JPS5922924A - Curable resin composition and cured product therefrom - Google Patents

Abstract

PURPOSE:To provide titled composition of excellent solvent solubility, high heat resistance, etc., capable of converting to cured product with high strength at elevated temperature by a short time heating at low temperature, comprising a xylene derivative and a bis-maleimide each having specific structure. CONSTITUTION:The objective composition comprising (A) a xylene derivative of formula I (X is expressed by formula II, III, IV, etc.) and (B) an N,N'-substituted bis-maleimide of formula V (Y is H or methyl; Z is a divalent organic group) (e.g., N,N'-ethylene dimaleimide), generally in a weight ratio (A)/(B) of 10/1-1/10. It is recommended that the component (A) be prepared, for example, by the reaction of the corresponding X-substituted isocyanurate such as diallyl isocyanurate, with an alpha,alpha'-xylene halide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition that has excellent heat resistance, moisture resistance, and storage stability and can be cured into a heat-resistant resin, and a cured product thereof.

BACKGROUND ART In recent years, insulating materials with excellent heat resistance have been required as electric and electronic devices have become larger in capacity, smaller and lighter, and have become more reliable.

Conventionally, heterocyclic polymers such as polyimide, silicone resins, and the like are known as heat-resistant resins. Most of the heterocyclic polymers are condensation type and have various drawbacks such as producing volatile components during curing, poor moldability, being expensive, and only certain polar solvents can be used in the field of convenience such as festivals. However, there are restrictions on its application, especially in the fields of molding materials, laminated materials, or powder materials.

On the other hand, silicone resins also have limited applications because of their low mechanical strength at high temperatures, poor adhesion, and high moisture permeability.

In order to improve these drawbacks, it is known that addition type imide (bismaleimide), epoxy compound, unsaturated polyester resin, etc. can be used in combination.

However, in this case, there are problems in achieving both fast curing and storage stability, solubility in various solvents, and material cost, which poses a major obstacle to commercialization for applications such as molding materials, prepregs, powder coatings, and adhesives. was.

The present invention has been made in view of the above K, and its purpose is to operate at a relatively low temperature (150°C to 200°C) and for a short period of time (1 to 5°C).
The object of the present invention is to provide a curable resin composition and a cured product thereof, which can be converted into a cured product with excellent high-temperature strength just by heating (0 minutes), and the resin composition before curing has excellent solubility in a solvent. To summarize the present invention, the first aspect of the present invention relates to a curable resin composition, (a) the following general formula 1: 110X [wherein X is -(EH,0H-OH, , -000H=O
H,, -COC(OH3)=OH,, -COOOH=O
H,,-COOC(OH,)=OH,,-0OC! 0k
OH, or -〇(X:C(OH3)=OH, represents a group)
A xylene derivative represented by, and (b) the following general formula II
: (In the formula, Y#″i represents a hydrogen atom or a methyl group, and 2 is 2
It is characterized by containing N,N'-tm bismaleimide represented by (representing a valent organic group).

The second invention of the present invention also relates to a curable resin composition, and includes (a) a xylene derivative represented by the general formula I, and (b) N, N' represented by the general formula M.
-substituted bismaleide, and (0) a polyfunctional epoxy compound.

A fifth invention of the present invention relates to a cured product, which is obtained by curing the curable resin composition according to the first invention.

A fourth aspect of the present invention relates to a cured product obtained by curing the curable resin composition according to the second aspect.

In the present invention, the compound represented by the general formula I is:
For example, it can be obtained by reacting with the corresponding X-substituted incyanure-)1α,α-quidyl dihalide. Examples include 0-m- or p-xylene-α,
α-diyl-bis[5,5-di(2-10benyl)
-1,5,5-triazine-2,4,6-(I H,5
H, 5H) trione], p-xylene-α, α′-
Diyl-bis[5゜5-divinyloxycarbonyl-1
,5,5-to1,1azine-2,4,6-(1to5H,
In the present invention, examples of the N,N'-substituted bismaleimide represented by the general formula (2) include N,N'-ethylene dimaleimide, N,N'-ethylene his(2 - Methishima 1/imide), N,N'-trimethylene simaleimide,
N,N'-tetramethylene dimaleimide, N,N'-hexamethylene dimaleimide, N,N-hexamethylenebis(2-methylmaleimide), N,N'-dodecamethylene dimaleimide, N,N' -m-phenylene dimaleimide, N, N'-p-phenylene dimaleimide, N, N'
-(oxy-di-p-phenylene) simaleimide, N,
N-(methylene-di-p-phenylene) simaleimide,
N, N'-(methylene-di-p-phenylene)bis(2
-methylmaleimide), N,N -2,4-tolylene dimaleimide, N,N'-2,6-)relevancy F L/
imide, N, N'-m-xylylene cymaleimide, N,
N'-p-xylylene cymaleimide, N.

Examples include N'-oxydiethylene cymaleimide, N,N'-oxydiethylene cymaleimide, and N,N-ethylene di(oxyditylene cymaleimide).

Next, in the present invention, the polyfunctional epoxy compound includes:
For example, glycidyl ether of bisphenol A, butadiene diepoxide, 5,4-epoxycyclohexylmethyl-(5,4-epoxy)cyclohexanecarboxylate, vinylcyclohexene dioxide, 4,4-di(1,2-epoxyethyl)diphenyl ether, 2,
2-bis(5,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,5-epoxycyclobentyl)ether, 2-( 5,4-epoxy)cyclohexane-5,5-subio(5,4-epoxy)cyclohexane-m-dioxane, bis-(S,4-epoxy-6
-methylcyclohexyl)adipate, N, N'-m-
Phenylenebis (bifunctional epoxy compounds such as 4,5-epoxy-1,2-cyclohexanedicarboximide, triglycidyl ether of para-aminophenol,
Polyallyl glycidyl ether, 1,5,5-tri(1
, 2-Eboxyethylbenzene, 2.2', 4.4
'-Tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolak resin, triglycidyl ether of glycerin, Torino f
O-# Epoxy compounds having five or more functional groups such as triglycidyl ether of furopane, halogenated epoxy compounds such as brominated epoxide, or hydantoin epoxy compounds are used.

Even if the mixing ratio of the xylene derivative and the N,N-substituted bismaleimide is varied over a fairly wide range, a cured product having good heat resistance can be obtained. In general, the weight ratio can be varied within the range of 1021 to 1:10, and the weight ratio of the polyfunctional epoxy compound to the total amount is 1=1.
Used in a ratio of 2 to 5:1.

Further, in the present invention, a curing catalyst such as an organic peroxide or an epoxy resin curing catalyst can be used in combination to promote the reaction.

Specific examples include benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclo-\xanone peroxide, bis(1-hydroxycyclo-\xyl peroxide),
Hydroxyhegetyl peroxide, t-butyl hydroperoxide, p-mentha/hydroperoxide,
Organic peroxides such as t-butyl perbenzoate, t-butyl peracetate, t-butyl peroctoate, t-butyl peroxyisobutyrate, di-t-butyl cibber phthalate, tetramethylbutanediamine, benzyldimethylamine , 2,4.6-tris(dimethylaminophenol λ, tetramethylguanidine, guanidine, 5-(p-chlorophenyl)-1,1-dimethylurea, 5-(5,4-dichlorophenyl)-1,1
-') Methyl RM, 2-methylimidazole, 2-
Ethyl-4-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2.4'-
Dimethylimidazole, etc. and their azine derivatives, tetraphenylborate, trimellitate, nitrile ethyl derivatives, 2-heptadecyl imidazole, 5-amino-1,2,4-)lyazole, 1-dodecyl-2-methyl-5 -Benzylimidazolium-chloride, 1-
Cyanoethyl-2-phenyl-4,5-cy(cyanoethoxyethyl)imidazole, 2-methylimidazole.
Examples include isocyanuric acid adducts, 2-7 enylimidazole-isocyanuric acid adducts, and tetrabutylammonium tetraphenylborate and tetramethylammonium fluoride.

In addition, the composition of the present invention may include, depending on various uses and purposes,
One or more of the following various materials may be used in combination.

For example, considering the use as a molding material, zircon, silica, fused silica glass, clay, alumina hydroxide, calcium carbonate, quartz glass, glass, asbestos, whisker, gypsum, magnesite, mica, kaolin, talc, graphite, Inorganic photoresist materials such as cement, carbonyl iron, barium, ferrite, lead compounds, molybdenum disulfide, zinc white, titanium white, carbon black, silica sand, and wollastonite, molding agents such as fat syrup and waxes, and epoxy. silane, vinyl silane,
Coupling agents such as poran compounds and alkoxy titanate compounds can be used. Also, if necessary, known flame retardants such as antimony and phosphorus can be used.

Next, a production example of the compound represented by the general formula I in the present invention will be shown.

Production Example 1 Diallyl isocyanurate 209f (1 mol) was placed in a 2 t 5-necked round bottom flask equipped with a stirrer and a cooler.
α,α-dichloro〇-xylene 87.59 (0,5
mol) and potassium carbonate (82.9 f ([16 mol)), and 1200 me DMF as a solvent were added, the temperature was raised while stirring, and the reaction was carried out at a reaction temperature of 110° C. for 90 minutes. At this point, it was confirmed by thin layer chromatography that the raw material α,α-dichloro〇-xylene had disappeared, and then, after distilling off DMF under reduced pressure, chloroform 900- was added to the reaction product to produce the desired product. I drew 111. This extract was washed with an aqueous sodium hydroxide solution and then with water for 10 minutes, dried over magnesium sulfate, and then the solvent was distilled off to obtain O-xylene-α,α'-diyl-bis[5, 5-di(2-propenyl) -1,
5゜5-triazine-2,4,6-(I H,5H,5
H)-trione] white crystals 25q, 41F (
A yield of 92%) was obtained. A part of this was recrystallized as a sample for analysis with about 25 times the amount of isopropyl alcohol to obtain white needle crystals with a purity of 100%. (Compound 1) Production Example 2 In a reaction apparatus similar to Production Example 1, diallylisocyanurate 250F (1.1 mol), α,α'-dibromo m-xylene 1521 (n, 5 mol), and potassium carbonate 947F (0,7 mol), DMF 10 as solvent
After stirring and reacting for 120 minutes at 90°C, DMF was distilled off under reduced pressure, and 700% of methylene chloride was added to the reaction product to extract the desired product. After washing with a 10% aqueous sodium dispersion solution and then water, drying over magnesium sulfate and distilling off the solvent, m-xylene-α,α'-diyl-bis[5,5-di(2 -propenyl) -1,5,
5-triazine-2,4,6-(IH.

5H,5111)-)Rion')242f (95% yield
) was obtained (Compound 2) Production Example 5 In a reaction apparatus similar to Production Example 1, diallylisocyanurate 250 f (11 mol), α, α'-dibromo p
- xylene 152f (0,5 morph and potassium carbonate 9
47f (α7 mol) and DMF j 200 d as a solvent were charged and reacted at 90° C. for 90 minutes with stirring. The subsequent operations were carried out in the same manner as in Production Example 1.
-xylene-α,α′-diyl-bis[5,5-di(
2-propenyl) -1,5,5-triazine-2,4
,6-(11(.

5H,5T()-)ion] white crystals 242f (yield 95%) were obtained. A part of this was recrystallized as a sample for analysis with about 20 times the amount of methanol to obtain white needle-like crystals with a purity of 100%.

(Compound 5) Table 1 shows the infrared absorption spectra, nuclear magnetic resonance spectra, molecular weights, and elemental analysis values of the compounds obtained in Production Examples 1.2 and 5.
As a result, the compound of Production Example 1 was 0-xylene-α,α-diyl-bis[S,5-di[2-probenicin-1,5,5-triazine-2,4,6-( IH
,5H,5H)-)ion], the compound of Production Example 2 is
m-xylene-α,α'-diyl-bis[5,5-di(2-propenyl)-1,5,5-)riazine-2,
4,6-(IH.

51(,5H)-)IJ-on], the compound of Production Example 5 is
p-xylene-α,α'-diyl-bis[5,5-di(2-propenyl)-1,5,5-triazine-2,
4,6-(11'!,5H,5H)-trion].

/' / / / / / The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 12 p-xylene-diyl-bis[5
,5-di(2-10benyl)-1,5゜5-triazine-2,4,6-(IH,5B,5H)-trione] (manufactured by Nippon Kasei Co., Ltd.) at 10,20.50 or Cresol novolak type epoxy resin gcN12 y 5 was added as a polyfunctional epoxy compound to a system in which 40 parts by weight of N, N''-(methylene-di-p-phenylene) simaleimide was separately blended with 50.50 parts by weight and 0 parts by weight of Huff. (
Ciba-Geigy) was added to each system in an amount of 50 parts by weight, and a catalyst was added to make a total of 12 formulations.
epoxysilane KBM 40 as a coupling agent
5 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 70 parts by weight each of silica as a filler were added.

These were heated at 80°C for 10
The resin composition was then coarsely pulverized to obtain the desired molding resin composition. This composition was transfer molded at 170°C, yoKy/- pressure, and for 5 minutes to improve the curability and bending strength of the molded product. 180℃), etc. were measured. 225℃, 5
The bending strength after 0 days was measured and used as a measure of heat resistance.

Examples 15 to 18 As a xylene derivative (A) 0-xylene-α,α-diyl-bis[5,5-di(2-propenyl)-1,5
,5-triazine-2,4,6-(IH,5H.

5H)-trione], (B) m-xylene-α,α-diyl-bis[5,5-di(2-propenyl)-1,5
,5-triazine-2,4,6-(IH,5J5H)
-trione], (C) p-xylene-α, α-diyl-
Bis[5,5-di(2-propenyl)-1,5,5-
) riazine-2,4,6-(j H,5H.

5H-thorion], (D) p-xylene-α, α
-diyl-bis(5,5-divinyloxycarbonyl-
1,5,5-triazine-2,4,6-(I H,5H
.

51()-1 ion], ("J p-xylene-α,
α-diyl-bis[5,5-diacryloyl-1,5,
5-triazine-2,4,6-(I H,5H,51(
)-trione), (F) p-xylene-α, α′-
diyl-bis[5,5-diacryloxy-1,5,5
-Triazine-2,4,6-(j H, 5H, 5H)-
Trion] and 50 parts by weight of each were N and N'.
-(methylene-di-p-phenylene) simaleimide 7
A blended composition was prepared by adding 0 parts by weight of each separately and further adding 2 parts by weight of dicumyl peroxide as a catalyst.

In addition to the above 6 types of compounding composition, 2 parts by weight of stearic acid as a mold release agent and epoxy silane KBM as a coupling agent.
405 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 250 parts by weight of silica as a filler were added.

These were heated at 150℃ for 10 minutes using two rolls with a diameter of 8 inches.
After roll kneading for a minute, the desired resin composition for molding was obtained by coarsely pulverizing the composition.
Transfer molding was performed for 5 minutes, and the curability and bending strength (180° C.) of the molded product were measured. 225℃, 50
The bending strength after a few days was measured and used as a measure of heat resistance.

Table 5 As explained in detail above, according to the present invention, a novel curable resin composition and a cured product thereof are provided, and the cured product exhibits a remarkable effect in terms of heat resistance.

Patent applicant: Hitachi, Ltd. Agent Hiroshi Moto

Claims (1)

[Claims] 1. (a) The following general formula l; [In the formula, X is -0H, OH, =OH,, -000H=O
H,, -Coo(cH,)==OH,, -aooaH=
aH-fu, -0000(OH8)=:OH,,-0000
H=OH, or -ooaa (OH,)=:OH, represents a group], and (b) the following general formula ■: (where Y represents a hydrogen atom or a methyl group, and 2 represents a 2
It contains an N,N'-substituted hismaleimide represented by (representing a valent organic group)! A curable resin composition having a Vi characteristic. 2. (a) The following general formula I: [wherein X is -0H! 0kOH,, -000H=OH,
, -000(OH1)=OH,, -aooaH=aa,
, -cooa (c+H,)=aH,, -0000H=
OR, also indicates Fi-0000(OH,)=OH, group]
xylene derivatives represented by, and (b) the following general formula...: (In the formula, Y#'i represents a hydrogen atom or a methyl group, and 2 represents a divalent organic group), N, N'- containing a substituted bismaleimide and (0) a polyfunctional epoxy compound;
A curable resin composition characterized by: 5, (al above general formula I: [wherein X is -0H,0H=OH,, -000H=OH
,,-Coo (OH3)=CH,,-0000kOH
,,-aooc (c+H,)=OH,,-6000H
=OH, or -0000(OH,):OH, indicates group]
A xylene derivative represented by (1)) the following general formula l
I: (where Y represents a hydrogen atom or a methyl group and 2 represents a divalent organic group) A curable resin composition containing an N, N'-substituted bismaleimide was cured. 4. (a) The following general formula I: [wherein X is -cH,C) 1=:cH,, -00CH:
=(H,,-COC(CHs)=OH,,-0000H
:OH,,-0000(OH,)-1,,-0OC! 0
H=OH, or Fi, -ooac(ca,)=cH, represents a group], and (b) the following general formula II: (wherein Y represents a hydrogen atom or a methyl group, is a cured curable resin composition containing an N, N'-substituted bismaleimide represented by λ indicating a divalent organic group, and (0) a polyfunctional epoxy compound. A cured product.