JPS638143B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition that makes it possible to provide molded articles with excellent heat resistance.

In recent years, the capacity of electrical or electronic equipment has increased,
Insulating materials and sealing materials with excellent heat resistance are required as devices become smaller and lighter and have higher reliability.

Conventionally, resins with excellent heat resistance include polyimide resins and silicone resins, but these are both expensive, and polyimide resins have many volatile components during curing and problems with moldability. The use of silicone resins has been limited due to their high moisture permeability and low mechanical strength at high temperatures.

Under these circumstances, various attempts have been made to develop heat-resistant materials that do not have the above-mentioned problems using conventionally used general-purpose materials.

Among these, polyamino bismaleimide resin is
It is known as a new thermosetting heat-resistant resin obtained by the addition reaction of N,N'-substituted bismaleimide and diamine. These materials have excellent mechanical properties at high temperatures, excellent heat deterioration resistance, and a very small coefficient of linear expansion.

Application examples of this resin include, for example, polyamines having a maleimide ring obtained by heating maleic anhydride and aromatic diamines, and N,N′-
Combinations with substituted bismaleimide compounds, combinations with epoxy compounds, etc. are known.

However, this polyamino bismaleimide compound is also produced by using a large amount of polar solvent for solution reaction and recrystallization during the synthesis process of N,N'-substituted bismaleimide, which is a synthetic intermediate. , N'-substituted bismaleimide and its derivatives are inevitably expensive.

The present invention was made as a result of intensive studies in consideration of the above circumstances, with the aim of providing a molding material that has excellent heat resistance as a cured product and can be manufactured at low cost.The present invention has the following characteristics: [A] (a) 1 mole of diisocyanate and (b) dicarboxylic acid anhydride having an ethylene type carbon-carbon double bond or a functional derivative thereof
an isocyanate compound reacted with 0.05 to 0.5 mol, [B] a polyfunctional epoxy compound having no active hydroxyl group, and [C] imidazoles, tetraphenylboron salts of tertiary amines, and tetraphenylboron salts of imidazoles. at least one selected from
A molding resin composition containing a curing accelerator consisting of seeds.

In the present invention, diisocyanate compounds include methane diisocyanate, butane-1.1 diisocyanate, ethane-1.2-diisocyanate, butane-1.2-diisocyanate, transvinylene diisocyanate, propane-1.3 diisocyanate, butane 11.4-diisocyanate, 2-butene-1.4-diisocyanate, 2- Methylbutane-1.4-diisocyanate, pentane-1.5-diisocyanate, hexane-1.6-diisocyanate, heptane-1.7-diisocyanate, octane-1.8-diisocyanate, nonane-1.9-diisocyanate, decane-1.10-diisocyanate, dimethylsilane diisocyanate, diphenyllandi diisocyanate , ω.ω′-1.3-dimethylbenzene diisocyanate ω.ω′-1.4-dimethylbenzene diisocyanate, ω.ω′-1.3-dimethylcyclohexane diisocyanate, ω.ω′-1.4
-dimethylcyclohexane diisocyanate,
ω.ω′-1.4-dimethylbenzene diisocyanate,
ω.ω′-1.4-dimethylnaphthalene diisocyanate, ω.ω′-1.5-dimethylnaphthalene diisocyanate, cyclohexane-1.3-diisocyanate, cyclohexane-1.4-diisocyanate,
Dicyclohexylmethane-4.4-diisocyanate, 1.3-phenylene diisocyanate 1.4-phenylene diisocyanate, 1-methylbenzene
2.4-diisocyanate, 1-methylbenzene-
2.5-diisocyanate, 1-methylbenzene-
2.6-diisocyanate, 1-methylbenzene-
3.5 Diisocyanate, diphenyl ether
4.4'-diisocyanate, diphenyl ether-
2.4′-diisocyanate, naphthalene-1.4-diisocyanate, naphthalene-1.5-diisocyanate, biphenyl-4.4′-diisocyanate,
3.3'-dimethylbiphenyl 4.4'-diisocyanate, 2.3'-dimethoxybiphenyl-4.4'-diisocyanate, diphenylmethane-4.4'-diisocyanate, 3.3'-dimethoxydiphenylmethane-
Difunctional isocyanate compounds such as 4.4′-diisocyanate, 4.4′-dimethoxydiphenylmethane-3.3′-diisocyanate, diphenylsulfide-4.4′-diisocyanate, diphenylsulfone-4.4′-diisocyanate, and 2 of these isocyanates. Quantities etc. can be used. In addition, in the present invention, trifunctional or higher functional compounds such as polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tris(4-phenyl isocyanate thiophosphate), and 3.3'.4.4'-diphenylmethane tetraisocyanate are used. Isocyanate compounds and trimers of the above-mentioned isocyanate compounds can also be mixed with the diisocyanate.

In addition, in the present invention, dicarboxylic acid anhydrides having an ethylene type carbon-carbon double bond include maleic anhydride, citraconic anhydride, etc. (In the formula, R ₁ and R ₂ are hydrogen, CH ₃ , and C ₂ H ₅ ).

Two or more types of these dicarboxylic acid anhydrides having an ethylene type carbon-carbon double bond can also be used. Furthermore, functional derivatives thereof such as carboxylic acid esters can also be used.

The molten reactant [A] that plays an important role in achieving the object of the present invention is the above-mentioned (a) diisocyanate and (b) a dicarboxylic acid anhydride having an ethylene type carbon-carbon double bond, or a dicarboxylic acid anhydride thereof. It is obtained by reacting the functional derivative in a ratio of 1 mole of the former (a) to 0.05 to 0.5 mole of the latter (b) under melting at 40 to 200°C for 10 to 60 minutes.

The reactant may be liquid or have a relatively low melting point (approximately
150℃ or less), it has the advantage of being easily mixed with solid epoxy compounds.

Note that if the ratio of (b) is less than the above, the cured resin becomes brittle, and if it is increased, the reaction product has a high melting point and becomes difficult to handle.

Next, in the present invention, it is important to use a polyfunctional epoxy compound that does not have active hydroxyl groups. When there is an active hydroxyl group, an isocyanate reacts with the group to form a urethane bond. Urethane bonding reduces the heat resistance of the cured resin,
In particular, heating in the presence of moisture is undesirable because it hydrolyzes. Examples of polyfunctional epoxy compounds without active hydroxyl groups include glycidyl ether of bisphenol A, butadiene diepoxide, and 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, diclycidyl 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, N-N'-m-phenylene bis(4.5-epoxy-1.2-cyclohexane dicarboximide, etc.) , triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1.3.5-
Tri(1.2-epoxyethyl)benzene 2.2'.4.4'-
Tri- or higher functional epoxy compounds such as tetraglycidoxybenzophenone, tetradalisidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolac, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane are used. .

In the present invention, the molten reactant [A] and
With polyfunctional epoxy compound [B] as an essential component, component [A] is added to 100 parts by weight of component [B].
It is added in a range of 20 to 400 parts by weight.

Note that 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.

Next, as the curing accelerator of the present invention, 2-methylimidazole, 2-ethylimidazole, 2-
Undecylimidazole, 2-heptadecylimidazole, 2-methyl, 4-ethylimidazole, 1-butylimidazole, 1-propyl-2
-Methylimidazole, 1-beezyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole, 1-azine-2-ethylimidazole Imidazoles such as , 1-azine-2-candecyl imidazole 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.

Further, the above curing accelerator and a radical polymerization catalyst such as dicumyl peroxide or t-butyl perbenzoate can also be used in combination.

It is preferable to use at least one of the above curing accelerators in an amount of 0.01 to 10% by weight based on the mixture of the molten reactant and 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.

Further, in the present invention, the following can be used as the filler. Namely, zircon, silica, clay, aluminum hydroxide, calcium carbonate, quartz glass, wollastonite, glass, mica, kaolin, talc, graphite, carbon black, cement, carbonyl iron, barium, ferrite, lead compounds, molybdenum disulfide. , zinc white, titanium white, silica stone, silica sand, etc. can be used.

Further, known flame retardants made of halogen compounds, antimony, phosphorus, etc. can also be used as necessary.

In the present invention, a reactant [A] component obtained from a diisocyanate compound and a dicarboxylic acid anhydride or a functional derivative thereof as raw materials, an epoxy compound [B] component, and a curing accelerator [C] component, Catalyst, filler, mold release agent, etc. are kneaded and mixed using a roll or kneader.

The kneading conditions vary depending on the application and the materials used, and are in the range of room temperature or higher and about 120°C, but preferably in the range of 50 to 100°C.

The above molding material composition has a shelf life of about one month at room temperature, and can be easily cured and molded by heating at 150 to 250°C for 20 to 180 seconds, and after curing can be heated to 200°C.
It has excellent heat resistance that allows it to be used for long periods even at high temperatures.

In addition, the molded product after curing has excellent electrical properties, chemical resistance, impact resistance, and self-extinguishing properties.
It is an excellent material for sealing electrical products and electronic parts that require heat resistance and flame retardancy.

Next, Examples will be described to explain the present invention in more detail. In the text, parts are parts by weight.

Example 1 100 parts of 4.4-diisocyanate diphenylmethane was heated and melted at 60 to 90°C, 30 parts of maleic anhydride was added thereto, and the mixture was heated and reacted at 100 to 150°C for 20 minutes. 100 parts of this reactant, epoxy novolac resin (ECN1273 manufactured by Ciba, epoxy equivalent 225)
150 parts, 3 parts of triethylamine tetraphenylborate as a curing accelerator, 3 parts of stearic acid as a mold release agent, 1 part of epoxy silane KBM403 as a coupling agent, 612 parts of fused silica glass powder (100-325 mesh) as a filler. Add 70 to 80
C. for 10 minutes using two 8''φ rolls to obtain the desired composition.

This composition was molded into a predetermined test piece using a 50-ton transfer machine under the conditions of 180° C., 3 minutes, and 70 kg/cm ² . This molded product is heated to 200℃.
After curing for 2 hours, various tests were conducted.

Glass transition point of molded product: 197℃, bending strength at 180℃: 590Kg/cm ² , 180℃ after being left at 200℃ for 30 days
The bending strength was 585 kg/cm ² .

Further, the hardness of the molded product immediately after molding at 180° C. for 3 minutes was Barcol hardness (No. 935) 60.

Example 2 100 parts of toluylene diisocyanate at 60-90°C
40 parts of maleic anhydride was added thereto, and the mixture was heated and reacted at 100 to 150°C for 20 minutes.

100 parts of this reactant, epoxy novolac resin
ECN1273, 100 parts, 1 part of undecyl imidazole as a curing accelerator, 3 parts of stearic acid as a mold release agent, epoxy silane as a coupling agent.
KBM403, 1 part, as a filler, 240 parts of silica, wollastonite
240 parts were added and kneaded at 70 to 80°C for 10 minutes using two 8″φ rolls to obtain the desired material composition.

Using this material composition, various specimens were created in the same manner as in Example 1.

Glass transition point of molded product: 192℃, bending strength at 180℃: 575Kg/cm ² , 180℃ after being left at 200℃ for 30 days
The bending strength at ℃ was 570 kg/cm ² .

Further, the hardness of the molded product immediately after molding at 180° C. for 3 minutes was Barcol hardness (No. 935) 65.

Example 3 4.4′-diisocyanate diphenylmethane 100
5 parts of maleic anhydride was added thereto and heated to react at 100 to 150°C for 30 minutes. Add epoxy to 100 parts of this reactant.
ECN1273, 100 parts, 2 parts of triethylamine tetraphenylborate as a curing accelerator, 3 parts of calcium stearate as a mold release agent, coupling agent
1 part of KBM403 and 450 parts of fused silica glass powder as a filler were kneaded at 70 to 80°C for 10 minutes using two 8″φ rolls to obtain the desired composition.

Various specimens were prepared from this composition in the same manner as in Example 1.

Glass transition point of molded product: 200℃, bending strength at 180℃: 575Kg/cm ² , 180℃ after being left at 200℃ for 30 days
The bending strength at ℃ was 580 kg/cm ² .

The hardness of the molded product immediately after molding at 180°C for 3 minutes was 55 on the Barcol hardness.

Claims (1)

[Scope of Claims] 1 [A] (a) 1 mol of diisocyanate and (b) dicarboxylic acid anhydride having an ethylene type carbon-carbon double bond or a functional derivative thereof
an isocyanate compound reacted with 0.05 to 0.5 mol, [B] a polyfunctional epoxy compound having no active hydroxyl group, and [C] imidazoles, tetraphenylboron salts of tertiary amines, and tetraphenylboron salts of imidazoles. at least one selected from
A molding resin composition containing a curing accelerator consisting of seeds.