JPH0481614B2 - - Google Patents

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermosetting resin composition comprising a phenylmaleimide derivative, an epoxy compound, and a curing catalyst that have excellent heat resistance, storage stability, and solubility. It is a laminated material, conductive paste,
The present invention provides a thermosetting resin composition useful as a heat-resistant adhesive, a resist agent, a powder coating, a molding material, and a fiber-reinforced composite material. [Prior Art] Epoxy resins are widely used as various electrical insulating materials, molded products, adhesives, and paints because they provide cured products with excellent electrical properties, mechanical properties, dimensional stability, and chemical resistance. In recent years, in the fields of electricity, electronics, and transportation equipment such as aircraft and vehicles, materials with better heat resistance, moldability, and storage stability have been needed as equipment becomes more sophisticated, smaller, and lighter. desired. Conventionally, epoxy resins, maleimide resins, polyimide resins, and the like have been used in this field. However, although epoxy resins have excellent mechanical and electrical properties, they do not necessarily have sufficient heat resistance. Further, although polyimide resin has excellent heat resistance, it is difficult to mold because it is insoluble and infusible. Polymaleimide, typified by N,N'-4,4-diphenylmethane bismaleimide, has high thermal stability, but has a slow curing rate and requires long-term heating at high temperatures for safe curing. On the other hand, a phenylmaleimide derivative having a group reactive with a polymaleimide resin or an epoxy group,
Compositions comprising an epoxy resin and a polyvalent amine compound (for example, JP-A-52-146498) have the disadvantages that heat resistance is not necessarily sufficient and storage stability is not satisfactory. [Problems to be Solved by the Invention] An object of the present invention is to provide a thermosetting resin composition with improved storage stability without impairing curability or workability. [Means for solving the problem] Phenylmaleimide derivative represented by the following formula () [In the formula, n is an integer of 0 to 1, R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a halogen atom], a thermosetting resin composition comprising a polyepoxy compound and a curing catalyst is storage stable. To provide a cured product with excellent properties and heat resistance. [Structure of the Invention] The present invention comprises (A) Component: 50 to 150 parts by weight of a phenylmaleimide derivative represented by the preceding formula () (B) Component: A polyepoxy compound having at least two epoxy groups in one molecule. 100 parts by weight (C) Ingredients: Curing catalyst selected from quaternary ammonium salts, imidazole compounds, and lithium salts
0.5 to 5 parts by weight A thermosetting resin composition comprising the above components (A), (B), and (C) is provided. (Phenylmaleimide derivative) The phenylmaleimide derivative used in the present invention is an aromatic amine compound represented by the following formula (2). [In the formula, n is an integer of 0 to 1; R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a halogen atom] and maleic anhydride per equivalent of the amino group of the aromatic amino compound. It is a compound obtained by reacting in a ratio of 1 mole of maleic anhydride. Examples of amino compounds include p, m and o-aminophenol, 2-amino-p-cresol, 4-amino-m-cresol, 6-amino-m-cresol, 2-amino-4-chlorophenol, p , m and o-aminobenzoic acid, etc. As a production method, an aromatic amine compound and maleic anhydride are reacted in the presence of an amide solvent to produce an amic acid, and then a carboxylic acid anhydride (such as acetic anhydride) and a dehydration catalyst ( For example, a generally known method is used in which imidization is carried out by adding triethylamine, sodium acetate, etc.) to the reaction system. (Polyepoxy compound) () Diglycidyl ether of bisphenol A; Its products include Epicote 827, Epicote 828, Epicote 834, Epicote 864, produced by Yuka Ciel Epoxy Co., Ltd.
1001, 1004, 1007, 1031, Ciba's Araltide GY250, 6099, Union Carbide's ERL2774, Dow Chemical's
DER332, DER331, DER661, (all of the above are product names), etc. () Epoxyphenol novolac; its trade names include Yuka Ciel Epoxy Co., Ltd.'s Epicote 152 and 154; Dow Chemical Company's Epicote 152 and 154;
DEN438, DEN448, Ciba Araldide
EPN1138, EPN1139 (all of the above are product names), etc. () Epoxy cresol novolac; its products include Ciba's Araldide ECN1235;
1273, 1280 (all of the above are product names), etc. In addition, epoxy resin obtained from phthalic acid or hexahydrophthalic acid and epichlorohydrin,
Epoxy resin obtained from parahydroxybenzoic acid and epichlorohydrin, epoxy resin obtained from aromatic amine such as toluidine or aniline and epichlorohydrin, vinylcyclohexene dioxide, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Examples include diglycidyl ether. (Curing Catalyst) Examples of the curing catalyst include the following (1) to (3). (1) Quaternary ammonium salts, such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide,
Examples include trimethylcetylammonium chloride, trimethylcetylammonium bromide, triethylmethylammonium chloride, triethylmethylammonium bromide, tetraethylammonium iodide, triethylcetylammonium chloride, triethylcetylammonium bromide, and the like. (2) Imidazole compound 2-ethyl-4-methylimidazole/
CNS, 2-ethyl-4-methylimidazole/AZIN, C ₁₁ -imidazole/CNS, C ₁₁ -
Imidazole/AZIN etc. (3) Lithium salts Lithium chloride, lithium bromide, etc. (Optional Components) The following components can be added to the curable composition of the present invention as necessary. (1) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide,
Metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powder silica, fused silica,
Crystalline silica, carbon black, kaolin, finely powdered mica, quartz powder, metal hydroxides such as aluminum hydroxide, graphite, asbestos, molybdenum disulfide, antimony trioxide, etc. Furthermore, fibrous reinforcements and fillers, such as inorganic fibers such as glass fibers, rock wool, ceramic fibers, asbestos, and carbon fibers, and synthetic fibers such as paper, pulp, wood flour, linters, and polyamide fibers. The amount of these powder or fibrous reinforcing materials and fillers used varies depending on the application, but as a laminated material or molding material, up to 500 parts by weight can be used per 100 parts by weight of the resin composition. (2) Colorants, pigments, flame retardants such as titanium dioxide, yellow carbon black, iron black, molybdenum red, navy blue, ultramarine blue, cadmium yellow, cadmium red, inorganic phosphorus such as red phosphorus, and organic such as triphenyl phosphate. Such as phosphorus. (3) Furthermore, various synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc. For example, phenolic resin, alkyd resin, melamine resin, fluororesin, vinyl chloride resin, acrylic resin, silicone resin, polyester resin, etc.
Mention may be made of species or combinations of two or more species. The amount of these resins to be used is within a range that does not impair the inherent properties of the resin composition of the present invention, that is,
Less than 50% by weight of the total resin amount is preferred. Examples of methods for blending the phenylmaleimide derivative, polyepoxy compound, curing catalyst, and various additives include heating and melt mixing, kneading using a roll kneader, etc., mixing using an appropriate organic solvent, and dry mixing. . Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 In a four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer, 49.6 g of maleic anhydride was added.
After completely dissolving 50.0 g (0.458 mol) of m-aminophenol in N,N-
A solution dissolved in 50 ml of dimethylformamide was added dropwise from the dropping funnel while cooling with ice. After the dropwise addition was completed, stirring was continued at that temperature for 1 hour.
Next, 58.4 g of acetic anhydride and 5.84 g of sodium acetate
g was added into the flask, the temperature was raised to 60°C, and the reaction was carried out for 2 hours. After cooling, the reaction solution was poured into 2.0 ml of water, and the precipitated crystals were filtered, washed with water, dried, and recrystallized using toluene to obtain 52.5 g of m-maleimidophenol (melting point: 129°C to 130°C).
I got it. Next, 100 parts by weight of the above m-maleimidophenol and 100 parts by weight of Epicote 828 (bisphenol A type epoxy resin manufactured by Yuka Ciel Epoxy Co., Ltd.) were added at 130°C.
After uniformly dissolving the mixture, 1.0 parts by weight of tetraethylammonium chloride (TEAC) was added and stirred for 30 minutes to obtain a resin composition. This resin composition is soluble in ketone-based solvents, cellosolve-based solvents, and alcohol-based solvents, and even when the resin composition is in the form of solutions in various solvents, it hardly gels at temperatures below 50°C and can be stored for long periods of time. I was able to withstand it. The cured product obtained by injecting the resin composition into a mold and curing it at 200℃ for 6 hours is
Heat distortion temperature (HDT) 189℃, 5.0 from thermobalance
The % weight loss temperature was 330°C. Example 2 A resin composition was obtained in the same manner as in Example 1 from 100 parts by weight of the m-maleimidophenol of Example 1, 100 parts by weight of Epicote 828, and 2.0 parts by weight of C ₁₁ imidazole/CNS. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. Example 3 A resin composition was obtained in the same manner as in Example 1 from 100 parts by weight of the m-maleimidophenol of Example 1, 100 parts by weight of Epicote 828, and 1.0 parts by weight of lithium chloride (anhydrous). The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. Example 4 A resin composition was prepared in the same manner as in Example 1 from 107 parts by weight of m-maleimidophenol of Example 1, 100 parts by weight of Epicote 154 (phenol novolac epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) and 1.0 parts by weight of TEAC. I got something. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. Example 5 p-maleimidophenol (melting point 180°C to 182°C) was obtained from p-aminophenol and maleic anhydride in the same manner as in Example 1. Next, 100 parts by weight of p-maleimidophenol,
A resin composition was obtained by kneading 100 parts by weight of Epikote 828 and 1.0 parts by weight of TEAC at 130°C using a heating roll. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. Example 6 107 parts by weight of p-maleimidophenol of Example 5, 100 parts by weight of Epicote 154 and 1.0 parts by weight of TEAC
A resin composition was obtained in the same manner as in Example 5 from parts by weight. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. Example 7 p-maleimidobenzoic acid (melting point 218°C to 219°C) was obtained from p-aminobenzoic acid and maleic anhydride in the same manner as in Example 1. Next, a resin composition was obtained in the same manner as in Example 5 from 114 parts by weight of p-maleimidobenzoic acid, 100 parts by weight of Epicote 828, and 1.0 parts by weight of TEAC.
The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. Example 8 123 parts by weight of p-maleimidobenzoic acid of Example 7,
A resin composition was obtained in the same manner as in Example 5 from 100 parts by weight of Epicote 154 and 1.0 parts by weight of TEAC. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. Comparative Example 1 A resin composition was obtained in the same manner as in Example 1 from 100 parts by weight of the m-maleimidophenol of Example 1 and 100 parts by weight of Epicote 828. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. Comparative Example 2 10 parts by weight of the m-maleimidophenol of Example 1, 100 parts by weight of Epicote 828, and 40 parts by weight of 4,4'-diaminodiphenylsulfone (DDS) were mixed to obtain a resin composition. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. (Example of JP-A-52-146498) Comparative Example 3 5 parts by weight of the m-maleimidophenol of Example 1, 100 parts by weight of Epicote 154 and 30 parts by weight of DDS were mixed to obtain a resin composition. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1 (Example of JP-A-52-146498). Comparative Example 4 15 parts by weight of the m-maleimidophenol of Example 1, 100 parts by weight of Epicote 154, and 35 parts by weight of 4,4'-diaminodiphenylmethane (DDM) were mixed to obtain a resin composition. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. (Tokukai Akira
52-146498 Example) Comparative Example 5 5 parts by weight of p-maleimidophenol of Example 5, 100 parts by weight of Epicote 154 and 30 parts by weight of DDS were mixed to obtain a resin composition. The same characteristics as in Example 1 were measured, and the obtained results are shown in Table 1. 【table】

Claims (1)

[Claims] 1 (A) Component: 50 to 150 parts by weight of a phenylmaleimide derivative represented by the following general formula. [In the formula, n is an integer of 0 to 1, R is a hydrogen atom,
Represents an alkyl group having 1 to 12 carbon atoms or a halogen atom] (B) Component: 100 parts by weight of a polyepoxy compound having at least two epoxy groups in one molecule (C) Component: Quaternary ammonium salt, imidazole compound and a curing catalyst selected from lithium salts.
0.5 to 5 parts by weight A thermosetting resin composition containing the above components (A), (B) and (C) in the above proportions.