JPS6023424A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:A heat-resistant resin composition providing a cured material having improved curing properties and heat resistance, especially a molding material and laminate, obtained by blending a specific polymaleimide with an epoxy compound and an amine compound. CONSTITUTION:(A) 100pts.wt. compound shown by the formula (X is H, halogen, or 1-4C alkyl or alkoxy) is blended with (B) 10-900pts.wt. epoxy compound (e.g., diglycidyl ether of bisphenol A, epoxyphenol novolak, epoxycresol novolak, diglycidyl ether of bisphenol F, etc.) and (C) 5-100pts.wt. amino compound shown by the formula Q-(NH2)n (Q is 1-150C organic group, n-functional organic group capable of containing H, O, S, halogen, N, P, or S; n is >=1).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-resistant resin composition with excellent curability. It is particularly useful as a molding material, sealant, and laminated paulownia material.

In general, epoxy resins provide cured products with excellent electrical properties, mechanical properties, dimensional stability, and chemical resistance, and are widely used as various electrical insulating materials, molded products, adhesives, and paints.

BACKGROUND ART In recent years, materials with better heat resistance have been desired in the electric/electronic field and the field of transportation equipment such as aircraft and vehicles as equipment becomes more sophisticated, smaller and lighter.

Conventionally, epoxy resins, maleimide resins, polyimide resins, etc. have been used in this field.

However, although epoxy resins have excellent mechanical and electrical properties, they do not necessarily have sufficient heat resistance. Although polyimide resin still has excellent heat resistance, it is difficult to mold because it is insoluble and infusible.

Polymaleimide, represented by N,N-4,4'-diphenylmethane bismaleimide, has high thermal stability, but has the problem of slow curing speed and requiring long-term heating at high temperatures for complete curing. are doing.

The present invention was made in order to improve the curability of polymaleimide, and by blending an epoxy resin and an amine compound with a specific polyfunctional polymaleimide, the curability is improved, and the resulting cured product is Heat resistance provides a curable resin composition that provides a very good product.

That is, the present invention provides component (4): Polymaleimide zx xz represented by the following formula (■) [wherein, X is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 is an alkyl group or an alkoxy group, and 2 is 1 1 100 parts by weight Q3) Component: 10 to 900 parts by weight of an epoxy compound having at least more than 1 1,2-epoxy group in one molecule (C) Component D General Amine compound represented by the formula, Q (NH2) n [wherein Q is an organic group having 1 to 150 carbon atoms, hydrogen,
An n-valent organic group that can contain oxygen, sulfur, halogen, nitrogen, phosphorus, and silicon, where n represents an integer of 1 or more] 5 to 100 parts by weight of the above @, [F]) and (C) component The object of the present invention is to provide a heat-resistant resin composition in which the following are blended in the above proportions.

In the present invention, the polymaleimide as the prisoner component has the general formula, [wherein, X is a hydrogen atom, and a halogen atom has 1 to 1 carbon atoms]
4 is an alkyl group or an alkoxy group] 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 dehydrating and cyclizing the polyamic acid (Japanese Patent Application No. 1983).
7-121465).

The aromatic dialdehyde used in the production of the intermediate polyamine for obtaining the above-mentioned polymaleimide is a compound represented by the general formula (Il'1), specifically 1,2-benzenedialdehyde, 1,3-benzenedialdehyde. )", 1,4-benzenedialdehyde is preferred, and may have a substituent such as a halogen group or an alkyl group.

In addition, the aromatic amines include aniline, 〇-toluidine, m)'luidine, p-yluidine, 0-ethylaniline, 0-isopropylaniline, p-2-1r-luaniline, 0-anisidine, m-7 nisidine, p- -Anisidine, 0-phenetidine, chloranilines, bromoanilines, etc.

The reaction between aromatic dialdehyde and aromatic amine is carried out using hydrochloric acid,
In the presence of an acidic catalyst such as mineral acids such as sulfuric acid, organic acids such as oxalic acid and para-toluenesulfonic acid, and other organic acid salts, 2 aromatic amines are added to 1 mole of aromatic dialdehyde.
40-1 in proportions of ~60 mol, preferably 5-50 mol
The condensation reaction is carried out at a temperature of 50° C. for 1 to 0 hours.

After completion of the reaction, the reaction mixture is hydroxylated). After neutralization with an alkali represented by IJum and washing with water, a polyamine can be obtained by removing excess aromatic amine under reduced pressure.

The obtained polyamine is solid at room temperature and has the following formula (III
) is 60% by weight or more.

N112 1Nh2 [In the formula, X is a hydrogen atom, a halogen atom, and a carbon number of 1 to
4 is an alkyl group or an alkoxy group].

In addition to the polyamine shown in this weapon, aromatic aldehyde is further condensed to the polyamine shown in (assistance), and NH2 groups further reacted with aromatic amine are 7
It is the same as the formula (Xid in the formula) obtained by side combination of 40% or more of the polyamine represented by the above (2); Y1, Y2, Ya
, Y4 is H or; Y', Y2', ya' is H or a
Yl'', Y2', Ya' are H or].

The presence of these polyamines having seven or more NH2 groups was confirmed by gel permeation chromatography.

Dissolve 1 mol of maleic anhydride in a suitable organic solvent per 1 equivalent of the amino group of this polyamine, and
．． The addition reaction is carried out for 5 to 2 hours to obtain polyamic acid. Examples of the organic solvent include N,N'-dimethylformamide, acetone, methyl ethyl ketone, dioxane, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

Next, acetic anhydride is added as a dehydrating agent for this polyamic acid, a tertiary amine and a catalyst are added as necessary, and 2
Heating at 0 to 80°C for 1 to 5 hours to perform a cyclodehydration reaction,
The purpose is to obtain a polymaleimide.

As the catalyst, cobalt acetate, nickel acetate, etc. can be used, and as the tertiary amine, triethylamine, tri-n-propylamine, tri-n-butylamine, etc. can be used.

The produced polymaleimide is purified by washing with water and drying.

is.

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

[X and 2 in the formula are the same dithia' as in formula (1)): Yt,
Y2, Y8, Y4 is H or; Yl', Y2', ya' is H, Yl'', Y2'', Y8'' is H or].

Next, as the polyepoxy compound of component (2), the following may be used.

(+), diglycidyl ether of bisphenol A:
The products include Epicoat 827, 828, 834, 864, and 100 from Yuka Shell Epoxy Co., Ltd.
1, 1004, 1007, 1031, Ciba Araldite GY250゜6099, Union Carbide ERL2774, Dow Chemical DER332
, 331, 661, (all of the above are product names), etc.

(++), epoxyphenol novolac; the product is Ebiko from Yuka Shell Epoxy Co., Ltd.) 15
2, 154, DOW Chemical Company DEN438, 44
B. Ciba's Araldite EPNI 138, EPNI 113
9 (all of the above are product names), etc.

(fil), epoxy cresol novolac; its products include Ciba's Araldite ECN1235 and ECN12
73, 1280 (all of the above are product names), etc.

Qv'L diglycidyl ether of bisphenol F;
For example, Epicoat 827 (trade name) manufactured by Yuka Shell Epoxy ■.

In addition, epoxy resins obtained from phthalic acid or hexahydroxybenzoic acid and epichlorohydrin, epoxy resins obtained from parahydroxybenzoic acid and epichlorohydrin, epoxy resins obtained from aromatic amines such as toluidine or aniline and epichlorohydrin, vinyl cyclohexene resins, etc. oxide, 1,4-butanediol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, and the like.

Among these, epoxy equivalent force 1 which is liquid at 20℃
Diglycidyl ether of bisphenol having a number of 60 to 230, epoxy cresol novolak, and epoxy phenol novolak are more preferable because they have excellent miscibility with fillers such as glass fiber, matsuki filler, and metal powder, and with polymaleimide.

The blending amount of the polyepoxy compound as component (B) is 10 to 900 parts per 1ool of the polymaleimide as component (■).
It is used in proportions of 50 to 500 parts by weight, preferably 50 to 500 parts by weight.

Furthermore, as the amine compound of component (C), aniline,
Toluidine, xylidine, vinylaniline, ingropenylaniline, phenylenediamine, diaminocyclohexane, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,
7-Shioxadecane-1. ,LO-diami/,4,4'
-diaminodicyclohexylmethane, m-xylylene diamine, p-xylylene diamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis(310 rho-4-aminophenyl)methane,
2゜2-bis(4-aminophenyl)propane, 4.4
'-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone 1,5-diaminonaphthalene, bis(4-7minophenyl)methylphosphine oxide, 4-methyl-2,4- Bis(4'-aminophenyl)pentene-1
,5-amino-1-(4'-aminophenyl)-1,
3,3= )limethylindane,')13s(4-aminophenyl)phosphate, 2,4-bis(4'-aminobenzyl)aniline, 2,2-bis(4(4//-
Examples include polymers of amino(enoxy)phenyl]propane and vinylanilines of dimer or higher type, and polyvalent amines of condensates of aniline and formaldehyde.

The amine compound is used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the polymaleimide of component (1). This amine compound has the aspect of a curing agent.

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, carbon dioxide powder, basic Magnesium silicate, fired ray, finely powdered silica, fused silica, crystalline silica, carbon black, kaolin, finely powdered mica, quartz powder, graphite, asbestos, molybdenum disulfide, antimony trioxide, etc. In addition, fibrous reinforcements and fillers, such as inorganic fibers such as glass fiber, rock wool, ceramic fibers, asbestos, and carbon fibers, and synthetic fibers such as paper, pulp, wood flour, linters, and polyamide fibers, etc. It is. The amount of these powder or fibrous reinforcing materials and fillers used varies depending on the application, but as a laminated material or molding material, it is 500 parts by weight per 100 parts by weight of the resin composition of the present invention.
It can be added up to parts by weight.

(2) Colorants, dyes, flame retardants, such as titanium dioxide,
Inorganic materials such as yellow lead carbon black, iron black, molybdenum red, navy blue, ultramarine blue, cadmium yellow, cadmium red, red phosphorous, etc.
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, one or a combination of two or more resins such as phenol resin, alkyd resin, mela-min resin, fluororesin, vinyl chloride resin, acrylic resin, silicone resin, and polyester resin can be used. The amount of these resins used is preferably within a range that does not impair the inherent properties of the resin composition of the present invention, that is, less than 50% by weight of the total resin amount.

(4) component, ω) component, (O component, and various additives) can be blended by heating and melt mixing, mixing using rolls, kneaders, etc., mixing using an appropriate organic solvent, and dry mixing. etc. can be mentioned.

The resin composition of the present invention provides a cured product with excellent curability and heat resistance compared to conventional polymaleimides.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Application Examples.

``S)'' (1 in a three-ring flask equipped with a thermometer, a condenser, and a stirrer)
, 3-benzenedialdehyde 30 f (0,224 mol), aniline 166.6 y (1,7-9 mol),
Concentrated hydrochloric acid 6,8? and reflux water (temperature 107℃)
The reaction was carried out for 5 hours.

After the reaction was completed, 20 g of aqueous sodium hydroxide solution 202 was added and stirred for 5 minutes, followed by a neutralization reaction. Next, 500 f of methyl isobutyl ketone was added to dissolve the precipitate, and then washing was performed three times in total with 3001 pure water to remove by-produced sodium chloride and excess sodium hydroxide.

Next, the solution was dissolved under reduced pressure (100-1 mm Hg/
Methylinobutylketone and unreacted aniline were completely removed at 180°C (80 to 180°C), and the residue was poured out at 180°C, cooled, and a transparent orange polyamine represented by the following formula 7
A mixture of polyamines 1 (j 1.11) having 7 h was obtained.

Next, in a 500+++ l four-day flask equipped with a thermometer, condenser, addition funnel, and stirrer, 39.39 ml of maleic anhydride and 78.5 ml of N,N'-dimethylformamide were added.
f was charged and stirred to dissolve maleic anhydride.

Then, the polyamine 47.2 f′f:N, N′-
A solution dissolved in dimethylformamide 118f was added dropwise while maintaining 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, add 0.4f of nickel acetate into this flask.

10 m of triethylamine and 61.3 f of acetic anhydride were added, 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 complete, the reaction product is poured into a large amount of water to precipitate polymaleimide crystals. ) It's a good deal.

The softening point (capillary method) of this polymaleimide is 166℃ ~
The temperature was 180°C.

Example 2 30 g (0,224 mol) of 1,4-benzenedialdehyde, 95.9 r (0,895 mol) of 0-toluidine
A yellow polymaleimide was obtained in the same manner as in Example 1, except that 83.3 f (0,895 mol) of aniline and 83.3 f (0,895 mol) of aniline were used as raw materials. The softening point of this product was 178-190°C.

Examples 3 to 11 In Example 1, the types of aldehydes and amines used are shown in Table 1.
Polyamines with the neutralization equivalents shown in the table were obtained in the same manner, except that the polyamines were changed to those shown in Example 1. Obtained maleimide.

The softening points of these polymaleimides are shown in the same table.

(Leaving space below) Example 1 30 parts of the polymaleimide obtained in Example 1 and 70 parts of bisphenol A diglycidyl ether "Epicote 828" (trade name manufactured by Yuka Shell Epoxy) were uniformly heated and dissolved at a temperature of 150°C. 100 parts of the mixture, 25 parts of 4,4'-diaminodiphenylmethane, and 200 parts of fused silica as a filler were kneaded for 20 minutes with a roll (temperature: 70 to 90°C).

After mixing, the mixture was pulverized using a pulverizer, and the pulverized product was transferred to a press mold, and then compression molded at 200° C. and a pressure of 100 V4/7 for 10 minutes, and cooled to 40° C. to obtain a molded product.

Length 12.7crn, width 1.27an, height 0.64cm
Table 2 shows the physical properties of this molded product.

Next, this molded product was stored in a greenhouse at 230° C. for 10 hours to be post-cured to obtain a cured product shown in Table 2.

Example 2 A molded product was obtained in advance, and then a cured product was obtained in the same manner as in Example 1 except that the polymaleimide was replaced with that obtained in Example 2.

Example 3 A molded product was previously obtained in the same manner as in Example 1, except that the polyepoxy compound was replaced with Epicote 154 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), and then a cured product was obtained. The physical properties are shown in Table-2.

Example 4 A molded product was obtained in advance in the same manner as in Example 1, except that the IJ epoxy compound was replaced with glycidylamine YH-434 (trade name, manufactured by Tobu Kasei Co., Ltd.) obtained from diaminodiphenylmethane, and then a cured product was prepared.

The physical properties are shown in Table-2.

Comparative Example 1 A molded product was obtained in advance and then a cured product was obtained in the same manner as in Example 1 except that commercially available N,N'-4,4'-diphenylmethane bismaleimide was used as the polymaleimide. The physical properties are shown in Ben-2.

Comparative Example-2 Polymaleimide is N, N'-4,4'-diphenylmethane bismaleimide, polyepoxy compound is Epico)
A molded product was obtained in advance, and then a cured product was obtained in the same manner as in Example 1 except that 154 was used. The physical properties are shown in Table-2.

Engraving Example-1 100 parts of diglycidyl ether of hisphenol A 6 Ebicote 828'', 26 parts of 4,4'-diaminodiphenylmethane and 200 parts of silica were kneaded for 20 minutes using a roll at 80 to 100°C, and then ground. 7. The resulting pulverized product was treated in the same manner as in Example 1 to obtain a molded product and a cured product.

The physical properties are shown in Table-2.

Examples 5 to 7, Comparative Example 3 A cured product was obtained in the same manner as in Example 1, except that the composition was changed as shown in Table 2, and the curing conditions were changed as shown in the same table.

(Margin below)

Claims (1)

[Claims] 1'), component (A) is a polymaleimide represented by the quadratic formula [
In the formula, 'X is a hydrogen atom, a halogen atom, or a carbon number of 1-
100 parts by weight (J3) 10 to 900 parts by weight of an epoxy compound having at least two or more 1,2-epoxy groups in each molecule. An amine compound represented by the general formula Q (NH2) H [wherein Q is an organic group having 1 to 150 carbon atoms, hydrogen,
An n-valent organic group that can contain oxygen, sulfur, halogen, nitrogen, phosphorus, and silicon, where n represents an integer of 1 or more] 5 to 100 parts by weight of the above compounds, [F]) and C) component A heat-resistant resin composition comprising the above-mentioned proportions.