JPH0692465B2 - Composition containing addition reaction type ether imide compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition containing an addition reaction type ether imide compound.

[Conventional technology]

As typical ones of the conventional unsaturated bisimides, for example, in JP-A-47-8644 and JP-A-47-11500, Alternatively, It is used as a material that gives a heat resistant cured product. However, the compound is almost insoluble in inexpensive general solvents such as ketone solvents and petroleum solvents, metals,
Improvements have been desired in terms of poor adhesion to inorganic substances and difficulty in achieving both heat resistance and flexibility of the cured product. For this reason, a great number of formulations have been studied depending on the purpose of use.

[Problems to be solved by the invention]

Conventionally, as raw materials for heat-resistant polymers, maleic anhydride and
N, N'-substituted bismaleimides obtained from diamine compounds 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.

An object of the present invention is to provide a composition containing an addition reaction type ether imide compound having excellent heat resistance and flexibility.

[Means for solving problems]

 The above object is achieved by the means described in detail below.

The gist of the present invention is represented by the general formula [I]: [Wherein D ₁ and D ₂ are And may be the same or different from each other. ] The addition reaction type ether imide compound (A) and the polymerizable compound (B) represented by the above (A)
A composition containing an addition reaction type ether imide compound, characterized in that 0.1 to 9.0 parts by weight of (B) is mixed with 1 part by weight.

In the present invention, the addition reaction type ether imide compound represented by the general formula [I] is, for example, There is.

In the present invention, the addition reaction type ether imide compound represented by the general formula [I] includes a diamine compound having an ether bond represented by the general formula [II], a general formula [III] and a general formula [III]. IV] and a dicarboxylic acid anhydride having an ethylenically unsaturated double bond are obtained by dehydration condensation reaction.

That is, the following reaction Is obtained.

Examples of the unsaturated dicarboxylic acid anhydride represented by the general formula [III] and the general formula [IV] include maleic anhydride,
Endomethylenetetrahydrophthalic anhydride, dichloroendomethylenetetrahydrophthalic anhydride, dibromoendomethylenetetrahydrophthalic anhydride, endodichloromethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyldichloroendomethylenetetrahydrophthalic anhydride, methyl At least one kind of dibromoendomethylene tetrahydrophthalic anhydride, and examples of the unsaturated dicarboxylic acid anhydride represented by the general formula [IV] include, for example, the above-mentioned acid anhydride,
Maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, phenyl maleic anhydride, monochloromaleic anhydride, monobromomaleic anhydride, dichloromaleic anhydride, dibromomaleic anhydride, itaconic anhydride, etc., at least these One kind is used.

The synthesis of the etherimide compound of the present invention is carried out, for example, by contacting a diamine compound having an ether bond of the general formula [II] and an ethylenically unsaturated dicarboxylic acid anhydride of the general formulas [III] and [IV] in an organic solvent. Can be obtained.

A stoichiometric ratio of the amine compound to the unsaturated dicarboxylic acid anhydride is 1: 1 equivalent, and industrially 1: 0.95 to 1.05 equivalent. By this reaction, an amic acid represented by the following formula [V] is once produced.

Examples of the solvent include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-methylcaprolactam, tetrahydrofuran, dioxane, acetone and diethylketone. Next, as the second step, the ethermaleamic acid is cyclized and dehydrated to generate an imide ring. As this method, known methods described in USP 3,018,290, USP 3,018,292 and USP 3,127,414 may be used. That is, dehydration from the amic acid represented by the formula [IV] is carried out by adding acetic anhydride as an anhydride at 1.05 to 1 mol per mol of amic acid group.
Used in an amount of 1.5 mol, 0.15 to 0.5 mol of a tertiary amine, for example triethylamine, is added to 1 mol of amic acid groups, and, as a catalyst, 0.1 mol to 1 mol of amic acid groups.
It is preferably carried out in acetone in the presence of 5 to 0.05 mol of nickel acetate.

The ether imide compound of the present invention is polymerized in the presence of an amine compound to form a heat resistant resinous material. here,
Examples of the amine compound include m-phenylenediamine and p-, in addition to the above-described amine compound having an ether bond.
Phenylenediamine, benzidine, 3,3'-dimethyl-
4,4'-diaminobiphenyl, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane, 1,1-bis (4-aminophenol)
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'-diaminodiph Phenyl ether, 4,4'-diaminodiphenyl sulphide, 3,3'-diaminodiphenyl sulphide, 4,4'-diaminodiphenyl sulphoxide, 4,4'-
Diaminodiphenyl phonone, 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'-diaminoazobenzene, 3,3'-diaminoazobenzene, bis (3-aminophenyl) diethylsilane, bis (4-aminophenyl) phenyl Phenylphosphine oxide, bis (4
-Aminophenyl) ethylphosphine oxide, 1,5-
Diaminonaphthalene, 2,6-diaminopyridine, 2,5-diamine-1,1,4-oxadiazole, m-xylylenediamine, p-xylylenediamine, 2,4 (p-β-amino-t- Butylphenyl) ether, p-bis-2-
(2-methyl-4-aminobenzyl) 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-dimethylenehexamethylene Diamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methinonamethylenediamine, 1,4-diaminocyclohexane, bis (p-aminocyclohexyl) methane, Examples thereof include 3-methoxyhexamethylenediamine, 1,2-bis (3-aminopropoxy) ethane, bis (3-aminopropyl) sulfide, N, N-bis (3-aminopropyl) methylamine and the like. Further, 2,4-diaminodiphenylamine, 2,4-diamino-5-methyldiphenylamine, 2,4-diamino-4'-methyldiphenylamine, 1-anilino-2,4-diaminonaltalene, There are N-aryl substituted aromatic triamines such as 3,3'-diamino-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 is 2,2'-
In the present invention, bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, etc. may have an ether bond represented by the general formula [V]. It is a diamine compound that has.

[In the formula, R _{4 to} R ₇ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₈ and R ₉ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group, and may be the same or different from each other. ] A diamine compound having an ether bond represented by, for example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-bromo-4- (4-aminophenoxy) phenyl] propane, 2, 2-bis [3
-Ethyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-propyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-isopropyl-4- (4- Aminophenoxy) phenyl]
Propane, 2,2-bis [3-butyl-4- (4-aminophenoxy) phenyl] propane, 2,2 [3-sec-butyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [ 3-methoxy-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-
Aminophenoxy) phenyl] ethane, 1,1-bis [3
-Methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-bromo-
4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- ( 4-aminophenoxy) phenyl] methane, bis [3-bromo-4-
(4-Aminophenoxy) phenyl] methane, 1,1,1,3,
3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexachloro-2,2-bis- [4- (4- Aminophenoxy)
Phenyl] propane, 3,3-bis [4- (4-aminophenoxy) phenyl] pentane, 1,1-bis [4- (4
-Aminophenoxy) phenyl] propane, 1,1,1,3,3,
3-hexafluoro-2,2-bis [3,5-dimethyl-4-
(4-Aminophenoxy) phenyl] propane, 1,1,1,
3,3,3-hexafluoro-2,2-bis [3,5-dibromo-
4- (4-aminophenoxy) phenyl] propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-
4- (4-aminophenoxy) phenyl] propane and the like, and at least one of them is used.

Further, a composition which gives a cured product having low temperature, fast curing property and heat resistance by adding at least one kind of monomer having a polymerizable CH ₂ ═C group such as vinyl, allyl or acrylic compound You can get things. Examples of the monomer include methylene, vinyltoluene, α-methylstyrene, divinylbenzene, diallylphthalate,
Diallyl phthalate brepolymer, chlorostyrene, dichlorostyrene, promstyrene, dibromostyrene, diallylbenzenephosphonate, diallylarylphosphyl ester, acrylic acid, methacrylic ester, triallyl cyanurate, triallyl cyanurate prepolymer, Examples include tribromophenol allyl ether.

Also, by adding a known unsaturated polyester,
It can be modified before curing. 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. To esterification, polyester resin matrix containing an unsaturated group synthesized by condensation or addition polymerization utilizing a reaction such as transesterification, for example, a vinyl group, a polymerizable compound having an allyl group, and It is composed of a mixture with a peroxide catalyst. In addition to these, 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 anhydride, mesaconic acid, and itacone Acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, methyl glitalic acid, pimelic acid, hexahydrophthalic acid and its anhydride, tetrahydrophthalic acid, carbic anhydride , Hettic acid and its anhydride, tetrachlorophthalic acid and its anhydride, tetrabromophthalic acid and its anhydride, and their lower alkyl esters, etc. are used, and the diol components include ethylene glycol, diethylene glycol, triethylene glycol, Ethylene glycol Lumpur, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 2,2-diethyl propane diol, 1,3-neopentyl glycol, dibromo neopentyl 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,
Phenyl glycidyl ether, allyl glycidyl ether and the like are used. 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 cross-linking agent include styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, diallylbenzenephosphonate, diallylarylphosphyl ester. , Acrylic acid ester, methacrylic acid ester, triallyl cyanurate, triallyl cyanurate prepolymer, tripromophenol allyl ether and the like are used. In the present invention, the acid component, alcohol component, and 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.

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

Examples of the epoxy compound in the present invention include glycidyl ether of bisphenol A, butadiene diepoxyside, 3,4-epoxycyclohexylmethyl- (3,4-
Epoxy) cyclohexanecarboxylate, vinyl cyclohexane dioxide, 4,4'-di (1,2-epoxyethyl) diphenyl ether, 2,2-bis (3,4-epoxycyclohexyl) propane, glycidyl ether of resorcin, fluoro Diglycidyl ether of glycine, diglycidyl ether of methyl phloroglucin, bis-
(2,3-Epoxycyclobenzyl) ether, 2- (3,4
-Epoxy) cyclohexane-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, bis- (3,4
-Epoxy-6-methylcyclohexyl) adipate,
Bifunctional epoxy compounds such as N, N'-m-phenylene bis (4,5-epoxy-1,2-cyclohexanedicarboximide, triglycidyl ether of paraaminophenol, polyallylglycidyl ether, 1,3,5-triene (1,2-epoxyethyl) benzene, 2,2 ', 4,4'-tetraglycidoxybenzophenone, phenol formaldehyde novolac resin polyglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl A trifunctional or higher functional epoxy compound such as ether, a halogenated epoxy compound such as brominated epoxy, or a hydantoin epoxy compound is used.

In addition, by adding an epoxy compound or the like in combination with the phenol-formaldehyde condensate or the combination thereof, molding processability is increased, and it becomes easy to dissolve in a solvent, so that a molding composition suitable for casting use can be obtained. Obtainable.

Further, the etherimide compound of the present invention has the following formula [In the formula, R ₁₀ represents hydrogen or a methyl group, and R ₁₁ represents a divalent organic group. ] It can also be used in combination with a known bismaleimide compound represented by the above formula, and a cured product having excellent heat resistance can be obtained. Examples of the bismaleimide compound include N, N'-ethylenedimaleimide, N, N'-ethylenebis [2-methylmaleimide], N, N'-trimethylenedimaleimide, N, N'-tetramethylenediamine. Maleimide, N, N′-hexamethylenedimaleimide, N, N′-hexamethylenebis [2-methylmaleimide], N, N′-dodecamethylenedimaleimide, N,
N'-m-phenylenedimaleimide, N, N'-p-phenine dimaleimide, N, N '-(oxy-p-phenylene)
Dimaleimide, N, N '-(methylene-di-p-phenylene) dimaleimide, N, N'-(methylene-di-p-phenylene) bis [2-methylmaleimide] -N, N'-2,4-
Tolylene dimaleimide, N, N'-2,4-tolylene dimaleimide, N, N'-m-xylylene dimaleimide, N, N'-p
-Xylylene dimaleimide, N, N'-oxypropylene dimaleimide, N, N'-ethylenebis (oxypropylene maleimide), N, N'-oxydiethylene dimaleimide, etc. can be used alone or in combination of two or more. It

In the present invention, in particular, as a most suitable additive compound, it is possible to achieve both heat resistance and flexibility, and to construct a composition that is extremely soluble in general ketones and petroleum compounds. , General formula [VI] (In the formula, R _{4 to} R ₇ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₈ and R ₉ are hydrogen, a methyl group, Ethyl group, trifluoromethyl group or trichloromethyl group,
D ₁ and D ₂ represent a divalent organic group having 2 to 24 carbon atoms. ) An ether imide compound represented by
2,2-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-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-maleimidophenyloxy) 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-maleimidophenoxy) ) Phenyl] propane and the like.

Further, the compound represented by the general formula [I] of the present invention, (A is the same as above.) By using it in combination with the ortho-diallyl bisphenol compound represented by, it is possible to form a solventless varnish, and to provide a cured product having excellent heat resistance and flexibility. sell.

Examples of ortho-diallyl bisphenol compounds include: Etc., and one or more kinds can be used in combination.

The ether imide compound of the present invention is at least one of allyl esters of polyvalent carboxylic acid or cyanuric acid.
When used in combination with a seed, a resin composition having excellent high-temperature strength and fast curing is obtained, which is particularly 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. Ether, triallyl cyanurate, triallyl cyanurate prepolymer and the like. 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- Copolymers with pyrrolidone, acrylonitrile, allyl alcohol, allyl acetate, ethylene, maleic anhydride, methyl methacrylate, styrene, vinyl acetate, vinyl cyclolide, vinylene, carbonate, vinyl cyclohexyl ether, vinyl phenyl ether, etc., or Further, there are polyvinylpyrrolidone and the like, 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-stalene copolymer and butadiene-acrylonitrile copolymer,
Further, at least one kind of those having a carboxyl group, a hydroxyl group, an amino group, an aldehyde group, a nitro group, an isocyanate group and a vinyl group as a reactive group at the terminal of each of the above-mentioned polymers is used.

The ether imide 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, 3,4,9,10
-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, 3,3 ', 4,4'-benzophenone tetracarboxylic acid ,
3,3 ', 4,4'-azoxybenzenetetracarboxylic acid, 3,
3 ', 4,4'-azobenzenetetracarboxylic acid and 3,3',
There are dianhydrides such as 4,4'-diphenyloxytetracarboxylic acid.

In order to impart flexibility to the cured product obtained by heating the resin composition described in detail above, a known compound that exerts a plasticizing effect on the resin composition, such as silylphenylphosphate or trique Add at least one of resyl phosphate, trioctyl phosphate, dioctyl phthalate, dioctyl hexahydrophthalate, dilauryl succinate, higher resin family amide, silicone polymer, diglycidyl ester of diamic acid, etc. You can

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-butyl peroxyisobutyrate, di-t-butyl diperphthalate, etc. Organic peroxides are useful, and one or more of them can be used.

In the present invention, the above-mentioned polymerization catalyst includes, for example, lauryl mercaptan, N-butyl sulfite, diphenyl sulfite, p-toluenesulfonic acid, quaternary ammonium salt, β-diketone acid, peracetic acid type epoxy compound, sulfonium salt. Examples thereof include salts, manganese naphthenate, panadyl octoate, copper naphthenate, calcium naphthenate, other metal salts of naphthenic acid, metal chelate compounds, amines, phosphorus-containing compounds and sulfur-containing compounds. Further, the following polymerization inhibitors can also be used. For example, p-penzoquinone, naphthoquinone, phenanthraquinone, paraxyloquinone, 2,5-diphenyl-p-benzoquinone, 2,5
-Quinones such as diacetoxy-p-benzoquinone, hydroquinone, pt-butylcatechol, 2,5-di-
Hydroquinones such as t-butyl hydroquinone and mono-t-butyl hydroquinone, di-t-butyl, para-cresol, hydroquinone monomethyl ether, phenols such as alphanaphthol, organic and inorganic copper salts such as copper naphthenate, acetamidine acetate,
Uses amidines such as acetamidine sulphate, hydrazine salts such as phenylhydrazine hydrochloride and hydrazone hydrochloride, other quaternary ammonium salts, amines, nitro compounds, oximes, sulfur, polyvalent phenols and amine hydrochlorides To do.

〔Example〕

Example 1 2,4-bis [4- (4-aminophenoxy) phenyl]
45.2 parts by weight of 2-methylpentane was dissolved in 500 ml of acetone, and 19.6 parts by weight of maleic anhydride was added thereto, and the mixture was heated to 5 ° C.
After reacting with stirring under the following conditions, 50 parts by weight of acetic anhydride and 0.1 part by weight of potassium acetate were added in a nitrogen gas-displaced atmosphere, and 60 to 8 parts were added.
The reaction was carried out at 0 ° C for about 3 hours. Then, filtration, washing and drying were performed to obtain an etherimide compound (a).

As a result of measuring infrared absorption spectrum (IR spectrum), characteristic absorption of ether bond at 1230 to 1240 cm ⁻¹ , 1712 cm
Characteristic absorption derived from imide bond was observed at ^-1 and 1778 cm ^-1 .

Example 2 2,4-bis [4- (4-aminophenoxy) phenyl]
2-Methylpentane (45.2 parts by weight) was dissolved in methylethylketone (500 ml), and endmethylenetetrahydrophthalic anhydride (25.6 parts by weight) was stirred and reacted at 5 ° C or lower for 2 hours in a nitrogen stream, and then acetic anhydride (30 parts by weight) was added. , Lithium acetate 0.05 part by weight, triethylamine 5 ml were added, and the temperature was 60 to 80 ° C.
Then, it was reacted for 3 hours. Then, the above reaction product was treated with about 3060
Dropped into ml of distilled water to form a precipitate. This was filtered, washed, and dried to obtain an etherimide compound (b).

The IR spectrum of the ether imide compound (b), ether bond 1235cm ^-1, characteristic absorption derived from the imide bond was observed at 1715 cm ^-1 and 1780 cm ^-1.

Application Examples 1 to 11 Ether imide compounds (a) and (b) obtained in Examples 1 and 2, unsaturated polyester (PS-518 manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis [4] -(4-Aminophenoxy) phenyl] propane and an epoxy compound (novolak type; epoxy equivalent 225) were separately blended in the proportions (parts by weight) shown in Table 1 to prepare 11 kinds of blends. After further adding the fillers and additives shown in Table 1 to these, respectively, uniformly mixing with a kneader and heat-molding at 150 to 170 ° C. for 1 to 5 minutes to obtain various cured products ( A test piece) was created. Table 1 shows the properties of various cured products.

Example 3 2,4-bis [4- (4-aminophenoxy) phenyl]
Methyl pentane (45.2 parts by weight) was dissolved in acetone-toluene mixed solution (500 ml), and 12.8 parts by weight of endomethylenetetrahydrophthalic anhydride and 9.8 parts by weight of maleic anhydride dissolved in acetone were added thereto. After stirring in a nitrogen stream for a period of time, add 150 parts by weight of acetic anhydride, 0.1 parts by weight of sodium acetate and 10 ml of triethylamine,
The reaction was carried out at -80 ° C for about 3 hours. Then, this reaction product
It was added to 5000 ml of distilled water to form a precipitate. afterwards,
The etherimide compound (c) was obtained by performing filtration, washing and drying.

The IR spectrum of this etherimide compound (c) is
1235～1240Cm ^-1 ether bond, characteristic absorption derived from the imide bond was observed at 1710 cm ^-1 and 1780 cm ^-1.

Example 4 2,4-bis [4- (4-aminophenoxy) phenyl]
Dissolve 45.2 parts by weight of methyl pentane in 500 ml of acetone,
12.8 parts by weight of endomethylenetetrahydrophthalic anhydride dissolved in acetone, tetrahydrophthalic anhydride
After reacting 11.2 parts by weight at 5 ° C. or lower in a nitrogen stream for about 2 hours, 200 parts by weight of acetic anhydride, 1 part by weight of potassium acetate and 5 ml of triethylamine were added and reacted at 60 to 80 ° C. for 3 hours. Then, the above reaction product was added to 5000 ml of butyl alcohol to form a precipitate, which was then filtered, washed, and dried to obtain an etherimide compound (d).

The IR spectrum of this etherimide compound (d) is
1230～1240Cm ^-1 ether bond, characteristic absorption derived from the imide bond was observed at 1710 cm ^-1 and 1782cm ^-1.

Application Examples 12 to 19 Ether imide compounds (c) obtained in Examples 3 and 4
Various additives shown in Table 2 are added to and mixed with (d), and a test piece is prepared in the same manner as in the above-mentioned application example.
These properties were measured. The results are shown in Table 2. The compounding ratio is the polymerized part.

Example 5 2,4-bis [4- (4-aminophenoxy) phenyl]
Methylpentane (weight part) was dissolved in acetone (500 ml), methylendmethylenetetrahydrophthalic acid (18 parts by weight) was added thereto, and the mixture was stirred and reacted at 5 ° C. or lower. Add 0.2 parts by weight of lithium acetate and 3 parts by weight of triethylamine, and add at 3
Reacted for hours. Then, filtration, washing and drying were performed to obtain an etherimide compound (e).

The IR spectrum of the ether imide compound (e), ether bond 1238cm ^-1, characteristic absorption derived from the imide bond was observed at 1712 cm ^-1 and 1778cm ^-1.

Example 6 2,4-bis [4- (4-aminophenoxy) phenyl]
Dissolved in 500 parts by weight of methylpentane and 500 ml of acetone, and added to it dichloroendomethylenetetrahydrophthalic anhydride.
10 parts by weight and 6 parts by weight of maleic anhydride were added, and the mixture was reacted in a nitrogen atmosphere at room temperature or below for 5 hours with stirring.
100 parts by weight, 0.3 parts by weight of potassium acetate and 4 parts by weight of triethylamine were added, and the mixture was reacted at 60 to 80 ° C for 3 hours. Then, washing and drying were performed to obtain an etherimide compound (f).

The IR spectrum of the ether imide compound (f), ether bond 1235cm ^-1, and 1710 cm ^-1, characteristic absorption derived from the imide bond to 1780 cm ^-1 were observed.

Application Examples 20 to 31 The ether imide compounds (a), (b), (e), obtained in the above-mentioned Examples 1, 2, 5, and 6.
(F) was blended separately with various materials shown in Table 3 to prepare 12 kinds of blends. The coupling agent in Table 3 is tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate. The mixing ratio of each material is parts by weight. The obtained blend was kneaded under the same conditions as in Application Example 1 to prepare test pieces for various characteristic tests. Table 3 shows the properties of various cured products [Effects of the Invention] According to the present invention, it is possible to provide an addition reaction type resin material which gives a cured product excellent in heat resistance and flexibility and is easily dissolved in a general solvent such as ketones.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08G 59/40 NKG 8416-4J 61/12 NLJ 8215-4J 73/12 NTH 9285-4J (56) References JP-A-48-36163 (JP, A) JP-A-56-103162 (JP, A) JP-A-56-104865 (JP, A) JP-B-50-24998 (JP, B2)

Claims (1)

[Claims] 1. A general formula [I]: [Wherein D ₁ and D ₂ are And may be the same or different from each other. ] Addition reaction type ether imide compound (A), aromatic diamine, polymerizable CH ₂ ═C
At least one compound (B) selected from the group-containing monomers, unsaturated polyesters, epoxy compounds, phenol formaldehyde condensates, bismaleimides and butadiene-based compounds.
A composition containing an addition reaction type ether imide compound, characterized in that 0.1 to 9.0 parts by weight of (B) is blended with respect to parts by weight.