JPH0316371B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a thermosetting resin composition having good heat resistance, workability, and excellent storage stability.

[Technical background of the invention and its problems]

Conventionally, maleimide resins, such as polymaleimide and polymaleimide/polyamine resins, are well known as heat-resistant thermosetting resins.

Although these are generally satisfactory in terms of heat resistance, they have high melting points and viscosity, and are only soluble in special dipolar solvents such as N,N'-dimethylformamide and N-methyl-2-pyrrolidone. Furthermore, due to its slow curing speed, it has poor workability compared to general-purpose resins such as epoxy resins and unsaturated polyester resins, which has been a major obstacle and has limited applications.

In order to improve this, it has also been proposed to use it in combination with an epoxy resin. However, among maleimide resins, particularly polymaleimide, has poor compatibility with epoxy resins, and high temperatures are required to make them compatible in a solvent-free system, which has the disadvantage of shortening pot life.

On the other hand, polymaleimide/polyamine resin (an adduct obtained by reacting polymaleimide and polyamine in advance) has extremely good compatibility with epoxy resin, but since it is thermosetting itself, it cannot be mixed with epoxy resin. It is difficult to obtain resins suitable for That is, this is because the resin tends to harden during production, and has disadvantages such as poor fluidity due to increased viscosity.

[Purpose of the invention]

An object of the present invention is to eliminate the drawbacks of the prior art described above, to provide a thermosetting resin composition that has improved heat resistance and workability at the same time, and has excellent storage stability.

[Summary of the invention]

In order to achieve the above object, the present invention provides (A) general formula (In the formula, R ¹ is an n-valent organic group, X ¹ and X ² are the same or different monovalent atoms or groups selected from hydrogen atoms, halogen atoms, or organic groups, and n is an integer of 2 or more, respectively. ) Polymaleimides represented by (B) General formula (In the formula, R ² represents a group selected from a hydrogen atom, a halogen atom, or an organic group.) A thermosetting compound consisting of an aminobenzamide represented by (C) an epoxy compound having at least two epoxy groups. resin composition.

Examples of the polymaleimides of component (A) used in the present invention include ethylene bismaleimide, hexamethylene bismaleimide, m- or p-phenylene bismaleimide, 4,4'-diphenylmethane bismaleimide, 4,4' -diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 4,4'-dicyclohexylmethane bismaleimide, m- or p-xylylene bismaleimide, 4,4'-diphenylcyclohexane bismaleimide, 4 , 4'-diphenylenebismaleimide, poly(phenylmethylene)polymaleimide, and the like.

In addition, N-3-chlorophenylmaleimide, N-4
- A monomaleimide such as nitrophenylmaleimide can also be used in combination.

As the aminobenzamide of component (B), o-aminobenzamide is generally used.

As the epoxy compound having at least two epoxy groups as component (C), bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polyglycidyl ester of polycarboxylic acid, polyglycidyl edote of polyol , urethane-modified epoxy resins, aliphatic or alicyclic polyepoxides made by epoxidizing unsaturated compounds, epoxy resins with heterocycles, epoxy resins with heterocyclic rings, epoxy resins with glycidylated amines, etc., each of which has one type. Alternatively, a mixture of two or more types can also be used.

The reaction conditions for heating the three components (A), (B), and (C) of the present invention to obtain a thermosetting resin composition are 80 to 200°C.
The reaction is carried out by heating for several minutes to several tens of hours without a solvent or in a solvent such as methyl cellosolve, cellosolve acetate, dioxane, etc. Further, it is desirable that the polymaleimides of component (A) and the aminobenzamides of component (B) be blended in a molar ratio of 1/0.2 to 1/2. If component (B) is less than 0.2 mole, the curability will be poor and the cured product will become brittle. If the amount exceeds 2 moles, the heat resistance of the cured product will decrease. The blending amount of the epoxy resin as component (C) is 5 to 5% based on the total amount of components (A), (B), and (C).
Desirably, it is 70% by weight. If component (C) is less than 5% by weight, the curability will be poor, and if it exceeds 70% by weight, the heat resistance of the cured product will be reduced. The heating reaction procedure for obtaining the resin composition of the present invention includes the following steps:
(A), (B), and (C) may be heated at the same time, or
A method may be used in which components (A) and (B) are reacted and then component (C) is added, or a method in which component (C) is added and then further reacted. The effects of the present invention can also be obtained by reacting components (B) and (C), adding component (A), and carrying out the heating reaction.

The resin composition of the present invention thus obtained is thermosetting and hardens by heating. The heating temperature is generally preferably 130 to 250°C. In order to accelerate the curing of the composition, hardened products such as tertiary aminos, imidazoles, quaternary ammonium salts, boron trifluoride amine complex salts, Kalibol salts, peroxides, organic acids, etc. are added. be able to.

The composition of the present invention includes fillers such as talc, alumina, silicon, zircon, quartz glass powder, and glass fiber, colorants such as carbon black and red iron, coupling agents such as glycidoxypropyltriethoxysilane, stearic acid, and carnauba. A mold release agent such as wax may also be added as appropriate.

The composition of the present invention has excellent heat resistance, workability, and storage stability, and can be used in a wide range of applications such as lamination, molding, adhesion, and impregnation.

[Embodiments of the invention]

Next, examples of the present invention will be described. In the following, "parts" refer to "parts by weight" unless otherwise specified.

Example 1 4,4'-diphenylmethane bismaleimide 179
(equivalent to 1 equivalent of maleimide group) and 40.8 g (0.3 mol) of o-aminobenzamide were mixed and heated at 150°C for 50 min.
After reacting for a minute, 146.5 g of bisphenol A type epoxy resin (epoxy equivalent: 190) was added and uniformly mixed and dissolved to obtain a red transparent resin. 100 parts of this resin was dissolved in methyl cellosolve-MEK (7-3) together with 0.1 part of 2-ethyl-4-methylimidazole to obtain a resin solution.

Next, this resin solution was impregnated into an aminosilane-treated glass cloth (250 x 250 x 0.18 mm) and
A prepreg was obtained by drying at 150°C for 10 minutes. Stack 9 sheets of this pregrek at a temperature of 160 to 180℃, 40kg/
Press molding was performed for 120 minutes at a pressure of cm ² to obtain a laminate with a thickness of 1.6 mm. The glass transition point of the laminate is 229℃, and when the bending strength (according to JIS-C-6481) was measured, it was 58Kg/mm ² at room temperature, 48Kg/mm ² at 200℃, and 500Kg/mm 2 at 250℃. Even after heating for hours, it remained an excellent value of 53 Kg/mm ² .

Furthermore, the resin solution remained stable with no change in viscosity even after one month at room temperature.

Comparative example 1 4,4'-diphenylmethane bismaleimide 179
g and 49.5 g of 4.4′-diaminodiphenylmethane
(0.25 mol) and reacted at 100°C for 30 minutes to obtain a red transparent resin. This resin is N-methyl-2
- A resin solution was obtained by dissolving in pyrrolidone.

Next, a laminate was obtained in the same manner as in Example 1.
In order to reduce the bending strength at 30% or less compared to room temperature, a long after cure at a temperature of 200°C or higher was required. Furthermore, after one month had passed at room temperature, the resin solution had significantly increased viscosity and could not be used.

Comparative Example 2 67 parts of bisphenol A type epoxy resin (epoxy equivalent: 190) was dissolved in 100 parts of the resin of Comparative Example 1 in N-methyl-2-pyrrolidone to obtain a resin solution.

Next, a laminate was obtained in the same manner as in Example 1. The glass transition point of this laminate is 218℃, and the bending strength was 55Kg/mm ² at room temperature and 37Kg/mm 2 at 200℃.
Obtained the value of Kg/mm ² and after heating at 250℃ for 500 hours 46
It was Kg/ ^mm2 .

Furthermore, after one month had passed at room temperature, the resin solution had significantly increased viscosity and could not be used.

Example 2 4,4'-diphenylmethane bismaleimide 179
g and o-aminobenzamide 54.4 g (0.4 mol)
After mixing and reacting at 150℃ for 20 minutes, the phenol novolac type epoxy resin (epoxy equivalent
180) 106.2g was added, mixed and dissolved uniformly, and then kept at 130°C for another 10 minutes to obtain a red transparent resin.
100 parts of this resin and 3 parts of benzyldimethylamine,
Using a mixing roll with 3 parts of stearic acid and 150 parts of quartz glass powder (passed 325 mesh)
The mixture was kneaded at 120°C for 10 minutes, cooled, and then ground to obtain a molded powder.

Next, using this molding powder, 200℃, 3 minutes, 60℃
Transfer molding was performed at Kg/cm ² to obtain a molded product. This molded product has a glass transition point of 210℃,
Bending strength (according to JIS-C-6481) is 10.0 at room temperature
Kg/mm ² and 9.3 Kg/mm ² at 200°C.

Example 3 4,4'-diphenylmethane bismaleimide 179
68 g (0.5 mol) of o-aminobenzamide and 98.8 g of a glycidyl ester type epoxy resin (epoxy equivalent: 190) were mixed and reacted at 130° C. for 20 minutes to obtain a red transparent resin. 100 parts of this resin and 1-
0.5 part of benzyl-2-methylimidazole was dissolved in methyl cellosolve-MEK (7-3) to obtain a resin solution.

Next, the resin solution was applied to both sides of a 50 μm thick polyimide film using a coating device and dried at 130 to 150° C. for 10 minutes. This is a 100 x 25 x 1 mm mild steel plate 2
The sheets were sandwiched with an overlap of 10 mm and heated and pressed at 180°C for 30 minutes at a pressure of 10 kg/cm ² using a hot plate press, followed by after-curing at 200°C for 3 hours.

When the tensile shear strength of the obtained substrate was measured at a speed of 1 mm/min, it was 148 Kg/cm ² at room temperature and 200°C.
An excellent value of 118 Kg/cm ² was obtained at 200° C., and an excellent value of 132 Kg/cm ² was obtained even after heating at 220° C. for 50 hours.

Claims (1)

[Claims] 1 (A) General formula (In the formula, R ¹ is an n-valent organic group, X ¹ and X ² are the same or different monovalent atoms or groups selected from hydrogen atoms, halogen atoms, or organic groups, and n is an integer of 2 or more, respectively. ) Polymaleimides represented by (B) General formula (wherein R ² represents a group selected from a hydrogen atom, a halogen atom, or an organic group) and (C) a thermosetting compound comprising an epoxy compound having at least two epoxy groups. Resin composition. 2 Component (A): Component (B) molar ratio is 1:0.2 to 1:2
The thermosetting resin composition according to claim 1. 3 Component (C) is 5 to 70 relative to the sum of components (A), (B), and (C)
% by weight of the thermosetting resin composition according to claim 1.