JPS58136618A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition having excellent heat resistance, low boiling point and excellent solubility in inexpensive solvents and used suitably in the production of laminates, comprising an amine adduct comprising a specified diamine compound and an epoxy compound, a polymaleimide and a specified epoxy compound. CONSTITUTION:The titled composition is prepared from (A) an amine adduct (in an amount 1.5-10 times of a chemically equiv. amt. of the below described epoxy compound) prepared by reacting a diamine compound of formulaI(whe rein R<1> is a 2C or higher bivalent organic group) with an epoxy compound having at least two epoxy groups, (B) a polymaleimide of formula II (wherein R<2> is an n-valent organic group, X<1> and X<2> are each a monovalent atom or group selected from the group consisting of H, a halogen and an organic group, and n>2; the molar ratio of component A to component B is 0.2:1-2:1) and (C) an epoxy compound having at least two epoxy groups. Component C is used in an amount of 5-70wt% of the total of the three components A, B and C.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention provides a thermosetting material that is soluble in low-boiling point, low-cost solvents such as ketones at the B-stage, has excellent workability, and has excellent heat resistance after curing. The present invention relates to a synthetic resin composition.

[Technical background of the invention]

Dehydrated condensation type polyimide and amine-cured maleimide are well known as materials with heat resistance class H or higher, but amine-cured maleimide, which does not have problems such as condensed water, is becoming mainstream. However, since these materials dissolve only in high-boiling point solvents, their workability is poor and their properties cannot be utilized effectively.

[Problems with background technology]

A three-dimensional polyimide made by thermally polymerizing a polymaleimide alone is known as a heat-resistant resin, but this three-dimensional polyimide has the drawback of being extremely brittle and is therefore unsuitable for practical use. Furthermore, as an amine-curing maleimide in which a polymaleimide and a polyamine are reacted, aminobismaleimide having a bismaleimide skeleton is mainly used. Amino bismaleimide is a prepolymer in which diamine is added to the double bonds of bismaleimide. When heated, the addition of amines and the radical polymerization of double bonds form complex crosslinks, resulting in an insoluble and infusible material with excellent heat resistance. It becomes a heat-resistant resin. However, when using this as a mold, N-
It dissolves only in dipolar, high boiling point, expensive special solvents such as methyl-2-pyrhodrine and N,N'-dimethylformamide. Therefore, when removing the solvent by drying, a high temperature is required, and the remaining solvent affects the properties, which is a major obstacle in terms of workability and heat resistance properties. In addition, aminobismaleimide resin has poor curability and requires long heating at a high temperature of 200°C or higher to fully cure it, so it is modified with epoxy resin, which can improve curability, but it is difficult to use solvents. The solubility of has not yet been improved.

[Purpose of the invention]

The present invention was made in view of the drawbacks of the above-mentioned amine-curing maleimides, and includes dioxane, methyl ethyl ketone,
A thermosetting resin composition that dissolves in low-boiling point, low-cost solvents such as methyl cellosolve, has excellent workability, and can be cured at temperatures below 200°C without any adverse effects from residual solvent after molding. The purpose is to provide something.

[Summary of the invention]

The present invention provides (A) (a)-general formula H2N-R'-NH2(
In the formula, R1 represents a divalent organic group having at least 2 carbon atoms. ) An amine adduct obtained by reacting the diamine compound of (b) with an epoxy compound having at least two epoxy groups; , the same or different monovalent atoms or groups selected from halogen atoms or organic groups (t, ``represents an integer of 2 or more, respectively'') and 0 epoxy having at least 2 or more epoxy groups. The (a) diamine compound and (b) epoxy compound are mixed in a thermosetting resin composition consisting of a thermosetting resin composition consisting of a compound (a) and (b) an epoxy compound for several minutes to several hours without a solvent or in dioxane. , methyl ethyl ketone, methyl cellosolve, etc. The diamine compound has a chemical equivalent of 1.5 to 10 times, preferably 2 to 8 times, the chemical equivalent of the epoxy compound.
It is effective to use twice as much. Diamine compound is 1.5
If the amount is less than twice that, it will be difficult to control the long reaction to prevent gelation during the reaction. If the amount is more than 10 parts, the solubility of the resin composition, which is the final reactant of the present invention, in low-boiling point, low-cost solvents will decrease.

■Component amine adduct and component 03) polymaleimide in a molar ratio of 0.2:1 to 4:1 in a ratio of 50 to 200.
A resin is obtained by heating and reacting at a temperature of .degree. C. for several minutes to several hours without a solvent or in the presence of a low boiling point solvent such as dioxane, methyl ethyl ketone, or methyl cellosolve. If the amount of amine adduct is less than 0.2 mole, the solubility in low boiling point solvents will be poor and the cured product will become brittle. If the amount is more than 4 moles, the heat resistance of the cured product decreases1
There will be no more coming.

Further, the epoxy compound of component C) is added to the above resin and mixed uniformly, and it is blended in an amount of 5 to 70% by weight, preferably 8 to 60% by weight of the total of component) and C). (If the O component is less than 5% by weight, the curability will be poor,
If it exceeds 70% by weight, the heat resistance of the cured product will decrease and the effect of the present invention will be lost.

In addition, as a procedure for obtaining a resin composition, in advance (
A) a diamine compound and (b) an epoxy compound are pre-reacted to obtain a captive amine adduct, which is then reacted with a) polymaleimide and then an epoxy compound is added. However, separately synthesized (AJ) was reacted with (C) fr
, may be added. -11 Drops of this invention)
Examples of the diamine compound (a) constituting the amine/adduct tube include the following.

4.4'-diaminodicyclohexylmethane, 1,4-
Diaminocyclohexane, 2,6-diamitubiridine,
m-7enylenediamine, p-phenylenediamine,
4,4'-diaminodiphenylmethane, 2,2'-bis(4-aminophenyl)furopane, benzidine, 4.4
'-diaminophenyl oxide, aminophenyl) methylphosphine oquinde, bis(4-aminophenyl) phenylphosphine oxide, bis(4-aminophenyl) methylamine, 1,5-diaminonaphthalene, m-xylylenediamine, 1 , 1-bis(p-aminophenyl)furatane, p-xylylene diamine, hexamethylene diamine, 6,6'-diamine-2,2'-diglycidyl, 4,4'-diaminobenzophenone, 4,4'-diamino Azobenzene, bis(4-aminophenyl)phenylmethane, 1,1-bis(4-aminophenyl)cyclohexane, 1,1'-bis(4-7mino=3-methylphenyl)cyclohexane, 2,5-bis( m-aminophenyl) -1,3,4-oxadiazole, 2,5
-bis(p-aminophenyl)-1゜3.4-oxadiazole, 2,5-bis(m-aminophenyl)thiazolo(4,5-d)thiazole, 5.5'-di(m-amino phenyl) -(2,2')-bis(1,3,4-oxadiazole), 4,4'-diaminodiphenyl ether, 4,4'-bis(p-aminephenyl) -2,2
'-Dithiazole, m-bis(4-p-yminophenyl-2-thiazolyl)benzene, 4,4'-diaminobenzanilide, 4,4'-diaminophenylbenzoate, N,N'-bis(4-aminobenzyl) )-p-phenylenediamine, 4,4'-methylenebis(2-chloroaniline), and at least one kind or a mixture thereof is used.

Examples of the epoxy compound having at least two epoxy groups in the present invention (b) and C) include diglycidyl ether of bisphenol A, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4. 4'-(1,2-x boxyethyl) biphenyl, 4,4'-di(1,2-epoxyethyl) diphenyl ether, resorci/diku1 lysidyl ether, bis(2,3-epoxycyclobentyl) ether,
N,N'-m-phenylenebis(4,5'-epoxy-
2 such as 1,2-cyclohexanedicarboximide)
Functional engineered poxy compounds, triglycidyl compounds of p-aminophenol, 1,3.5-)su(1,2-epoxyethyl)benzene, tetraglycidoxytetrapheninoethane, polyglycidyl ethers of phenol formaldehyde novolac resins Trifunctional or higher functional epoxy compounds such as are used. In addition, epoxy compounds having a hydantoin skeleton, epoxy compounds containing rogen, etc. are also included. At least one kind or a mixture of these may be used.

As the polymaleimide which is the ω) component of the present invention, u, N
, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-4,4'- N,N'-4,4'-cyphenyl ether bismaleimide, N,N'-methylenebis(3-chloro-
p-phenylene) bismaleimide, N,N'-4,4
'-Diphenylsulfone bismaleimide, N, N'-
4,4? -dicyclohexylmethane bismaleimide, N
, N'-α, α'-4,4' dimethylene cyclohexane bismaleimide Maleimide, the following structural formula (
c) to (e), such as triimide and poly(phenylmethylene)polymaleimide, and at least one of these
Seeds or mixtures may be used. If necessary, monoimides such as N-phenylmaleimide, N-3-chlorophenylmaleimide, and N-4-nitrophenylmaleimide can also be used together with the polymaleimides.

The resin composition of the present invention thus obtained is thermosetting and hardens by heating. Generally, a heating temperature of 120 to 200°C is sufficient, but this does not preclude heating and curing at a temperature of 200°C or higher. Additionally, a curing agent such as tertiary amines, imidazoles, peroxides, and organic acids can be added to the composition to accelerate curing. The amount of curing agent added is suitably about 0.01 to 0.5% by weight of the resin composition. The composition further includes talc, alumina, silicon, zircon,
Fillers such as quartz, glass powder, and glass fibers, colorants such as carbon black and red iron oxide, coupling agents such as glycidoxyprobyltriethoxysilane, and mold release agents such as stearic acid may also be added as appropriate.

The resin composition of the present invention has excellent heat resistance, low boiling point, and solubility in low-cost solvents, and can be used in a wide range of applications such as lamination, adhesion, and molding.

[Embodiments of the invention]

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

In the following, "parts" indicate "parts by weight" unless otherwise specified.

Example 1 198 parts (1 mol) of 4.4'-diaminodiphenylmethane and 95 parts of bisphenol A type epoxy resin Epicoat 828 (epoxy equivalent: 190) manufactured by Shell Co. were mixed and 1
The mixture was heated and melted at 00° C. for 1 hour to obtain an amine adduct. Furthermore, 4,4'-diphenylmethane bismaleimide 7
After adding 16 parts (2 moles) and heating and melting reaction at 100° C. for 20 minutes, 252 parts of Epikote 828 was added and mixed uniformly to obtain a red transparent resin. This resin was soluble in dioxane, methyl ethyl ketone, and methyl cellosolve with a solid content of 50% or more.
Mix 72 parts of N-438 (epoxy equivalent: 180) and make 10
The mixture was heated and melted at 0° C. for 1 hour to obtain an amine adduct.

Furthermore, 4,4'-diphenylmethane bismaleimide 716
After heating and melting reaction at 100°C for 10 minutes, 186 parts of CIBA-GEIGY's clean crucible epoxy resin ECN, -1280 (epoxy equivalent: 230) was added and mixed uniformly to give a red transparent color. Resin was obtained. This resin was soluble in dioxane, methyl ethyl ketone, and methyl cellosolve at a solid content of 50% or more.

Example 3 267 parts (1 mol) of methylene bis(o-chloroaniline) and glycidyl ether type epoxy resin S manufactured by Showa Denko
117 parts of -508 (epoxy equivalent: 195) were mixed and subjected to heating and melting reaction at 150° C. for 1 hour to obtain an amine adduct. Furthermore, N,N'-methylenebis(3-chloro-p-
phenylene) Bismale'f mi)" 1067.5 copies (
After adding 2.5 mol) and heating and melting reaction at 130°C for 20 minutes, halogenated epoxy resin Pico) 1 manufactured by Shell Co.
484 parts of 045 (epoxy equivalent: 460) were added and mixed uniformly to obtain a red transparent resin. This resin was soluble in dioxane, methyl ethyl ketone, and methyl cellosolve with a solid content of 50 g or more.

Example 4 198 parts (1 mol) of 4.4'-diaminodiphenylmethane and 95 parts of Epicoat 828 were mixed and subjected to heating and melting reaction at 100° C. for 1 hour to obtain an amine adduct. Furthermore, poly(
After adding 928 parts (corresponding to 2 moles) of phenylmethylene polymaleimide and carrying out a heating and melting reaction at 100° C. for 20 minutes, 190 parts of Epicoat 828'k were added and mixed uniformly to obtain a red transparent resin. This resin was soluble in dioxane, methyl ethyl ketone, and methyl cellosolve with a solid content of 50 g or more.

Next, a glass cloth (250X250X0
．． 18ff) and dried at 130 to 150°C for 10 minutes to obtain a prepreg. Nine sheets of this prepreg were stacked and press-molded at a temperature of 160° C. to 180° C. and a pressure of 40 Kq/cd to obtain a laminate having a thickness of 1.6 mm.

The properties of the laminate are shown in Table 1.

For comparison, a polyamino bismaleimide resin (Kerimid 601 manufactured by Rhône Bouran) was used.
Imide laminates A and Ker produced in the same manner as above using N-methyl-2-pyrrolidone as a solvent.
imid 601'fr70 parts, Epicote 828'
Imide laminate B and epoxy laminate (MEL-44A manufactured by Toshiba Chemical Co., Ltd. manufactured by Toshiba Chemical Co., Ltd.) were manufactured in the same manner as above by blending 30 parts of
, NEMA standard G-10) characteristics were also shown.

Table 1 Measurement method Bending strength: Retention rate of bending strength at each temperature with respect to bending strength at 25°C (A) Bending strength after O deterioration = Retention rate of bending strength with respect to the initial value after heating at 220°C for a specified time ( b) Weight loss at 0 weight loss starting temperature, 500°C: Based on weight loss analysis at a heating rate of 5C10 in air.

○ Boiling water absorption rate: As is clear from the JIS-6911 Examples and Table 1, the laminate using the varnish made from the resin of the present invention is inferior in heat resistance to the imide laminates A and B. It has the advantage of being able to work with low-boiling point, low-cost solvents such as dioxane, methyl ethyl ketone, and methyl cellosolve.

-color

Claims (1)

[Claims] 1■ (a) General formula H2N -R1-NH2 (in the formula R1
An amine adduct obtained by reacting a diamine compound represented by C) representing a divalent organic group having at least 2 carbon atoms with (b) an epoxy compound having at least 2 epoxy groups; R2 is an n-valent organic group, x', x2 is a hydrogen atom,
The same or different 1 selected from halogen Kishiko or organic group
n represents a valence atom or group, and n represents an integer of 2 or more. A thermosetting resin composition comprising a polymaleimide represented by C) and an epoxy compound having at least two epoxy groups. 2 (b) Regarding the component (a) Diamine compound'e (b
) The thermosetting resin composition according to claim 1, which is used in a chemical equivalent of 1.5 to 10 times the epoxy compound. 3. The thermosetting resin composition according to claim 1, wherein the molar ratio of the active component to the component (B) is 02:1 to 4:1. 4. The thermosetting resin composition according to claim 1, wherein component (C) is contained in an amount of 5 to 70% by weight of the total of component (4), component (2), and component (0).