JPS6331499B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermosetting resin compositions. Polyimides are already known to have a high degree of heat resistance, chemical resistance, and other excellent properties, and are particularly useful in films used at high temperatures, wire coatings, laminates, paints, adhesives, and molded products. It is very useful for applications such as Among these, homopolymers of maleimide compounds have excellent thermal properties, but due to their molecular structure they inevitably have a drawback in mechanical strength, so by copolymerizing them with other materials, the thermal properties Currently, the mechanical strength is improved and used even if it sacrifices a certain amount of strength. On the other hand, aromatic polyimides such as "Vespel" and "Polyimide 2080" have poor mechanical properties,
Although it has excellent thermal properties, it has difficulty in processability, and is used in various applications such as films and wire coatings, but requires high temperatures and pressures for molding and laminating. The disadvantage is that processing equipment for general thermosetting resins such as resins cannot be used as is, and special equipment for this resin is required, so it is only used in a few fields. The current situation is that there is no such thing. As a result of intensive studies to solve these problems, the present inventors developed a mixed system of benzophenonetetracarboxylic acid or its derivative and a polyamine having at least two amino groups in an organic solvent at 20 to 200°C. General formula (1) and general formula (2) are added to the imide solution heated to
The present invention provides a thermosetting resin composition obtained by dissolving one or more of the maleimide compounds shown in the following. That is, the present invention comprises (A) 85 to 15% by weight of a maleimide compound represented by general formula (1) or general formula (1) and general formula (2); (However, R ₁ is an alkyl group or a hydrogen atom, and R ₂ is

【formula】

【formula】

【formula】

[Formula] R ₃ is

【formula】

【formula】

[Formula] (-CH ₂ )- _o Indicates CH ₃ . where n is 3 to 5) (B) 15 to 85% by weight of an organic solvent-soluble polyimide obtained from benzophenonetetracarboxylic acid or its derivative represented by general formula (3); (However, R ₂ is the same as above.) (C) Mapping the imidazole compound represented by general formula (4) (However, R ₄ to _{R 7} represent an alkyl group or a hydrogen atom, and may be the same or different.) Mix 0.5 to 5% by weight of a leimide compound in a solvent and apply it to lamination or molding materials. It is a thermosetting resin composition that can be used. The present invention will be explained in detail below. Examples of the maleimide compound constituting a component of the thermosetting resin composition in the present invention include 4,4'-
Methylenebis(N-phenylmaleimide), 4,
4′-oxybis(N-phenylmaleimide), N,
N'-sulfone bis(N-phenylmaleimide),
N,N'-dithiobis(N-phenylmaleimide)
Bismaleimide such as N-phenylmaleimide, N-3-chlorophenylmaleimide, N-4
- Monomaleimides such as nitrophenylmaleimide can be mentioned. Among these embodiments, one or more bismaleimides or one bismaleimide
Most preferred is the use of one or more species and one or more monomaleimides. These maleimide compounds are used in a range of 85-15% by weight. If the composition ratio of the maleimide compound is less than 15%, desired processability cannot be obtained and workability is not improved. Moreover, when it is 85% or more, workability is improved, but the mechanical strength is decreased, and it is ultimately impossible to obtain a heat-resistant molding material, which is one of the goals. Examples of the organic solvent-soluble polyimide which is a component of the thermosetting resin composition in the present invention include Polyimide 2080 manufactured by Updillon Co., Ltd.; things are also used. Another component, the imidazole compound, serves as a curing accelerator for the maleimide compound, and is used in an amount of 0.5 to 5% by weight of the maleimide compound. If it is less than 0.5%, it is meaningless, and 5
% or more is not preferable because the effect is large and workability and processability are adversely affected. In carrying out the present invention, the above resin composition, that is, maleimide compound-organic solvent soluble polyimide-imidazole compound, is usually dissolved in, for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, etc., and a glass cloth is added to the solution. The prepregs obtained by immersing or applying a resin solution to these base materials and removing the solvent by volatilization are stacked, pressed, and heat molded. By carrying out this process, a laminate product with excellent heat resistance and electrical properties can be obtained. When applied to molding materials, a powder material that can be molded at 180 to 200°C can be obtained by pouring the resin solution into a large excess of water to separate only the resin and drying it. These molding materials produce molded products that are excellent both mechanically and thermally. Thus, the composition of the present invention can be said to be an industrially excellent composition since it mutually covers the drawbacks of polymerized aromatic polyimide and maleimide compounds, and has heat resistance, processability, and mechanical properties. EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. Example 1 64.4gr. (0.2mol) of benzophenonetetracarboxylic dianhydride (BTDA) and 39.6gr. (0.2mol) of 4,4'-diaminodiphenylmethane (DAM) were mixed with N-methyl-2-pyrrolidone. (NMP), stirred and heated, and held at a reaction temperature of 200° C. for 4 hours while removing condensed water from the system. Then NMP
Added 100gr. The viscosity of the solution thus obtained was 106 poise (23°C). To this solution, 200 gr. of 4,4'-methylenebis(N-phenylmaleimide), 2 gr. of 4-ethyl-2-methyl-imidazole, and 400 gr. of dimethylformamide were added, and the mixture was heated to 60°C to form a uniform resin solution. A solution was obtained.
This solution was applied to a satin-type glass cloth treated with γ-aminopropyltriethoxysilane and heated to 150°C.
A prepreg was obtained by drying for 3 minutes and 5 minutes at 170°C. Next, stack multiple sheets of this prepreg at 200°C.
The sample was preformed with degassing twice in a press heated to 100 mL, and then held at a pressure of 50 kg/cm ² for 60 minutes, at which point the pressure was removed to produce a laminate. After curing this product for 15 hours at 220℃, the bending strength was measured and found that it was 55Kg/mm ² at room temperature, 43Kg/mm 2 even at 250℃, and 52Kg/mm ² even after 20 days of deterioration at 250℃. The values in ^mm2 are shown. The thermal decomposition curve is shown in FIG. Example 2 140gr. of N,N'-oxybis(N-phenylmaleimide) and 2.1gr. of 2MZ-Ogine (trade name of imidazole manufactured by Shikoku Kasei Co., Ltd.) were mixed with dimethylformamide.
Put 250gr. into a flask and melt at 50℃, dissolve 60gr. of polyimide 2080 (manufactured by Appujiyon Co., Ltd.) into the solution to make a uniform solution, disperse this in a large amount of water to form a powdery precipitate, and filtrate 100gr. It was dried at ℃ for 5 hours to obtain a molding material. When this material was put into a mold heated to 200℃ and molded at a pressure of 120Kg/ ^cm2 , 3
It maintained sufficient hardness when removed from the mold after being molded for a few minutes. The bending strength of the molded product, which was then post-cured at 250℃, was measured to be 12.5Kg/mm ² at room temperature and 11Kg/mm ² even in a 250℃ atmosphere.
11.5Kg/mm ² even after heating for 20 days (room temperature measurement)
maintained its strength.

[Brief explanation of the drawing]

The figure is a thermal decomposition curve diagram.

Claims (1)

[Scope of Claims] 1 (A) 85 to 15% by weight of a maleimide compound represented by general formula (1) or general formula (1) and general formula (2); (However, R ₁ represents an alkyl group or a hydrogen atom, R ₂ is [Formula] [Formula] [Formula] or [Formula] R ₃ is [Formula] [Formula] [Formula] -(CH ₂ ) _o -CH ₃ where n is 3 to 5) (B) 15 to 85% by weight of an organic solvent soluble polyimide obtained from benzophenonetetracarboxylic acid or a derivative thereof represented by the general formula (3); (However, R ₂ is the same as above) (C) An imidazole compound represented by general formula (4)
0.5 to 5% by weight of (A) (However, R ₄ to _{R 7} represent an alkyl group or a hydrogen atom, and may be the same or different.) A thermosetting resin composition.