JPS63245429A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which can give a cured product excellent in workability and heat resistance, by adding a specified polymaleimide to a mixture of an epoxy resin with an acid anhydride. CONSTITUTION:A resin composition prepared by mixing 100pts.wt. epoxy compound having at least two epoxy groups in the molecule with 5-900pts.wt. polymaleimide of the formula (wherein X is H, a halogen or a 1-4C alkyl or alkoxy) and 5-300pts.wt. acid anhydride compound. Any epoxy resin can be used as said epoxy compound, and examples thereof include bisphenol A diglycidyl ether, epoxy phenol novolac and epoxy cresol novolac. In order to accelerate curing of this epoxy resin composition, a curing catalyst (e.g., tert. amine) can be added thereto.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a thermosetting resin composition with excellent heat resistance useful as a packaging material for electronic parts, an electrical insulation material, a powder coating, and a molding material. We have something to offer.

[Conventional technology]

It is known that epoxy resins can be cured by acid anhydrides, and this cured product has a comparatively good balance in electrical properties, chemical ratios, mechanical properties, etc. In addition, acid anhydride hardeners are generally less irritating to the skin and generate less heat during curing, making it easier to produce large molded products. widely used.

BACKGROUND ART In recent years, materials with better heat resistance have been desired in the electric/electronic field and the transportation field such as aircraft and vehicles as equipment becomes more sophisticated, smaller and lighter. Epoxy-anhydride cured resins conventionally used in this field have poor mechanical and electrical properties at high temperatures. A method of increasing heat resistance by curing various epoxy resins with polyfunctional acid anhydrides such as pyromellitic anhydride and benzophenone tetracarboxylic anhydride has also been used. However, these polyfunctional acid anhydrides have a high melting point and high reactivity, resulting in poor workability and problems in the mechanical properties and thermal stability of the cured product.

In order to improve these problems, a method has been proposed in which bismaleimide is mixed with an epoxy resin and an acid anhydride and then cured. (Japanese Patent Publication No. Sho 48-11359) [Problems to be Solved by the Invention] However, common bismuths such as N,N'-4,4'-diphenylmethane bismaleimide in this resin composition Maleimide has significantly poor compatibility with epoxy resins and acid anhydrides, so it is necessary to dissolve it at high temperatures.
Furthermore, there are significant drawbacks in workability, such as precipitation of crystals during compounding treatment, during storage after treatment, or during subsequent heat curing. Furthermore, the cured product obtained by curing this blended resin has insufficient effect of improving thermal stability, and a resin that is fully satisfactory in mechanical properties and electrical properties has not been obtained.

An object of the present invention is to provide a thermosetting resin composition that is excellent in workability, mechanical properties, and electrical properties, and has an improved heat resistance ratio.

[Means for solving problems]

The present invention is a deficient component in which polymaleimide is added to an epoxy resin and an acid anhydride composition in order to improve heat resistance; an epoxy compound having at least two or more epoxy groups in one molecule; [F]) Component: Polymaleimide O represented by the following formula (1) [wherein, X is a hydrogen atom, a halogen atom, or a carbon number of 1 to
5 to 900 parts by weight (component 0: 5 to 300 parts by weight of acid anhydride compound) Thermosetting resin containing the above (4), (B) and component 0 in the above proportions A composition is provided.

(Epoxy compound) As the epoxy compound used in the composition of the present invention, most of the known epoxy resins can be used. Specific examples of epoxy resins include the following.

(i) Diglycidyl ether of bisphenol A; its products include Epicote 827, 828, 834, 1001, and 1002 from Yuka Shell Epoxy Co., Ltd.
, 1004, 1007, 1009, Ciba Araldite GY250. 6099, Union Carbide's ERL2774, Dow Chemical's DER332,
3311, 661, etc. (all of the above are product names), etc. (ii) Epoxyphenol novolak; the products include Epicoat 152, manufactured by Yuka Shell Epoxy Co., Ltd.
154, DOW Chemical Company's DEN438, 448,
G11) Epoxy cresol novolak such as Teva's Araldite EPN1138 and 1139 (all of the above are trade names); such products include Ciba's Araldite ECNI 235 and 127
3, 1280. Nippon Kayakusha's EOCN102, EOCN10
3. Brominated epoxy resin such as 104 (all of the above are trade names); the product is Epicoat 5050 from Yuka Shell Epoxy Co., Ltd. Nippon Kaisha's BREN (all of the above are trade names), etc., glycidyl ester compounds obtained from diglyphyl ether of bisphenol F, phthalic acid, hexahydrophthalic acid, dimer acid, etc. and epichlorohydrin, aminophenol, diaminodiphenylmethane, etc. Epoxy resin obtained from aromatic amine and epichlorohydrin, epoxy resin obtained from synchropentadiene, etc. and peracetic acid, 1.
Examples include 4-butanediol diglyzodyl ether and 1,6-hexanesiol diglycidyl ether.

(Polymaleimide) The polymaleimide of component (E3) has the general formula (Il), H2 [wherein, X is a hydrogen atom, a halogen atom, or a carbon number of 1 to
is an alkyl group or an alkoxy group of No. 4] to obtain a polyamine by reacting an aromatic amine represented by 2 to 60 moles, and then adding maleic anhydride to the polyamine to obtain a polyamic acid; It is produced by cyclodehydrating the polyamic acid (Japanese Unexamined Patent Application Publication No. 1989-1993)
(See Publication No. 9-12931).

The obtained polymaleimide is solid at room temperature and has a curved structure (1
) is 60% by weight or more.

In addition to the polymaleimide represented by the formula (1), a polymaleimide represented by the following formula (to) coexists.

(Left below) [In the formula, X is the same as in formula (1) and is H or demeri: Yl, Y2, Y3 are H or,
Yl, Y2, Y3 are ■ or].

(Acid Anhydride Compound) Examples of the acid anhydride compound of component C) include the following.

Heptallic anhydride, trimellitic anhydride, pyromellitic anhydride, penzophenonetetho dicarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), maleic anhydride, anhydride Cono-phosphoric acid, tetrahydroheptalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 4-(4-methyl-3- pentenyl) tetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride,
Examples include maleated fatty acid, methylcyclohexenetetracarboxylic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, chlorendic anhydride, and tetrabromophthalic anhydride.

The blending amounts of these (3), (BJ and (0) components are (4
) component is 100 double positive parts, Q3) component is 5~'1o0
7i, I'i part, (inversion) component is 5 to 300i! Used at a rate of ＾.

If the blending ratio of the polymaleimide component (CB) is less than 5 parts by weight based on the epoxy compound component (4), the heat resistance of the cured product will be poor. Moreover, if the weight exceeds 900 parts, the fluidity of the resin composition will deteriorate.

[Curing catalyst]

For the purpose of promoting curing of the thermosetting resin composition of the present invention,
A curing catalyst can be added.

Such curing catalysts include tertiary amines, tertiary amine salts,
Examples include boric acid esters, Lewis acids, organometallic compounds, imidazoles, and the like.

One or more of these curing catalysts (4) are used in an amount of 0.05 to 10 parts per 100 parts by weight of the component epoxy compound.
Used in parts by weight.

(Optional Components) The following components can be added to the curable composition of the present invention as necessary.

(1) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, Basic magnesium silicate, fired clay, fine powder, fused silica, crystalline silica, carbon black, kaolin, fine powder mica, quartz powder, metal hydroxide such as aluminum hydroxide, graphite, asbestos, nickel 1 Himolybdenum, antimony trioxide, etc. Additionally, there are fibrous reinforcements and fillers, such as inorganic fibers such as glass fibers, rock wool, ceramic fibers asbestos, and carbon fibers, and synthetic fibers such as paper, bulbs, wood flour, linters, and polyamide fibers. The usage of these powder or fibrous reinforcing materials and fillers varies depending on the purpose, but up to 500 parts by weight can be used as a laminated material or molding material based on 100 parts by weight of the resin composition.

(2) Colorants, pigments, flame retardants such as titanium dioxide, yellow lead carbon black, iron black, molybdenum red, navy blue,
These include inorganic phosphorus such as ultramarine blue, cadmium yellow, cadmium red, and red phosphorus, and organic phosphorus such as triphenyl phosphate.

(3) Furthermore, various synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc. For example, alkyd resin,
Examples include one or a combination of two or more of melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, and polyester resins. These resins are preferably used within a range that does not impair the inherent properties of the resin composition of the present invention, that is, preferably less than 50% by weight of the total resin amount.

Examples of methods for blending the active ingredients, (odor ingredients) ingredients, and various additives include heating melt mixing, kneading using a roll kneader, mixing using an appropriate organic solvent, and dry mixing. .

The thermosetting resin composition of the present invention has excellent workability and
Provides a cured product with excellent heat resistance.

〔Example〕

The present invention will be described in detail in the following examples.

Production example of polymaleimide (Example 1) K in a three-ring flask equipped with a thermometer, cooler, and stirring device
1.3-benzenedialdehy)'30? (0,22
4 mol), aniline 166.6 y (1,79 mol)
, 6.82% of concentrated hydrochloric acid was charged, and the water was refluxed (temperature: 107°C).
) for 5 hours.

After the reaction is complete, add 20% aqueous sodium hydroxide solution to 20? was added and stirred for 5 minutes, followed by a neutralization reaction. Next, add 500f of methyl in butyl ketone to dissolve the precipitate, and then add 300f of pure water. Washing with water was performed three times in total to remove by-product sodium chloride and excess sodium hydroxide.

Next, the solution was heated under reduced pressure (100 to 1 txm Hg/
80 to 180°C) to completely remove unreacted amines and IJs supported by methylinobutylketone, take out the residue at 180°C, cool it, and obtain 77% of the orange transparent polyamine represented by the following formula. A mixture of polyamines 101.1 f was obtained.

(Left below) Next, 39.3 t of maleic acid and 78 t of N,N-dimethylformamide were placed in a 500 */4 volume flask equipped with a thermometer, a condenser, a dropping funnel, and a stirring device.
5 f was charged and stirred to dissolve maleic anhydride.

Next, a solution obtained by dissolving the polyamine 47.29 in N,N-dimethylformamide 1182 was added to the flask while keeping the temperature of the flask at 20 to 30°C, and after the dropwise addition was completed, stirring was continued at the same temperature for 30 minutes.

Next, 0.49 nickel acetate, 10 d1 triethylamine, 6 d1 acetic anhydride, 3 j' were added to the flask, and the mixture was stirred for 3 hours while maintaining the temperature at 60° C. to carry out a dehydration cyclization reaction.

After the reaction is completed, the reaction product is poured into a large amount of water to precipitate polymaleimide crystals, which are then washed with water and dried to produce a pale yellow polymaleimide with a weight of 83.9 cm. (yield 9.7%).

The softening point (capillary method) of this polymaleimide is 166-1
The temperature was 80°C.

(Example 2) 1,4-benzenedialdehyde 30 F (0,224
mol), 0-toluidine 95.5F (0,895 mol)
A yellow polymaleimide was obtained in the same manner as in Example 1, except that 83.3 r (0,895 mol) of aniline and 83.3 r (0,895 mol) of aniline were used as raw materials. The softening point of this product was 178-190°C.

Practical Example 1 70 parts by weight of diglycidyl ether 1 of bisphenol A Epikote 82B# (trade name) manufactured by Yuka Shell Epoxy ■, 30 parts by weight of the polymaleimide obtained in Production Example 1, and methyltetrahydrophthalic anhydride manufactured by Hitachi Chemical ■. HN-2
56 parts by weight of 200'' (trade name) were stirred and mixed at a temperature of 100°C until the mixture became uniform. Even when the resulting resin composition was cooled to room temperature, there was no precipitation of crystals and the liquid had uniform fluidity. there were.

A cyanethyl group adduct of 2-ethel-4-methylimidazole (2F4MZ) was added to this resin composition as a curing catalyst.
-CN) was added and mixed, and after defoaming, it was poured into a metal mold, and cured at 120℃ for 3 hours, then at 200℃ for 5 hours, measuring 127cm long, 12.7m wide, and 6cm thick. .4 m
A cured product was obtained. Table 1 shows the physical properties of this cured product.

Examples 2 to 8 Cured products were obtained in the same manner as in Example 1, except that the epoxy compound, polymaleimide, and acid anhydride shown in Table 1 were used.

The results are shown in light 1.

Comparative example 1 Epikote 828 70 nail discharge part, NUN'4+4'
- 30 parts by weight of diphenylmethane bismaleimide and H
N-220056 was stirred and mixed until the mixture became 100 liters using a needle 000, and then cooled to room temperature, whereupon bismaleimide crystals were precipitated. Then, the mixture was heated to 100° C. again to dissolve the crystals, one part of double 4MZCN was added, and the same operation as in Example 1 was carried out to obtain a cured product. The results are shown in Table 1.

Comparative Example 2 Epicote 828100 parts by weight and HN-22008
A cured product was obtained by carrying out the same operation as in Example 1 except that 0 parts by weight was used. The results are shown in Table 1.

(Less than blank space)

Claims (1)

[Claims] 1) Component (A): 100 parts by weight of an epoxy compound having at least two or more epoxy groups in one molecule (B) Component: Polymaleimide represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, ), (B) and (C) components in the above proportions.