JPS5952891B2 - thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition, and its objects are heat resistance and mechanical strength.

Electrical insulating materials, resin materials for laminated products, coating materials, etc. that not only have excellent electrical properties and water resistance, but also have excellent curability.
The object of the present invention is to provide a thermosetting resin composition that is extremely useful as a molding material. Conventionally, polyester resins, phenol resins, epoxy resins, and the like are well known as thermosetting resins used for electrical insulation materials, structural materials, and the like.

However, these generally do not have sufficient heat resistance, and their fields of use are naturally limited. However, in recent years, as electrical equipment, chemical-related equipment, etc. have become more sophisticated, more compact, and have harsher operating conditions, the electrical insulating materials used there are now required to have excellent heat resistance. I'm getting old. Currently, typical heat-resistant resin materials include polyimide resin, silicone resin, and diphenyl ether resin, but each of them has the following drawbacks.

That is, polyimide resin requires a special solvent, has extremely poor curability, and has poor workability and processability. Silicone resin cannot be used as a structural material because its mechanical strength is extremely low. Diphenyl ether resins have the advantage of being soluble in common general-purpose solvents and having great strength at high temperatures, but on the other hand, they have extremely poor curing properties and require a great deal of time and energy for molding and after-curing. The present inventors believe that heat resistance, mechanical strength,
The challenge was to develop electrical insulating materials and structural materials that have excellent electrical properties, water resistance, etc., as well as excellent workability and processability, and various research efforts were conducted to solve these challenges. As a result, a diphenyl ether/phenylphenol cocondensation type resol resin (hereinafter referred to as a DPE-PP type resol resin) was obtained.

) and a quinazolone ring-containing epoxy resin blended with a curing catalyst as necessary, the present invention has been made based on the new discovery that a thermosetting resin composition in which all of the above-mentioned drawbacks are solved can be provided. I've come to the point where I can complete it. In other words, the present invention provides electrical insulating materials, structural materials, etc. that can easily form a cured resin layer with excellent heat resistance, mechanical strength, electrical properties, water resistance, etc. by heat treatment at 150 to 220°C. A useful thermosetting resin composition is provided. The present invention will be explained in detail below.

The thermosetting resin composition of the present invention has the general formula (A) (where Y is a halogen atom, a hydroxy group, or an alkoxy group having 1 to 4 carbon atoms, and the average value of m+n of the substituted isomers is 1. The range is 8 to 2.2.

) A DPE-PP resole resin obtained by resole-forming a novolak-type condensate of a diphenyl ether derivative and paraphenylphenol or orthophenylphenol, and a DPE-PP resole resin of the general formula (B) (wherein R represents an aliphatic or aromatic divalent group.

) and a quinazolone ring-containing epoxy resin obtained by reacting a dicarboxylic acid compound having two quinazolone rings in one molecule with an epoxy compound having two or more epoxy groups in one molecule. It contains a curing catalyst. D, which is one of the components constituting the present invention
PE-PP resol resins can generally be produced as follows.

For example, it is expressed by the general formula (A). 70 to 140 parts of paraphenylphenol or orthophenylphenol per 100 parts by weight of diphenyl ether derivative
parts by weight and, if necessary, a Friedel-Crafts catalyst such as zinc chloride, ferric chloride, tin chloride, hydrochloric acid, sulfuric acid, cloth sulfonic acid, etc., generally at 150-260°C.
A novolak type condensate is obtained by heating at a temperature of 1 to 10 hours. This novolac type condensate is mixed with formalin, trioxane, paraformaldehyde, hexamethylenetetramine, etc., which are usually used as a formaldehyde source, in an appropriate organic solvent such as methanol-toluene mixture, cellosolve, caustic soda, ammonia triethylamine, pyridine, etc. DPE by heating to about 50 to 120°C in the presence of a basic catalyst such as tri-n-butylamine or diethylenetriamine.
- A PP-based resol resin is produced. Here, the average number of substituents (m+n) of the diphenyl ether derivative is 1.8
The reason for setting the value to 2.2 is that when used as a cured resin, if the average number of substituents is 1.8 or less, both mechanical strength and heat resistance decrease.
If it is 2.2 or more, it is not preferable because not only is it difficult to synthesize the diphenyl ether derivative, but also gelation is likely to occur during the process of producing the resol resin. Furthermore, the reason why paraphenylphenol or orthophenylphenol is set at 70 to 140 parts by weight per 100 parts by weight of the diphenyl ether derivative is that below this range, heat curing will be slow and a cured resin with sufficient strength will not be obtained. This is because, above this range, heat resistance, electrical properties, etc. tend to deteriorate. Further, the quinazolone ring-containing epoxy resin, which is one of the components constituting the present invention, can generally be produced as follows.

For example, a dicarboxylic acid compound having a quinazolone ring represented by the general formula (B) and an epoxy compound having two or more epoxy groups in one molecule are mixed, with 1 equivalent of the epoxy group per 1 equivalent of the carboxyl group. .2 to 3 equivalents and heated at 100 to 250°C without a catalyst or in the presence of a catalyst such as an amine or a quaternary ammonium salt.
It is obtained by reacting at a temperature of about 0.5 to 5 hours.

Here, the reason why the ratio of the epoxy group of the epoxy compound to 1 equivalent of carboxyl group of the dicarboxylic acid compound having a quinazolone ring is set to 1.2 to 3 equivalents is because if it is less than that, the molecular weight of the product will increase too much. This is because compatibility with the DPE-PP resol resin becomes difficult, resulting in poor workability, and if it exceeds this, the resulting cured product will not have sufficient heat resistance. The quinazolone ring-containing dicarboxylic acid compound of the general formula (B) used in the present invention is prepared by adding 4,4''-diaminodiphenylmethane-3,3''-dicarboxylic acid to acetic anhydride or acetyl chloride. Using bisoxazinone obtained by acetylation etc. as a starting material, 1 mol of the bisoxazinone and the general formula H2N-R-COOH (in the formula, R
represents an aliphatic or aromatic divalent group.

), for example, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, β-aminopropionic acid, γ-aminobutyric acid and glycine, and m-talesol, N,N in an organic solvent such as monodimethylacetamide, N,N-dimethylformamide, or N-methylpyrrolidone at 80-220°C.
It can be easily obtained by heating for ~10 hours. The epoxy compound used in the present invention is usually a diglycidyl ether type of bisphenol A and preferably has an epoxy equivalent of about 1000 or less.

Various such epoxy resins are commercially available, such as Epicote 828 (manufactured by Ciel Chemical Co., Ltd., trade name, epoxy equivalent weight 190), Epicote 1001 (manufactured by Ciel Chemical Co., Ltd., trade name, epoxy equivalent weight 480), and Epicote 1004 (manufactured by Ciel Chemical Co., Ltd., trade name, epoxy equivalent weight 480). (Epoxy equivalent: 970), but other alicyclic, glycidyl ester type, and novolac type epoxy resins can also be used. Further, as the oxidation catalyst, acidic catalysts such as phosphoric acid, P-toluenesulfonic acid, P-xylenesulfonic acid, and oxalic acid are extremely effective.

In the present invention, if the blending ratio of the DPE-PP resol resin and the quinazolone-containing epoxy resin is in the range of 40 to 70 for the former and 60 to 30 for the latter,
Desirable for imparting excellent heat resistance and mechanical strength to cured products.

In other words, cured products with a composition of 70% by weight or more of DPE-PP resol resin and 30% by weight or less of quinazolone-containing epoxy resin tend to be brittle and susceptible to mechanical shock. is 4
0% by weight or less, quinazolone-containing epoxy resin 60% by weight
Above this, the curability tends to be low, and the strength at high temperatures, heat resistance, etc. tend to decrease. Depending on the purpose of the curing catalyst,
The amount to be used is determined, but in general, it is not preferable to mix 5% by weight or more based on the total amount of the resin from the viewpoint of the electrical properties and chemical resistance of the cured product.

The thermosetting resin composition of the present invention contains known fillers, such as:
Silica powder, glass powder, calcium carbonate powder, glass fiber, carbon black, etc., pigments, other flame retardants, oxidative deterioration inhibitors, etc. can also be blended.

When using the thermosetting resin composition of the present invention, it is usually dissolved in a suitable solvent and used in the form of a varnish, but it can also be used as it is as a powder mixture.

Next, the present invention will be explained with reference to examples.

The structural formulas and abbreviations of the quinazolone ring-containing dicarboxylic acid compounds used in each example are shown below. Example 1 88 parts by weight of chloromethyl diphenyl ether having an average of 1.96 chloromethyl groups per diphenyl ether skeleton (hereinafter simply abbreviated as parts).

), 107 parts of paraphenylphenol, and 0.0 parts of ferric chloride.
A novolak-type condensate was obtained by mixing 2 parts of 0.02 parts and heating and stirring at 150 to 180° C. for about 3 hours while removing hydrogen chloride produced under a nitrogen gas flow. To this novolac type condensate were added 76 parts of 37% formalin, 1.7 parts of caustic soda, 9 parts of methanol, and 120 parts of toluene, and after heating and stirring at 85 to 87°C for 10 hours, 1 part of toluene was added.
40 parts were added and cooled. Thereafter, the mixture was washed with 20% sulfuric acid, and the toluene layer was separated, followed by washing with a large amount of water.
Thereafter, heating dehydration and concentration were performed to obtain a DPE-PP resol resin solution with a concentration of 50%. Next, the abbreviation QA
-1 and 286 parts of a quinazolone ring-containing dicarboxylic acid compound and Epicoat 1001 (manufactured by Ciel Chemical, trade name, bisphenol A-based epoxy resin, epoxy equivalent: 4
80) and 720 parts of benzyltriethylammonium chloride as a catalyst at 200°C.
Allowed time to react.

The product is a solid resin at room temperature with an epoxy equivalent of 2040
It was hot. When this material was analyzed by infrared absorption spectrum, there was no absorption based on carboxylic acid at 2500 to 2200 cm-1, and at 1690 cm-1,1600 cm
Absorption based on the quinazolone ring near -1, 1290 cm1
There was an absorption based on the ester group near -1, and the formation of a quinazolone ring-containing epoxy resin was confirmed. By dissolving this resin in dioxane, a quinazolone ring-containing epoxy resin solution with a concentration of 50% was obtained. To 50 parts of the quinazolone ring-containing epoxy resin solution thus obtained, 50 parts of the previously prepared DPE-PP resol resin solution was mixed, and further 2.5 parts of a 20% acetone solution of para-toluenesulfonic acid was added. , mix well and make resin varnish. After this resin varnish was applied onto a copper plate, it was cured by heating at 100°C for 1 hour and then at 200°C for 3 hours to obtain a coating film with a thickness of 0.04 mm and a smooth surface.

The volume resistivity of this coating film is 2.1X101 at normal room temperature.
6Ω-Cm and 0.8×10 after 10 days immersion in water.
It was 16ΩCm. Further, 3 g of varnish was cured in an aluminum shear with a diameter of 7 cm. 24 of the obtained cured product
The weight loss rate after heating at 0° C. for 500 hours was 71%. The bending strength was measured on a sample obtained by impregnating a helical coil made by winding an amide-imide enameled wire with a diameter of 1 mm around a round bar with a diameter of 6 mm and curing it under the same conditions (described above). . The bending strength of this product at a distance of 5 cm between supports is 22.1 k at 25°C.
g, and 6.2 kg at 150°C. Example 2 100 parts of hydroxymethyl diphenyl ether having an average of 1.8 hydroxymethyl groups per diphenyl ether skeleton, 100 parts of orthophenyl phenol, and 0.05 part of zinc chloride were mixed, and nitrogen gas was added. under air current, 19
The mixture was heated and stirred at 0 to 210°C for about 6 hours, during which water produced was distilled off to obtain a novolak type condensate.

Paraformaldehyde 26.
4 parts, 0.3 parts of sodium hydroxide, 20 parts of methanol,
120 parts of toluene was added, and after heating and stirring at 86 to 90°C for 8 hours, 140 parts of toluene was added and cooled. After that, 2
After washing with 0% sulfuric acid and separating the toluene layer,
Washed with plenty of water. Thereafter, heating and dehydration and concentration were performed to obtain a DPE-PP resol resin solution with a concentration of 50%. Next, 286 parts of a quinazolone ring-containing dicarboxylic acid compound represented by the abbreviation QA-2, 1440 parts of Epicote 1001 (described above), and 0.9 parts of trimethylbenzylammonium chloride were mixed, and the mixture was heated and stirred at 180°C for 2 hours. I twisted it and reacted.

The product was solid at room temperature, and as in Example 1, the formation of a quinazolone ring-containing epoxy resin was confirmed by infrared absorption spectrum. By dissolving this resin in dioxane, a quinazolone ring-containing epoxy resin solution with a concentration of 50% was obtained. To 40 parts of the quinazolone ring-containing epoxy resin solution thus obtained, 60 parts of the DPE-PP resol resin solution prepared previously was mixed, and further 5 parts of a 20% acetone solution of paraxylene sulfonic acid was added. They were mixed to make a resin varnish.

The coating film obtained by curing this resin varnish under the same conditions as in Example 1 was brown and transparent and tough, and the volume resistivity was 3.1 under normal conditions when measured at 25°C. ×1
016Ω-Cm and 0.9× after 10 days immersion in water.
It was 1016Ω-Cm.

The weight loss rate after heating at 240° C. for 500 hours in air was 7.3%. Example 3 P,p'-dipoxymethyl diphenyl ether 170
parts, paraphenylphenol 119 parts, ferric chloride 0.
A novolak type condensate was obtained by mixing 3 parts of 0 and 0 and heating and stirring at 210 to 220° C. for about 3 hours while distilling off the butanol produced under a nitrogen gas stream.

To this novolak type condensate, 56 parts of 37% formalin,
3 parts caustic soda, 10 parts methanol, 140 parts toluene
After heating and stirring at 88 to 92°C for 8 hours, 140 parts of toluene was added and the mixture was cooled. Then neutralize with 20% sulfuric acid,
And after separating the toluene layer, it was washed with a large amount of water. After that, heat dehydration and concentration are performed to obtain D with a concentration of 50%.
A PE-PP resol resin solution was obtained. Next, structural formula QA
Quinazolone ring-containing dicarboxylic acid compound 1 represented by -2
43 parts and Epicote 1004 (manufactured by Ciel Chemical, trade name,
Bisphenol A epoxy resin, epoxy equivalent 970
) and 0.5 parts of benzyltriethylammonium chloride were charged into 1114 parts of dimethylformamide and reacted at 153° C. for 5 hours to obtain a 50% solution of a quinazolone ring-containing epoxy resin in dimethylformamide.

To 60 parts of the quinazolone ring-containing epoxy resin solution thus obtained, 40 parts of the DPE-PP resol resin solution prepared previously was mixed, and then 20 parts of paraxylene sulfonic acid was added.
% acetone solution was added and mixed well to obtain a resin varnish.

After applying this resin varnish on a copper plate, it was heated to 30℃ at 130℃.
Thickness 0.04m obtained by heating and curing at 200℃ for 4 hours
The coating film of No. m was brown, transparent, and glossy.

Moreover, in the mandrel test, it passed the test with a diameter of 3 mm. J
The thermal weight loss rate of the material was 8.6%, the appearance maintained its gloss, and there was no change in shape. Example 4 90 parts of methoxymethyl diphenyl ether having an average of 2.2 methoxymethyl groups per diphenyl ether skeleton, 126 parts of paraphenylphenol, and 0.02 parts of ferric chloride were mixed, and nitrogen A novolak type condensate was obtained by heating and stirring at 220 to 230° C. for about 3 hours while distilling off the generated methanol under a gas stream.

This novolak type condensate was mixed with 96 parts of 37% formalin, 5 parts of triethylamine, 11 parts of methanol, and 12 parts of toluene.
After heating and stirring at 87 to 92°C for 8 hours, 140 parts of toluene was added. Thereafter, heating dehydration and concentration were performed to obtain a DPE-PP resol resin solution with a concentration of 50%. Next, 224 parts of a quinazolone ring-containing dicarboxylic acid compound having the abbreviation QA-3 and Epicoat 828 (
228 parts of bisphenol A-based epoxy resin manufactured by Ciel Chemical, trade name, epoxy equivalent 190) and 0.7 parts of benzyltriethylammonium chloride were charged into 452 parts of dimethylformamide and reacted at 153°C for 5 hours to form a quinazolone ring. A 50% dimethylformamide solution of the epoxy resin was obtained.

To 30 parts of the quinazolone ring-containing epoxy resin solution obtained in this way, 70 parts of the DPE-PP resol resin solution prepared previously was mixed, and 1.5 parts of phosphoric acid was added and mixed thoroughly. Got varnish.

Apply this resin varnish to a silane-treated glass cloth and
A prepreg was prepared by drying at 50° C. for 10 minutes. After that, several sheets of this prepreg were stacked together and a pressure of 100k was applied.
g/Crff, after heating and pressure molding at 200°C for 1 hour,
Furthermore, it was heated at 200° C. for 10 hours to obtain a laminate.

Claims (1)

[Claims] 1 General formula (A) ▲ Numerical formula, chemical formula, table, etc. The average value of is in the range of 1.8 to 2.2.) A diphenyl ether/phenylphenol co-condensation obtained by resole-forming a novolac-type condensate of a diphenyl ether derivative represented by () and para-phenylphenol or orthophenylphenol. type resol resin 40 to 70% by weight, general formula (B)▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (In the formula, R represents an aliphatic or aromatic divalent group) A dicarboxylic acid compound having two quinazolone rings in one molecule and two quinazolone rings in one molecule. A thermosetting resin composition comprising 60 to 30% by weight of a quinazolone ring-containing epoxy resin obtained by reacting the above epoxy compound having an epoxy group with a curing catalyst, if necessary.