JPH06157457A - Unsaturated imido-based compound having alicyclic structure and its production - Google Patents

Abstract

PURPOSE:To provide a new compound highly soluble to organic solvent, to be served as a raw material for laminates for use in the electrical and electronic fields, sealers, electrical insulating materials, sliding materials and other molding materials etc., useful in the form of cured product excellent in heat resistance, low water absorptivity and flexibility. CONSTITUTION:The compound of formula I (Q is divalent organic group; A1 is of formula II, etc.; A2 is of formula III, etc.; A3 is of formula IV, etc.; R1-R6 are each H, halogen, hydrocarbon, etc.; D is divalent unsaturated organic group; x and y are each 0-10; p, q, r and s are each 1-20; t is 0 or 1), e.g. N,N'-bis(4- aminophenoxyphenyl)methanebismaleimide. The compound of the formula I can be obtained by reaction of an aromatic amino compound of formula V (B1 is of formula VI, etc.; B2 is of formula VII, etc.; B3 is of formula VIII, etc.) with an unsaturated dicarboxylic anhydride of formula IX. The compound of the formula I can be cured by mixing with a polyamine optionally in a molten state followed by press molding.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has good solubility in an organic solvent which is a raw material for laminates, encapsulating materials, insulating materials, sliding materials, and other molding materials in the fields of electricity and electronics, and heat resistance. , A novel unsaturated imide compound which gives a cured product having low water absorption and excellent flexibility, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, 4,4'-diphenylmethane bismaleimide has been known as a general-purpose bismaleimide thermosetting resin. The cured product of this compound is excellent in heat resistance, but is fragile and has high hygroscopicity. Further, the solubility in a general-purpose organic solvent is low, and it is difficult to prepare a varnish when producing a laminated plate or the like.

[0003]

The cured products of these conventional unsaturated imide compounds have excellent heat resistance and the like, but have problems such as brittleness and high hygroscopicity as described above. There was a limitation in application development.

The object of the present invention is to overcome the drawbacks of the conventional unsaturated imide compounds, and the solubility of the cured product in a general-purpose organic solvent is not significantly impaired.
It is intended to provide a novel unsaturated imide compound having improved low water absorption and flexibility of a cured product. Another object is to provide a method for producing the compound in good yield.

[0005]

As a result of intensive studies, the present inventors have found an unsaturated imide compound satisfying the above object and completed the present invention. That is,
The present invention is as follows. (1) General formula (1)

[0006]

[Chemical 8] [In formula, Q represents a C10-C15 bivalent organic group containing an alicyclic structure. A ₁ , A ₂ and A ₃ are each represented by the general formula (1) -1, the same (1) -2 and the same (1) -3.

[0007]

[Chemical 9] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogenated carbon atom having 1 to 6 carbon atoms. Represents a hydrogen group, and D represents a divalent unsaturated organic group having 2 to 24 carbon atoms). At least two of the groups including A ₁ , A ₂ and A ₃ each contain an imide group. x and y each independently represent an average repetition number of 0 to 10, and p, q, r and s each independently represent 1 to 20.
Represents the average number of repetitions of. t is 0 or 1. t =
When it is 0, a hydrogen atom is bonded to one of the three bonds from A ₃ . ] The unsaturated imide type compound represented by these. (2) General formula (2)

[0008]

[Chemical 10] [Wherein B ₁ , B ₂ and B ₃ are each represented by the general formula (2)
-1, the same (2) -2 and the same (2) -3

[0009]

[Chemical 11] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ have the same meanings as those in formula (1) -1). At least two of the groups including B ₁ , B ₂ and B ₃ each include an amino group. When t = 0, a hydrogen atom is bonded to one of the three bonds out of B ₃ . Q,
x, y, p, q, r, s and t have the same meanings as those in the general formula (1). ] And an aromatic amino compound represented by the general formula (3)

[0010]

[Chemical 12] (In the formula, the meaning of D is the same as that of the general formula (1).) An unsaturated dicarboxylic acid anhydride represented by the general formula (1) is reacted with the compound represented by the general formula (1). A method for producing a saturated imide compound.

These inventions will be described. In the unsaturated imide-based compound represented by the general formula (1), typical examples of the divalent organic group having 10 to 15 carbon atoms and containing the alicyclic structure of Q are represented by the formulas (a) and (b): (C), (d) and (e)

[0012]

[Chemical 13] And the like.

R _{1 to} R ₆ in A _{1 to} A ₃ represented by the general formula (1) -1, the same (1) -2 and the same (1) -3.
Specific examples of hydrogen atom; halogen atom such as fluorine, chlorine, bromine, iodine; linear or branched alkyl group such as methyl, ethyl, propyl, butyl, amyl and hexyl; cyclohexyl group; phenyl group 1 to 6 carbon atoms
A hydrocarbon group; a group in which one or more hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom.

The unsaturated imide compound of the present invention is obtained by reacting the aromatic amino compound represented by the general formula (2) with the unsaturated dicarboxylic acid anhydride represented by the general formula (3). Can be manufactured by. The aromatic amino compounds represented by the general formula (2) are represented by the general formula (4)

[0015]

[Chemical 14] [In formula, Q represents a C10-C15 bivalent organic group containing an alicyclic structure. C ₁ , C ₂ and C ₃ are each represented by the general formula (4) -1, the same (4) -2 and the same (4) -3.

[0016]

[Chemical 15] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogenated carbon atom having 1 to 6 carbon atoms. It represents a hydrogen group). At least two of the combined groups of C ₁ , C ₂ and C ₃ contain a nitro group. x and y
Each independently represents an average repeat number of 0 to 10,
p, q, r and s each independently represent an average repeat number of 1 to 20. t is 0 or 1. When t = 0, a hydrogen atom is bonded to one of the three bonds out of A ₃ . ] It can manufacture by reducing the aromatic nitro compound represented by these.

The reduction can be carried out by applying a known method. For example, Industrial Organic Chemistry (Tokyo Kagaku Dojin)
Examples include the catalytic reduction method described and the method of treatment with hydrazine in the presence of ferric chloride hexahydrate described in Chem. Lett., 259 (1975).

Typical examples of the aromatic nitro compounds represented by the above general formula (4) are as follows. In the formula, x = t = 0, q = 1, Q is a group derived from dipentene, and a nitro group is at the 4-position in C ₁ .
And R _{1 to} R ₄ are both hydrogen,
1,8-bis [4- (4-nitrophenoxy) phenyl] menthane, 1,8-bis [2- (4-nitrophenoxy) phenyl] mentane, 1- [2- (4-nitrophenoxy) phenyl]- Examples include 8- [4- (4-nitrophenoxy) phenyl] menthane and the like.

In the equation, x = t = 0 and q = 1,
Q is a group derived from dipentene, and R _{1 to} R
_As a group in which at least one of ₄ is a group other than a hydrogen atom, 1,8-bis [4- (4-nitrophenoxy)
-3-Methylphenyl] menthane, 1,8-bis [4-
(4-nitrophenoxy) -3,5-dimethylphenyl] menthane, 1,8-bis [4- (4-nitrophenoxy) -3-butyl-6-methylphenyl] mentane,
1,8-Bis [4- (4-nitro-5-methylphenoxy) -3-methylphenyl] menthane, 1,8-bis [4- (4-nitro-5-methylphenoxy) -3,5
-Dimethylphenyl] menthane, 1,8-bis [4-
(4-Nitro-5-methylphenoxy) -3-butyl-
6-methylphenyl] menthane, 1,8-bis [2-
(4-Nitrophenoxy) -3-methylphenyl] menthane, 1- [2- (4-nitrophenoxy) -3-methylphenyl] -8- [4- (4-nitrophenoxy)-
3-methylphenyl] menthane, 1,8-bis [4-
(3-Nitrophenoxy) -3-methylphenyl] menthane, 1,8-bis [4- (3-nitrophenoxy)-
3,5-Dimethylphenyl] menthane, 1,8-bis [4- (3-nitrophenoxy) -3-butyl-6-methylphenyl] mentane, 1,8-bis [4- (3-nitro-6- Methylphenoxy) -3-methylphenyl]
Menthane, 1,8-bis [4- (3-nitro-6-methylphenoxy) -3,5-dimethylphenyl] menthane, 1,8-bis [4- (3-nitro-6-methylphenoxy) -3 -Butyl-6-methylphenyl] menthane, 1,8-bis [2- (3-nitrophenoxy) -3
-Methylphenyl] menthane, 1- [2- (3-nitrophenoxy) -3-methylphenyl] -8- [4- (3
-Nitrophenoxy) -3-methylphenyl] menthane and the like are exemplified. Furthermore, in the same equation, x = t = 0, q
= 1 and Q is a group derived from dicyclopentadiene, the nitro group in C ₁ is at the 4-position, and R ₁ to
As a group in which both R ₄ are hydrogen atoms, bis [4
-(4-nitrophenoxy) phenyl] dicyclopentane, bis [2- (4-nitrophenoxy) phenyl] dicyclopentane, [2- (4-nitrophenoxy) phenyl]-[4- (4-nitrophenoxy) Examples include phenyl] dicyclopentane.

In the equation, x = t = 0 and q = 1,
As a group in which Q is a group derived from dicyclopentadiene, and at least one of R _{1 to} R ₄ is a group other than a hydrogen atom, bis [4- (4-nitrophenoxy) -3-methylphenyl ] Dicyclopentane, bis [4- (4-nitrophenoxy) -3,5-dimethylphenyl] dicyclopentane, bis [4- (4-nitrophenoxy) -3-butyl-6-methylphenyl] dicyclopentane , Bis [4- (4-nitro-5-methylphenoxy) -3-methylphenyl] dicyclopentane, bis [4- (4-nitro-5-methylphenoxy) -3,
5-dimethylphenyl] dicyclopentane, bis [4-
(4-Nitro-5-methylphenoxy) -3-butyl-
6-methylphenyl] dicyclopentane, bis [2-
(4-Nitrophenoxy) -3-methylphenyl] dicyclopentane, [2- (4-nitrophenoxy) -3-
Methylphenyl]-[4- (4-nitrophenoxy)-
3-methylphenyl] dicyclopentane, bis [4-
(3-Nitrophenoxy) -3-methylphenyl] dicyclopentane, bis [4- (3-nitrophenoxy)-
3,5-Dimethylphenyl] dicyclopentane, bis [4- (3-nitro-6-methylphenoxy) -3,5
-Dimethylphenyl] dicyclopentane, bis [4-
(3-Nitro-6-methylphenoxy) -3-butyl-
6-methylphenyl] dicyclopentane, bis [4-
(3-nitro-6-methylphenoxy) -3-methylphenyl] dicyclopentane, bis [2- (3-nitrophenoxy) -3-methylphenyl] dicyclopentane,
Examples include [2- (3-nitrophenoxy) -3-methylphenyl]-[4- (3-nitrophenoxy) -3-methylphenyl] dicyclopentane.

The aromatic nitro compounds represented by the general formula (4) are represented by the general formula (5)

[Chemical 16] [Wherein, E ₁ , E ₂ and E ₃ are each represented by the general formula (5)
-1, the same (5) -2 and the same (5) -3

[0022]

[Chemical 17] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are represented by the general formula (1)-
It has the same meaning as that of 1. ) Is a group represented by. t
When = 0, a hydrogen atom is bonded to one of the three bonds out of E ₃ . Q, x, y, p, q, r, s and t
Has the same meaning as that of the general formula (1). ] And the general formula (6)

[0023]

[Chemical 18] (In the formula, X represents a halogen atom or a nitro group, and R ₅
And R ₆ have the same meanings as in general formula (1) -1. It can be produced by reacting with nitrobenzene represented by the formula (1) in the presence of a basic compound.

The method for producing aromatic nitro compounds by reacting polyphenols and nitrobenzenes is as follows:
It can be carried out by a known method of reacting a phenol and a nitrobenzene derivative in the presence of a basic compound. Org.Synth., 445,
(Vol. II), US Pat. No. 4,538,006, J.Org.Che.
m., 50 (20) , 3717 (1985), J.Org.Chem., 50 (17) , 3091
(1985), JP-A-61-194055, JP-A-62-70347, Macromolecules, 25 , 64 (1992) and the like.

The polyphenols represented by the general formula (5) here are alicyclic hydrocarbons having a divalent reaction site and phenols as catalysts such as boron trifluoride and boron trifluoride ether complex. Friedel-Cra in the presence of
It can be obtained by a known method which is a kind of fts reaction (for example, Chemich Berichte, 57 , 854 (1924), British Patent No. 1043159 (1963), Dutch Patent No. 6513).
720 (1967), JP-A-4-139142, etc.).

The alicyclic hydrocarbons having a divalent reaction site used here include dipentene which gives polyphenols in which p, q, r or s is 1 in the general formula (5). , Limonene, terpinolene, terpenes such as α-, β- or γ-terpinene,
Examples thereof include dicyclopentadiene, and among these, dipentene and dicyclopentadiene are preferable.

In the general formula (5), the alicyclic hydrocarbons as a raw material which gives polyphenols in which p, q, r or s is 2 to 20 are 2 of the above-exemplified alicyclic hydrocarbons.
.About.20 mer. These oligomers are obtained by reacting the above-mentioned alicyclic hydrocarbon monomers under acidic conditions. In addition, when the alicyclic hydrocarbons and phenols described below are reacted with each other, both reactions are performed, and both reactions are simultaneously performed by selecting conditions under which the alicyclic hydrocarbons react with each other to form an oligomer. You can also

The phenols used here to react with alicyclic hydrocarbons to synthesize polyphenols include phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, butylphenol and amylphenol. ,
Hexylphenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, cyclohexylphenol, phenylphenol, chlorophenol, chlorocresol, chloroxylenol, bromophenol, bromocresol, bromoxylenol, etc. However, cresol, xylenol, and methylbutylphenol are preferable.

When synthesizing the polyphenols represented by the general formula (5) by reacting the alicyclic hydrocarbons with phenols, a compound of t = x = 0 in the general formula (5) is prepared. Is to react in the presence of an excess amount of raw material phenols with respect to the alicyclic hydrocarbons. It is a general method that phenols more than stoichiometrically required are charged in a kettle in advance, and then alicyclic hydrocarbons are dropped little by little.

At that time, in the general formula (5), t =
In order to prepare a compound of 0, x = 1 to 10, two ortho positions and one para position of the phenol molecule, a total of three reaction active points, one activity such as o-cresol, p-cresol, etc. A point is blocked by a substituent, and two active points are alive (hereinafter referred to as having two active points). It is sufficient to react a phenol with an alicyclic hydrocarbon. Since the raw material phenol has two active sites, the polyphenols produced have a chain structure without branching.

At that time, in the general formula (5), t =
1, x = 1 to 10 and y = 0 are prepared by first reacting a phenol having two active sites such as o-chlorophenol and p-bromophenol with an alicyclic hydrocarbon, and then One active point such as 2,6-xylenol, 2,4-xylenol, etc. is reacted with this (hereinafter referred to as having one active point) phenols are reacted to block the reaction active point at the end of the molecule. By synthesizing halogenated polyphenols of, and then removing the halogen atom which is a protective group by reduction, polyphenols with a chain structure having no branching and one reaction active point for each phenol in the main chain Is generated. In this case, the protecting group is limited to the halogen atom,
Similar results can be obtained by using other protecting groups depending on the reaction conditions. Then add to it 2,6-xylenol, 2,
The desired product is obtained by reacting a phenol having one active site such as 4-xylenol with a 1: 1 adduct composed of alicyclic hydrocarbons.

At this time, in the general formula (5), t =
1, x = 1 to 10 and y = 1 to 10 are produced by a method in which three active points are alive (hereinafter referred to as having three active points) and an equivalent ratio of alicyclic hydrocarbons. May be brought into close contact with each other within a range where gelation does not occur and reacted. By adjusting the charging ratio and reaction conditions in the reaction, polyphenols having a desired structure and number of nuclides can be obtained. Usually, phenols are 1 for alicyclic hydrocarbons.
It is preferably a molar ratio or more.

The nitrobenzenes represented by the general formula (6) include p-fluoronitrobenzene, p-chloronitrobenzene, p-bromochloronitrobenzene and p-
Examples thereof include iodonitrobenzene, m-dinitrobenzene, o-chloronitrobenzene and the like, but p-chloronitrobenzene and m-dinitrobenzene are preferable. Nitrobenzenes are usually used in an amount of 1.4 times or less mol, preferably 1.1 times or less mol, per 1 mol of hydroxyl groups of polyphenols. If the amount used exceeds 1.4 times, unreacted nitrobenzenes tend to remain in the product, which is not preferable. Further, an unreacted hydroxyl group may remain in the molecule of the aromatic nitro compound represented by the general formula (4) (see the explanation of C ₁ , C ₂ or C _{3 in} the same formula). If the proportion is too high, the hygroscopicity of the product becomes high, which is not preferable. Therefore, in order to avoid this, the proportion of nitrobenzenes used in the synthesis reaction is preferably 0.5 times or more moles with respect to 1 mole of hydroxyl groups of polyphenols.

Examples of the unsaturated dicarboxylic acid anhydride represented by the general formula (3) include maleic anhydride, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, pyrocinconic anhydride, and tetrahydrophthalic anhydride. Etc., or Diels-Alder reaction products of these unsaturated carboxylic acid anhydrides and dienes, such as cyclopentadiene,
At least one of cycloaddition reaction products of furan, terpinene and maleic anhydride can be used.

The aromatic amino compound represented by the general formula (2) and the unsaturated dicarboxylic acid anhydride represented by the general formula (3) are used as starting materials and represented by the general formula (1) of the present invention. The method for synthesizing the unsaturated imide compound is not limited to this, but the amic acid is prepared in the first step, and then the ring closure reaction is performed in the second step to obtain the unsaturated imide compound. There is a method.

The method for preparing the amic acid in the first step is generally a method in which an unsaturated dicarboxylic acid anhydride and an aromatic amino compound are brought into contact with each other in an organic solvent. Commonly used solvents are ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and benzonitrile, ethers such as diethyl ether, tetrahydrofuran and dioxane, methylene chloride,
Halogenated hydrocarbons such as chloroform, carbon tetrachloride and chlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, chain or cyclic esters such as ethyl acetate, butyl acetate and butyl lactone, dimethylformamide, 1-methyl An aprotic solvent such as 2-pyrrolidone, dimethylsulfoxide, dimethylacetamide, sulfolane, 1,3-dimethyl-2-imidazolidinone is used. These may be used alone or in combination of two or more.

The amount of the solvent used is 1 to 30 times by weight based on the total weight of the unsaturated dicarboxylic acid anhydride and the aromatic polyamine compound. Reaction temperature is -20 to 10
It is carried out in the range of 0 ° C, preferably in the range of room temperature to 60 ° C. If the temperature is too low, the reaction progresses slowly, and if it is too high, the purity of the target product is lowered due to by-products such as polymers. As an example of the reaction method, to an organic solvent solution of unsaturated dicarboxylic acid anhydride, aromatic polyamino compounds directly, or 0.5 ~ while stirring the organic solvent solution under a nitrogen stream.
Add slowly over 6 hours, keep warm until reaction is complete,
Continue stirring. Usually, the reaction is completed in about 2 hours after the addition is completed. After completion of the reaction, the produced amic acid may be used in the next step without isolation, or the amic acid may be isolated and purified.

The amide acid ring-closing method in the second step is carried out by advancing the dehydration reaction of the amic acid produced in the first step in an organic solvent in the presence of a catalyst. As the reaction conditions, known methods described in US Pat. No. 2444536, US Pat. No. 3018292, US Pat. No. 3018292, US Pat. No. 3127414, etc. can be applied. The dehydrating agent used is usually an acid anhydride. Among them, acetic anhydride is preferable because it is easy to handle, post-process, and industrially easily available. The amount used is 1.05 to 1.5 mol per 1 mol of amic acid. As a catalyst, 0.05 to 0.8 mol of a tertiary amine such as triethylamine is used with respect to 1 mol of amic acid.
In addition, 0.005 to 0.5 mol of a metal acetate such as nickel acetate is used with respect to 1 mol of amic acid. Reaction time is usually 3 ~
It takes about 12 hours.

As the organic solvent usually used, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and benzonitrile, ethers such as diethyl ether, tetrahydrofuran and dioxane, methylene chloride, chloroform and carbon tetrachloride. , Halogenated hydrocarbons such as chlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, chain or cyclic esters such as ethyl acetate, butyl acetate and butyl lactone, dimethylformamide, 1-methyl-
Aprotic solvents such as 2-pyrrolidone, dimethylsulfoxide, dimethylacetamide, sulfolane, and 1,3-dimethyl-2-imidazolidinone can be mentioned. These may be used alone or in combination of two or more.

As an example of the reaction method, triethylamine is added to the acetone solution of the amic acid prepared in the first step, stirred at room temperature, and then nickel acetate is added. Next, under a nitrogen stream, acetic anhydride is added dropwise in the temperature range of room temperature to 60 ° C. The time required for dropping is usually about 0.5 to 3 hours.
Insulation and stirring are continued in the temperature range of room temperature to 60 ° C. After the reaction is completed, the precipitated target substance is collected by filtration. In order to efficiently obtain the desired product, the reaction solvent may be distilled off under normal pressure or reduced pressure, or the reaction solution may be concentrated or concentrated as long as the fluidity is not impaired. good. The solvent is preferably distilled off at a temperature which does not exceed the reaction temperature for the purpose of suppressing side reactions derived from the dehydrating agent. The solvent may be distilled off while the reaction is proceeding.

After the completion of the reaction, the target substance may be dissolved in the solvent due to the difference in the type and amount of the solvent, so that it may not be precipitated in the reaction solution. In this case, the reaction solvent is distilled off under normal pressure or reduced pressure, or after the reaction mixture is concentrated to such an extent that fluidity is not impaired, it is discharged into a poor solvent such as water or methanol, or a poor solvent is used. Can be added dropwise to the reaction mixture to obtain the desired product as a solid. The amount of the poor solvent used is 0.5 to 20 times the amount of the solvent used in the reaction.

The target product obtained by the above operation is washed with a small amount of a volatile organic solvent such as acetone, and then washed with water.
After washing with water, water may be replaced with a poor solvent such as methanol.
Subsequently, the target product is dried under normal pressure or reduced pressure. The unsaturated imide compound obtained by such a method has a sufficient purity as an industrial raw material, but may be further purified by a method such as recrystallization from a solvent such as an alcohol solvent, if necessary.

The unsaturated imide compound of the present invention can be molded and cured by mixing with a polyamine, particularly a diamine, as a powder as it is, or by melt-mixing and then press-molding at a temperature of about 180 to 250 ° C. . The unsaturated imide compound of the present invention is used for laminated plates, sealing materials, insulating materials, sliding materials, and other molding materials in the fields of electricity and electronics.

[0044]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Reference Example 1 (Synthesis of Aromatic Amino Compounds Used in Example 1) (1) Synthesis of Polyphenols 188 g of phenol and 1 toluene in a 1-liter four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel.
Charge 88 g, boron trifluoride ether complex 13 g,
Dissolve under a stream of nitrogen. A solution of 136 g of dipentene dissolved in 136 g of toluene was added dropwise at a temperature of 0 to 5 ° C over 2 hours. 2 hours at 0-5 ° C, 2 at room temperature
After continuing the reaction for an hour, the temperature was raised to 60 ° C. to complete the reaction. When 250 g of a 5% aqueous sodium hydroxide solution was added and stirring was continued at room temperature for 10 minutes, the brown solution became pale yellow. After liquid separation, the organic layer was washed with 250 g of pure water three times. Dean-Stark
The reaction solution was refluxed under reduced pressure using the azeotropic dehydrator of No. 1 to separate and remove water. The solvent was concentrated under reduced pressure, and the concentrate was allowed to stand to obtain crystals. The crystals were heated under reduced pressure and dried to obtain a colorless transparent compound (176.9 g, yield 61.0).
%). The hydroxyl equivalent of this product was 162 g / eq.

(2) Synthesis of aromatic nitro compounds Polyphenols which are reaction products of dipentene and phenol obtained in (1) above in a 1 liter four-necked flask equipped with a thermometer, a stirrer and a dropping funnel. 77.5 g
And p-chloronitrobenzene 78.5g, 1-methyl-2
-Prepare 263.2 g of pyrrolidone and dissolve at 50 ° C under a nitrogen stream. Add 20.6 g of 99% powdered caustic soda, 50 ℃
After keeping the temperature at 80 ° C. for half an hour, the reaction was continued at 80 to 85 ° C. for 3 hours, and the disappearance of the raw material polyphenols was confirmed by LC (high performance liquid chromatography, the same applies hereinafter). After the temperature is raised to 125 ° C. and kept for 3 hours, the internal pressure is gradually reduced to 200 Torr, and the water in the system generated by the reaction is recovered. Next, the internal pressure was carefully reduced to 125 Torr, and the reaction solvent, 1-methyl-2-pyrrolidone, was recovered to such an extent that the fluidity of the reaction mixture was not lost.
The reaction mixture was discharged into 600 g of pure water while stirring, and the precipitated crystals were separated by filtration and washed with 300 g of water. The crystals are then washed with 200 g of warm methanol. The crystals obtained were heated under reduced pressure and dried, yielding 133.5 g (yield 97.7%).
I got the target. This compound is bis (4-nitrophenoxyphenyl) menthane. The infrared absorption spectrum of this product showed absorption at 1340 and 1512 cm ^-1 (nitro group).

(3) Synthesis of aromatic amino compounds 113.3 g of the aromatic nitro compounds obtained in (2) above, 11 g of activated carbon, 0.65 g of ferric chloride hexahydrate in a 3-liter four-necked flask. , 2-methoxyethanol (566.5 g) was charged and dissolved under a nitrogen stream. 40.0 g of hydrazine monohydrate was added dropwise at 70 to 80 ° C. over 3 hours and the reaction was continued at the same temperature, and it was confirmed by LC that the starting aromatic nitro compounds disappeared. After continuing the reaction for further 3 hours, neutralization was carried out with a 10% caustic aqueous solution, and then activated carbon was filtered off by hot filtration. After 80% of the solvent was distilled off under reduced pressure, the reaction mixture was added dropwise to 2 kg of water while stirring. The pH of the aqueous layer was adjusted to 7.0 to 9.5 with a 10% caustic aqueous solution, and stirring was continued, and then crystals were filtered. The crystals were washed with water, heated under reduced pressure and dried to obtain the desired product in an amount of 100.8 g (yield 99.5%). This compound is bis (4-aminophenoxyphenyl) menthane. This showed a solubility of 50 or more in a general-purpose solvent such as acetone or toluene (gram of solute in 100 g of solution, the same applies hereinafter). The physical properties of this product are as follows.

Mass spectrum M ⁺ = 506; Amine equivalent (by titration method) 254 g / eq; ¹ H-NMR spectrum δ: 0.6 to 2.1 ppm (m, aliphatic), 2.7 ppm (m, methine) , 3.5 ppm (brs, amino group), 6.6 to 7.3 ppm (m, aromatic); ・ Infrared absorption spectrum: 1228 cm ^-1 (ether bond), 3210, 3360, 3440 cm ^-1 (amino bond); Results (calculated as C ₃₄ H ₃₈ N ₂ O ₂ )

[0048]

[Table 1]

Reference Example 2 (Synthesis of Aromatic Amino Compounds Used in Example 2) (1) Synthesis of Polyphenols In (1) of Reference Example 1, phenol was changed to 2,6-xylenol and the reaction temperature was changed. The same reaction operation and post-treatment were carried out except that the temperature was changed to 110 ° C. The toluene solution of the reaction mixture was concentrated under reduced pressure to remove toluene. Subsequently, nitrogen was introduced under reduced pressure, and unreacted substances were removed by steam distillation to obtain a light brown crystal compound in an amount of 209.4 g (yield 55.1%). The hydroxyl equivalent of this product was 191 g / eq.

(2) Synthesis of Aromatic Nitro Compounds (2) of Reference Example 1 except that 91.3 g of the reaction product of the dipentene obtained in (1) above with 2,6-xylenol was used as the polyphenols. Perform the same reaction operation as
The desired product was obtained with 146.6 g (yield 98.3%). This compound is bis [4- (4-nitrophenoxy) -3,5-dimethylphenyl] menthane. The infrared absorption spectrum of this product showed absorption at 1338 and 1515 cm ^-1 (nitro group).

(3) Synthesis of Aromatic Amino Compounds Reduction reaction with hydrazine was carried out in the same manner as in (3) of Reference Example 1 except that 120 g of the compound obtained in (2) above was used as the aromatic nitro compounds. The desired product was obtained in an amount of 107.1 g (yield 98.8%). This compound is bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] menthane. This product exhibited a solubility of 50 or more in general-purpose solvents such as acetone and toluene. Other physical properties are shown below.

Mass spectrum M ⁺ = 562; Amine equivalent (by titration method) 282 g / eq; ¹ H-NMR spectrum δ: 0.5 to 2.4 ppm (m, aliphatic), 2.1 ppm (s, methyl) , 2.7 ppm (m, methine), 3.4 ppm (brs, amino group), 6.6 to 7.3 ppm (m,
Infrared absorption spectrum: 1218 cm ^-1 (ether bond), 3210, 3350, 3430 cm ^-1 (amino bond); Elemental analysis result (calculated as C ₃₈ H ₄₆ N ₂ O ₂ )

[0053]

[Table 2]

Reference Example 3 (Synthesis of Aromatic Amino Compounds Used in Example 3) (1) Synthesis of Polyphenols In a 1 liter four-necked flask equipped with a thermometer, a stirrer and a dropping funnel, 2,6- Xylenol (488 g) and boron trifluoride ether complex (7.1 g) are charged and heated under a nitrogen stream to dissolve. Keep the internal temperature at 100-110 ℃, and add 132.2g of dicyclopentadiene at 100-110 ℃.
Was added dropwise at the temperature of 4 hours. After continuing the reaction at a temperature of 110 ° C for 6 hours, transfer it to another container and add toluene 12
When 00 g and 1000 g of 10% aqueous sodium hydrogen carbonate were added and stirring was continued for 10 minutes at room temperature, the brown solution became pale yellow. After liquid separation,
The organic layer was washed 3 times with 500 g of pure water. The reaction solution was refluxed under reduced pressure using a Dean-Stark azeotropic dehydrator to separate and remove water. The solvent was concentrated under reduced pressure, and then excess 2,6-xylenol was distilled off. Then, nitrogen was introduced under reduced pressure, and then unreacted substances were removed by steam distillation to obtain a light yellow solid target substance. The yield was 328.3 g (yield 87.2%). The hydroxyl equivalent of this product was 188 g / eq.

(2) Synthesis of Aromatic Nitro Compounds As a polyphenol, the reaction product 30 of the dicyclopentadiene obtained in the above (1) and 2,6-xylenol 30.
The same reaction operation as in (2) of Reference Example 1 was carried out except that 0 g was used to obtain the target product in a yield of 482.3 g (yield 97.7%).
This compound is bis [4- (4-nitrophenoxy)-
3,5-dimethylphenyl] dicyclopentane.
The infrared absorption spectrum of this product is 1338, 1510 cm.
^It showed absorption at ^-1 (nitro group).

(3) Synthesis of aromatic amino compounds Reduction with hydrazine was carried out in the same manner as in (3) of Reference Example 1 except that 309.4 g of the compound obtained in (2) above was used as the aromatic nitro compounds. The reaction operation was performed to obtain the desired product in an amount of 277.2 g (yield 99.2%). This compound is bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane. This product exhibited a solubility of 50 or more in general-purpose solvents such as acetone and toluene. Other physical properties are shown below.

Mass spectrum M ⁺ = 558; Amine equivalent (by titration method) 280 g / eq; ¹ H-NMR spectrum δ: 1.1 to 3.5 ppm (m, aliphatic), 2.1 ppm (s, methyl) , 3.2 ppm (brs, amino group), 6.6 to 7.1 ppm (m, aromatic); ・ Infrared absorption spectrum: 1206 cm ^-1 (ether bond), 3200, 3350, 3430 cm ^-1 (amino bond); Results (calculated as C ₃₈ H ₄₂ N ₂ O ₂ )

[0058]

[Table 3]

Reference Example 4 (Synthesis of Aromatic Amino Compounds Used in Example 4) (1) Synthesis of Aromatic Nitro Compounds As a polyphenol, a reaction product of 2,6-xylenol and dicyclopentadiene (oligomer) ) (Nippon Oil Co., Ltd., trade name DXP-L-9-1, hydroxyl group equivalent 191 g /
eq), the same reaction operation as in (2) of Reference Example 1 was carried out to give an oligomer of dicyclopentadiene and 2,6-xylenol having a 4- (4-nitrophenoxy) -3,5-dimethylphenyl group. Obtained.

(2) Synthesis of Aromatic Amino Compounds Using the compounds obtained in (1) above as aromatic nitro compounds, the same reaction procedure as in (3) of Reference Example 1 was performed, and both ends were 4- (4-aminophenoxy) -3,5-
An oligomer of dicyclopentadiene and 2,6-xylenol having a dimethylphenyl group was obtained. This is GP
From C measurement, bis [4- (4-aminophenoxy) -3,
Contains 90% of 5-dimethylphenyl] dicyclopentane. The amine equivalent of this product is 275 g / eq.

Reference Example 5 (Synthesis of Aromatic Amino Compounds Used in Example 5) (1) Synthesis of Aromatic Nitro Compounds Oligomers of phenol and dicyclopentadiene as polyphenols (trade name, manufactured by Nippon Oil Co., Ltd.) DPP-60
0-L, hydroxyl equivalent 166 g / eq, in the general formula (5), t = 0, p = q = 1, x = 0 is 70%, and x = 1 is 22.
%, X = 2 consists of 8%. ) The same reaction operation as in (2) of Reference Example 1 was performed except that 300 g was used, and the yield was 502.0.
The desired product was obtained with g (yield 98.0%). This was a mixture of aromatic natro compounds containing 65% of bis (4-nitrophenoxyphenyl) dicyclopentane as measured by GPC. The infrared absorption spectrum of this product is 134
Absorption was observed at 0,1510 cm ^-1 (nitro group).

(2) Synthesis of Aromatic Amino Compounds As the aromatic nitro compounds, 400.0 g of the compound obtained in (1) above was used to carry out a reduction reaction with hydrazine in the same manner as in (3) of Reference Example 1. went. After the reaction, the reaction mixture was neutralized with a 10% caustic aqueous solution, activated carbon was filtered off by hot filtration, and the reaction solvent was concentrated under reduced pressure. The reaction product was dissolved in toluene and washed with water. With 10% caustic aqueous solution, the pH of the aqueous layer is
Adjusted to be 7.0-9.5. After the water content of the organic layer was removed using the Dean-Stark azeotropic dehydrator, the solvent was recovered under reduced pressure to obtain the resinous target product in an amount of 355.7 g (yield 99.1 g).
%). This is a screw (4
It was a mixture of aromatic amino compounds containing 68% of -aminonitrophenoxyphenyl) dicyclopentane.
This compound is 5 against general-purpose solvents such as acetone and toluene.
It had a solubility of 0 or higher. Other physical properties are shown below.

Mass spectrum M ⁺ = 820, 502, 452; ¹ H-NMR spectrum δ: 1.0 to 3.6 ppm (m, aliphatic), 3.2 ppm (brs, amino group), 6.5 to 7.2 ppm
(M, aromatic); ・ Infrared absorption spectrum: 1212 cm ^-1 (ether bond), 3210, 3350, 3440 cm ^-1 (amino bond); ・ Amine equivalent 257 g / eq;

Example 1 [Synthesis of N, N'-bis (4-aminophenoxyphenyl) menthane bismaleimide (Compound 1)] Maleic anhydride 1 was added to a 300 ml four-necked flask.
0.8 g and 25.2 g of acetone were charged and dissolved under stirring in a nitrogen stream. Reference Example 1 while maintaining the temperature between room temperature and 35 ° C
25.3 g (amine equivalent 253 g / eq) of bis (4-aminophenoxyphenyl) menthane synthesized in
The solution dissolved in g was added dropwise over 2 hours. Stirring was continued for another 3 hours. Next, after adding 3.04 g of triethylamine and stirring at room temperature for half an hour, 0.11 g of nickel acetate was added and the temperature was raised to 40 ° C. After adding 13.3 g of acetic anhydride dropwise over 1 hour, the reaction was continued at the same temperature. After the reaction was completed, 200 g of pure water was added dropwise to crystallize the reaction mixture. The crystals were collected by filtration, washed with water, then with methanol and dried. This was recrystallized from methyl cellosolve / isopropanol to obtain 23.5 g (yield 70.6%) of yellow crystals. Table 7 shows the solubility of this product in acetone and toluene. Other physical properties are shown below.

Mass spectrum M ⁺ = 666; Melting point 96 to 98 ° C. ¹ H-NMR spectrum δ: 0.6 to 2.1 ppm (m, aliphatic), 2.8 ppm (m, methine), 6.8 ppm (s, Imido group), 6.9 to 7.4 ppm (m, aromatic); Infrared absorption spectrum: 1238 cm ^-1 (ether bond), 1712 cm ^-1 (imide bond); Elemental analysis result (C ₄₂ H ₃₈ N ₂ O ₆ Calculated as)

[0066]

[Table 4]

Example 2 [Synthesis of N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] menthane bismaleimide (Compound 2)] Maleic anhydride was placed in a 500 ml four-necked flask. 3
2.6 g and 76 g of acetone were charged, and they were dissolved by stirring under a nitrogen stream. Reference Example 2 while maintaining the temperature between room temperature and 35 ° C
Bis [4- (4-aminophenoxy) -3, synthesized in
5-Dimethylphenyl] menthane (amine equivalent 281 g
/ Eq) 84.9 g dissolved in 198 g of acetone was added dropwise over 2 hours. Stirring was continued for another 3 hours. Next, after adding 3.04 g of triethylamine and stirring at room temperature for half an hour, 0.29 g of nickel acetate was added and the temperature was raised to 40 ° C. Acetic anhydride 4
After 0.1 g was added dropwise over 1 hour, the temperature was maintained at the same temperature until the reaction was completed. After the reaction was completed, the reaction mixture was discharged into 600 g of pure water. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried. Yield of yellow crystals 1
It was obtained in an amount of 08.0 g (yield 98.9%). A portion was recrystallized from methyl cellosolve / isopropanol. Table 7 shows the solubility of this product in acetone and toluene. Other physical properties are shown below.

Mass spectrum M ⁺ = 722; ¹ H-NMR spectrum δ: 0.6 to 2.2 ppm (m, aliphatic), 2.1 ppm (m, methyl group), 6.8 ppm (s, imide group), 6.8 to 7.2 ppm (m, aromatic); and infrared absorption spectrum: 1222cm ^-1 (ether bonds), 1716 cm ^-1 (imide bond); elemental analysis (calculated as _{C 46 H 46 N 2 O 6} )

[0069]

[Table 5]

Example 3 [Synthesis of N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane bismaleimide (Compound 3)] Anhydrous in a 1-liter four-necked flask. 51.3 g of maleic acid and 119.7 g of acetone were charged and dissolved by stirring under a nitrogen stream. While maintaining the temperature at room temperature to 35 ° C., 132.5 g of bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane synthesized in Reference Example 3 (amine equivalent of 279 g / eq) was added to 309.2 g of acetone. 2 melted solutions
Dropped over time. Stirring was continued for another 3 hours. Next, 14.4 g of triethylamine was added and stirred at room temperature for half an hour, 0.50 g of nickel acetate was added, and the temperature was raised to 40 ° C. Acetic anhydride
After 63.0 g was added dropwise for 1 hour, the temperature was kept at the same temperature until the reaction was completed. After the reaction was completed, the reaction mixture was discharged into 1000 g of pure water. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried. The desired product of yellow crystals was obtained in a yield of 141.7 g (83.0% yield). Table 7 shows the solubility of this product in acetone and toluene. Other physical properties are shown below.

Mass spectrum M ⁺ = 718; ¹ H-NMR spectrum δ: 1.0 to 2.4 ppm (m, aliphatic), 2.1 ppm (m, methyl group), 2.7 ppm (m, methine), 6.8 ppm ( s, imide group), 6.6 to 7.3 ppm (m, aromatic); ・ Infrared absorption spectrum: 1222 cm ^-1 (ether bond), 1714 cm ^-1 (imide bond); ・ Elemental analysis result (C ₄₆ H ₄₂ N ₂ Calculated as O ₆ )

[0072]

[Table 6]

Example 4 [4- (4-aminophenoxy)]
Synthesis of Maleimide (Compound 4) Derived from Oligomers of 2,6-Xylenol Having a 3,5-Dimethylphenyl Group and Dicyclopentadiene] A 1-liter four-necked flask was charged with 58.8 g of maleic anhydride and 137.2 g of acetone. Then, the mixture was stirred and dissolved under a nitrogen stream. While maintaining the temperature at room temperature to 35 ° C., 150.0 g of an oligomer of 2,6-xylenol and dicyclopentane having a 4- (4-aminophenoxy) -3,5-dimethylphenyl group synthesized in Reference Example 4 was added to 350 g of acetone. The solution dissolved in was added dropwise to the flask over 2 hours. Stirring was continued for another 3 hours. Next, after adding 16.6 g of triethylamine and stirring at room temperature for half an hour, 0.58 g of nickel acetate was added and the temperature was raised to 40 ° C. After 72.4 g of acetic anhydride was added dropwise over 1 hour, the temperature was kept at the same temperature until the reaction was completed. After the reaction was completed, the reaction mixture was discharged into 1000 g of pure water. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried. Yield 189.4 g (97.9% yield) of the desired product as yellow crystals.
Got with. Table 7 shows the solubility of this product in acetone and toluene. Other physical properties are shown below.

Mass spectrum M ⁺ = 718; ¹ H-NMR spectrum δ: 1.0 to 2.5 ppm (m, aliphatic), 2.7 ppm (m, methine), 6.8 ppm (s, imido group), 6.5 to 7.3 ppm (m, aromatic); ・ Infrared absorption spectrum: 1220 cm ^-1 (ether bond), 1714 cm ^-1 (imide bond);

Example 5 [Synthesis of maleimide (compound 5) having 4-aminophenoxy group and derived from an oligomer of phenol and dicyclopentadiene] 62.9 g of maleic anhydride and 146.8 g of acetone were placed in a 1-liter four-necked flask. It was charged and stirred under a nitrogen stream to dissolve it. A solution prepared by dissolving 150.0 g of an oligomer of phenol and dicyclopentadiene (amine equivalent 257 g / eq) having 4-aminophenoxyphenyl groups at both ends synthesized in Reference Example 5 while keeping the temperature at room temperature to 35 ° C in 350.0 g of acetone. Was dropped into the flask in 2 hours. Stirring was continued for another 3 hours. Next, add 17.7 g of triethylamine and stir at room temperature for half an hour, then add 0.62 g of nickel acetate and 40 ° C.
The temperature was raised to. After adding 77.4 g of acetic anhydride over 1 hour,
The temperature was maintained at the same temperature until the reaction was completed. After the reaction was completed, the reaction mixture was discharged into 1000 g of pure water. The crystals are filtered off,
It was washed with water and then with methanol, heated under reduced pressure and dried. Yield 191.7 g of the desired product as yellow crystals (yield 97.4
%). Table 7 shows the solubility of this product in acetone and toluene. Other physical properties are shown below.

Mass spectrum M ⁺ = 662, 1060; ¹ H-NMR spectrum δ: 1.0 to 2.5 ppm (m, aliphatic), 2.7 ppm (m, methine), 6.8 ppm (s, imido group), 6.6 -7.3 ppm (m, aromatic);-Infrared absorption spectrum: 1222 cm ^-1 (ether bond), 1712 cm ^-1 (imide bond);

[0077]

[Table 7]

Table 7 shows the solubilities of the compounds 1 to 5 and the comparative compound in acetone and toluene at 25 ° C. When the solubilities are 40 or more, ◯ is shown, and when the solubilities are less than 40, x is shown.

The notes to Table 7 are: * 1) N, N'-bis (4-aminophenoxyphenyl)
Menthane bismaleimide (synthetic product of Example 1); * 2) N, N'-bis [4- (4-aminophenoxy)-
3,5-Dimethylphenyl] menthane bismaleimide (synthetic product of Example 2); * 3) N, N′-bis [4- (4-aminophenoxy)-
3,5-Dimethylphenyl] dicyclopentane bismaleimide (synthetic product of Example 3); * 4) 2,6-xylenol having a 4- (4-aminophenoxy) -3,5-dimethylphenyl group and di- Maleimide derived from cyclopentadiene oligomer (synthetic product of Example 4); * 5) Maleimide derived from phenol having 4-aminophenoxyphenyl group and dicyclopentadiene oligomer (synthetic product of Example 5); * 6 ) N, N'-4,4'-diphenylmethane bismaleimide (Sumitomo Chemical Co., Ltd., trade name Bestlex BH-18
0);

Application Examples 1 to 3, Comparative Application Example 1 As unsaturated imide compounds, obtained in Examples 1 to 3.
Compounds 1, 2 and 3 were used with the respective curing agents
As 4,4'-diaminodiphenylmethane (Sumitomo Chemical
200 after blending with a trade name, Sumicure M)
℃, 70kg / cm ²After press molding for 1 hour at 4 ° C at 200 ° C
After curing for 2 hours, a cured product having a thickness of 2 mm was obtained. In addition, unsaturated
As the amide-based compound, N, N'-4,4'-diphenylme
Tanbismaleimide (Sumitomo Chemical Co., Ltd., trade name best
Rex BH-180) except that the same as the above application example
To produce a cured product (Comparative Application Example 1). These cured products
The physical properties of are shown in Table 8.

The methods for measuring the physical properties of the cured product are as follows. -Heat resistance: Shown by the glass transition temperature (Tg). It was measured using a thermomechanical analyzer (SHIMADZU DT-4).・ Bending strength and flexural modulus: According to JIS K-6911,
It was measured at 240 ° C. with an Instron universal material testing machine (SHIMADZU IS-10T). -Absorptivity: The absorptivity after boiling for 3 hours was shown.

[0082]

[Table 8]

The notes to Table 8 are: * 1) N, N'-bis (4-aminophenoxyphenyl)
Menthane bismaleimide; * 2) N, N'-bis [4- (4-aminophenoxy)-
3,5-Dimethylphenyl] menthane bismaleimide; * 3) N, N′-bis [4- (4-aminophenoxy)-
3,5-Dimethylphenyl] dicyclopentane bismaleimide; * 4) N, N'-4,4'-diphenylmethane bismaleimide (Sumitomo Chemical Co., Ltd., trade name Bestlex BH-18
0); * 5) 4,4'-diaminodiphenylmethane (Sumitomo Chemical Co., Ltd., trade name Sumicure M);

[0084]

INDUSTRIAL APPLICABILITY The unsaturated imide compound having an alicyclic structure of the present invention has excellent solubility in general-purpose organic solvents, and its cured product has heat resistance, low absorption, flexibility and the like. Are better. Further, according to the production method of the present invention, the above unsaturated imide compound can be obtained in high yield.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location // C08F 299/02 MRR 7442-4J (72) Inventor Shuichi Kanagawa 6 Kitahara, Tsukuba, Ibaraki Sumitomo Industrial stock company

Claims (4)

[Claims] 1. A general formula (1): [In formula, Q represents a C10-C15 bivalent organic group containing an alicyclic structure. A ₁ , A ₂ and A ₃ are each represented by the general formula (1) -1, the same (1) -2 and the same (1) -3. (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogenated carbon atom having 1 to 6 carbon atoms. Represents a hydrogen group, and D represents a divalent unsaturated organic group having 2 to 24 carbon atoms). At least two of the groups including A ₁ , A ₂ and A ₃ each contain an imide group. x and y each independently represent an average repetition number of 0 to 10, and p, q, r and s each independently represent 1 to 20.
Represents the average number of repetitions of. t is 0 or 1. t =
When it is 0, a hydrogen atom is bonded to one of the three bonds from A ₃ . ] The unsaturated imide type compound represented by these. 2. In the general formula (1), x = t = 0 and q
= 1 and Q is formula (a) or formula (b) The unsaturated imide compound according to claim 1, which is a group represented by: 3. In the general formula (1), x = t = 0 and q
= 1 and Q is the formula (c) The unsaturated imide compound according to claim 1, which is a group represented by: 4. A general formula (2): [Wherein B ₁ , B ₂ and B ₃ are each represented by the general formula (2)
-1, the same (2) -2 and the same (2) -3 (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ have the same meanings as those in formula (1) -1). At least two of the groups including B ₁ , B ₂ and B ₃ each include an amino group. When t = 0, a hydrogen atom is bonded to one of the three bonds out of B ₃ . Q,
x, y, p, q, r, s and t have the same meanings as those in the general formula (1). ] And an aromatic amino compound represented by the general formula (3): (In the formula, the meaning of D is the same as that of the general formula (1).) An unsaturated dicarboxylic acid anhydride represented by the formula (1) is reacted with the unsaturated imide compound according to claim 1. Production method.