JPS6377928A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in storage stability, workability and heat stability, by mixing a specified prepolymer with an epoxy resin. CONSTITUTION:A prepolymer (A) is obtained by performing an addition reaction of a bismaleimide (a) of formula I (wherein X is a 40 C or lower bivalent group which may contain H, O, S, a halogen, N or P) with an alkyl-substituted diamine (b) of formula II (wherein R1 is H, methyl or ethyl, and R2 is methyl or ethyl) at an (a) to (b) molar ratio of 0.5-20/1 at 50-250 deg.C for several min to 10hr in, optionally, an inert polar solvent (e.g., dimethylformamide). 100pts.wt. is total of 100pts.wt. said prepolymer and 10-900pts.wt. epoxy resin (e.g., bisphenol A diglycidyl ether) is mixed with a latent curing agent (e.g., BF3), 500pts.wt. or below powdery filler (e.g., CaCO3) and a colorant, a flame retardant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermosetting resin composition having excellent storage stability, workability, and thermal stability. This thermosetting resin composition is particularly useful for multilayer laminates, conductive pastes, printing inks, electronic device protective films, adhesives, paints, emotional materials, sealing materials, composites with glass fibers, carbon fibers, aramid fibers, etc. Useful as material and base material.

[Conventional technology]

In general, epoxy resins provide cured products with excellent electrical properties, mechanical properties, dimensional stability, and chemical resistance when cured using various hardening agents, so they can be used as various electrical insulating materials, molding materials, etc. Widely used as adhesives and paints.

However, although epoxy resins have these excellent properties, they are insufficient in terms of heat resistance, and various methods have been investigated to further improve heat resistance.

On the other hand, it has been known for a long time that maleimide resins can be polymerized to give resins with extremely high heat resistance. In particular, the heat resistance of resins obtained by homothermal polymerization of N,N'-substituted bismaleimides is extremely excellent.

However, this resin has too high a crosslinking density and is brittle, so it cannot be heated or
It easily cracks due to cooling, impact, etc., and is not suitable for practical use. In order to take advantage of the characteristics of both resins and at the same time compensate for their shortcomings to obtain resins with excellent performance, maleimide compounds are blended into epoxy resins.

However, bismaleimide compounds have significantly poor compatibility with epoxy resins, so they must be dissolved at high temperatures.
There are significant drawbacks in workability, such as precipitation of crystals during the subsequent heating and hardening process.
'-4,4'-diphenylmethane bismaleimide with 4,
A method has been adopted in which an epoxy resin is blended into a prepolymer to which 4'-diaminodiphenylmethane has been added and then cured.

[Problem that the invention seeks to solve]

However, the resin produced by the above method has significant storage stability because the reaction between the primary amine or secondary amine contained in the prepolymer and the epoxy group proceeds even at room temperature. The present invention solves the problem of conventional bismaleimide, which is inferior and also has a big problem in terms of heat resistance.
This was done to improve the storage stability, workability, and thermal stability of epoxy resins.

[Means for solving problems]

The present inventors have discovered that a bismaleimide-epoxy resin with excellent storage stability can be obtained by adding an epoxy resin to a prepolymer obtained by subjecting bismaleimide to an addition reaction with a special alkyl-substituted diamine. The present invention has now been completed.

That is, the present invention provides compounds of the general formula (1) [wherein X represents a divalent group having 40 or less carbon atoms and includes hydrogen, oxygen, sulfur, nitrogen, phosphorus, and silicon atoms] Bismaleimide represented by the general formula (n) R2R2 [In the formula, R1 represents a hydrogen atom, a methyl group, or an ethyl group, and the bird represents a methyl group or an ethyl group.] The present invention provides a thermosetting resin composition characterized in that an epoxy resin is blended into a prepolymer obtained by reacting the following.

(Bismaleimide) Examples of the bismaleimide of general formula (1) include the following.

% NIN'-4,4'-cyphenylmethanepismaleimi)',NIN'-4,4'-diphenyl ether bismale-(mi)', N,N'-methylenebis(3-
Chloro-p-phenylene] bismaleimide, N, N'-
4,4'-diphenylsul7one bismaleimide, N,
N'4s4'-dicyclohexylmethane bismaleimide, N, N'-α, α/-4.4'-dimethylenecyclohexane bismaleimide, NtN'-m-xylylene bismaleimide, N, N'-4,4' -diphenylcyclohexane bismaleimide, N,N'-4,4'-diphenyl-1,1-propane bismaleimide, N,N'
-414'-triphenyl-i,i,t-ethanebismaleimide, N,N'-4,4'-triphenylmethanebismaleimide)',N,N'-3,5-triazole-
bismaleimides such as 1,2,4-bismaleimide;

(Alkyl group-substituted diamine) Examples of the alkyl group-substituted diamine represented by general 2〇I) include the following.

3.3'-dimethyl-4,4'-diaminodiphenylmethane, 3.3'-diethyl-4,4'-diaminodiphenylmethane, 3.3'-5,5'-tetramethyl-4,
4'-diaminodiphenylmethane, 3.3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3.3'-5,5'-tetraethyl-4,4'
-Diamine of diaminodiphenylmethane.

When the substituent of the diamine is an alkyl group greater than or equal to a propyl group, the water resistance of the resulting cured product improves, but the heat resistance decreases, which is not preferable.

(Method for producing prepolymer) The amount of bismaleimide and alkyl-substituted diamine used for producing 7'L/polymer is such that the molar ratio of the alkyl-substituted diamine is in the range of o, s/l to 20/l. , preferably 1/1
A range of ~5/1 is desirable.

Both components are reacted directly without using a solvent, or as dissolved or suspended in an inert polar solvent such as dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone. be able to. The reaction is carried out for several minutes to 10 minutes at a temperature of 50 to 250 °C.
This is achieved by heating for a period of time. At this time, in order to promote the addition reaction of amine groups to maleimide groups, various catalysts (■ tertiary amines, ■ tertiary amine salts, ■ imidazoles, ■
(Lewis acid amine complexes, carboxylic acid metal salts, alcoholic) U, etc.) (Epoxy resin) Most of the known epoxy resins can be used in the thermosetting resin composition of the present invention. Epoxy resins can be used. Specific examples of epoxy resins include the following.

(1) Diglycidyl ether of bisphenol A:
The products include Epicoat 827, 828, 834, 864, and 100 from Yuka Shell Epoxy Co., Ltd.
1, 1004, 1007, 1050, Ciba Araldite GY250, 6099, Union Carbide ERL 2774, Dow Chemical DER33
2, 331, 661, (all of the above are product names), etc.

(11) Epoxyphenol novolac; its product is Epicoat 15 from Yuka Shell Epoxy Co., Ltd.
2, 154, DOW Chemical Company DEN438, 44
8. Chipa's Araldite EPN1138, EPN1139
(All of the above are trade names) etc. 0 (II+) Epoxy cresol novolak; Examples of the products include Ciba's Araldite ECNI 235, 1273, and 1280 (all of the above are trade names).

Other examples include diglycidyl ether of bisphenol F, epoxy resin obtained from phthalic acid or hexahydrophthalic acid toebichlorohydrin, epoxy resin obtained from rosehydroxybenzoic acid and epichlorohydrin, toluidine-? Examples include epoxy resins obtained from aromatic amines such as 72IJ 7 and epichlorohydrin, vinylcyclohexene dioxide, 1,4-butanediol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, and the like.

(Thermosetting resin composition) The thermosetting resin composition of the present invention has as main components the prepolymer obtained as described above and an epoxy resin. The prepolymer is usually directly mixed with the epoxy resin, but the prepolymer can also be dissolved in a solvent.

The mixing ratio of the prepolymer and the epoxy resin is in the range of 10 to 900 parts by weight of the epoxy resin per 100 parts by weight of the prepolymer. If the amount of epoxy resin is less than 10 parts by weight, the cured resin tends to become brittle.
If the amount exceeds parts by weight, the heat resistance will decrease.

Furthermore, a latent curing agent for epoxy resins can be blended with the thermosetting resin of the present invention. Examples of such latent agents include BF, pFl, and BCI.

Examples include complex compounds of Lewis acids and amines such as dicyandiamides, organic acid hydrazides, azine derivatives of imidazole, trimellitic acid derivatives, and isocyanuric acid adducts.

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

(1) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnetum oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth 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, there are fibrous reinforcements and fillers, such as inorganic fibers such as glass fibers, rock wool, ceramic fiber asbestos, and carbon fibers, and synthetic fibers such as paper, pulp, wood flour, linters, and polyamide fibers. The amount of these powdered or fibrous reinforcing materials or fillers used 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, ultramarine blue, cadmium yellow, cadmium red, inorganic phosphorus such as red phosphorus,
These include organic phosphorus such as triphenyl phosphate.

(3) Furthermore, various synthetic resins can be blended for the purpose of improving the properties of the resin used in the final coating film, adhesive layer, resin molded product, etc. Examples include one or a combination of two or more of phenol resins, alkyd resins, melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, polyester resins, and the like. The amount of these resins to be used is within a range that does not impair the inherent properties of the thermosetting resin of the present invention, that is, the amount of the resin composition 1 oz.
It is preferably less than 100 parts by weight based on oi parts.

Examples of methods for blending the resin composition of the present invention and various additives include heating and melt mixing, mixing using a roll, kneader, etc., mixing using an appropriate organic solvent, and dry mixing.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.0 Example 1 N+N'-'s t 70 parts by weight of 4'-diphenylmethane bismaleimide was added with 3,3'-dimethyl-4,4'-
Mix 22.2 parts by weight of diaminodiphenylmethane and add 1
The mixture was heated to 40° C. and reacted for 20 minutes with stirring to obtain a reddish brown prepolymer. In this prepolymer, diglycidyl ether of bisphenol A 1 shrimp: 7-) 828
Add 30 parts by weight, heat and mix until homogeneous, and
It was poured into a mold of 2.6 crIM, length 1.26 m, height 0.64 ott, and cured in an oven at 240° C. for 1 hour.

Table 1 shows the physical properties of the obtained cured product.

Further, the blended resin 50f [all of which was dissolved in 50 parts by weight of N-methyl-2-pyrrolidone, and the change in viscosity of the solution at 30°C was measured. The results are shown in Table 1.

Example 2 26.1 parts by weight of 3,3',5.5'-tetramethyl-4,4'-diaminodiphenylmethane was mixed with 60 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide, The mixture was heated to 150°C and reacted for 30 minutes with stirring to obtain a reddish brown prepolymer. 40 parts by weight of this Grebolimani x Hiko) 828 were added, heated and mixed until uniform, and the same operation as in Example 1 was performed to measure the physical properties and viscosity changes of the cured product. The results are shown in Table 1.

Example 3 23.7 parts by weight of 3,3'-diethyl-4,4'-diaminodiphenylmethane was mixed with 80 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide, and the mixture was heated at 140°C.
The mixture was reacted for 30 minutes with stirring to obtain a reddish-brown prepolymer. This prepolymer is coated with Epicoat 828.
20 parts by weight were added and heated and mixed until uniform (;), and the same operations as in Example 1 were performed to measure the physical properties and viscosity changes of the cured product. The results are shown in Table 1.

Example 4 3,3'-dimethyl-5,5'-diethyl-4,4' was added to 50 parts of N,N'-metaphenylene bismaleimide.
34.4 parts by weight of -diaminodiphenylmethane were mixed, heated to 160°C, and reacted for 15 minutes with stirring to obtain a reddish brown prepolymer. 50 parts by weight of Epikote 828 was added to this prepolymer and mixed with heat until uniform. The same operations as in Example 1 were performed to measure the physical properties and viscosity changes of the cured product. The results are shown in Table 1.

Example 5 90 parts by weight of NtN""-414'-diphenyl ether bismaleimide was mixed with 20 parts by weight of 3,3'-dimethyl-4,4'-diaminodiphenylmethane to produce 160'C1.
: A reddish-brown prepolymer was obtained by reacting for 15 minutes while heating and stirring. This prepolymer contains 2 pico)828
Example 1
The same operations as above were performed to measure the physical properties and viscosity changes of the cured product. The results are shown in Table 1.

Example 6 Prepolymer 70 obtained in Example 1! 30 parts of Epicote 828! and 2 parts by weight of C, Z-CN S (manufactured by Shikoku Fine Chemicals Co., Ltd.) were added, heated and mixed until uniform, and the same operation as in Example 1 was performed. Table 1 shows the results.
Shown below.

Example 7 Diglycidyl ether 1 of bisphenol F 1 Epicoat 807'' was added to 70 parts by weight of the prepolymer obtained in Example 1.
(manufactured by Yuka Shell Epoxy Co., Ltd.) 30 parts by weight and C, 1Z-A
2 parts by weight of ZINE (manufactured by Shikoku Fine Chemicals Co., Ltd.) was added, heated and mixed until uniform, and the same operation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example I 70 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide and 23.2 parts by weight of 4,4'-diaminodiphenylmethane were mixed, and the mixture was heated to 140°C and reacted for 10 minutes with stirring. A reddish brown prepolymer was obtained. To this prepolymer, 30 parts by weight of Epikote 828 was added and mixed by heating until uniform.The same operation as in Example 1 was carried out, and the physical properties and viscosity changes of the cured product were measured.The results are shown in Table 1.
Shown below.

Example 8 30 parts by weight of N,N'-4j4'-diphenylmethane bismaleimide and 22 parts by weight of 2,3,3'-dimethyl-4,4'-diaminodiphenylmethane were mixed and heated to 140°C while stirring. The reaction was carried out for 20 minutes to obtain a brown prepolymer. This prepolymer and Talesol novolac epoxy resin “EOCN-104” (manufactured by Nippon Kayaku Co., Ltd.) 7
0 parts by weight and 200 parts of fused silica! 100-12 parts
The mixture was kneaded for 10 minutes using a heated roll at 0°C. The mixture was ground into powder using a grinder, and heated to 180°C using a heating press.
Compression molding was performed for 10 minutes at a pressure of 501 g/- to obtain a molded product with dimensions of 127 cm x 12.75 ai x 6.4 cm. This molded product was post-cured at 230°C for 10 hours in an oven. A cured product having the physical property values shown in Table 21 was obtained.

Comparative Example 2 22 parts by weight of 3.3'-dimethyl-4,4'-diaminodiphenylmethane was mixed with 2 parts by weight of 4.4-diaminodiphenylmethane.
A cured product was obtained by carrying out the same operation as in Example 8 except for changing to 1 ffit part. The results are shown in Table 2.

Table 2 $15 Bending strength measurement temperature 23℃ after heating in air at 230℃ for a specified time

Claims (1)

[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X represents a divalent group having 40 or less carbon atoms, hydrogen, oxygen, sulfur, halogen, [Can contain nitrogen, phosphorus, and silicon atoms] Bismaleimide and the general formula: ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents a hydrogen atom, a methyl group, or an ethyl group, and R_2 represents a methyl group or an ethyl group] A thermosetting resin composition characterized in that an epoxy resin is blended into a prepolymer obtained by reacting an alkyl group-substituted diamine represented by the following.