JPS6159328B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermosetting resin composition, and particularly to an epoxy resin composition that can be converted into a heat-resistant cured product. In recent years, as electric machines and electronic devices have become larger in capacity, more reliable, and smaller, there has been a demand for insulating materials with excellent heat resistance. While heterocyclic polymers such as polyimide resins have been put into practical use,
Efforts have also been made to develop heat-resistant compositions for epoxy resins that can be used in either solvent-free or solution forms and provide cured products with low curing shrinkage and good strength, adhesive strength, and electrical properties. However, they have limitations, such as having a high melting point or containing a polyfunctional curing agent, making it difficult to pre-react, and also causing local early gelation when heated, making it difficult to obtain a homogeneous cured product, and being relatively expensive. There were quite a few. The present invention has been made in view of the above, and is a thermosetting resin composition that can undergo a melting reaction and be converted into a cured product with excellent high-temperature strength by heating at a relatively low temperature (150 to 200°C) for a short time. The purpose is to provide something. Its characteristics are: (A) (a) 1 mole of diamine; (b) dicarboxylic acid anhydride or its functional derivative with an ethylene type carbon-carbon double bond;
A reactant obtained by heating and reacting both at a ratio of 0.05 to 0.8 mol,
and (B) a polyfunctional epoxy compound as an essential component. In the present invention, (a) diamine is, for example, m
-phenylenediamine, P-phenylenediamine, benzidine, 3,3'-dimethyl-4,4-diaminobiphenyl, 3,3'-dichlorobenzidine, 3,3'-dimethquinbenzidine, 4,4'- Diaminodiphenylmethane, 1,1-bis(4-aminophenyl)ethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-
bis(4-aminophenyl)-1,3-dichloro-1,1,3,3-tetrafluoropropane,
4,4'-diaminodiphenyl ether, 4,4'-
Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3, 3′-diaminodibenzophenone,
4,4'-diaminobenzophenone, 3,4'diaminobenzophenone, N,N-bis(4-aminophenyl)aniline, N,N-bis(4-aminophenyl)methylamine, N,N-bis( 4-aminophenyl)-n-butylamine, m-aminobenzoyl-p-aminoanilide, 4-aminophenyl-3-aminobenzoate, 4,4'-diaminoazobenzene, 3,3'-diaminoazobenzene, bis(3-aminophenyl) Diethylsilane, bis(4-aminophenyl)phenylphosphine oxide, bis(4-aminophenyl)ethylphosphine oxide, 1,5-diaminonaphthalene, 2,6-diaminopyridine, 2,5-diamino-1,3, 4-oxadiazole, m-xylylene diamine, p-xylylene diamine, 2,
4-(p-β-amino-t-butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, etc. can be mentioned. In addition, (b) dicarboxylic acid anhydrides having an ethylene type carbon-carbon double bond or functional derivatives thereof of the present invention include, for example, maleic anhydride, various maleic esters, citraconic anhydride, itaconic anhydride, etc. Can be used. plays an important role in achieving the purpose of the present invention
(A) The molten reaction product consists of (a) the diamine and (b) a dicarboxylic acid anhydride having an ethylene type carbon-carbon double bond or a functional derivative thereof, for each mole of the former (a) to the latter. (b) in a ratio of 0.05 to 0.8 mol, 90 to 200
Obtained by reacting in the melt at ℃ for 10 to 60 minutes. Since the reactant is a liquid or a solid having a relatively low melting point (approximately 150° C. or less), it has the advantage that it can be easily roll-kneaded with a solid epoxy compound. Note that when the ratio of (b) is less than the above, the heat resistance of the cured resin is not much different from that of the amine cured resin, and when it is increased, the reaction product has a high melting point and becomes difficult to handle. Next, in the present invention, as the polyfunctional epoxy compound (B), for example, diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-
Epoxycyclohexylmethyl-(3,4-epoxy)cyclohexanecarboxylate, vinylcyclohexane dioxide, 4,4'-di(1,2
-epoxyethyl)diphenyl ether, 4,
4′-(1,2-epoxyethyl)biphenyl,
2,2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,3-epoxycyclopentyl) ether, 2-( 3,4-epoxy)cyclohexane-
5,5-spiro(3,4-epoxy)-cyclohexane-m-dioxane, bis-(3,4-epoxy-6-methylcyclohexyl)adipate,
Bifunctional epoxy compounds such as N,N'-m-phenylenebis(4,5-epoxy-1,2-cyclohexane)dicarboximide, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3,5- Tori (1,2
-epoxyethyl)benzene, 2,2',4,4'-
Tri- or higher functional epoxy compounds are used, such as tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolac, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane. In the present invention, the above-mentioned (A) molten reaction product and (B) polyfunctional epoxy compound are essential components, and the former (B)
For 100 parts by weight, add 10 parts of the former (A) depending on its composition.
Add in a range of ~60 parts by weight. A composition can be obtained by kneading the two using, for example, a heated roll. Taking the molding material as an example, this composition has a shelf life of about one month, which is more than three times longer than that of a system using diamine, and it also has a shelf life of about 1 to 250°C at 150 to 250°C.
It hardens into a heat-resistant resin by heating for 30 minutes. In addition, when the component ratio is outside the above range, the curability decreases, and the glass transition point and bending strength of the cured product decrease. The thermosetting resin composition of the present invention can further contain a phenol novolak resin as a component. For example, one or two of phenols such as phenol, cresol, xylenol, resorcinol, chlorophenol, phenylphenol or bisphenol A, and aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, etc.
A resin obtained by addition condensation of two or more species in the presence of an acidic catalyst is used. These phenol novolac resins are added to a composition containing the (A) melt reaction product and (B) a polyfunctional epoxy compound as essential components in an amount of 10 to 50 parts by weight per 100 parts by weight of the (B) polyfunctional epoxy compound. Contains within a range. The addition of the phenol novolac resin extends the storage stability of the resin composition, and also makes the surface of the molded cured product smoother and improves its appearance. If the amount of phenol novolak resin is too large, problems such as a decrease in hardness when heated and a decrease in heat resistance will occur. Next, in order to achieve rapid curing in the resin composition of the present invention, a curing accelerator cannot be ignored. Such curing accelerators include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-methyl-4-ethylimidazole, 1-
Butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole, 1-Azine-2-ethylimidazole, 1-
Imidazoles such as azine-2-undecylimidazole are useful. In addition, tetraphenylboron salts of tertiary amines such as tetraphenylphosphonium tetraphenylborate, triethylamine tetraphenylborate, and 2-ethyl-4-methylimidazole tetraphenylborate, 2-ethyl-
Tetraphenylboron salts of imidazoles such as 1,4-dimethylimidazole tetraphenylborate are particularly useful. Also useful are mixed promoters of tertiary amines and tricresyl borate, and amine titanate compounds. It is preferable to use at least one type of the curing accelerator in an amount of 0.01 to 10% by weight based on the mixture of (A) the molten reaction product and (B) the epoxy compound. By using the above-mentioned curing accelerator, it is possible to achieve a good balance between storage stability, which is essential for molding materials, prepregs, varnishes, etc., and rapid curing at temperatures above 150°C. Furthermore, one or more of the following various materials can be used in combination with the composition of the present invention, depending on its use and purpose. For example, considering its use as a molding material, zircon, silica, fused silica glass, glass, alumina, calcium carbonate, magnesite, gypsum, zinc white, titanium white, lead compounds, clay, kaolin,
Inorganic fillers such as talc, silica sand, whiskers, carbonyl iron, ferrite, molybdenum disulfide, graphite, carbon black, asbestos, and wollastonite, fatty acids, mold release agents such as waxes, epoxy silane, vinyl silane, borane compounds, alkyl Coupling agents such as titanate compounds can be used. Also, if necessary,
Known flame retardants or flexibilizers may also be added. Next, examples will be described. Example 1 Preparation of molten reaction product 4,4'-diaminodiphenylmethane (abbreviation
DDM) and maleic anhydride (abbreviation: MA) were used to prepare seven types of reactants with different molar ratios as shown in Table 1. First, a predetermined amount of 4,4'-diaminodiphenylmethane was taken and heated to 100 to 130°C to melt it, and a predetermined amount of maleic anhydride was added thereto and reacted with stirring. After a while, foaming occurred and the temperature rose to 150-180°C due to the heat of reaction. After continuing to heat and stir for 30 to 50 minutes until the foaming subsides,
After cooling, each reaction product was obtained. They were either liquids or yellow-brown solids with relatively low melting points.

[Table] Example 2 Novolac type epoxy resin ECN1273 (Chiba
Manufactured by Geigy. Epoxy equivalent: 225, softening point: 73℃)
To 100 parts by weight, the above-mentioned molten reactants No. 1 to 7 were added in the weight parts listed in Table 2, and the following materials were further blended. Hardening accelerator C ₁₁ Z-AZIN (imidazole compound manufactured by Shikoku Kasei Co., Ltd.) 4 parts by weight Filler Fused silica glass powder QG-100 70% by weight of the total composition Coupling agent KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight Mold release agent Stearic acid 1 part by weight Hoechstwax E 1 part by weight Colorant carbon black 1 part by weight These blends were kneaded for 10 minutes at a roll temperature of 70 to 80°C, and then coarsely ground to prepare the desired molding material. . Using this molding material, molding conditions: 180℃, 1.5 minutes,
Various test pieces were prepared by transfer molding at a pressure of 70 kg/cm ² . The properties measured for these test pieces are as shown in Table 2. In the table, as a guideline for the curability of the molding material,
We adopted Barcol hardness when heated immediately after transfer molding. In addition, as a measure of heat resistance, the strength retention rate of the bending strength (measured at 180°C) after heat treatment at 200°C for 30 days with respect to the initial value and the weight loss rate after heating at 240°C for 168 hours are shown.

【table】

[Table] Example 3 To 100 parts by weight of novolak-type epoxy resin ECN1273, the above melt reaction product and phenol novolak resin (HP203N manufactured by Hitachi Chemical Co., Ltd.) were added in parts by weight as shown in Table 3, and the following materials were added. was blended. Curing accelerator C ₁₁ Z-AZIN 3 parts by weight Filler QG-100 70% by weight of the total composition Coupling agent KBM403 1 part by weight Mold release agent Stearic acid 1 part by weight Hoechstwax 1 part by weight Colorant Carbon black 1 part by weight These mixtures were kneaded for 10 minutes at a roll temperature of 70 to 80°C, and then coarsely ground to prepare the desired molding material. Using this molding material, molding was performed in the same manner as in Example 2, and the characteristics were evaluated. The results are shown in Table 3. The surface smoothness of the molded product was superior to that of molded products that did not contain phenolic resin.

【table】

【table】

Claims (1)

[Claims] 1 [A] (a) 1 mol of diamine (b) Dicarboxylic acid anhydride having an ethylene type carbon-carbon double bond or a functional derivative thereof
A thermosetting resin composition comprising, as essential components, an imidization reaction product whose both terminals are capped with amino groups, obtained by heat-reacting both in a ratio of 0.05 to 0.8 mole, and [B] a polyfunctional epoxy compound. 2. The thermosetting resin composition according to claim 1, wherein the diamine is 4,4'-diaminodiphenylmethane and the dicarboxylic anhydride is maleic anhydride. 3 [A] (a) 1 mol of diamine (b) Dicarboxylic acid anhydride having an ethylene type carbon-carbon double bond or a functional derivative thereof
An imidization reaction product whose both terminals are capped with amino groups obtained by heat-reacting both at a ratio of 0.05 to 0.8 moles, [B] a polyfunctional epoxy compound, and [C] a phenol novolak resin as essential components. A thermosetting resin composition. 4. The thermosetting resin composition according to claim 3, wherein the diamine is 4,4'-diaminodiphenylmethane and the dicarboxylic anhydride is maleic anhydride.