KR850000702B1 - A process for producing thermosetting prepolymer from polyfunctional maleimide and bismaleimide - Google Patents

Abstract

Prepolymer of thermosetting maleimide is prepared from multivalence maleimide(A), bismaleimide(B), diamine(C) of which the chemical formula is H2N-R2-NH2, and an epoxy compd.(D) by reaction the compd. for 5-240 min. at 50-145≰C. The composition of (A) in the mixture of (A) and (B) is 3-80 wt.%; mole ratio of (A) + (B) to (C) = 1:2-1:0.1; and composition of (D) in the mixture of total components is 5-80 wt.% when(D) is not used, the reaction temperature is 70-180≰C.

Description

Process for preparing thermosetting maleimide crab prepolymer

The present invention is a thermosetting maleimide-based prepolymer which is soluble in low boiling point solvents such as ketones in the B-stage (semi-cured state) and can be converted into a cured product having excellent heat resistance by heating. It relates to a manufacturing method.

Dehydration condensation-type polyimides and amine-curable maleimides are well known as materials having a heat resistance class H (180 ° C) or higher, but amine-curable maleimides without problems such as condensation water have become mainstream.

As the amine-curable maleimide, amino bismaleimide having a bismaleimide as a skeleton is mainly used. Amino bismaleimide is a prepolymer in which a diamine is added to a double bond of bismaleimide. An insoluble, heat-resistant polymer having excellent heat resistance due to complex crosslinking by radical polymerization of double bonds by heating an amine is added. Becomes

However, when the amino bismaleimide prepolymer is used as the solvent type, it is insoluble in bipolar compounds such as N-methyl-2-pyrrolidone and N-N'-dimethylformamide, except for high boiling point and expensive special solvents. . Therefore, when the solvent is dried and removed, a high temperature is required and the residual solvent adversely affects characteristics, which is a major obstacle in terms of workability and moisture resistance. In addition, the amino bis maleimide resin is poor in curability, and thus the curability is improved by a modification test with an epoxy resin, but the solvent solubility is not improved yet.

It is an object of the present invention to provide a thermosetting resin which is easy to use in common low boiling point solvents such as acetone and methyl ethyl ketone and gives a heat resistant resin excellent in curability in view of such drawbacks of imide resins.

The prepolymer of the present invention is a polyhydric maleimide (A) of the following general formula (I), a bismaleimide (B) of the general formula (II) of the general formula H ₂ NR ₂ -NH ₂ diamine (C) and an epoxy compound (D) is characterized in that prepolymerization is carried out by heating four kinds of reactions.

Wherein n is 0.1 to 3.0 and R ₁ represents a divalent group containing at least two carbon atoms, and R ₂ represents a divalent group containing at least two carbon atoms.

The obtained prepolymer is dissolved at least 50% by weight of solids in a low boiling point solvent such as acetone, methylethylkerone and methyl cellosolve. In order to improve the solubility in acetone or the like, it is effective that the blending ratio of (A) is 3% by weight or more of the total weight of (A) and (B), but the effect is somewhat lower than 3% by weight.

Moreover, since the gel time of the obtained prepolymer is too short if the compounding ratio of (A) is 80 weight% or more of the total weight of (A) and (B), 80 weight% or less is preferable.

It is also clear that the epoxy compound of (D) is not only imparted with curability but also sufficiently provided with solubility in acetone and the like.

That is, when the compounding amount of (A) is 10% by weight or less of the total weight of (A) and (B), sufficient solubility in acetone or the like is not obtained only by the prepolymers of only (A), (B) and (C) It is clear that the epoxy compound of (D) gives not only curability but also solubility too much.

The order of the heating reaction for obtaining the prepolymer may be carried out simultaneously with (A), (B), (C) and (D), and after (A), (B) and (C) are pre-reacted, (D) ) May be reacted. Moreover, after making (C) and (D) react preliminarily, the method of heating and adding (A) and (B) may be sufficient. The reaction conditions of these heating reactions are 5 to 240 minutes at 50 to 150 ° C., preferably 10 to 150 minutes at 60 to 140 ° C., and most preferably 70 to 135 ° C. when the epoxy compound (D) is present in the reaction system. 15 to 90 minutes at 5 to 240 minutes at 70 to 180 ° C., preferably 10 to 180 minutes at 90 to 160 ° C. and most preferably 20 to 20 to 150 ° C. when there is no epoxy compound (D) in the reaction system. 90 minutes. Moreover, as for the compounding quantity of diamine (C), the sum total of (A) and (B) and (C) have a range of 1: 2 to 1: 0.1 by molar ratio. In addition, it is preferable that (D) is 80% or less in weight ratio of the total amount, in order to maintain heat resistance.

The above-described series of reactions can be freely selected depending on the use even in the melting reaction or in a solvent such as methyl cellosolve.

The polyvalent maleimide of (A) used in the present invention is obtained by obtaining a polyamine obtained from aniline and formalin as a raw material and maleic anhydride through a dehydration reaction of amic acid, which is commonly known, and n is in the range of 0.1 to 3.0. It is preferable in terms of heat resistance.

Examples of the bismaleimide compound of (B) include N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleide, N, N'-4,4'-diphenyl Methanebismaleimide, N, N'-4,4'-diphenylether bismaleimide N, N'-methylene bis (3-chloro-p-phenylene) bismaleimide, N, N'-4,4 '-Diphenyl sulfone bismaleimide N, N'-4,4'-dicyclohexyl methane bismaleimide, N, N'-α, α-4,4'-dimethylene cyclohexane bismus maleimide, N , N'-m-xylene bismaleimide, N, N'-4,4'-diphenyl cyclohexane bismaleimide, N, N'-m-phenylene bistetraphthalimide, N, N'-4 And 4'-diphenylmethane biscitracon imide.

Specific examples of the diamine of (C) include 4,4'-diamino dicyclohexyl methane, 1,4-diamino cyclohexane, 2,6-diamino pyridine, m-phenylenediamine, p-phenyl Lene diamine, 4,4'-diamino diphenylmethane, 2,2'-bis4-aminophenyl) propane, benzidine, 4,4'-diaminodiphenyl sulfone, bis (4-aminophenyl) methylphosphine Oxide, bis (4-aminophenyl) phenylphosphineoxide, bis (4-aminophenyl) methylamine, 1,5-diamino naphthalene, m-xylene diamine, p-xylenediamine, hexamethylene diamine, 6'6 ' -Diamino-2,2'-dipyridyl 4,4'-diamino benzophenone, 4,4'-diamino azobenzene, bis (4-amino phenyl) phenylmethane 1,1'-bis (4-amino Phenyl) cyclohexane, 1,1-bis (4-amino-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-aminophenyl) -2,2'-bis (1,3,4-oxadiazolyl), 4,4'-diamino diphenylether, 4,4'-bis (p-aminophenyl) 2 -2'-diazole, m-bis (4-p-aminophenyl-2-thiazolyl) benzene, 4,4'-diaminobenz anilide, 4,4'-diaminophenyl benzoate, N, N ' -Bis (4-amino benzyl) -p-phenylene diamine, 4,4'-methylene bis (2-chloro aniline), and the like, and at least one thereof or a mixture thereof is used. Examples of the epoxy compound of (D) include phenylglycidyl ether, diglycidyl ether of bisphenol A (bisphenol A-epichlorohydrin epoxy resin), cresol novolak type epoxy resin, 3,4-epoxy cyclohexyl methyl 3,4-epoxy cyclohexane carboxylate, 4,4 '-(1,2-epoxyethyl) biphenyl, 4,4'-di- (1,2-epoxy ethyl) diphenyl ether, resorcin diglyci Bifunctional epoxy compounds, such as dil ether, bis (2,3-epoxy cyclobenzyl) ether, N, N'-m-phenylenebis (4,5-epoxy-1,2-cyclohexane dicarboxy imide), triglycidyl compounds of p-amino phenol, 1,3,5-tri (1,2-epoxy ethyl) benzene, tetraparaglycithoxy tetraphenylethane, polyglycidyl ethers of phenol formaldehyde novolak resins, and the like Trifunctional or higher functional epoxy compounds are used. In addition, epoxy compounds having a hydantoin skeleton, such as XB-2818 and XB-2793 manufactured by Ciba-Geigy Co., Ltd., epoxy compounds containing halogen, such as DER-542 and DER-511, manufactured by Dow Chemical Co., Ltd. The brand name Araldide 8001, the Epicoat 1045 by a shell chemical company, etc. are mentioned. The molecular weight of the epoxy compound is preferably 2000 or less.

Example 1

(B) 40 parts by weight of N, N'-4,4'-diphenylmethanebismaleimide

(C) 10 parts by weight of 4,4'-diamino diphenylmethane

(D) 40 parts by weight of Bisfemol A type epoxy resin epicote 828 made by Shell Corporation

(A), (B), (C) and (D) are melt-reacted for 40 minutes at a temperature of 90 to 120 占 폚 to obtain a red transparent B-state resin. This resin is dissolved in acetone, methyl ethyl ketone and methyl cellosolve by 50% or more by weight of solids.

Next, 100 parts by weight of this resin and 1.5 parts by weight of dicyandiamide are dissolved in a solvent of methyl ethyl ketone methyl cellosolve (6: 4) to obtain a varnish.

The remaining volatile content of the prepreg made by impregnating Iwanis into a glass cloth (trade name WE-18G-104BX manufactured by IsoSung Co., Ltd.) having a thickness of 0.18 mm of epoxy silane and drying at 110 to 130 ° C. for 10 minutes was 0.2% or less.

Example 2

(B) 45 parts by weight of N, N'-4,4'-diphenylmetal bismaleimide

(C) 6 parts by weight of benzoguanamine

8 parts by weight of 4,4'-diaminodiphenyl methane

(D) 35 weight part of phenol noburak type epoxy resin DEN-438 made by Dow Chemical Corporation

(A), (B) and (C) are reacted for 30 minutes at 120 ° C. in 50 parts by weight of methyl cellosolve, and then (D) is added and reacted at 90 ° C. for 30 minutes. The varnish is then cooled to room temperature and 50 weight percent methylethyl ketone is added to give a red transparent varnish of about 50% by weight solids.

This varnish is used to make prepregs in the same manner as in Example 1. The remaining volatile matter of the prepreg is 0.2% or less.

Example 3

(B) 30 parts by weight of N, N'-4,4'-diphenyletherbis maleimide

(C) 10 parts by weight of 4,4'-methylenebis (2-chloro aniline)

2 parts by weight of 4,4'-diaminodiphenylmethane

(D) 60 parts by weight of hydantoin type epoxy resin XB-2818 made by Shiba GIGI Corporation

(A), (B), (C) and (D) were reacted for 50 minutes at about 80 to 120 ° C. in 60 parts by weight of methyl cellosolve, and then cooled to room temperature, followed by 2 parts by weight of dicyanic diamide and 64 parts by weight. Methyl ethyl ketone is added to give a red transparent weiss of about 50% by weight solids.

In the same manner as in Example 1, prepregs of 0.2% or less of the remaining volatile matter are made.

Example 4

(B) 30 parts by weight of N, N'-methylenebis (3-chloro-p-phenylene) bismaleimide

17 parts by weight of N, N'-4,4'-diphenylmethane bismaleimide

(C) 10 parts by weight of 4,4'-diamino diphenylmethane

(D) DEN-438 = 40 parts by weight

(A), (B) and (C) are melt reacted at 110 to 130 ° C. for 20 minutes, and then (D) is added to melt the reaction at 100 to 110 ° C. for 15 minutes to obtain a red transparent B-state resin. . This resin is dissolved in acetone, methyl ethyl ketone and methyl cellosolve at room temperature by 50% or more as a solid content weight.

Next, 100 parts by weight of the resin and 8 parts by weight of benzoguanamine are dissolved in a solvent of methylethylketone-methyl cellosolve (6: 4) to obtain a varnish having a solid content of 50% by weight.

In the same manner as in Example 1 below, prepreg having a residual volatile content of 0.2% or less was made.

[Comparative Examples 1 to 4]

The resin of Examples 1 and 4 as a result of mixing at room temperature without heat-reacting the polyhydric maleimide which is (A) component in Examples 1-4 and the epoxy compound which is (D) component, and examined the solubility to this mixture The solubility in acetone, methyl ethyl ketone, and methyl cellosolve was 10% or less, and in the system of Examples 2 and 3, an insoluble precipitate of 20% by weight or more was formed in the varnish.

Therefore, in Comparative Examples 1-4, a varnish is obtained using N-methyl- 2-pyrrolidone which is a bipolar solvent of boiling point 202 degreeC as a solvent.

Next, prepreg was prepared in the same manner as in Example 1 using Iwanis. Drying conditions were carried out at 150 to 160 ° C. for 10 minutes at a higher temperature than Example 1, but the remaining volatiles of the prepregs of Comparative Examples 1 to 4 were 0.8 to 1.2% and 0.2% or less of Examples 1 to 4, respectively. Much more.

Next, eight prepregs of Examples 1 to 4 and Comparative Examples 1 to 4 were used, respectively, and pressurized for 100 minutes at a temperature of 170 to 200 ° C. and a pressure of 40 kg / cm 2 to obtain 10 kinds of laminated plates having a thickness of about 1.6 mm. .

The properties of the laminate are shown in Table 1. And, for comparison, an ethoxy laminated plate (glass-epoxy, Hitachi Chemical Co., Ltd. product name L E-61, NEMA standard G-10) and an amino bismaleimide type prepolymer (Ronufran company name KERMID 601) are used. And the characteristic of the imide laminated board manufactured by the same method as above using N-methyl- 2-pyrrolidone as a solvent was also shown.

MEASUREMENT BENDING STRENGTH: Strength retention at each temperature with respect to bending strength at 120 ° C.

Bending strength after deterioration: Retention rate to initial value of bending strength after heating for a predetermined time at 220 ° C. in air.

The weight loss start temperature, the weight loss analysis at 500 ° C., is determined by the weight loss analysis at a temperature increase rate of 5 ° C./min in air.

Flame retardant: UL-94 vertical method.

Self-absorption rate: JISK 6911

As is clear from the table, the laminate using the prepolymer made by the manufacturing method of the present invention is inferior in heat resistance to the imide laminate, and has a low boiling point and low cost solvent such as acetone, methyl ethyl ketone, methyl cellosolve, etc. It is very advantageous in that it can work with a low self-absorption rate.

Claims (1)

Next polyvalent maleimide (A) represented by the general formula (Ⅰ), the following formula (Ⅱ) bismaleimide (B), diamines (C) and an epoxy compound represented by the general formula NR ₂ -NH ₂ H ₂ (D) of, The weight ratio of the above-mentioned (A) component is 3 to 80 weight% with respect to the total amount of (A) component and (B) component, and the molar ratio of (A) component and (B) component total amount and (C) component is 1: 2. To 1: 0.1, and the weight ratio of the component (D) is 5 to 80% by weight based on the total amount of the components (A), (B), (C) and (D), in the presence of the component (D) in the reaction system. A process for producing a thermosetting maleimide-based prepolymer, characterized in that the reaction is carried out at 50 to 145 ° C. for 5 to 240 minutes and in the absence of component (D) in the reaction system at 70 to 180 ° C. for 5 to 240 minutes in at least one step.

In the general formula, R ₁ and R ₂ each represent a divalent group containing at least two carbon atoms, and n is 0.1 to 0.3.