JPH041010B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to a thermosetting composition that reacts when heated to give a cured product with excellent heat resistance. [Background of the Invention] Addition-polymerized polyimides such as bismaleimide are well known as heat-resistant class H class resin molding materials. This maleimide is often used in combination with a diamine or an epoxy resin. Further, British Patent No. 1322332 describes a homopolymer of aromatic dicyanamide. Although this polymer is superior to the polyimide in terms of heat resistance, it has poor flexibility and is extremely inconvenient not only as a molding material but also as a film, coating or prepreg material. [Object of the invention] The object of the present invention is to cure by heating,
The object of the present invention is to provide a thermosetting composition that provides a cured product with excellent heat resistance, flexibility, and moldability. [Summary of the Invention] The thermosetting composition of the present invention has (a) the general formula [] A(-NRCN)m...[] (wherein A is an organic group having at least one aromatic ring, R is hydrogen, benzenesulfonyl group, benzenecarbonyl group, benzyl group, m is 2 or more)
Cyanamide compounds represented by and the general formula [] B(-NH ₂ ) n ... [] (wherein B is an organic group having at least one aromatic ring, and n represents 2 or more) It is characterized by containing at least one compound selected from the following: an aromatic amine compound and (b) an epoxy compound, a maleimide compound, an allyl compound, a vinyl compound, a carboxylic acid compound, an anhydride compound, a polybutadiene compound, and a phenol compound. This composition has an isomelamine ring and a melamine ring, which are heat-resistant skeletons, and provides a thermosetting cured product with excellent heat resistance and flexibility, and good moldability. In the present invention, a prepolymer as shown in the following formula [] is produced by the reaction between an aromatic cyanamide compound and an aromatic amine compound by preheating, and by further heating, a structure shown in the following formula [] [] is produced. produces a cured product containing The above example shows the case where a dicyanamide compound and a diamine compound are used. In the present invention, a compound having the formula [] or a structure like [] can be polymerized by itself,
Compounds that polymerize by bonding with formula [] or molecules in formula [], epoxy, maleimide, allyl compounds, vinyl compounds, carboxylic acid compounds, anhydride compounds, polybutadiene compounds, phenol compounds, polybutadiene compounds, phenol compounds It is a thermosetting composition containing at least one of these, and is useful as a molding material, and because it is easily dissolved in organic solvents, it is also useful as an impregnating varnish, a laminating varnish, a coating agent, etc. Examples of the aromatic cyanamide compound represented by the general formula [] in the present invention include m-phenylene dicyanamide, p-phenylene dicyanamide, 4,4'-dicyanamide diphenylmethane,
2,2'-bis(4-cyanamidophenyl)propane, 4,4'-dicyanamidophenyl oxide,
4,4'-dicyanamidophenyl sulfone, bis(4-cyanamidophenyl)phosphine oxide, bis(4-dicyanamidophenyl)phenylphosphine oxide, bis(4-cyanamidophenyl)methylamine, 1,5-dicyanamide naphthalene, m-xylylene dicyanamide, 1,1-
Bis(p-cyanamidophenyl)furan, p-xylylene dicyanamide, hexamethylene dicyanamide, 6,6'-dicyanamide-2,2'-dipyridyl, 4,4'-dicyanamide benzophenone, 4,
4'-dicyanamide azobenzene, bis(4-cyanamidophenyl)phenylmethane, 1,1-bis(4-cyanamidophenyl)cyclohexane, 1,
1-bis(4-cyanamido-3-methylphenyl)-1,3,4-oxadiazole, 4,4'-
Dicyanamid diphenyl ether, 4,4'-bis(p-cyanamidophenyl)-2,2'-dithiazole, m-bis(4-p-cyanamidophenyl-2
-thiazolyl)benzene, 4,4'-dicyanamidebenzanilide, 4,4'-dicyanamide phenylbenzoate, 2,2'-bis[4-(4-cyanamidophenoxy)phenyl]propane, 2,2 ′−
Bis[3-methyl-4-(4-cyanamidophenoxy)phenyl]propane, 2,2-bis[3-
Ethyl-4-(4-cyanamidophenoxy)phenyl]propane, 2,2-bis[3-propyl-
4-(4-cyanamidophenoxy)phenyl]propane, 2,2-bis[3-isopropyl-4-
(4-cyanamidophenoxy)phenyl]propane, bis[4-(4-cyanamidophenoxy)phenyl]methane and the following formula [] At least one type of cyanamide-terminated sulfone ether oligomer represented by (x is 0 to 3) is used. The reason why aromatic cyanamide compounds are used in the present invention is that aromatic compounds are advantageous in terms of heat resistance. Examples of aromatic amine compounds represented by the general formula [] include aniline, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-bis(4-aminophenyl)propane. , benzidine, 4,4'-diaminophenyl oxide, 4,4' diaminophenyl sulfone, bis-(4-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)
Phenylphosphine oxide, bis(4-aminophenyl)methylamine, 1,5-diaminonaphthalene, m-xylylenediamine, 1,1-bis(p-aminophenyl)furan, p-xylylenediamine, hexamethylenediamine, 6,6'-diamino-2,2'-dipyridyl, 4,4'-diaminobenzophenone, 4,4'-diaminoazobenzene, bis(4-aminophenyl)phenylmethane, 1,1-bis(4-aminophenyl) Cyclohexane, 1,1-bis(4-amino-3-methylphenyl)cyclohexane, 2,5-bis(m
-aminophenyl)-1,3,4-oxadiazole, 2,5-bis(p-aminophenyl)-1,
3,4-oxadiazole, 2,5-bis(m-
aminophenyl)thiazolo(4,5-d)thiazole, 5,5'-di(m-aminophenyl)-(2,
2′) bis(1,3,4-oxadiazolyl), 4,
4'-diaminodiphenyl ether, 4,4'-bis(p-aminophenyl)-2,2'-diazole, m
-bis(4-p-aminophenyl-2-thiazolyl)benzene, 4,4'-diaminobenzanilide, 4,4'-diaminophenylbenzoate,
N,N'-bis(4-aminobenzyl)-p-phenylenediamine, 4,4'-methylenebis(2-dichloroaniline), benzoguanamine, methylguanamine, 1,2,4-triaminobenzene,
1,3,5-triaminobenzene, 2,4,6-
triaminotoluene, 2,4,6-triamino-
1,3,5-trimethylbenzene, 2,4,4'-
Triaminodiphenyl ether, 2,4,4'-triaminodiphenylmethane, 2,4,4'-triaminodiphenyl sulfone, 2,4,4'-triaminobenzophenone, 3,5, 3',5'-tetraaminobenzophenone, 1,2,4,5-tetraaminobenzene or (In the formula, y is 1 to 6.) An aniline resin represented by the following is used. In the case of amine compounds, aromatic ones are more advantageous than aliphatic ones in terms of heat resistance, as in the case of cyanamide compounds. One or more aromatic amine compounds may be used. Examples of polyfunctional epoxy compounds include diglycidyl ether of bisphenol A, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4'-(1,
2-epoxyethyl)biphenyl, 4,4'-di(1,2-epoxyethyl)diphenyl ether,
Resorcin diglycidyl ether, bis(2,3
-epoxycyclopentyl)ether, N,
N'-m-phenylenebis(4,5'-epoxy-
1,2-cyclohexanedicarbodiimide), triglycidyl compounds of p-aminophenol, 1,3,5-tri(1,2-epoxyethyl)benzene, tetraglycidoxytetraphenylethane, phenol At least one type of epoxy compound such as a trifunctional or higher functional epoxy compound such as polyglycidyl ether of formaldehyde novolac resin, an epoxy compound having a hydantoin skeleton, and an epoxy compound containing a halogen atom such as a brominated epoxy compound is used.
Further, the above-mentioned epoxy compound may be used after being preliminarily reacted with a phenolic resin compound or a triallylisocyanurate compound. In the present invention, the blending ratio of the compound (a) and the polyfunctional epoxy compound can be arbitrarily selected over a wide range. Examples of maleimide compounds include N,
N'-methylene bismaleimide, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-trimethylene bismaleimide, N,N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide,
N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-methylenebis(3-chloro-p-phenylene)bismaleimide, N, N'-
4,4′-diphenylsulfone bismaleimide,
N,N'-4,4'dicyclohexylmethane bismaleimide, N,N'-α,α'-4,4'-dimethylenecyclohexane bismaleimide, N,N'-m-xylene bismaleimide, N,N' A polyvalent maleimide [formula] represented by the following formula [ ] obtained by reacting a bismaleimide compound such as -4,4'-diphenylcyclohexane bismaleimide, a condensate of aniline and formaldehyde, and maleic anhydride. (n is 0.1 to 3) Moreover, in the present invention, the following monomaleimide compounds can also be combined. For example, N
-Methylmaleimide, N-ethylmaleimide, N
-propylmaleimide, N-butylmaleimide,
N-allylmaleimide, N-vinylmaleimide,
N-phenylmaleimide, N-3-chlorophenylmaleimide, N-o-tolylmaleimide, N-
m-tolylmaleimide, N-p-tolylmaleimide, N-o-methoxyphenylmaleimide, N-
m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-benzylmaleimide, N-pyridylmaleimide, N-hydroxyphenylmaleimide, N-acetoxyphenylmaleimide, N-dichlorophenylmaleimide, N-
At least one monomaleimide compound such as benzophenone maleimide, N-diphenyl ether maleimide, N-acetylphenyl maleimide, N-cyclohexyl maleimide, etc. can be used in combination. Allyl compounds include triallyl trimellitate, diallyl terephthalate, diallyl isophthalate, diallyl orthophthalate, triallyl isocyanurate, triallyl cyanurate,
p,p'-diallyloxycarbonyl diphenyl ether, m,p'-diallyloxycarbonyl diphenyl ether, o,p'-diallyloxycarbonyl diphenyl ether, m,m'-diallyloxycarbonyl diphenyl Ether, polyvalent carboxylic acid allyl ester such as diallyl chlorendate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-
Propyl acrylate, isopropyl acrylate, n-pentyl acrylate, n-hexyl acrylate, trimethylolpropane triacrylate, 2-ethylhexyl acrylate, 2-
Acrylic acid esters such as hydroxyethyl acrylate, tetraethylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl Methacrylic acid esters such as methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyli methacrylate, trimethylolpropane trimethacrylate, ethylene dimethacrylate, diethylene dimethacrylate, tris (acryloyloxyethyl) isocyanurate, tris (methacryloyloxyethyl) Isocyanurate and the like are used. Examples of vinyl compounds include styrene, α-methylstyrene, vinyltoluene, vinylbenzene, and N-vinylpyrrolidone; examples of carboxylic acids include maleic acid, itaconic acid, isophthalic acid, terephthalic acid, and tetrahydrophthalic acid.
Examples of acid anhydrides include hexahydrophthalic acid, fumaric acid, succinic acid, adipic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. acids, pyromellitic anhydride, cyclopentatetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, copolymers of maleic anhydride and vinyl ether, copolymers of maleic anhydride and styrene, etc. Examples of polybutadiene compounds include butadiene homopolymer, α,ω-polybutadiene glycol, α,ω-polybutadiene dicarboxylic acid, and the like. Examples of phenolic compounds include phenolic novolak resin, phenolic cresol resin, cresol novolak resin, cresol resol resin, poly-p-vinylphenol resin, diphenyl ether-modified phenolic novolak resin, and phenolic and p-vinylphenol resins. A condensation resin with -xylene-dimethyl ether or the like is used. In the present invention, in order to promote the reaction, a curing catalyst such as a conventional curing catalyst for maleimide or a curing catalyst for epoxy resin can be used in combination. Specific examples include tetramethylbutanediamine, benzyldimethylamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, guanidine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-
Imidazole compounds such as ethylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2,4'-dimethylimidazole, azine derivatives of the above imidazole compounds, onium salts, trimerizate Examples include acid salts, nitrile ethyl derivatives, tetraphenylphosphonium tetraphenylborate, tetraphenyl ammonium tetraphenylborate, tetrabutylammonium tetraphenylborate, and tetramethylammonium fluorite. Also,
Examples of curing catalysts for allyl compounds and vinyl compounds include benzoyl peroxide and dicumyl peroxide. The appropriate amount of these curing catalysts is generally 0.1 to 5% by weight of the total composition. The composition of the present invention may contain known inorganic fillers, glass fibers, flame retardants, flexibilizers, pigments, coupling agents, mold release agents, and the like. In terms of the properties of the cured product, as the proportion of the compound (a) increases, the heat resistance and hardness increase, and vice versa, there is a tendency to give a cured product with high flexibility. Furthermore, in terms of the properties of the prepolymer, as the amount of the compound (b) increases, the moldability (fluidity) and solubility in organic solvents improve. Even if the blending ratio in the composition of the present invention is varied over a fairly wide range, a cured product having good heat resistance can be obtained. Generally, for 100 parts by weight of prepolymer as component (a), 5 parts by weight of component (b)
~100 parts by weight is suitable. As the proportion of the cyanamide compound increases, heat resistance improves, but viscosity tends to increase. In the present invention, the most preferable condition for the preliminary reaction between the aromatic cyanamide compound and the aromatic amine compound is to carry out the preliminary reaction in a solvent at a temperature of 60 to 150°C. In the present invention, a cured product may be directly produced without temporarily stopping the reaction in the B state. Examples of the solvent include methyl ethyl ketone, methyl acetyl ketone, 2-methoxyethanol, 2-
(methoxymethoxy)ethanol, 2-isoproxyethanol, 2-(ethoxyethoxy)ethanol, dioxane, dimethyldioxane, monopropylene glycol methyl ether, N,N-
One or a mixed solvent of two or more thereof such as dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone can be used. Particularly preferred are methyl ethyl ketone, 2-methoxyethanol, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dioxane. The composition of the present invention reacts and cures as an organic solvent solution or varnish, or by heating in the absence of a solvent. The latter is a so-called melt reaction. In this reaction, if a solvent is used, it is heated at a temperature of about 50 to 150°C, and then the temperature is increased.
Preferably, heating is performed at about 150 to 250°C. On the other hand, in the case of a melt reaction, it can be carried out at a relatively high temperature from the beginning, that is, by heating to about 150 to 250°C. When obtaining a prepolymer, preferably
It is preferable to carry out the reaction at about 60 to 130°C and stop heating when the state B is reached. In the case of reaction in a solvent, heating is stopped before solid matter (hardened product) is precipitated. Examples 1 to 5 The aromatic cyanamide compound and aromatic amine compound shown in Table 1 were dissolved in methyl cellosolve (30% as solid content) and heated at 70°C for 60 minutes to pre-react and form a prepolymer. The desired thermosetting composition was obtained by adding the components shown in the table below. However, in Examples 3 and 5, 1 part by weight of benzoyl peroxide was added after the preliminary reaction.

[Table] *...Phenol novolac type epoxy compound The thermosetting compositions shown in Examples 1 to 5 were heated at 240°C.
The weight loss starting temperature and weight loss rate at 500°C were measured after heating and curing on a hot plate for 2 hours. In addition, after impregnating a glass cloth treated with aminosilane with a thickness of 0.18 mm with varnish, it was dried at 90 to 150°C for about 10 minutes to create a coated cloth, and 10 sheets of this coated cloth were stacked to produce a weight of 40 kg. A laminate was obtained by pressure molding at 240° C. for 90 minutes under a pressure of /cm ² . The glass transition temperature and bending strength of this product were measured. These results are summarized in Table 2. In addition, in the table, the weight loss starting temperature is
This is the weight loss starting temperature when heating in air at a heating rate of 4°C/min and measuring weight loss characteristics, and is 500°C.
The weight loss in is the weight loss rate when the temperature reaches 500°C. Further, the bending strength is the retention rate of the bending strength at each temperature with respect to the bending strength at 20°C.

【table】

Claims (1)

[Claims] 1 (a) General formula [] A(-NRCN)m ... [] (wherein A is an organic group having at least one aromatic ring, R is hydrogen, a benzenesulfonyl group , benzenecarbonyl group, benzyl group, m represents 2 or more) and the general formula [] B( _-NH2 )n...[] (wherein, B represents at least one aromatic A prepolymer obtained by preliminary reaction with an aromatic amine compound represented by an organic group having a ring (n represents 2 or more) and (b) an epoxy compound, a maleimide compound, an allyl compound, a vinyl compound, a carboxylic acid compound , anhydride compounds, polybutadiene compounds, and phenol compounds.