JPH0655795B2 - Curable composition containing unsaturated bisimide compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable composition containing an unsaturated bisimide compound useful as an intermediate for polymers.

[Prior art]

Conventionally, as raw materials for heat-resistant polymers, maleic anhydride and
N, N'-substituted bismaleimides obtained from diamine compounds (JP-A-60-156669) and reaction products of maleic anhydride and aniline resin are known. However, although these conventional imide compounds have good heat resistance, they have drawbacks such as difficulty in imparting flexibility and poor solubility in solvents such as acetone and toluene.

[Problems to be solved by the invention]

An object of the present invention is to provide a curable composition containing an unsaturated bisimide compound useful as a raw material for a polymer having excellent heat resistance and flexibility (molding processability, adhesiveness).

[Means for solving problems]

The present invention has the general formula [I] (In the formula, X ₁ and X ₂ are -O-, , Which may be the same or different from each other. However, both X ₁ and X ₂ are -O- and It never becomes. D ₁ and D ₂ are divalent organic groups having an ethylenically unsaturated double bond group and may be the same or different. R _{1 to} R ₄ represent hydrogen, a lower alkyl group or a perfluoroalkyl group, and may be the same as or different from each other. R ₅ and R ₆ are hydrogen, a lower alkyl group or a perfluoroalkyl group, and may be the same as or different from each other. ) An unsaturated bisimide compound represented by the formula (1) and an ethylene-based polymerizable compound are mixed in an amount of 0.1 to 9.0 parts by weight of the polymerizable compound with respect to 1 part by weight of the unsaturated bisimide compound. It is a curable composition containing a saturated bisimide compound.

The present invention will be described in detail below.

In the present invention, the general formula [I] The unsaturated bisimide compound represented by (X ₁ , X ₂ , D ₁ , D ₂ , R _{1 to} R ₄ , R ₅ , and R ₆ is as described above) is, for example, and so on.

General formula [II] used in the method for producing an aromatic unsaturated bisimide compound represented by the general formula [I] Examples of the diamine compound represented by (X ₁ , X ₂ , R _{1 to} R ₄ , R ₅ , and R ₆ are as described above) include, for example, and so on.

In addition, the general formula [III] And the general formula [IV] Examples of the ethylenically unsaturated dicarboxylic acid anhydride represented by (D ₁ and D ₂ are as described above) include maleic anhydride,
Citraconic anhydride, itaconic anhydride, pyrocinconic anhydride, dichloromaleic anhydride, etc., or at least one Diels Alder adduct of these compounds and dicyclodiene is used.

From the general formulas [II] and [III] and the general formula [IV],
The reaction method for obtaining the general formula [I] of the present invention is not particularly limited, but in order to produce the unsaturated bisimide compound of the general formula [I], in the first step, the reaction of the formula [V] An aromatic unsaturated bisamic acid represented by (X ₁ , X ₂ , R _{1 to} R ₄ , R ₅ , R ₆ , D ₁ , and D ₂ are as described above) is produced. Known methods are applied for this purpose. As an advantageous method, a method of contacting the diamine compound of the general formula [II] and the ethylenically unsaturated dicarboxylic acid anhydride of the general formula [III] and the general formula [IV] in an organic liquid which is a solvent of both is there. Usually, commonly used solvents include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-methylcaprolactam, tetrahydrofuran, dioxane, acetone and diethylketone. Next, as the second step, the unsaturated bisamidic acid is cyclized and dehydrated to generate an imide ring. As this method, USP 3,018,290, USP 3,0
Well-known methods described in 18,292 and USP 3,127,414 may be used. That is, dehydration from the amic acid of the formula [V] is carried out by using acetic anhydride as an anhydride in an amount of 1.05 to 1.5 mol per mol of amic acid group, and using a tertiary amine such as triethylamine per 1 mol of amic acid group. 0.15 to 0.5 mol is added, and the reaction is preferably carried out in acetone in the presence of 0.5 to 0.05 mol of nickel acetate, sodium acetate, potassium acetate or the like as a catalyst with respect to 1 mol of amic acid group.

In the curable composition containing the unsaturated bisimide compound represented by the general formula [I] of the present invention, the polymerizable compound will be specifically described below. That is, as the polymerizable compound (monomer), for example, styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallylphthalate, diallylphthalate prepolymer, chlorostyrene,
There are dichlorostyrene, bromstyrene, dibromostyrene, diallylbenzenephosphonate, diallylaryl phosphonate, acrylic acid, methacrylic acid ester, triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether, etc., These can be used alone or in combination of two or more.

Further, the unsaturated bisimide compound represented by the general formula [I] of the present invention can be modified before curing by adding a known unsaturated polyester. Here, the unsaturated polyester means an unsaturated dibasic acid, a saturated dibasic acid and an anhydride thereof or a lower alkyl ester derivative thereof and a diol or an alkylene monooxide and a derivative thereof in the presence or absence of a catalyst. A polyester resin matrix containing an unsaturated group synthesized by condensation or addition polymerization utilizing a reaction such as esterification or transesterification, and an ethylene-based (eg vinyl group, allyl group, etc.) polymerizable compound, And a mixture with a peroxide catalyst. In addition, vinyl ester resins obtained by reacting bisphenol A type and novolak type epoxy compounds with methacrylic acid or acrylic acid are also useful. Here, as the representative of the unsaturated dibasic acid and the saturated dibasic acid, maleic acid,
Maleic anhydride, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, citraconic acid anhydride, mesaconic acid, itaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, Terephthalic acid, methyl glutaric anhydride, pimelic acid, hexahydrophthalic acid and its anhydride, tetrahydrophthalic acid, carbic acid anhydride, het acid and its anhydride, tetrachlorophthalic acid and its anhydride, tetrabromophthalic acid and its Anhydrous,
These lower alkyl esters and the like are used, and as the diol component, ethylene glycol, diethyl glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Trimethylene glycol, tetramethylene glycol,
Hexamethylene glycol, 2,2-diethylpropane diol, 1,3-neopentyl glycol, dibromoneopentyl glycol, bisphenol dioxydiethyl ether, hydrogenated bisphenol A, 2,2-di (4-hydroxypropoxyphenyl) propane , Ethylene oxide, propylene oxide, 3,3,3-trichloropropylene oxide, 2-methyl-3,3,3-trichloropropylene oxide, phenylglycidyl ether, allylglycidyl ether and the like are used.
Further, if necessary, a tribasic or higher functional polybasic acid and / or a polyhydric alcohol may be used in combination as long as the object of the present invention is not impaired. Examples of the crosslinking agent include styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallylphthalate, diallylphthalate prepolymer, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, diallylbenzenephosphonate, diallylarylphosphyl ester. , Acrylic acid ester, methacrylic acid ester, triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether and the like are used. In the unsaturated polyester to be added, the acid component, the alcohol component and the crosslinking agent are not limited to one type, and two or more types can be used in combination. Further, various types of modification and modifiers can be added. Further, the unsaturated polyester is not limited to one kind, and two or more kinds may be mixed.

The unsaturated bisimide compound represented by the general formula [I] of the present invention reacts with a polyamine, particularly a diamine, and becomes a heat resistant material having excellent flexibility. Here, as the amine compound, for example, m-phenylenediamine, p-phenylenediamine, benzidine, 3,3′-dimethyl-4,4′-
Diaminobiphenyl, 3,3'-dichlorobenzidine, 3,
3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane, 1,1-bis (4-aminophenyl) ethane,
2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2
-Bis (4-aminophenyl) -1,3-dichloro-1,1,
3,3-tetrafluoropropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminophenyl sulfide, 4,4 '
-Diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodibenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, N, N-bis (4-aminophenyl) methylamine,
N, N-bis (4-aminophenyl) -n-butylamine, N, N-bis (4-aminophenyl) amine, m-aminobenzoyl-p-aminoanilide, 4-aminophenyl-3-aminobenzoate, 4 4,4'-diaminoazobenzene, 3,3'-diaminoazobenzene, bis (3-
Aminophenyl) diethylsilane, bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) ethylphosphine oxide, 1,5-diaminonaphthalene, 2,6-diaminopyridine, 2,5-diamino-1, 1,4-oxadiazole, m-xylylenediamine, p-xylylenediamine, 2,4 (p-β-amino-t-butylphenyl) ether, p-bis-2- (2
-Methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,11 -Diaminododecane, 1,12-diaminooctadecane, 2,2-dimethylpropylenediamine,
2,5-dimethylenehexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,
5-methylnonamethylenediamine, 1,4-diaminocyclohexane, bis (p-aminocyclohexyl) methane, 3-methoxyhexamethylenediamine, 1,2-bis (3-aminopropoxy) ethane, bis (3-aminopropyl) Examples thereof include sulfide and N, N-bis (3-aminopropyl) methylamine. Also, 2,4-diaminodiphenylamine, 2,4-diamino-5-methyldiphenylamine, 2,4-diamino-4'-methyldiphenylamine, 1-anilino-2,4-diaminonaphthalene, 3,3'-diamino- There are N-aryl substituted aromatic triamines such as 4-anilinobenzophenone. Furthermore, the general formula (In the formula, X is an alkylidene group containing a methylene group, and m is an average number of 0.1 or more.) A polyamine represented by the formula is also useful. Particularly effective in imparting flexibility are 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl. Propane or 2,4-bis [4-
(4-Aminophenoxy) phenyl] -2-methylpentane, 2,4-bis [4- (4-aminophenoxy) phenyl] -2- (fluoro) -methylpentane, 1- [4
-(3-Aminophenoxy) phenyl] -1,3,3-
Trimethyl-6- (3-aminophenoxy) indane,
6,6'-bis (3-ainophenoxy) -3,3,
3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) -3,3,3
3 ', 3'-tetramethyl-1,1'-spirobiindane and the like. Of course, in the present invention, the compound represented by the above general formula [II] can also be used.

Further, the aromatic unsaturated bisimide compound represented by the general formula [I] of the present invention can be used in a wider range of applications by being used in combination with a conventionally known N, N′-substituted bismaleimide compound. . The N, N′-substituted bismaleimide compound has the formula: [Wherein A represents an alkylene group, an arylene group or a divalent organic group substituted therewith], for example, N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide , N, N'-dodecamethylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-di 4,4'-phenyl ether bismaleimide, N, N'-4,4'-diphenylmethane bis Maleimide,
N, N'-4,4'-dicyclohexylmethane bismaleimide, N, N'-4,4'-metaxylene bismaleimide, N,
N'-4,4'-diphenylcyclohexane bismaleimide or general formula [IV] (In the formula, R _{2 to} R ₅ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₆ and R ₇ are hydrogen, a methyl group, or ethyl. Group, trifluoromethyl group or trichloromethyl group,
D represents a divalent organic group having 2 to 24 carbon atoms. ) An ether imide compound represented by
2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-bromo-4- (4-
Maleimidophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (maleimidophenoxy) phenyl] propane, 2,2-bis [3-propyl-4- (4-
Maleimidophenoxy) phenyl] propane, 2,2-bis [3-isopropyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-butyl-4
-(4-maleimidophenoxy) phenyl] propane,
2,2-bis [3-sec-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methoxy-4- (4-maleimidophenoxy) phenyl] propane, 1,1- Bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4-
(4-maleimidophenoxy) phenyl] ethane, 1,1
-Bis [3-chloro-4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3-bromo-4-
(4-maleimidophenoxy) phenyl] ethane, bis [4- (4-maleimidophenoxy) phenyl] methane, bis [3-methyl-4- (4-maleimidophenoxy) phenyl] methane, bis [3-chloro-4- (4-
Maleimidophenoxy) phenyl] methane, bis [3-
Bromo-4- (4-maleimidophenoxy) phenyl]
Methane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4
-(4-maleimidophenoxy) phenyl] propane,
1,1,1,3,3,3-hexachloro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3-bis [4- (4-maleimidophenoxy) phenyl] pentane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2
-Bis [3,5-dibromo-4 (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4 (4-maleimide) Phenoxy) phenyl] propane, 2,4-bis [4- (4-
Maleimidophenoxy) phenyl] -2-methylpentane and the like can be mentioned. Also, two or more of these may be mixed and used. Furthermore, a mixture with a mono-substituted maleimide, a tri-substituted maleimide or a tetra-substituted maleimide can also be appropriately used.

Further, 2,4-bis [4- (4-endomethylenetetrahydrophthalimidophenoxy) phenyl] -2-methylpentane, 2,4-bis [4- (4-maleimidophenoxy) phenyl] -2- (fluoro)- Methyl pentane,
1- [4- (3-maleimidophenoxy) phenyl]
-1,3,3-Trimethyl-6- (3-maleimidophenoxy) indane, 1- [4- (3-Endomethylenetetrahydrophthalimidophenoxy) phenyl] -1,3,3-
Trimethyl-6- (3-endomethylenetetrahydrophthalimidophenoxy) indane, 1- [4- (3-maleimidophenoxy) phenyl] -1,3,3-trimethyl-6- (3-endomethylenetetrahydrophthalimidophenoxy) indane, 6,6'-Bis (3-maleimidophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-
Spirobindan and the like can also be used.

Also, by adding an epoxy compound, heat resistance,
It also becomes a cured product with excellent moldability.

Examples of the epoxy compound used in the present invention include diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl- (3,4-
Epoxy) cyclohexanecarboxylate, vinylcyclohexanedioxide, 4,4'-di (1,2-epoxymethyl) diphenyl ether, 2,2-bis (3,4-epoxycyclohexyl) propane, glycidyl ether of resorcin, dilogue of phloroglucin Glycidyl ether, diglycidyl ether of methyl phloroglucin, bis (2,
3-epoxycyclopentyl) ether, 2- (3,4-epoxy) cyclohexane-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxy-6-methylcyclohexyl) adipate , N,
N'-m-phenylene bis (difunctional epoxy compounds such as 4,5-epoxy-1,2-cyclohexanedicarboximide, triglycidyl ether of paraaminophenol, polyallylglycidyl ether, 1,3,5-tri ( 1,2
-Epoxyethyl) benzene, 2,2 ', 4,4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolac resin, triglycidyl ether of glycerin, trimethylolpropane and triglycidyl ether An epoxy compound, a halogenated epoxy compound such as brominated epoxy, or a hydantoin epoxy compound is used.

Further, by adding an epoxy compound or the like in combination with the phenol-formaldehyde condensate or in the combination, the molding processability is increased and the compound is easily dissolved in a solvent, so that it can be used for casting.

Further, it is effective to use a known curing agent for an epoxy compound in combination in order to improve the curability. For example, Hiroshi Kakiuchi; Epoxy Resins (published in September, 1970), pages 109-149; Lee, Neville; Epoxy Resins (Mc Graw-Hill Book)
Company Inc. New York, 1957) 63-141 pages,
By PE Brunis; Epoxy Resins Technology (Interscienc
e Publishese, New York, 1968) pages 45 to 111 and the like, for example, aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, carboxylic anhydrides. , Aliphatic and aromatic polyamide oligomers and polymers, boron trifluoride-amine complexes, phenolic resins,
Synthetic resin initial condensates such as melamine resins, urea resins and urethane resins, as well as dicyandiamide, carboxylic acid hydrazides, polyaminomaleimides and poly-p-hydroxystyrene.

One or more of the above-mentioned curing agents can be used depending on the application and purpose.

In the present invention, the general formula [In the formula, Y is none, -CH _2- , It is one of -O-, -CO-, -S-, -SO _2- . ] By combining the orthodiallyl bisphenol compounds represented by the above formula, it is possible to obtain a highly compatible varnish capable of providing a cured product having excellent heat resistance and flexibility. As such a compound, for example, Etc., and one or more kinds can be used in combination.

Further, the unsaturated bisimide-based compound of the present invention is used in combination with at least one kind of allyl ester of polyvalent carboxylic acid or cyanuric acid to obtain a resin composition having excellent high temperature strength and fast curing property, and particularly It is useful as a composite material. Here, examples of the allyl ester compound of polyvalent carboxylic acid or cyanuric acid include, for example, triallyl trimellitate, diallyl phthalate, p, p′-diaryloxycarbonyldiphenyl ether, m, p′-diaryloxycarbonyldiphenyl ether, and triethyltriphenylate. Examples include allyl cyanurate and triallyl cyanurate prepolymer. The above compounds may be used as a mixture of two or more kinds.

It can also be used in combination with an N-vinyl-pyrrolidone compound.

Examples of the N-vinyl-pyrrolidone compound include N-
Vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinyl-5
-Methyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, 3-methyl-2-pyrrolidone or N-vinyl-2-pyrrolidone dimer, or N-vinyl- A copolymer of pyrrolidone and acrylonitrile, allyl alcohol, allyl acetate, ethylene, maleic anhydride, methyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinylene, carbonate, vinyl cyclohexyl ether, vinyl phenyl ether, or the like. , Polyvinylpyrrolidone, etc., and at least one of them can be used.

Further, when used in combination with a butadiene-based compound, a cured product having excellent heat resistance and flexibility can be obtained. The butadiene-based compound has a molecular weight of about 30.
0 to 10,000 of 1,2-polybutadiene, 1,3-polybutadiene, 1,4-polybutadiene and butadiene-styrene copolymer and butadiene-acrylonitrile copolymer,
Further, at least one of those having a carboxyl group, a hydroxyl group, an amino group, an aldehyde group, a nitro group, an itocyanate group, and a vinyl group as a reactive group at the terminal of each of the above-mentioned polymers is used.

The unsaturated bisimide compound of the present invention can be used in combination with a carboxylic acid compound. For example, pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 3,4,9,1
0-perylenetetracarboxylic acid, 3,3 ', 4,4'-diphenyltetracarboxylic acid, 3,3', 4,4'-diphenylmethanetetracarboxylic acid, ethylenetetracarboxylic acid, 2,2
-Diphenyl-3,3 ', 4,4'-propane tetracarboxylic acid, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid, 3,4,3 ', 4'-benzophenone tetracarboxylic acid, 3 , 3 ', 4,4'-Azoxybenzenetetracarboxylic acid, 3,3', 4,4'-azobenzenetetracarboxylic acid and
There are dianhydrides such as 3,3 ', 4,4'-diphenyloxytetracarboxylic acid.

In order to impart flexibility to a cured product obtained by heating the resin composition described in detail above, a known compound that causes plastic curing to the resin composition, for example, triphenyl phosphate, tricresyl phosphate At least one of trioctyl phosphate, dioctyl phthalate, dioctyl hexahydrophthalate, dilauryl succinate, higher aliphatic amide, silicone polymer, diglycidyl ester of dimer acid and the like can be added.

It is desirable to add a polymerization initiator to the above resin composition for the purpose of completing the curing by heating for a short time. Examples of such a polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide and 2,4-
Dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, t
-Butyl hydroperoxide, p-menthane hydroperoxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroctoate, t-
Organic peroxides such as butyl peroxyisobutyrate and di-t-butyl diperphthalate are useful.
One kind or two or more kinds can be used.

In the present invention, examples of the above-mentioned polymerization catalyst include lauryl mercaptan, N-butyl sulfite, diphenyl sulfite, p-toluenesulfonic acid, quaternary ammonium salts, β-diketones, peracetic acid type epoxy compounds, sulfonium salts. , Manganese naphthenate, vanadyl octoate, copper naphthenate, calcium naphthenate, other metal salts of naphthenic acid, metal chelate compounds, amines, phosphorus-containing compounds, sulfur-containing compounds and the like. The following polymerization inhibitors can also be used. For example, quinones such as p-benzoquinone, naphthoquinone, phenanthraquinone, paraxylone quinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p-benzoquinone, hydroquinone, pt-butylcatechol, 2,
Hydroquinones such as 5-di-t-butylhydroquinone and mono-t-butylhydroquinone, phenols such as di-t-butyl, para-cresol, hydroquinone monomethyl ether and alpha naphthol, organic and inorganic copper such as copper naphthenate Salts, amidines such as acetamidine acetate and acetamidine sulfate, hydrazine salts such as phenylhydrazine hydrochloride and hydrazine hydrochloride, other quaternary ammonium salts, amines, nitro compounds, oximes, sulfur, polyphenols, amines Hydrochloric acid can be used.

〔Example〕

Synthesis Example 1 19.6 parts by weight of maleic anhydride was dissolved in 200 m of acetone and stirred under a nitrogen gas atmosphere at 5 ° C. or lower to 2,2-
A solution of 46.6 parts by weight of bis [4- (4-aminobenzcarboxylate) phenyl] propane in 500 m of acetone was gradually added dropwise. After reacting with stirring at room temperature for 4 hours, 200 m of acetic anhydride and 1.0 part by weight of potassium acetate were added,
The reaction was carried out for about 2 hours under acetone reflux. Then, the reaction product was poured into about 3000 m of pure water to form a precipitate, which was then filtered, washed and dried to obtain the aromatic unsaturated bisimide compound [A] of the present invention. .

Infrared absorption of the aromatic unsaturated bisimide compound (I
As a result of measurement of (R) spectrum, characteristic absorption derived from an imide bond was observed at 1712 cm ^-1 and 1777 cm ^-1 .

Synthesis Example 2 19.6 parts by weight of maleic anhydride of Synthesis Example 1 was changed to 10 parts by weight, and further, endomethylenetetrahydrophthalic anhydride 1
Aromatic unsaturated bisimide compound [B] of the present invention was obtained by the same method as in Synthesis Example 1 except that 5.2 parts by weight was added.

As a result of measuring the IR spectrum of the aromatic unsaturated bisimide compound, characteristic absorption derived from an imide bond was observed at 1714 cm ^-1 and 1781 cm ^-1 .

Synthesis Example 3 The same procedure as in Synthesis Example 1 was repeated except that 19.6 parts by weight of maleic anhydride in Synthesis Example 1 was replaced with 30.4 parts by weight of endomethylenetetrahydrophthalic anhydride. A compound [C] was obtained.

As a result of measuring the IR spectrum of the aromatic unsaturated bisimide type compound, characteristic absorption derived from an imide bond was observed at 1713 cm ^-1 and 1780 cm ^-1 .

Examples 1 to 8 The aromatic unsaturated bisimide compounds [A], [B], and [C] obtained in Synthesis Examples 1 to 3 and unsaturated polyester (Hitachi Chemical Co., Ltd .; PS-518), N, N'-4,4'-bis (diphenylmethane) maleimide, 4,4'-diaminobiphenylmethane and an epoxy compound (orthocresol novolac type; epoxy equivalent 195) were added in the prescribed amounts (parts by weight) shown in Table 1. Each of them was blended separately to prepare 8 kinds of blends. In addition to these, the curing accelerators (dicyandiamide and dicumyl peroxide) shown in Table 1, 40% by weight of fused silica glass powder as a filler, and 45% by weight of spherical Al ₂ O ₃ powder having an average particle size of 1 μm ,
As a coupling agent, 3 parts by weight of an acylate-type alkoxy titanate compound and an epoxysilane compound KBM4
03.1 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.), 2 parts by weight of carnauba wax as a release agent and 1 part by weight of carbon black as a colorant were added, and then uniformly mixed by a kneader.

The composition is then 150-180 ° C., 70 kg / cm ² , 3-5
Heat-press molding was carried out under the condition of minutes to prepare various cured products (specimens for measuring characteristics).

Table 1 shows the properties of various cured products.

Synthesis Example 4 19.6 parts by weight of maleic anhydride was dissolved in 300 m of N-methyl-2-pyrrolidone (NMP), and 2,2-bis [4- (4-amino) was added thereto while stirring in a nitrogen gas atmosphere. Benzcarboxylate) phenyl] hexafluoropropane 5
A solution of 7.8 parts by weight in NMP500m was gradually added dropwise. After reacting with stirring for 4 hours at room temperature, acetic anhydride 300m
And potassium acetate 1 part by weight, triethylamine 0.5 m
Was added, and the mixture was reacted at 80 to 100 ° C for about 2 hours with stirring. Then, the reaction product is poured into about 3000 m of cooled pure water,
A precipitate formed. Then, the precipitate was filtered, washed and dried to obtain the aromatic unsaturated bisimide compound [D] of the present invention. As a result of measuring the IR spectrum of the aromatic unsaturated bisimide compound, 1710 cm ^-1 and 1782 cm ^-1
The characteristic absorption derived from the imide bond was observed.

Synthesis Example 5 Aromatic unsaturated bisimide of the present invention was prepared in the same manner as in Synthesis Example 4 except that 19.6 parts by weight of maleic anhydride in Synthesis Example 4 was replaced with 32 parts by weight of methylendomethylenetetrahydrophthalic anhydride. A system compound [E] was obtained.

As a result of measuring the IR spectrum of the aromatic unsaturated bisimide compound, characteristic absorption derived from an imide bond was observed at 1710 cm ^-1 and 1778 cm ^-1 .

Examples 9 to 14 The aromatic unsaturated bisimide compounds [D] and [E] obtained in Synthesis Example 4 and Synthesis Example 5, and the epoxy compound EOCN-1.
02S (Nippon Kayaku Co., Ltd.), novolac type phenol resin HP-
607N (manufactured by Hitachi Chemical Co., Ltd.), N, N'-bismaleimide-diphenylmethane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane, poly-p
-Hydroxystyrene M resin (manufactured by Maruzen Petroleum Co., Ltd.) was separately mixed in the proportions (parts by weight) shown in Table 2 to prepare various kinds of formulations. Further, 5 parts by weight of dicyandiamide, 2 parts by weight of triphenylphosphine as a curing accelerator, 4 parts by weight of an acylate-type alkoxy titanate compound S-181 (manufactured by Nippon Soda Co., Ltd.) as a coupling agent, and epoxysilane KBH303. (Shin-Etsu Chemical Co., Ltd.)
1 part by weight, 2 parts by weight of calcium stearate as a release agent, 1 part by weight of Hoechst wax E, as a filler,
60% by weight of spherical alumina powder having an average particle size of 1 μm, 25% by weight of spherical fused silica glass powder having an average particle size of 5 to 44 μm, and 2 parts by weight of carbon black as a coloring agent are added, and then uniformly mixed by a kneader. did.

The above composition was then pressure-heat molded under the conditions of 175 to 180 ° C., 70 kg / cm ² , and 2 minutes to prepare various cured products (specimens for property measurement).

Table 2 shows the properties of various cured products.

In addition, Table 2 shows the characteristics when 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (DAPP-BMI) was used as a comparative example of the aromatic unsaturated bisimide compound.

Example 15 60 parts by weight of Sumiepoxy ESA-110 (bisphenol A type epoxy resin manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 480), 40 parts by weight of aromatic unsaturated bisimide (A) was added to 40 parts of methyl ethyl ketone.
Parts by weight, dissolved in 40 parts by weight of N-methylpyrrolidone, 1.6 parts by weight of dicyandiamide, 1,2,3-benzotriazole
2.0 parts by weight of (B7A) was added and uniformly dissolved to obtain an epoxy resin composition. A glass cloth (KS-1600 plain weave manufactured by Kanebo Glass Fiber Co., Ltd.) was impregnated with the composition, air-dried and then heated at 130 ° C. in a constant temperature bath for 25 minutes to obtain a prepreg.

Six layers of prepreg were press-molded under the conditions of 160 ° C., 100 kg / cm ² and 20 minutes, and further post-cured in a constant temperature bath at 180 ° C. for 60 minutes to obtain a laminated plate. Further, a copper-clad laminate was obtained from copper foil (Furukawa Electric Co., Ltd., 32 μm) and 6 layers of prepreg under the same conditions as above. The properties of these obtained laminated plates measured according to JIS-C-6481 are shown in Table 3.

As shown in Table 3, the laminated plate of this example has a larger peel strength of the copper clad plate after boiling and a lower water absorption rate than the conventional one.

Furthermore, it has excellent solder heat resistance after boiling and has a high glass transition point.

Comparative Example 2 4,4′-Bismaleimide-diphenylmethane 40 was used in place of 40 parts by weight of the aromatic unsaturated bisimide [A] of Example 15.
A copper clad laminate was prepared in the same manner as in Example 15 except that parts by weight were used, and the characteristics were measured according to JIS-C-6481. The results are shown in Table 4.

Synthesis Example 6 196 g of maleic anhydride was placed in a 3 L 3-neck separable flask and dissolved in 500 m of methyl ethyl ketone. While maintaining the solution at 5 ° C. or below, the following formula was used as a diamine component while stirring. A solution prepared by dissolving 4.38 g of 2-2- [4- (4-aminophenoxy) (4-aminophenyl ester) phenyl] propane represented by 1 in 1 L of methyl ethyl ketone is added dropwise. After completion of dropping, the mixture was stirred at 5 to 15 ° C for 7 hours, and then acetic anhydride 150m,
Add 1 g of sodium acetate and stir for another 3 hours. Next, 1 L of water is added dropwise to the reaction solution under stirring to form and precipitate an unsaturated bisimide compound [(a) below].

The precipitate is filtered and washed repeatedly and then dried under reduced pressure to obtain the target unsaturated bisimide compound [(a) below].
The IR spectrum of the compound was measured and found to be 1228 cm ^-1 .
1788Cm ^-1 imide bond, ether bond 1260 cm ^-1, 1660
Characteristic absorption of ester bond was observed at cm ^-1 .

Examples 16 to 34 As unsaturated bisimide compounds, the following (a) to (e) 5 types of epoxy compounds, EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), novolac type phenol resin HP607N (manufactured by Hitachi Chemical Co., Ltd.), N, N′-bismaleimide-diphenylmethane (DDM), 2,2-bis 4- (4-maleimidophenoxy) phenyl] propane (DAP-BMI) and poly-p-hydroxystyrene: M resin: (manufactured by Maruzen Petroleum Co., Ltd.) were mixed at a predetermined ratio (parts by weight) shown in Table 5 19
A variety of compositions were prepared. Then, in each of these compositions, separately, 5 parts by weight of dicyandiamide, 2 parts by weight of triphenylphosphine as a curing accelerator, and 4 parts by weight of an acylate-type alkoxy titanate compound S-181 (manufactured by Nippon Soda Co., Ltd.) as a coupling agent. And epoxy silane KB
1 part by weight of M303 (manufactured by Shin-Etsu Chemical Co., Ltd.), 2 parts by weight of calcium stearate and 1 part by weight of Hoechst Wax E (manufactured by Hoechst Japan) as a release agent, and 60% by weight of spherical alumina powder having an average particle size of 1 μm as a filler. And average particle size 5 to 44 μm
25% by weight of spherical fused silica glass powder and 2 parts by weight of carbon black as a coloring agent are added, and then 70 to 11 by a kneader.
Mix for 10 minutes at 0 ° C. Then, various compositions were subjected to transfer molding under the conditions of 175 to 185 ° C., 70 kg / cm ² , and 2 minutes to prepare samples for measuring various characteristics. Fifth
The glass transition point, bending strength (at 180 ° C) of the cured product (molded product) prepared using various compositions in the table, and the retention rate of bending strength after being left for 30 days at 200 ° C, bending strain, and moldability. , Showing adhesive properties.

From this result, it can be seen that a molded and cured product having excellent heat resistance and flexibility can be provided, and that it has excellent moldability and adhesiveness.

〔The invention's effect〕

As described above, according to the present invention, a novel unsaturated bisimide compound useful as a polymer raw material is provided, and by using this compound or another polymer raw material, heat resistance, flexibility and molding It is possible to obtain a polymer having excellent processability and adhesiveness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshikazu Narahara 4026 Kuji Town, Hitachi City, Ibaraki Prefecture, Hitachi Research Institute, Ltd. Inside Hitachi Research Laboratory (56) Reference JP-A-48-36163 (JP, A) JP-A-56-103162 (JP, A) JP-B-50-24998 (JP, B2)

Claims (1)

[Claims] 1. A general formula [I] (In the formula, X ₁ and X ₂ are -O-, , Which may be the same or different from each other. However, both X ₁ and X ₂ are -O- and It never becomes. D ₁ and D ₂ are divalent organic groups having an ethylenically unsaturated double bond group and may be the same or different. R _{1 to} R ₄ represent hydrogen, a lower alkyl group or a perfluoroalkyl group, and may be the same as or different from each other. R ₅ and R ₆ are hydrogen, a lower alkyl group or a perfluoroalkyl group, and may be the same as or different from each other. The unsaturated bisimide compound represented by the formula (1) and the ethylene-based polymerizable compound are blended in an amount of 0.1 to 9.0 parts by weight with respect to 1 part by weight of the unsaturated bisimide compound. A curable composition containing an unsaturated bisimide compound.