JPH0627193B2 - Thermosetting resin composition - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a thermosetting resin composition having excellent heat resistance, mechanical properties and processability.

[Technical background of the invention and its problems] Polyimide has a high degree of heat resistance, chemical resistance and other excellent properties, and is particularly useful for use at high temperatures in films, electric wire coatings, laminated products, Used as paints, adhesives, molded products, etc. Of these, the homopolymers of maleimide compounds are excellent in thermal properties, but their molecular structure is inferior in mechanical strength, so by copolymerizing with other materials, their thermal properties are sacrificed to some extent. Even so, the current situation is to improve the mechanical strength. On the other hand, “Vespel” and “Polyimide 2080”, which are marketed as aromatic polyimides, have mechanical properties,
Since it has excellent thermal properties, it is used in various applications such as film and wire coating, but it is difficult to process and is currently on the market in fields such as molding, lamination, and adhesion that require relatively high temperature and high pressure. Since the processing equipment for general thermosetting resin such as phenol resin and epoxy resin cannot be used as it is, there is a drawback that special equipment is required. It was used only for the department.

[Object of the invention] The object of the present invention has been made in view of the above-mentioned drawbacks.
It is intended to provide a thermosetting resin composition having excellent heat resistance, mechanical properties and processability.

[Summary of the Invention] As a result of intensive studies to achieve the above object, the present inventor has found that a thermosetting resin composition having the composition described below has excellent heat resistance, mechanical properties, and processability. The inventors have found that the objects can be achieved and completed the present invention.

That is, the present invention provides (A) general formula (However, in the formula, R ¹ is Or In which n represents an integer of 2 or more) and an organic solvent-soluble polyimide (B) (a) general formula containing benzophenonetetracarboxylic acid or its derivative as a condensed acid component. (However, in the formula, R ² is an n-valent organic group, X ¹ and X ² are the same or different one atom or group selected from a hydrogen atom, a halogen atom or an organic group, and n is an integer of 2 or more. And (b) the general formula (Wherein R ³ is a hydrogen atom, a halogen atom or an atom or group selected from an organic group, and m is an integer of 1 to 5), and 1 equivalent of the maleimide group of polymaleimide is used. In addition, addition reaction product having a structure in which the amino group of aminophenol is added to the maleimide group at a ratio of 0.1 to 1 mol of aminophenol, and (C) the general formula (Wherein R ^{4 to} R ⁷ represent the same or different atoms or groups selected from a hydrogen atom or an alkyl group), the organic solvent-soluble polyimide (A) and the addition reaction product (B). With respect to the total amount of [(A) + (B)], the organic solvent-soluble polyimide is 5 to 80% by weight, and the addition reaction product is 95 to
The thermosetting resin composition comprises 20% by weight and 0.5 to 5% by weight of imidazole (C) with respect to the addition reaction product (B).

Examples of the (A) organic solvent-soluble polyimide used in the present invention include polyimide “2080” manufactured by Upjohn Co.
(Product name) and the like. This is represented by the above-mentioned general formula, and is obtained by reacting benzophenonetetracarboxylic acid or its derivative with polyamines or polyisocyanates by a conventional method, and dimethylformamide,
It is soluble in aprotic organic solvents such as dimethylacetamide and N-methyl-2-pyrrolidone. Examples of the polyamines include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diamino-3,3′-dichlorodiphenylmethane, and the like. Further, as the polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-tolylene diisocyanate, 2,6'-
Examples include tolylene diisocyanate.

The (B) addition reaction product used in the present invention is obtained by reacting (a) polymaleimide with (b) aminophenol. (B) As the polymaleimide, for example, ethylene bismaleimide, hexamethylene bismaleimide, m- or p-phenylene bismaleimide, 4,4'-diphenylmethane bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'- Diphenyl sulfone bismaleimide, 4,4'-dicyclohexylmethane bismaleimide, m- or p-xylylene bismaleimide, 4,4'-
Diphenylcyclohexane bismaleimide, 4,4'-diphenylene bismaleimide, poly (phenylmethylene)
Examples thereof include polymaleimide. Examples of (b) aminophenol include o-, m- or p-aminophenol and aminocresol, aminoxylenol containing various substituent isomers, aminochlorophenol, aminobromphenol, aminocatechol, aminoresorcin, aminobis (hydroxy). Phenol) propane, aminooxybenzoic acid and the like can be mentioned. From each of these polymaleimide and aminophenol, one kind or two or more kinds are selected and reacted to obtain an addition reaction product. The compounding ratio of polymaleimide and aminophenol is such that aminophenol is 0.1 to 0.1 equivalent per 1 equivalent of maleimide group of polymaleimide.
It is preferable to add 1 mol. This compounded amount is 0.1
If it is less than the molar amount, the processability and mechanical strength of the resin composition are deteriorated, which is not preferable. On the other hand, if the amount exceeds 1 mol, the amino groups become excessive and the heat resistance and stability of the resin composition deteriorate, which is not preferable. The temperature of the addition reaction is generally 50
To 200 ° C, more preferably 80 to 180 ° C, and the reaction time can be arbitrarily selected depending on the temperature in the range of several minutes to several tens hours. Further, these reaction components may be melt-reacted without a solvent, but may be reacted in a solvent. As a solvent when reacting in a solvent,
In addition to polar solvents such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, low boiling point solvents such as acetone, methyl ethyl ketone, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate and cyclohexane can be mentioned. Alternatively, two or more kinds may be mixed and used. The (B) addition reaction product thus obtained is blended with the (A) organic solvent-soluble polyimide, but with respect to the total amount [(A) + (B)] of the organic solvent-soluble polyimide and the addition reaction product,
It is preferable to add 5 to 80% by weight of an organic solvent-soluble polyimide and 95 to 20% by weight of an addition reaction product. If the addition amount of the addition reaction product exceeds 95% by weight, mechanical strength is lowered, which is not preferable. On the other hand, if it is less than 20% by weight, the workability is deteriorated, which is not preferable.

The imidazole (C) used in the present invention is represented by the above general formula. Imidazole serves as a curing accelerator for the addition reaction product, and is 0.
Add 5 to 5% by weight. If the blending amount is less than 0.5% by weight, there is no effect in promoting curing, and if it exceeds 5% by weight, workability and heat resistance are deteriorated, which is not preferable.

The thermosetting resin composition of the present invention may contain a filler and other additives as long as it does not violate the object of the present invention, which comprises an organic solvent-soluble polyimide, an addition reaction product, and imidazole. As the filler, inorganic powder such as carion, clay, talc, calcium carbonate, silica, alumina, aluminum hydroxide is used, and other additives such as silane coupling agent, titanate coupling agent,
Examples thereof include stearic acid and carnauba wax, and these can be selected and used as necessary.

In carrying out the present invention, the thermosetting resin composition is usually used by dissolving it in N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide or the like.
When applied to a molding material, a resin solution can be poured into a large excess of water, and only the resin can be separated and dried to obtain a powder material. The thus obtained product can be heated and cured at 170 to 250 ° C.

[Examples of the Invention] Next, the present invention will be specifically described by examples. In the following examples and comparative examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Example 1 358 g (1 mol) of 4,4′-diphenylmethane bismaleimide and 32.7 g (0.3 mol) of m-aminophenol were mixed and kneaded by heating at 140 ° C. for 15 minutes to obtain an addition reaction product. 60 parts of polyimide 2080 (trade name, manufactured by Upjohn),
40 parts of the addition reaction product and 1 part of 2E4M7 (imidazole manufactured by Shikoku Kasei Co., Ltd., trade name) were dissolved in 400 parts of dimethylformamide to obtain a uniform solution. This solution is dispersed in a large amount of water to form a powdery precipitate, which is then filtered at 60 ° C.
A molding material was manufactured by drying under reduced pressure for an hour. The molding material thus obtained was placed in a mold heated to 200 ° C. and molded at a pressure of 120 kg / cm ² , and when it was taken out from the mold after molding for 3 minutes, sufficient hardness was maintained. Then, it was post-cured at 250 ° C. for 3 hours. When the bending strength of the molded product was measured, it was
15.1 kg / mm ^2, even in the 250 ° C. atmosphere has a strength of 11.2 kg / mm ^2, holds the strength of further 250 ° C. with 13.2 kg / mm ² even when heated for 20 days (room temperature measurement), the invention The effect of was confirmed.

Example 2 358 g (1 mol) of 4,4′-diphenylmethane bismaleimide and 54.5 g (0.5 mol) of m-aminophenol were mixed with 1,4-
It was dissolved in 275 g of dioxane and reacted by heating at 100 ° C. for 5 hours to obtain a uniform near reaction solution. Next, polyimide 20
80 parts (supra), 50 parts of addition reaction product, and 2MZ-A
0.5 parts of ZINE (imidazole manufactured by Shikoku Kasei Co., Ltd., trade name) was dissolved in a mixed solution of N-methyl-2-pyrrolidone / dioxane = 4/1 to prepare a resin solution having a concentration of 20%. The resin solution thus obtained was impregnated with aminosilane-treated glass cloth (250 × 250 × 0.18 mm) and the temperature was maintained at 120 ° C for 10
The prepreg was made by drying at 170 ° C for 5 minutes. Nine sheets of this prepreg were stacked and press-molded at 180 ° C and a pressure of 40 kg / cm ² for 90 minutes to obtain a 1.6 mm thick laminated plate.

The bending strength of this laminate was measured after curing at 200 ° C for 15 hours. It was 68kg / mm ^{2 at} room temperature and 53k at 250 ° C.
The strength of g / mm ² was maintained, and it was 55 kg / mm ² at room temperature even after heating and aging at 250 ° C for 20 days. The effect of the present invention was confirmed.

Example 3 358 g (1 mol) of 4,4′-diphenylmethane bismaleimide and 43.6 g (0.4 mol) of m-aminophenol were mixed and kneaded by heating at 140 ° C. for 15 minutes to obtain an addition reaction product. Next, 35 parts of polyimide 2080 (supra), 65 parts of addition reaction product,
And 2MZ-AZINE (supra) 0.5 parts by weight of N-methyl
-2-Pyrrolidone / dioxane = 3/1 was dissolved in a mixed solvent to prepare a resin solution having a concentration of 20%. Add this resin solution to 24
Apply to mild steel plate (SS41, 100 × 25 × 1mm) degreased with trichlene after polishing with No. 0 emery paper, and apply at 120 ° C for 10
After drying for 5 minutes at 170 ° C., a coating film having a thickness of 25 μm was formed. Two sheets of this coating film are wrapped by 10 mm and sandwiched, and the whole is press-molded under the conditions of 200 ° C, 5 kg / cm ² and 10 minutes,
Further, post-curing was performed at 220 ° C. for 5 hours. The tensile shear strength of this product was measured and found to be 220 at room temperature.
kg / cm ^2, 250 and ℃ even retain the strength of 185kg / cm ^2, 250
It was 180 kg / cm ² at room temperature even after heating and aging for 20 days. The effect of the present invention was confirmed.

[Advantages of the Invention] The thermosetting resin composition of the present invention compensates for the drawbacks of aromatic polyimide and maleimide with each other, and has heat resistance, mechanical strength,
It has excellent workability and is extremely useful as a laminate, molding material, and adhesive for electrical equipment.

Claims (1)

[Claims] 1. A general formula (A) (However, in the formula, R ¹ is Or Where n represents an integer of 2 or more), an organic solvent-soluble polyimide having a condensed acid component of benzophenonetetracarboxylic acid or a derivative thereof, (B) (b) (However, in the formula, R ² is an n-valent organic group, X ¹ and X ² are the same or different one atom or group selected from a hydrogen atom, a halogen atom or an organic group, and n is an integer of 2 or more. And (b) the general formula (Wherein R ³ is a hydrogen atom, a halogen atom or an atom or group selected from an organic group, and m is an integer of 1 to 5), and 1 equivalent of the maleimide group of polymaleimide is used. To 0.1 to 1 mol of aminophenol, an addition reaction product having a structure in which the amino group of aminophenol is added to the maleimide group, and (C) the general formula (Wherein R ^{4 to} R ⁷ represent the same or different atoms or groups selected from a hydrogen atom or an alkyl group), the organic solvent-soluble polyimide (A) and the addition reaction product (B). With respect to the total amount of [(A) + (B)], the organic solvent-soluble polyimide is 5 to 80% by weight, and the addition reaction product is 95 to
A thermosetting resin composition comprising 20% by weight and 0.5 to 5% by weight of imidazole (C) with respect to the addition reaction product (B).