally contain copolymerizable ethylene thread additives such as diallyl isophthalate, triallyl cyanurate, triallyl in cyanurate, etc., as a flow regulator or diluent to the extent that the heat resistance is not compromised. It can be used as an agent in a range less than the weight of SO in the resin component.

The resin composition of the present invention can be widely used as a molding material laminate, an insulating board, etc. When using the resin composition of the present invention as a molding material, reinforcing materials such as glass fiber and carbon fiber, charcoal-brown calcium, silica,
Inorganic fillers such as alumina, Merck, clay, kaolin, mica powder, calcium stearate and other mineral soaps, mm agents such as fatty acid amide, preparations such as carbon black, titanium fermentation, nohydroquinone, benzoquinone, etc. Various additives such as curing retarders, organic peroxides, or modifiers such as silane coupling agents can be added as appropriate.

The amount of reinforcing material and inorganic filler added can be changed as appropriate depending on the purpose of use, but normally, if the total amount of both exceeds 3 oozg parts per 1ooxh part of the mixed resin, moldability will be impaired.

The molding material made in this way can be used to make electrical parts that require heat resistance, such as connectors and switches, by compression molding, transfer molding, or injection molding.
, flags, magnet cores, etc. can be molded.

The resin composition of the present invention is dissolved in a suitable inert organic solvent, for example, ketones such as methyl ethyl ketone, esters such as ethyl acetate, amides such as dimethylformamide, etc. alone or using a mixed solvent of λ or more. To this, an organic sensitizer or, if necessary, a curing retarder is added to form a mixed solution.

This mixed solution is impregnated into a base material such as glass fiber, carbon fiber-based woven fabric, non-woven fabric, or paper, air-dried, and then heat-treated to produce a prepreg.The laminated 1#L6 layer for printed wiring boards is heated and pressed. can be used as a decorative board.

Add the above mixed solution to '#IL11! ! Alternatively, it can be applied to a metal plate and heated to be used as an insulation board. - The cured resin thus obtained has excellent heat resistance, electrical properties, and mechanical properties9, and can be applied to various applications where these properties are required.

EXAMPLES The present invention will be specifically explained below using Examples.

Examples/Comparative Example 1 1 r) A mixture of λ,2-upper 2-≠-cyanatophenyl)propane obtained by the reaction of bisphenol A and cyanogen halide and this prepolymer. (West German Bayer AG KIJ617J) 11) 1 mole of bismaleimide made from maleic anhydride and I-bisamino-7enylmethane is reacted at a ratio of +, u'-bisamino phenylmethane O, SS moles. bismaleimide-diamine prepolymer made by

(From Loos-Boulin KER Engineering M 60/) Above i)
of? A mixture of 7-fold*S, 11) in 10N1'4 and λ-ethyl-μm methylimidazole 3-fold'Ik% is referred to as "mixed resin A."

*Note (1) Number average molecular weight 71,00. flli point i
oo~iio°C Bromination 63. Content of triallyl in cyanurate unit j O, 0 mol - The above mixture was uniformly dissolved, and the resin liquid was degreased to make a soft
The Xfi/I4 plate was heat-treated at 0°C for 20 minutes to obtain a slightly dark brown transparent thin film of 20 to 30 microns. Table 1 shows the results of solvent resistance, lead hardness and bending tests for this thin film.

Example λ, Comparative example *t), (17 number average molecular size 00.@A100
-/10°C, containing 1127.3 mol of triallylisocyanurate units with A prime value of 60 (2i mixed resin At-N
-6ogs solution bath-scaled in methylpyrrolidone (3) Jw+long chopped strand manufactured by Asahi Fiberglass Co., Ltd. (4) Made by Nitto Funka Kogyo Co., Ltd. Average particle size l
-1μ (5) A/7g manufactured by Nippon Unicar Co., Ltd. The above mixture excluding glass fibers, calcium carbonate, and stearinic calcium is dissolved in 100 parts by weight of acetone, and this solution is transferred to a kneader. The premix of calcium carbonate and calcium stearate and the glass fibers were sequentially added and mixed. Take out the carcass mixture from the kneader, spread it on a tray and dry it overnight, then mix it with a roller at 100℃ and mix it into a sheet shape. Grind it into a powder or granule. It was used as a molding material.

Various test pieces were prepared from the obtained molding materials by pressure #i or injection molding using various molds.

Table 2 shows the size of the test piece and molding conditions for each test item. The shape of the test piece is J Engineering SK6ri/or one based on this, and the measurement method is rlBK6ri//
Based on. The results of these measurements are shown in Table 3.

* [E (IJ) Glass cloth (Arisawa Seisakusho G [F
3-60JJ was immersed, air-dried, and then dried at ro°C for 20 minutes to produce a Gripreg with a resin content of ≠6% by weight. T sheets of this prepreg were stacked, and a copper foil (manufactured by Kashitsu Metal Foil & Powder Industry Co., Ltd. (-T!BJ) was placed on top of it, and a cellulose triacetate film was placed on both sides of the laminate using hot pressure press (iro℃). J
After 30 minutes, the pressure was maintained and the product was water-cooled for 10 minutes to obtain a single-sided steel-clad laminate having a thickness of 6 mm and having no warp. This laminate was further exposed to ir.

After cure for 7 hours at ℃.

The cured laminate was subjected to various physical property tests in accordance with JIS C6≠ri, and the results are shown in the table below.

:18′′・I Applicant: Nipponka, JL, Sei Co., Ltd.
1 other person

Claims (1)

[Scope of Claims] (a) Copolymer polymer of triallyl isocyanurate and diallyl phthalate (b) 2.2-bis(darcyanatophenyl)propane or its prepolymer (C) Represented by the general formula A heat-resistant resin composition comprising: a bismaleindo compound or a prepolymer thereof; and (d) an amine.