JPH0323572B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel heat-resistant resin composition. In recent years, various properties have been required for so-called electrically insulating materials such as electrical parts and electronic parts, 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 insulating varnishes. Diallyl phthalate resin has been known as a heat-resistant electrical insulating material, and diallyl orthophthalate or diallyl isophthalate prepolymers have been used. The molded products obtained by curing these prepolymers have excellent electrical properties,
In addition to being heat resistant, it also has excellent chemical resistance and mechanical properties, and is used in a variety of electrical parts. However, diallyl phthalate resin cannot be used in fields where higher heat resistance is desired, for example, in fields where H type (180°C) is required 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 copolymer prepolymer of these copolymers as an alternative to these diallyl phthalate prepolymers, which satisfies the field requiring such heat resistance. A patent application has been filed for a curable resin composition containing a polymer as a main component. (Patent application 1986-142702, Patent application 1984-132705,
55-65603) The molded product obtained by curing this resin composition is
It has performance equivalent to class H in the heat resistance category of insulating materials, and also satisfies various electrical and mechanical properties. However, these cured products are somewhat brittle and have poor adhesion to glass, so when applied to molded products filled with short glass fibers or laminates of glass woven fabric, 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 2,2-bis(4-cyanate) It has been found that a resin composition containing (phenyl)propane, a bismaleimide compound, and an amine can provide a resin composition that eliminates the above drawbacks while maintaining heat resistance of class H in the heat resistance category of electrical insulating materials. That is, the present invention provides: (a) a copolymer prepolymer of triallyl isocyanurate and diallyl phthalate, (b) 2,2-bis(4-cyanatophenyl)propane or a prepolymer thereof, and (c) a general formula (Here, X is

【formula】

【formula】

[Formula] is shown. ) A novel heat-resistant resin composition containing a bismaleimide compound or its prepolymer represented by (d) amine is the main feature. Although any ratio of each component in the copolymer prepolymer of triallyl isocyanurate and diallyl phthalate (hereinafter sometimes simply referred to as copolymer prepolymer) used in the present invention can be used, usually triallyl Those containing 20 to 80 mol% of isocyanurate are preferably used.
The copolymerized prepolymer preferably has a number average molecular weight of 5,000 to 15,000 from the molding surface and a melting point of 50 to 200°C. The 2,2-bis(4-cyanatophenyl)propane or its prepolymer used in the present invention is composed of P,P'-isopropylidene diphenol (hereinafter abbreviated as bisphenol A) and cyanogen halide. The monomer obtained by the reaction of It can be obtained by polymerization in the presence of a catalyst such as This prepolymer preferably has a weight average molecular weight of 800 to 4000 and a softening point of 50 to 70°C. The bismaleimide compound used in the present invention has the general formula (Here, X is

【formula】

【formula】

[Formula] is shown. ). Specifically, N,N'-p-phenylene bismaleimide, N,N'-(methylene-di-p-phenylene)bismaleimide, N,N'-(oxy-di-p-phenylene)
-phenylene) bismaleimide. These can be obtained by dehydrating bismaleamic acid, which is usually obtained by reacting maleic anhydride with the corresponding diamine, by various methods. In addition, these bismaleimide compounds can be substituted with monomers such as metaphenylenediamine, 4,4'-bisaminophenylmethane, 4,
It can also be used in the form of a prepolymer with diamines such as 4'-bisaminophenyl sulfone and 4,4'-bisaminophenyl ether. In this case, the blending ratio of the bismaleimide compound and the diamines is not limited, but a ratio of 0.5 to 1.0 moles of diamine to 1.0 mole of bismaleimide is particularly suitable. The resin composition of the present invention can contain amines such as diamines, if necessary. These amines include metaphenylene diamine, 4,
4'-bisaminophenylmethane, 4,4'-bisaminophenyl sulfone, 4,4'-bisaminophenyl ether, metaxylene diamine, paraxylene diamine, 2,2-bis(4-aminophenyl)propane Diamines such as 2-methylimidazole, 2-ethyl-4-methylimidazole,
Imidazoles such as 1-propyl-2-methylimidazole can be used. These amines can be present in the composition in free form or, as described above, can be used in the form of prepolymers with bismaleimides. The mixing ratio of the copolymerized prepolymer, 2,2-bis(4-cyanatophenyl)propane or its prepolymer, and the bismaleimide compound or its prepolymer in the resin composition of the present invention can be selected arbitrarily. , moldability, and other physical properties, 2,2-bis(4-cyanatophenyl)propane is 0.2 to 28% by weight, and bismaleimide compound is 95 to 50% by weight of the copolymerized prepolymer. is suitably used in a range of 0.3 to 22% by weight.
Moreover, it is preferable to add amines to the resin composition in an amount of 0.5 to 2.5% by weight. The composition of the present invention is air-cured by heating at high temperatures, and organic peroxides such as benzoyl peroxide, tertiary peroxide, etc. are added to accelerate curing.
It is preferable to add a small amount of butyl perbenzoate, ditertiary butyl peroxide, dicumyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, and the like. The amount added is based on 100 parts by weight of the mixed resin, taking into consideration the curing speed and physical properties of the cured product.
A range of 0.2 to 5 parts by weight is suitable. The curing temperature of the composition of the present invention is not particularly limited, but is preferably 100 to 300°C. If necessary, copolymerizable ethylene monomers such as diallyl isophthalate, triallyl isocyanurate, and triallyl isocyanurate may be added to the composition of the present invention as a flow regulator or diluent to the extent that the heat resistance is not impaired. It can be used within a range of 50% by weight or less in the ingredients. The resin composition of the present invention can be widely used as a molding material laminate, an insulating varnish, or the like. When the resin composition of the present invention is used as a molding material, reinforcing materials such as glass fiber and carbon fiber, inorganic fillers such as calcium carbonate, silica, alumina, talc, clay, kaolin, mica powder, calcium stearate, etc. various metal soaps, mold release agents such as fatty acid amide, pigments such as carbon black and titanium oxide, hydroquinone,
Curing retarders such as benzoquinone, organic peroxides,
Alternatively, various additives such as 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 300 parts by weight per 100 parts by weight of the mixed resin, moldability will be impaired. From the molding material thus produced, electrical parts requiring heat resistance, such as connectors, switches, plugs, magnetic cores, etc., can be molded by compression molding, transfer molding, or injection molding. The resin composition of the present invention is mixed with a suitable inert organic solvent,
For example, it is dissolved in a ketone such as methyl ethyl ketone, an ester such as ethyl acetate, an amide such as dimethylformamide, etc. alone or in a mixed solvent of two or more, and an organic peroxide or a curing retardant is added to this as necessary. Add the agent to make a mixed solution. This mixed solution is impregnated into woven fabrics such as glass fibers and carbon fibers, or base materials such as non-woven fabrics and paper.
After air-drying, heat treatment is performed to produce a prepreg, which can be pressed under heat and pressure and used as a laminate for printed wiring boards or a decorative board. Further, the above mixed solution can be applied to an electric wire or a metal plate and heated to be used as an insulating varnish. The cured resin obtained in this way has heat resistance,
It has excellent electrical and mechanical properties and can be applied to a variety of applications that require these properties. The present invention will be specifically explained below using Examples. Example 1, Comparative Example 1) A mixture of 2,2-bis(4-cyanatophenyl)propane obtained by the reaction of bisphenol A and cyanogen halide and this prepolymer. (Bayer GmbH, West Germany KU6573)) 1 mole of bismaleimide made from maleic anhydride and 4,4'-bisaminophenylmethane is reacted with 0.55 mole of 4,4'-bisaminophenylmethane. bismaleimide-diamine prepolymer made by (Rhône-Poulenc KERIMID601) 87% by weight of the above, 10% by weight of ) and 2-
A mixture containing 3% by weight of ethyl-4-methylimidazole is referred to as "mixed resin A."

[Table] The above mixture was uniformly dissolved, this resin liquid was coated on a degreased soft steel plate, and heat treated at 180°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, pencil hardness and bending tests performed on this thin film.

【table】 Example 2, comparative example 2

[Table] Dissolve the above mixture excluding glass fiber, calcium carbonate, and calcium stearate in 100 parts by weight of acetone, transfer this solution to a kneader, and sequentially add the premix of calcium carbonate and calcium stearate and glass fiber. Add and mix. The mixture was removed from the kneader and spread on a tray to dry overnight. After drying, use a roll
The mixture was kneaded at 100° C. for 5 minutes to form a sheet, which was then ground into a powder or granule molding material. Various test pieces were created by compression or injection molding the obtained molding material 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 JIS K 6911 or compliant, and the measurement method is also JIS K.
Based on 6911. The results of these measurements are shown in Table 3.

[Table] (2) Injection molding

【table】

[Table] *Note (1) Measured values after immersion in boiling water for 2 hours

[Table] Same.
A glass cloth ("S-603" manufactured by Arisawa Seisakusho Co., Ltd.) was immersed in the above resin solution for impregnation, air-dried, and then dried at 80° C. for 40 minutes to prepare a prepreg with a resin content of 46% by weight.
Copper foil (T5B manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.) was placed on top of 8 sheets of these pre-regs, and a cellulose triacetate film was placed on both sides of the laminate using hot pressure press (150℃ 30Kg/ cm ² ), and after 30 minutes, the pressure was maintained while cooling with water to 80° C. to obtain a single-sided copper-clad laminate with a thickness of 1.6 mm and no warpage. This laminate was further after-cured at 180°C for 2 hours. The cured laminate was subjected to various physical property tests in accordance with JIS C 6481, and the results are shown in Table 4.

【table】

Claims (1)

[Scope of Claims] 1 (a) Copolymerized prepolymer of triallyl isocyanurate and diallyl phthalate (b) 2,2-bis(4-cyanatophenyl)propane or a prepolymer thereof (c) General formula (Here, X represents [Formula] [Formula] [Formula]) A heat-resistant resin composition comprising a bismaleimide compound represented by the following or a prepolymer thereof and (d) an amine.