JPS60228528A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in curability and the heat resistance of a cured product, comprising a specified polymaleimide, an epoxy compound and an amine compound. CONSTITUTION:A polymaleimide (A) (e.g., a mixture comprising at least polymaleimides of formulas II and III) is obtained by the dehydrative ring closure of a polyamic acid obtained by an addition reaction between maleic anhydride and a polyamine obtained by reacting 1mol of an aldehyde mixture comprising 5- 95wt% HCHO and 95-5wt% aromatic dialdehyde (e.g., 1,2-benzenedialdehyde) and 2-60mol of an aromatic amine of formula I (wherein X is H, a halogen, a 1-4C alkyl, or an alkoxy). 100pts.wt. component A is mixed with 10-900pts.wt. (B) epoxy compound having at least two epoxy groups in the molecule (e.g., bisphenol A diglycidyl ether) and 5-100pts.wt. (C) amine compound of formula IV (wherein Q is a 1-150C n-valent organic group which may contain H, O, S, N, P, etc., and n>=1).

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the invention, industrial field of application] The present invention relates to a resin composition with excellent thermosetting properties. It is useful as a molding material, sealant, and laminated material.

[Conventional technology]

BACKGROUND ART In recent years, materials with better heat resistance have been desired in the field of electric/electronic decomposition, transportation equipment such as aircraft and vehicles, etc., 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 or curing speed. Also,
Although polyimide resin has excellent heat resistance, it is difficult to mold because it is insoluble and infusible.

Although N,N'-4,4'-diphenylmethane bismaleimide has high thermal stability, it has poor solubility in solvents, and has a slow curing speed, requiring long-term heating at high temperatures for complete curing. I have a problem.

In addition, poly(phenylmethylene) polymaleimide h represented by the general formula, [λ oki, m is an integer of θ ~ 4]
, N,N'4.4'-Diphenylmethane bismaleimide has a lower softening point, better workability, and slightly better solubility in solvents, but it has lower curing speed.
It has the same problem of slowness as NJ'-4,4'-diphenylmethane bismaleimide.

[Problem that the invention seeks to solve]

The present invention was made in order to improve the curability of conventional polymaleimides and the heat resistance of cured products.

[Structure of the invention]

That is, the present invention 1d.

■Ingredients: General formula (1), [wherein, Number 1~
The aromatic amine represented by 4 is an alkyl group or an alkoxy group] is reacted in a ratio of 2 to 60 moles to obtain a polyamine, and then the polyamine and maleic anhydride are subjected to an addition reaction to obtain a polyamic acid. , 100 parts by weight of polymaleimide obtained by cyclodehydration of the polyamic acid (ω) component, 10 to 90 parts by weight of an epoxy compound having at least two or more 1,2-epoxy groups in one molecule (0 components D general formula % formula %) [In the formula, QFi is an organic group having 1 to 150 carbon atoms, and is an n-valent organic group that can contain hydrogen, oxygen, sulfur, ), rogene, nitrogen, phosphorus, and silicon. , n is an integer of 1 or more] 5 to 100 parts by weight of the amine compound (2), Aromatic dialdehyde is a compound represented by the general formula ([l), specifically flies. 2-benzenedialdehyde,
1,3-benzenedialdehyde and 1,4-benzenedialdehyde are preferred, and they may have a substituent such as a halogen group or an alkyl group.

The other formaldehyde may be formalin, which is an aqueous solution, or paraformaldehyde, which is a polymer thereof.

The aromatic dialdehyde represented by the above formula (I+) is 5 to 95% by weight, preferably 10 to 90 g by weight of the aldehydes.
It is used at a rate of k%. If the amount of aromatic dialdehyde used is less than 5% by weight, the effect of improving the curability of the resulting polymaleimide is small. On the other hand, if it exceeds 95% by weight, the effect of improving solubility in solvents is insufficient.

Next, the aromatic amines include aniline, 0-toluidine, m-toluidine, p-yluidine, 0-ethylaniline, 0-isopropylaniline, p-butylaniline, 0-anisidine, m-anisidine, p-anisidine,
Examples include O-7 enetidine, chloranilines, and bromoanilines.

The reaction between aldehydes and aromatic amines involves hydrochloric acid, sulfur W'
In the presence of an acidic catalyst such as mineral acids of J, organic acids such as oxalic acid and para-toluenesulfonic acid, and other organic acid salts, 2 to 60 moles of aromatic amine, preferably 3 to 60 moles, per mole of aldehyde. The condensation reaction is carried out in a proportion of 50 mol at a temperature of 40 to 150° C. for 1 to 10 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 liquid to solid at room temperature.

1 mole of maleic anhydride was dissolved in a suitable organic solvent per 1 equivalent of amine group of this polyamine, and the solution was heated to 0 to 40℃.
．． The addition reaction is carried out for 5 to 2 hours to obtain polyamic acid. Organic solvents include N,N'-dimethylformamide, acetone, methyl ethyl ketone, dioxane, N,N'-
Examples include dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and the like.

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

Catalysts include alkali metal salts, alkaline earth metal salts, 2
nickel salts, divalent or trivalent iron salts, and cobalt salts. In addition, chlorides, bromides, carbonates, acetates, etc. of these metals can also be used. As the tertiary amine, triethylamine, tri-n-propylamine, tri-n-butylamine, etc. can be used. The produced polymaleimide reaction solution Precipitate the polymaleimide using a precipitating agent such as water, wash with water or neutralize with a basic substance such as sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide as necessary, and then dry. It is purified by

The polymaleimide obtained in this way is generally a mixture, of which 60% by weight or more (the following is a blank) MI MI [wherein Xt- is a hydrogen atom, a halogen atom, or a carbon number of 1 to 4] is the same as the alkyl group or alkoxy 1 [in the formula, X is the same as the formula Tsukuda], and is an integer from mFio to 4].

In addition to the polymaleimides represented by formulas (■) and 0ffi, polymaleimides represented by the following formulas (■), M), etc. coexist.

[In the formula] X, 'Ztj:011] is the same as the formula; Y
1% Y2, Y8. Y4 tiH or: Y1', Y2', η' keH or,
Y1'% Y2', Y/ket H or X].

[wherein,

[Epoxy compound]

Next, examples of the polyepoxy compound as component (B) include the following: (1) Diglycidyl ether of bisphenol A: Products include Epicoat 827 and 828 from Yuka Shell Epoxy Co., Ltd. 834, 864, 1001
, 1004, 1007, 1031, Ciba Araldite GY250゜6099, Union Carbide ERL2774, Dow Chemical DER332,
331, 661, etc. (all of the above are product names) Epoxyphenol novolak: The products include Epicort 152 and 1 from Yuka Shell Epoxy Co., Ltd.
54, DOW Chemical Company's DEN438, DEN448, Chipa Company's Araldite EPNI 138, DEN1139 (all of the above are trade names), etc.

(18), Epoxy cresol novolac: Its products include Kechiba's Araldite ECN1235 and ECN127.
3. 1280 (all of the above are product names), etc.

←), 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 hexahydrophthalic acid and epichlorohydrin, epoxy resins obtained from rosehydroxybenzoic acid and epichlorohydrin, epoxy resins obtained from aromatic amines such as toluidine or aniline and epichlorohydrin, vinylcyclohexene Dioxide, 1,4-butanediol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, and the like.

Among these, epoxy equivalent which is liquid at 20℃ is 1
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 fibers, inorganic fillers, and metal powders, and with polymaleimide.

The blending amount of the polyepoxy compound as component (B) is (4
) 10 to 9 parts per 100 parts by weight of the component polymaleimide
00 parts by weight, preferably 15 to 300 parts by weight.

[Amine compound]

Furthermore, as the amine compound of component C), aniline, toluidine, xylidine, vinylaniline, infrobenylaniline, phenylenediamine, diaminocyclohexane, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,7
-Shioxadecane-1,10-diamine, 4,4'-diaminodicyclohexylmethane, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane , 3.4'-diaminodiphenylmethane, bis(3-chloro-4-aminophenyl)methane, 2
゜2-bis(4-aminophenyl)furopuff, 4.4'
-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, bis(4-aminophenyl)methylphosphine oxide, 4-methyl-2,4-bis( 4'-aminophenyl)pentene-1
,5-amino-1-(,i'-aminophenyl)-1
, 3,3-)rifthylindane, tris(4-aminophenyl)phosphate, 2,4-bis(4'-aminobenzyl)aniline, 2,2-bis(4-(4''-aminophenoxy)phenyl)propane and Examples include polymers of vinyl anilines of dimer or more, polyvalent amines of condensates of aniline and formaldehyde, and the like.

The amine compound is used in an amount of 5 to 100 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of the polymaleimide of component (1). This amine compound has the function of a curing agent.

[Optional ingredients]

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, carbonate powder, basic Magnesium silicate, fired clay, finely powdered silica, fused silica, crystalline silica, carbon black, kaolin, finely powdered mica, quartz powder, metal hydroxides such as aluminum hydroxide, graphite, asbestos, molybdenum disulfide, trioxide such as antimony. Additionally, 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, pulp, wood flour, linters, and polyamide fibers. . The amount of these powder or fibrous reinforcing materials and fillers used varies depending on the purpose, but as a laminated material or molding material, up to 500 parts by weight can be used per 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, ultramarine blue, cadmium yellow, cadmium red, red phosphorus, and other inorganic phosphorus; organic phosphorus such as triphenyl phosphate; etc.

(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. Examples include one type of phenol resin, alkyd resin, melamine resin, fluororesin, vinyl chloride resin, acrylic resin, silicone resin, polyester resin, etc., or a combination with F12 or more. The use of these resins is within a range that does not impair the original properties of the resin composition of the present invention, that is, 50% of the total resin amount.
Weight less than - is preferred.

(4) Ingredients, (2) Ingredients, 0 Ingredients, and various additives can be blended by heating and melt mixing, mixing using a roll kneader, etc., mixing using an appropriate organic remover, 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. Example 1 of Polymaleimide Production Example 500 equipped with a thermometer, cooler, dropping funnel, and stirring device
Wl! In a four-day flask, add l,4-benzenedialdehyde 28. IP, (proportion of aldehydes 70.6%), aniline 301.6f, concentrated hydrochloric acid 1 s, a
y e preparation, then 37% formaldehyde aqueous solution 3
1.69 was added dropwise. After the dripping is complete, water is refluxed (temperature 1
02°C) for 5 hours.

After completion of the reaction, 10% hydroxide) IJium aqueous solution 79.
2 f was added into the flask, and the mixture was stirred for 5 minutes, and the system was then turned into an alkaline solution. Next, methyl isobutyl ketone 50
After adding 0d into the flask and dissolving it, add 300I of pure water
Washing with water was carried out three times in total to remove by-product sodium chloride and excess sodium hydroxide.

Next, the solution was heated under reduced pressure (100-1 mHg/80-1
Methyl isobutyl ketone and unreacted aniline were completely removed at 180° C.), and the residue was poured off at 180° C. and cooled to obtain an orange solid 165f.

A solution obtained by dissolving 53.19% of this polyamine in 159.39% of acetone was placed in a dropping funnel.

50 equipped with thermometer, condenser, dropping funnel and stirring device
Maleic anhydride 48.6 in a four-hole flask
f and 97.2 f of acetone were charged and stirred to dissolve maleic anhydride.

Next, a polyamine solution dissolved in acetone was added dropwise while maintaining the temperature of the flask at 20 to 30°C, and after completion of the dropwise addition,
Stirring was continued for 30 minutes at the same temperature.

Next, add 0.5 F of nickel acetate into this flask.

11.3 M of triethylamine and 57.42 M of acetic anhydride were added, and the mixture was stirred under reflux (65° C.) for 2 hours to carry out a dehydration cyclization reaction.

After completion of the reaction, the reaction product was poured into 1.5 μm of water to precipitate the polymaleimide, which was extracted with F, washed with a large amount of water, and dried to give a yellowish brown polymaleimide (ss, 9f (yield) 98
．． 5.) Obtained.

The softening point of this polymaleimide (capillary method) Fi114 ~
The temperature was 120°C.

Examples 2 to 8 Polymaleimides having the physical properties shown in Table 1 were obtained in the same manner as in Example 1, except that the aldehyde and amine used in Example 1 were changed to those shown in Table 1.

[Example-1] 80 parts by weight of the polymaleimide obtained in Example 1 and 4.4'-
21 parts by weight of diaminodiphenylmethane was added to a pressure kneader (
After kneading for 5 minutes at a temperature of 130°C to obtain a prepolymer, 20 parts by weight of bisphenol A diglycidyl ether 6 Epicote 828'' (trade name manufactured by Yuka Shell Epoxy) and 100 parts of fused silica were added and further kneaded at the same temperature. Kneaded for 5 minutes.

After kneading, the crushed product is crushed with a crusher, transferred to a press mold, and then crushed at 180°C and a pressure of 10t1Kg/rtA.
Compression molding was performed for 0 minutes and cooled to 40°C to obtain a molded product.

Length 12.7r1n, width 1.27m, height 0.64crn
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.
-1 post-curing to obtain cured products shown in Table 2.

[Example-2] 50 parts by weight of the polymaleimide obtained in Example 2 and 50 parts by weight of phenol novolak epoxy "Epicote 154" (trade name manufactured by Yuka Shell Epoxy) were uniformly dissolved at a temperature of 131)'C. Mixture 100% weight N14.24 parts of 4'-diminodiphenylmethane and filler 100 parts by weight of melting strength Whole roll (temperature 1i80-100°C)
The mixture was kneaded for 10 minutes.

After kneading, a molded product was obtained in the same manner as in Example-1, and then a cured product was obtained. Table 2 shows the physical properties of the cured product.

[Example-3] A molded product was obtained in the same manner as in Example-1, except that the polyepoxy compound was replaced with orthocresol novolak epoxy "gOcN-102" (trade name of Nippon Kayaku Co., Ltd.), and then a cured product was obtained. .

Table 2 shows the physical properties of the cured product.

[Example-4] A molded product was obtained in the same manner as in Example-2, except that the polyepoxy compound was replaced with "Epicote 828", and then a cured product was obtained. Table 2 shows the physical properties of the cured product.

[Comparative Example-1] A molded product was obtained in the same manner as in Example-1 above, except that N,N-4,4'-diphenylmethane bismaleimide (DDM-BMI) was used as the polymaleimide, and then a cured product was obtained. . Table 2 shows the physical properties of the cured product.

[Comparative Example-2] A polyepoxy compound was added to the polymaleimide N,N-4,4'-diphenylmethane bismaleimide with 'EOCN'.
A molded product was obtained in the same manner as in Example 1, except that the molded product was replaced with "-1+12", and then a cured product was obtained.

[Comparative Example-3] A molded product was obtained in the same manner as in Example-2, except that the polymaleimide was replaced with polyesterminobismaleimide “Kelimide 601” (trade name manufactured by Loos-Boulin), and then a cured product was obtained. Ta. Table 2 shows the physical properties of the cured product.

[Examples 5 to 8] Cured products having the physical properties shown in Table 2 were obtained in the same manner as in Example 1, except that the composition was changed as shown in Table 2.

(Margin below)

Claims (1)

[Scope of Claims] 1 [Component (4): For 1 mole of an aldehyde consisting of a mixture of 5 to 95% by weight of formaldehyde and 95 to 5% by weight of aromatic dialdehyde, the general formula, [wherein, XH hydrogen atom , halogen atom or carbon number 1~
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, 100 parts by weight of a polymaleimide obtained by cyclodehydration of the polyamic acid 03) 10 to 900 parts by weight of an epoxy compound having at least two or more 1,2-epoxy groups in one molecule 0 Ingredients General formula: Q -4-NH2) n [In the formula, QH is an organic group having 1 to 150 carbon atoms, hydrogen,
5 to 100 parts by weight of an amine compound, which is an n-valent organic group that can contain oxygen, sulfur, halogen, nitrogen, phosphorus, and silicon, where n is an integer of 1 or more; (A thermosetting resin composition characterized in that 0 components are blended in the above proportions. The manufacturing method according to claim 1, characterized in that the mixture contains at least maleimide [wherein X is a hydrogen atom, a halogen atom, or a carbon number of 1 to 1]
4 is an alkyl group or alkoxy group: mtiO
[is an integer from 4 to 4].