JPS5948055B2 - thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition with excellent heat resistance and fast curing properties, and particularly to a molding material.

[Background of the Invention] An organic carboxylic acid anhydride and an organic amine are reacted.

The reaction for obtaining amidecarboxylic acid and imide is widely known as a method for producing heat-resistant resins. However, among organic amine compounds, the amino group bonded to the triazine ring has a
Due to its low basicity, it was thought that the latter would not react with ordinary carboxylic anhydrides under the conditions in which they react. Therefore, it has conventionally been considered difficult to produce a compound having an imide group and a triazine ring in good yield from a carboxylic acid anhydride and an aminotriazine derivative, and naturally it has also been difficult to combine this reactant with an epoxy compound. . However, on the other hand, compounds with triazine rings have excellent heat resistance, and inexpensive compounds such as melamine and benzoguanamine can be used.As long as the yield problem is overcome, conventional amine compounds can be used. It is expected that an imide compound that is inexpensive and has excellent heat resistance can be obtained compared to the case where the method is used.

Conventionally, as a method for obtaining an imide compound by reacting an organic carboxylic acid anhydride and an organic amine, a solution reaction has been carried out to help the uniformity of the reaction. However, the range of use of imide compounds is extremely limited because the types of solvents are very limited in terms of their solubility, and a homogeneous solution can only be obtained in expensive polar solvents.

The present inventors have confirmed that when reacting an aminotriazine derivative with a normal carboxylic acid anhydride,
Phenol, cresol, formic acid, various polar solvents commonly used in low-temperature reactions with aromatic amines,
When using proton solvents such as sulfuric acid or solvents that are active at high temperatures such as dimethylhonumamide, dimethylacetamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide, they may cause complex side reactions with raw materials and reaction products. The yield of imidotriazine derivatives is too low to be practical.

In addition, the inventors have confirmed that in the method of conducting the reaction by heating and melting at high temperature without using a solvent, when conventional organic carboxylic acid anhydrides such as trimellitic anhydride are used, Because of its high melting point, it had the disadvantage that it did not form a homogeneous system and the reaction did not proceed uniformly.

[Purpose of the invention]

The present invention obtains a uniform reaction product of a carboxylic acid anhydride and an aminotriazine derivative in high yield, and by combining this reaction product with an epoxy compound, a thermosetting resin with excellent heat resistance and fast curing property is produced. The purpose is to obtain a composition.

[Summary of the invention]

The thermosetting resin composition of the present invention is characterized by containing the following two components (A) and 03).

(4) A compound having an unsaturated imide group and a triazine ring, which is a reaction product of a dicarboxylic acid anhydride having ethylene type carbon-carbon-double polymerization and an aminotriazine derivative.

(8) Epoxy compound.

In the present invention, maleic anhydride, pinlow (1,2,2
)-Octene-(7)-2,3,5,6-tetracarboxylic acid 2:3,5:6-Use dicarboxylic acid anhydride having an ethylene-type carbon-carbon-double bond with a low melting point, such as 2:3,5:6-Gabuki. This has made it possible to obtain a uniform reaction product even by heating and melting.

The catalytic effect of this reaction can also be produced by adding a small amount of a polar solvent such as the proton solvent or N-methyl-2-pyrrolidone.

The major advantages of this method are that an expensive polar solvent is not required, that removal of the polar solvent is not necessary, and that the imide compound can be produced at low cost.

In addition, in the presence of an aprotic polar solvent that is stable even at high temperatures, such as nitrobenzene or pyridine, a dicarboxylic acid anhydride having an ethylene-ethylene carbon double bond and a diaminotriazine derivative are reacted. Thus, an imidotriazine derivative can be obtained.

Even if the diimidotriazine derivative product obtained by the above-mentioned method contains the diamidecarboxylic acid triazine derivative as its driver, this does not pose any problem in obtaining the desired effects of the present invention.

Next, regarding the blending ratio of the dicarboxylic acid anhydride having an ethylene-ethylene type carbon double bond and the aminotriazine derivative, the latter should be used in a range of 10 to 500 parts per 100 parts by weight (hereinafter simply referred to as parts) of the former. Depending on the blending ratio, the terminal group of the imidotriazine derivative may be an amino group, an ethylene-ethylene type carbon double bond,
It becomes carboxylic acid and carboxylic acid anhydride.

In addition, regarding the reaction conditions at that time, 120-230℃
Melting and heating for 5-4 minutes and stirring is sufficient.

The imidotriazine derivatives obtained as above are excellent as raw materials for heat-resistant polymers due to their structural specificity, and by combining them with epoxy compounds,
The thermosetting resin composition, which is the object of the present invention, has excellent heat resistance and quick curing properties.

The mixing ratio of the imidotriazine derivative and the epoxy compound may be in the range of 10 to 600 parts per 100 parts of the former. The aminotriazine derivatives of the present invention include industrially inexpensive benzoguamine, acetoguanamine, melamine, and the like.

In addition, any triazine derivative having two or more amino groups can be used in the present invention, and one or more of the above compounds can be used in combination.

Further, the carboxylic acid anhydride having an ethylene-ethylene type carbon-carbon double bond of the present invention includes maleic anhydride,
Pinlow (2,2,2)-octene-(7)-2,3
, 5,6-tetracarboxylic acid-2:3,5:6-carboxylic acid, etc., and one or more of these compounds can also be used in combination.

In the present invention, the epoxy compound refers to a compound having an oxirane ring in the molecule, such as diglycylene ether of bisphenol A, butadiene diepoxide, 3,
4-Epoxycyclohexylmethyl mono(3,4-epoxy)cyclohexane carboxylate, vinylcyclohexene dioxide, 4,4-di(1,2-epoxy ester) diphenyl ether, 4,4'-di(1, 2
-epoxyethyl)biphenyl, 2,2'-bis(3.
4-epoxycyclohexyl)propane, diglycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglycin, 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, N-N'-m
-phenylene bis(4,5-epoxy-1,2-cyclohexanedicarboximide), hydantoin diepoxide, hydantointris epoxide, triglycidyl compound of para-aminophenol, polyallyl glycidyl ether, 1,3,5-tri(1,2 -epoxyethyl)benzene, 2,2',4,4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenyl urethane, polyglycidyl ether of phenol formaldehyde novolak, triglycidyl ether of glycerin, trimethylolpropane Triglycidyl ethers, polyfunctional hydantoin epoxy compounds, halogenated epoxy compounds, etc. are used.

Among these epoxy compounds, the most common bisphenol A diglycidyl ether and the polyglycidyl ether of phenol formaldehyde novolak are useful.

In addition, the composition of the present invention may include, depending on various uses and purposes,
One or more of the following materials may be used in combination.

For example, considering the use as a molding material, zircon, silica, fused silica glass, clay, alumina hydroxide, calcium carbonate, quartz glass, glass, asbestos, whisker, gypsum, magnesite, mica, kaolin, talc, graphite , cement, carbonyl iron, barium, ferrite, lead compounds, molybdenum disulfide, zinc white, titanium white, carbon black, silica sand, inorganic fillers such as wollastonite, fatty acids, mold release agents such as waxes, epoxy silane, Cut-off resins such as vinyl silane, borane compounds, and alkoxy titanate compounds can be used.

Further, if necessary, a known flame retardant material such as antimony or phosphorus, or a flexibilizing agent can be used. Further, a solvent can be used for varnish and the like. For example, as the organic polar solvent, N-methyl-2-pyrrolidone, N,
N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylformamide, dimethylsulfoxide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, hexamethylphosphoramide, pyridine , dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, and the like.Furthermore, the phenolic solvent group includes phenol, cresol, xylenol, and the like, as well as ketines such as methyl ethyl ketone and acetone. The above materials may be used alone or in combination of two or more. [Examples of the Invention] Next, the present invention will be specifically explained using Examples.

Examples 1 to 9 Melamine and maleic anhydride were added to 500 parts of N-methyl, 2-pyrrolidone in the proportions shown in Table 1, dissolved, and heated to 150° C. over 2 hours with stirring.

During this time, while gently bubbling N2 into the reaction solution to remove generated water, the reaction solution was subjected to ribuxing for about 1 hour. v
嘗、▼ The reaction product obtained as above was reprecipitated with 50,000 parts of water, washed, filtered, and dried.

Next, the blended composition shown in Table 2 was prepared using these three types of reactants, and rolled at 70°C/80°C using two rolls of 8″φ.
A molding material composition was obtained by roll kneading for 10 minutes.

Examples 10 to 18 Benzoguanamine and maleic anhydride were added to 500 parts of N-methylpyrrolidone in the proportions shown in Table 3, and the temperature was raised to 150°C over 2 hours while dissolving.

During this time, while gently bubbling N2 into the reaction solution to remove generated water, ribax was performed at 180° C. for 1 hour. The reaction product obtained as described above was reprecipitated with 5000 parts of water, washed, filtered, and dried.

Claims (1)

[Scope of Claims] 1. A thermosetting resin composition containing the following components (A) and (B). (A) A compound having an unsaturated imide group and a triandine ring, which is a reaction product of a dicarboxylic acid anhydride having an ethylene type carbon-carbon double bond and an aminotriazine derivative, (B)
Epoxy compound.