TWI551591B - Benzofuran derivative composition, polyimide precursor composition, polyimide resin and manufacturing method for the same - Google Patents

Description

Benzofuran derivative composition, polyimine precursor composition, Polyimine resin and method of producing the same

The present invention relates to a benzofuran derivative composition, a polyimide intermediate precursor composition, and a method for producing a polyimide resin.

Polyimine is a kind of super engineering plastics. Compared with other polymer materials, it is not only highly resistant to heat, but also has excellent performance in terms of mechanical strength or chemical resistance. Further, since it has a low dielectric constant, excellent electrical insulating properties, rich stretch characteristics, and small thermal expansion coefficient, it has been used in industrial products such as an insulating layer for an electronic circuit and a binder for supporting a conductive material.

In general, polyimine lacks solubility in a solvent and is difficult to process, and therefore, in many cases, it is used in a state of a composition containing a precursor and is formed into a desired shape, followed by heating to thereby form a poly Yttrium.

Such a composition is usually treated by coating, in order to avoid It is necessary to use a solvent having a high polarity and a high solubility without viscous modification or precipitation which hinders the film formation property at the time of coating, and N-methyl-2-pyrrolidone and dimethyl are widely used. Azulene, N,N-dimethylformamide, N,N-dimethylacetamide, and the like. On the other hand, it has been pointed out that reproductive toxicity may occur in these solvents or nitrogen oxides or sulfur oxides may be generated during incineration, and the environmental load is large, and the problem cannot be solved without special equipment or protective equipment. .

Polyimine precursors are more unstable to water, so they are When water is used as a water-based composition of a solvent or a dispersion medium, it is difficult to maintain a property suitable for coating without causing gelation or precipitation, and there is a problem in processing property or storage stability when the composition is applied and dried.

However, N- is used as a medium for the composition containing the polyimide precursor. Aprotic polar solvent such as methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylhydrazine, etc. The base has high skin permeability and is biologically toxic, and generates nitrogen oxides or the like upon combustion, and corresponds to a solvent having a high environmental load. Further, since these organic solvents are relatively expensive solvents, they also cause an increase in manufacturing cost.

Therefore, the polyimine precursor has been dissolved or dispersed in an aqueous medium. The water system composition was studied. For example, Patent Document 1 to Patent Document 3 disclose a method of producing an aqueous resin composition of a polyimide precursor by forming a salt of a polyimine precursor (polyglycine) and a specific amine, but When it is left for a long time at normal temperature, agglomerates, precipitates, and gels are generated, and good coating or the like cannot be performed, and sufficient storage stability cannot be obtained.

On the other hand, it is disclosed in Patent Document 4 that it is used as a polyimine. The carboxyl group of the polyglycine of the precursor reacts with a vinyl ether compound or the like, and introduces a protective group via a hemiacetal ester bond, but in the presence of water molecules, the hemiacetal ester bond is easy even at room temperature. Decomposition is carried out and deterioration of acetaldehyde and alcohol is caused, so that practical storage stability cannot be obtained.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Special Prozhao 43-13387

Patent Document 2: Japanese Patent Laid-Open No. 58-162658

Patent Document 3: Japanese Patent Laid-Open 2003-13351

Patent Document 4: Japanese Patent Laid-Open No. 2009-242539

Therefore, an object of the present invention is to provide an aqueous composition of a polyimide precursor which is excellent in coatability and storage stability, and which is excellent in solvent resistance and water resistance of a cured product, and a polyimide resin (hardened). Method of manufacturing).

The inventors of the present invention have made an effort to study the above-mentioned problems, and as a result, it has been found that the aqueous composition (polyimine precursor composition) of the polyimide intermediate precursor is excellent in applicability and storage stability, and The polyimine resin obtained by hardening is also excellent in solvent resistance and water resistance, and the present invention has been completed. The aqueous composition of the polyimide precursor is in an aqueous medium and will be specific benzofuran. Chemical The benzofuran derivative obtained by adding a specific tetracarboxylic acid to a double bond of a five-membered ring of a benzofuran compound is obtained by mixing with a specific polyamine.

That is, the present invention is the following (1) to (4).

(1) A benzofuran derivative composition comprising a benzofuran derivative represented by the following formula (1) and an aqueous medium.

In the formula (1), X is a tetravalent organic group (excluding a group having reactivity with an amine group), and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen. An atom, a halogen atom or a monovalent organic group (except for those which are reactive with an amine group or a carboxyl group). R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to represent a cyclic structure]

(2) A polyimine precursor composition comprising a benzofuran derivative represented by the following formula (1), a polyamine represented by the following formula (C), and an aqueous medium.

In the formula (1), X is a tetravalent organic group (excluding a group having reactivity with an amine group), and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen. An atom, a halogen atom or a monovalent organic group (except for those which are reactive with an amine group or a carboxyl group). R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to represent a cyclic structure. In the formula (C), Y is an m-valent organic group (excluding a group having reactivity with a carboxyl group), and m is an integer of 2 or more]

(3) A method for producing a polyimine resin, comprising: a step of producing a composition of a benzofuran derivative, wherein the benzofuran compound represented by the following formula (A) is represented by the following formula (B) a tetracarboxylic acid, and an aqueous medium are mixed and stirred; a polyiminoimine precursor composition manufacturing step, the benzofuran derivative obtained in the step of producing the benzofuran derivative composition, and The polyamine represented by the formula (C) and the aqueous medium are mixed and stirred; a polyimine resin manufacturing step of heat-treating the polyimine precursor composition containing the polyimine precursor and the aqueous medium obtained in the production step of the polyimide intermediate composition It hardens.

[In the formula (A), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a monovalent organic group (except for those having reactivity with an amine group or a carboxyl group) R ³ , R ⁴ , R ⁵ and R ⁶ may each be bonded to each other to represent a cyclic structure. In the formula (B), X is a tetravalent organic group (except for those having a reactivity with an amine group). In the formula (C), Y is an m-valent organic group (excluding a group having reactivity with a carboxyl group), and m is an integer of 2 or more]

(4) A polyimine resin obtained by the method for producing a polyimide resin according to the above (3).

According to the present invention, it is possible to provide an aqueous composition of a polyimide polyimide precursor which is excellent in coatability and storage stability, and which is excellent in solvent resistance and water resistance of a polyimide resin, and a polyimide resin. Production method.

One of the features of the present invention resides in that a hemiacetal ester bond is formed in a polyimine precursor by an addition reaction of a carboxyl group derived from a tetracarboxylic acid with a benzofuran compound.

The hemiacetal bond formed by the reaction of the benzofuran compound with a carboxyl group has hydrolysis resistance, and it is difficult to cause deprotection caused by the detachment of the protective group of the carboxyl group, and thus the stability of the polyimide precursor in an aqueous medium is obtained. The high-polyimine precursor composition has excellent storage stability. With regard to such hydrolysis resistance, the inventors have estimated that a hemiacetal ester bond formed by a reaction between a vinyl ether compound and a carboxyl group described in Patent Document 4 can have a planar structure, and water can be easily added, thereby being resistant to water. The solution is low, but the hemiacetal ester bond formed by the reaction of the benzofuran compound with the carboxyl group cannot obtain a planar structure due to the steric hindrance generated by the five-membered ring of the benzofuran compound, and the water It is difficult to add, whereby the hydrolysis resistance becomes high. Further, it is considered that the stability is not only high in an aqueous medium but also in an organic solvent.

Further, the hemiacetal bond formed by the reaction of the benzofuran compound and the carboxyl group is rapidly decomposed by heating to 170 ° C or higher, and the benzofuran compound is detached, so that the carboxyl group can be protected until it is heated at 200 ° C or higher. Until the imidization treatment. Further, since the detached benzofuran compound is vaporized by heating, the benzofuran compound remains extremely little in the ruthenium imidized polyimide, and the solvent resistance of the polyimide resin is not impaired. Water resistance.

Thereby, the following polyimine precursors can be obtained: although the carboxylate is preserved The group is protected and in a stable state, but becomes substantially pure polyimine resin after imidization.

Hereinafter, the present invention will be described in detail.

The method for producing a polyimine resin of the present invention comprises a step of producing a benzofuran derivative composition, a step of producing a polyimide precursor composition, and a step of producing a polyimide resin.

In the step of producing a benzofuran derivative composition, a benzofuran derivative composition containing a benzofuran derivative and an aqueous medium is produced, and a benzofuran derivative is produced in the production step of the polyimine precursor composition. A composition of a polyimine precursor of a composition and a polyamine and an aqueous medium.

1. A step of producing a benzofuran derivative composition

The step of producing a benzofuran derivative composition is a step of mixing an benzofuran compound, a tetracarboxylic acid, and an aqueous medium, and stirring to prepare an aqueous composition of a benzofuran derivative (benzofuran derivative composition) .

<benzofuran compound and tetracarboxylic acid>

The benzofuran compound used in the production step of the benzofuran derivative composition is represented by the following formula (A), and the tetracarboxylic acid is represented by the following formula (B).

In the formula (A), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a monovalent organic group (except for those having reactivity with an amine group or a carboxyl group). R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to represent a cyclic structure. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} determined according to the benzofuran compound.

Examples of the monovalent organic group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group. (aryl group) and so on. Among these, an alkyl group is preferred, and a C _1-3 alkyl group selected from a methyl group, an ethyl group, a propyl group and an isopropyl group is more preferred, and a methyl group is more preferred. Any hydrogen atom of the monovalent organic group may be substituted by a halogen atom. As the halogen atom, a fluorine atom is preferred. However, it is not limited to these bases.

Examples of the organic group reactive with the amine group include a carboxyl group, a carboxylic anhydride group, a carbonyl group, an aldehyde group, a halogeno-carbonyl group, and the like, but are not limited thereto. In addition, examples of the organic group reactive with a carboxyl group include an amine group, a hydroxyl group, a carboxyl group, a vinyloxy group, and the like, but are not limited thereto.

Specific examples of the benzofuran compound include 1-benzofuran (2,3-benzofuran), 2,3-dimethylbenzofuran, psoralen, and isopeptide. Bilisterol (angelicin) and the like. Among these, 1-benzofuran or 2,3-dimethylbenzofuran is preferred, and 1-benzofuran is more preferred.

The benzofuran compound may be used alone or in combination of two or more.

In the formula (B), X is a tetravalent organic group (except for those having a reactivity with an amine group). X is determined according to the tetracarboxylic acid.

Examples of the tetravalent organic group include a compound obtained by removing any four hydrogen atoms from a compound such as the following: a compound having a chain hydrocarbon such as ethylene or propane in the basic skeleton, and having a ring in the basic skeleton. a compound having a cyclic hydrocarbon such as an alkane, a compound having an aromatic hydrocarbon such as benzene or naphthalene in a basic skeleton, a compound having a benzophenone skeleton such as benzophenone, a compound having a diphenyl ether skeleton such as diphenyl ether, or the like. A compound having a diphenylfluorene skeleton such as phenylhydrazine or a compound having a biphenyl skeleton such as biphenyl. However, it is not limited to these bases.

Examples of the group reactive with the amine group include a carboxyl group, a carboxylic acid anhydride group, a carbonyl group, an aldehyde group, a halogenated carbonyl group, and the like, but are not limited thereto.

Specific examples of the tetracarboxylic acid include 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 1, 2,3,4-benzenetetracarboxylic acid (benzoic acid), 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6 -naphthalenetetracarboxylic acid, 3,4,9,10-nonanetetracarboxylic acid, 2,3,6,7-nonanetetracarboxylic acid, 1,2,7,8-phenanthrenetetracarboxylic acid (phenanthrene-1, 2 ,7,8-tetracarboxylic acid), 3,3',4,4'-benzophenone-3,3',4,4'-tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylate Acid, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}one, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}one, Bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}one, bis{4-[3-(1,2-dicarboxy)phenoxy}phenyl}one, 3, 3',4,4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2',6,6'-biphenyltetracarboxylic acid, double (3, 4-dicarboxyphenyl)ether, 4,4'-bis[4-(1,2-dicarboxy)phenoxy}biphenyl, 4,4'-bis[3-(1,2-dicarboxy) Phenoxy]biphenyl, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, 1,1-bis(2,3-dicarboxyphenyl)ethane , 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2-double {4-[4-(1,2 -dicarboxy)phenoxy]phenyl}propane, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}propane, 2,2-bis (3,4 -dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3 -hexafluoropropane, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3-hexafluoropropane, 2, 2-double {4-[3-(1,2-dicarboxyl) Phenoxy]phenyl}-1,1,1,3,3,3-hexafluoropropane, 1,3-bis[(3,4-dicarboxy)benzylidene]benzene, 1,4- Bis[(3,4-dicarboxy)benzylidene]benzene, bis(3,4-dicarboxyphenyl)fluorene, bis{4-[4-(1,2-dicarboxy)phenoxy]benzene碸}, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}indole, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl} Sulfide, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl} sulfide, and the like.

The tetracarboxylic acid is preferably an aromatic tetracarboxylic acid from the viewpoints of heat resistance and linear thermal expansion coefficient of the polyimine resin obtained by drying the polyimine precursor composition and hardening it. The acid is more preferably 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 1,2,3,4-benzenetetracarboxylic acid (benzoic acid), 3,3', 4, 4'-benzophenone tetracarboxylate Acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,3,2',3'-biphenyltetracarboxylic acid, 2,2',6,6'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1 , 3,3,3-hexafluoropropane, or bis(3,4-dicarboxyphenyl)ether.

As the tetracarboxylic acid, from the viewpoint of the stability of the hemiacetal ester bond, it is preferred Is 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,3,2',3'-biphenyltetracarboxylic acid, or Bis(3,4-dicarboxyphenyl)ether.

The tetracarboxylic acid may be used alone or in combination of two or more.

<aqueous medium>

The aqueous medium is a medium containing water as a main component. As the water, ion-exchanged water, distilled water, deionized distilled water, reverse osmosis-treated water (RO water) or the like can be used. Here, the term "water as a main component" means water containing 60% by mass or more, preferably 75% by mass or more, and more preferably 90% by mass or more.

The environmental load can be reduced by using an aqueous medium.

In order to impart wettability and anticorrosive effect to the substrate, a known alcohol or ether which has a small environmental load and does not adversely affect the volatility and drying property of water may be contained in the aqueous medium. For example, methanol, ethanol, n-propanol, 2-propanol (isopropanol), n-butanol, isobutanol, tert-butanol, butyl cellosolve, propylene glycol monomethyl ether, 1-(2-hydroxyl Ethyl)-2-pyrrolidone and the like.

These alcohols or ethers may be used alone or in combination of two or more.

The ratio of the alcohol in the aqueous medium when the alcohol is added to the aqueous medium is preferably 1% by mass or more, less than 40% by mass, and more preferably 5% by mass or more and 25% by mass or less. If the ratio of the alcohol is 1% by mass or more, the coating composition is based on the base. The effect of improving the wettability of the material is exerted, and the collapse of the coating composition on the substrate is suppressed. In addition, when the ratio of the alcohol is less than 40% by mass, the crystal is not precipitated in the polyimide precursor composition, and the coating composition is easily placed on the substrate in a film form. When the ratio of the alcohol is less than 1% by mass, the effect of improving the added alcohol may be insufficient, and the desired effect may not be obtained. In addition, when the ratio of the alcohol is 40% by mass or more, the crystal may be precipitated in the polyimide precursor composition, and it is difficult to arrange the coating composition on the substrate in a film form.

<Method for Producing Benzofuran Derivative Composition>

The benzofuran compound, the tetracarboxylic acid, and the aqueous medium are mixed and stirred to prepare an aqueous composition of the benzofuran derivative.

According to this method, it is not necessary to use an organic solvent having a high environmental load, and the benzofuran compound and the tetracarboxylic acid are reacted in an aqueous medium to obtain an aqueous composition of the benzofuran derivative, so that it is not necessary to recover the benzoic acid as a reaction product. The furan derivative is mixed in an aqueous medium, and the number of steps can be reduced.

In general, the molar number of the benzofuran compound is preferably from 0.5 to 4 times the number of moles based on the number of moles of the tetracarboxylic acid, and more preferably from 1 to 2 times the number of moles.

The method of mixing the benzofuran compound, the tetracarboxylic acid, and the aqueous medium is not particularly limited, and examples thereof include an aqueous composition containing a benzofuran compound and an aqueous medium, and an aqueous composition containing a tetracarboxylic acid and an aqueous medium. a method of mixing and stirring; adding a benzofuran compound to an aqueous composition containing a tetracarboxylic acid and an aqueous medium, and stirring; adding four to an aqueous composition containing a benzofuran compound and an aqueous medium A carboxylic acid, a method of stirring, and the like.

The temperature (reaction temperature) at the time of mixing and stirring is not particularly limited as long as it is a temperature at which an addition reaction can be carried out, but is preferably 5 to 45 ° C, more preferably 20 to 30 ° C, and still more preferably About 25 ° C.

The stirring time is not particularly limited as long as the addition reaction can be sufficiently carried out, but is preferably from 30 minutes to 6 hours, more preferably from 1 hour to 3 hours, still more preferably about 2 hours.

The environment in which the benzofuran derivative composition is produced is not particularly limited, and an environment such as an atmospheric environment, a nitrogen atmosphere, or an inert gas atmosphere can be used.

Further, the form for producing the benzofuran derivative composition may be in a continuous form or in a batch form.

<catalyst>

Further, a mixed solution of a benzofuran compound, a tetracarboxylic acid, and an aqueous medium may further contain a catalyst for promoting a reaction between the benzofuran compound and the tetracarboxylic acid.

The catalyst for promoting the reaction between the benzofuran compound and the tetracarboxylic acid is, for example, a catalyst for promoting the addition reaction of the double bond of the five-membered ring of the benzofuran compound and the carboxyl group of the tetracarboxylic acid. The catalyst is not particularly limited, and specific examples thereof include those in which an enol such as titanium tetrachloride or tin tetrachloride having a higher acidity than a carboxylic acid is promoted.

The catalyst may be used singly or in combination of two or more.

<benzofuran derivative composition>

Produced by the method for producing the benzofuran derivative composition A benzofuran derivative represented by the following formula (1) and a benzofuran derivative composition of an aqueous medium.

Formula (1), in ^{R 1, R 2, R 3} , R 4, R 5 and R meanings ^6, respectively of formula ^{(A) R 1, R 2} , R 3, R 4, R 5 and R ⁶ Similarly, the meaning of X is the same as X in the formula (B).

The benzofuran derivative composition may contain, in addition to the benzofuran derivative represented by the formula (1) and an aqueous medium, an unreacted benzofuran compound or a tetracarboxylic acid, and a molecular addition to the tetracarboxylic acid a benzofuran derivative of a benzofuran compound of 2 molecules to 4 molecules.

2. Polyimine precursor composition manufacturing steps

The polyimine precursor composition is produced by mixing a benzofuran derivative, a polyamine, and an aqueous medium, and stirring to produce an aqueous composition of the polyimide precursor (polyimine precursor composition) )A step of.

<benzofuran derivative / aqueous medium>

The benzofuran derivative is synthesized in the step of producing a benzofuran derivative composition, and becomes an aqueous composition when reacted in an aqueous medium.

The aqueous medium is as described above.

<polyamine>

The polyamine used in the production step of the polyimine precursor composition is represented by the following formula (C).

In the formula (C), Y is an m-valent organic group (containing a reaction with a carboxyl group) Except for the basic base, m is an integer of 2 or more. The upper limit of m is not particularly limited, but is preferably 600. Y and m are determined according to the polyamine.

The m-valent organic group is, for example, a compound such as the following A group having a chain of a hydrocarbon such as ethylene or a propane in a basic skeleton, a compound having a cyclic hydrocarbon such as cyclohexane in the basic skeleton, and a benzene or a naphthalene in the basic skeleton. a compound having an aromatic hydrocarbon, a compound having a benzophenone skeleton such as benzophenone, a compound having a diphenyl ether skeleton such as diphenyl ether, a compound having a diphenylfluorene skeleton such as diphenylphosphonium, or the like. A compound having a biphenyl skeleton. However, it is not limited to these bases.

Examples of the group reactive with a carboxyl group include an amine group and a hydroxyl group. A carboxyl group, a vinyloxy group or the like is not limited to these groups.

Specific examples of the polyamine include p-phenylenediamine and isophthalic acid. Amine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diamine Diphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylanthracene, 3,4'- Diaminodiphenylphosphonium, 4,4'-diaminodiphenylguanidine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4 '-Diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2 ,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl) Propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1, 1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminobenzene 1-(4-aminophenyl)-1-phenylethane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) Benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1, 3-bis(3-aminobenzimidyl)benzene, 1,3-bis(4-aminobenzimidyl)benzene, 1,4-bis(3-aminobenzylidene)benzene, 1 , 4-bis(4-aminobenzimidyl)benzene, 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino- α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α- Dimethylbenzyl)benzene, 1,3-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-two-three Fluoromethylbenzyl)benzene, 1,4-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-trisyl) Fluoromethylbenzyl)benzene, 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine, 4,4'-bis(3- Aminophenoxy)biphenyl, 4,4'-bis(4-amine Phenyloxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]one, bis[4-(4-aminophenoxy)phenyl]one, bis[4-(3 -aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl]anthracene, Bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)benzene Ether, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2, 2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) Phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis[4-(3-aminophenoxy)benzylidene]benzene, 1,3- Bis[4-(4-aminophenoxy)benzylidene]benzene, 1,4-bis[4-(3-aminophenoxy)benzylidene]benzene, 1,4-double [ 4-(4-Aminophenoxy)benzylidene]benzene, 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1, 3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α- Dimethylbenzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 4,4'-bis[4-(4- Amine Phenoxy)benzhydryl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4 '-Bis[4-(4-Amino-α,α-dimethylbenzyl)phenoxy]diphenylanthracene, 4,4'-bis[4-(4-aminophenoxy)benzene Oxy]diphenyl fluorene, 3,3'-diamino-4,4'-diphenoxy benzophenone, 3,3 '-Diamino-4,4'-dibiphenoxy benzophenone, 3,3'-diamino-4-phenoxy Benzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis(3-aminophenoxy)-3,3,3',3 '-Tetramethyl-1,1'-succinyl (6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane ,6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobisindole, 1,3-bis(3- Aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldioxane, α,ω - bis(3-aminopropyl)polydimethyloxane, α,ω-bis(3-aminobutyl)polydimethyloxane, bis(aminomethyl)ether, bis ( 2-Aminoethyl)ether, bis(3-aminopropyl)ether, bis[2-(aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)B Ether, bis[2-(3-aminopropoxy)ethyl]ether, 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy) Ethane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, Ethylene glycol bis(3-aminopropyl)ether, diethylene glycol bis(3-aminopropyl)ether, triethylene glycol bis(3-aminopropyl)ether, ethylenediamine, 1, 3-Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diamino-12 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-bis(2-aminoethyl)cyclohexane , 1,3-bis(2-aminoethyl)cyclohexane, 1,4-bis(2-aminoethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 2,6- Bis(aminomethyl)bicyclo[2.2.1]heptane, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, and the like.

Further, as the polyamine, it is also possible to use a selected one selected from a fluorine atom, a methyl group, A substituent in which a substituent in the group consisting of a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group replaces a part or all of a hydrogen atom on the aromatic ring of the polyamine.

As the polyamine, a polymer having two or more primary amino groups (-NH ₂ ) in one molecule (excluding a group having reactivity with a carboxyl group other than the primary amine group) may be used in addition to the polyamine. . Examples of such a polyamine include a main chain or a side chain of polystyrene, polyacrylic acid, polyurethane, polyamine, or polyimine which is modified by two or more primary amine groups. By. More specifically, the primary amino group-containing acrylic polymer obtained by grafting ethyleneimine to the side chain of the acrylic copolymer by utilizing the reactivity of the carboxyl group of the polymer side chain with ethyleneimine; A polyphthalic acid resin obtained by elongating a tetracarboxylic dianhydride by using an excess of a diamine or a triamine; a polyamine group obtained by elongating a urethane prepolymer by using an excess of a diamine or a triamine A formate urea resin; a modified epoxy resin obtained by stretching an epoxy resin with an excess of a diamine or a triamine.

Examples of the group reactive with a carboxyl group include a hydroxyl group, a carboxyl group, and a vinyloxy group, but are not limited thereto.

Further, in the polyamine, an ethynyl group or a benzocyclobuten-4 which is a crosslinking point in the case where a crosslinking reaction is carried out after the formation of polyfluorene and a benzocyclobuten-4 can be carried out in accordance with the purpose. Any one or two or more of -yl group), vinyl group, allyl group, cyano group, and isopropenyl group are introduced as a substituent. A part or all of the hydrogen atoms on the aromatic ring of the polyamine are used.

The polyamine can be selected depending on the target physical properties, and if a straight diamine such as p-phenylenediamine is used, the swelling ratio of the finally obtained polyimine is lowered. Examples of the rigid diamine include p-phenylenediamine, m-phenylenediamine, and 1,4-diaminonaphthalene which are diamines having two amine groups bonded to the same aromatic ring. 1,4-diaminonaphthalene), 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-di Amino naphthalene, 1,4-diamine hydrazine, and the like. Further, a dendrimer such as polyamine can also be used.

Further, examples of the polyamine include two or more aromatic rings bonded by a single bond, and two or more amine groups are directly bonded to different aromatic rings or as a part of a substituent. Specific examples of the polyamines bonded to the different aromatic rings include benzidine and tolidine.

Further, as the polyamine, a polyamine having a substituent on the benzene ring can also be used. The substituents are monovalent organic groups, but the substituents may be bonded to each other. Specific examples include 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethyl-4,4'-diaminobiphenyl) and 2,2'-ditrifluoro Methyl-4,4'-diaminobiphenyl (2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl), 3,3'-dichloro-4,4'-diaminobiphenyl (3, 3-dichloro-4,4'-diaminobiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl (3,3'-dimethoxy-4,4'-diaminobiphenyl), 3, 3'-Dimethyl-4,4'-diaminobiphenyl (3,3'-dimethyl-4,4'-diaminobiphenyl).

On the other hand, when a compound having a decane skeleton such as 1,3-bis(3-aminopropyl)tetramethyldioxane is used as the polyamine, the elastic modulus of the finally obtained resin composition is lowered. And can make the glass transfer temperature drop.

Here, from the viewpoint of heat resistance, the selected polyamine is preferably an aromatic polyamine, but may correspond to the target physical property, and may not exceed 60 mol% of the whole diamine, preferably 40 mol. A diamine other than an aromatic compound such as an aliphatic diamine or a decane-based diamine is used in the range of %.

Furthermore, polyamines can form hydrohalide salts such as hydrochlorides, hydrobromides, and the like. salt.

The polyamine may be used alone or in combination of two or more.

<Method for Producing Polyimine Precursor Composition>

The benzofuran derivative, the polyamine, and the aqueous medium are mixed and stirred to produce an aqueous composition of the polyimide precursor.

According to this method, similarly to the method for producing a benzofuran derivative composition, it is not necessary to use an organic solvent having a high environmental load, and the number of steps can be reduced.

The method of mixing the benzofuran derivative, the polyamine, and the aqueous medium is not particularly limited, and examples thereof include an aqueous composition containing a benzofuran derivative and an aqueous medium, and an aqueous composition containing a polyamine and an aqueous medium. A method in which the mixture is mixed and stirred; a method in which a polyamine is added to an aqueous composition containing a benzofuran derivative and an aqueous medium, and the mixture is stirred.

The temperature at the time of mixing and stirring is not particularly limited, but is preferably 5 ° C to 45 ° C, more preferably 20 ° C to 30 ° C, and still more preferably about 25 ° C.

The stirring time is not particularly limited, but is preferably from 30 minutes to 6 hours, more preferably from 1 hour to 3 hours, and still more preferably about 2 hours.

The environment in which the polyimide precursor composition is produced is not particularly limited, and an environment such as an atmospheric environment, a nitrogen atmosphere, or an inert gas atmosphere can be used.

In addition, the form for producing the polyimide precursor composition may be continuous or batch.

<Polyimine precursor composition>

The polyimine precursor composition of the present invention contains the compound represented by the formula (1) a benzofuran derivative, a polyamine represented by the formula (C), and an aqueous medium. The polyimine precursor composition of the present invention may be a mixture of these or a salt structure of the following formula (2) in which a carboxylate is bonded to ammonium (ammoninm).

(volatile amine)

In order to supplement the stability of the composition in water, the polyimide precursor composition may also contain a small amount of volatile amine.

The amount of such a volatile amine is desirably set to be not more than the number of moles of the carboxyl group which is not used in the addition reaction of the benzofuran compound and the tetracarboxylic acid, and is preferably, for example, ammonia, trimethylamine or triethylamine. , tributylamine, etc.

The volatile amines may be used alone or in combination of two or more.

(other ingredients that can be included)

The polyimide intermediate precursor composition can be further formulated with reinforcing materials, fillers, anti-aging agents, antioxidants, light stabilizers, anti-coking agents, and other crosslinking delays, as needed. Additives such as agents, plasticizers, processing aids, slip agents, adhesives, lubricants, flame retardants, mildew inhibitors, antistatic agents, colorants, surfactants, and the like.

Further, as long as the properties of the polyimide precursor composition are not impaired, other polymers may be formulated as needed. A resin component such as an elastomer.

The polyiminoimine precursor composition of the present invention can be prepared by blending the components by a suitable mixing method such as roll mixing, banbury mixing, spiral mixing, stirring and mixing.

(Organic solvents)

The polyimine precursor composition is substantially free of organic solvents except for an organic solvent such as an alcohol or an ether contained in an aqueous medium, an organic solvent contained in a volatile amine, and a trace amount of an organic solvent inevitably mixed. . Examples of such an organic solvent include N-methyl-2-pyrrolidone, dimethyl hydrazine, N,N-dimethylformamide, N,N-dimethylacetamide, and N. An organic solvent having a high environmental load such as methyl caprolactam, acetone, γ-butyrolactone, methyl ethyl ketone or methyl isobutyl ketone.

(Polymerity of polyimine precursor composition)

The viscosity of the polyimine precursor composition of the present invention is not particularly limited as long as it does not impair the coatability, but it is practically suitable to adjust the viscosity at 20 ° C to 50 mPa. s above, 200Pa. s below the range, adjust the viscosity at 22 ° C to 10 mPa. s above, 200Pa. s the following range.

3. Polyimine resin manufacturing steps

The polyimine resin manufacturing step is a step of heat-treating a polyimine precursor composition containing a polyimide precursor and an aqueous medium to harden it to produce a polyfluorene. The step of the imine resin.

<Polyimide precursor / aqueous medium>

The polyimine precursor is obtained in the production step of the polyimine precursor composition, and becomes an aqueous composition when mixed and stirred in an aqueous medium.

The aqueous medium is as described above. It may also be an aqueous medium contained in the polyimide intermediate precursor composition produced by the polyethyleneimine precursor composition production step.

<heat treatment / hardening>

Drying of the polyimide precursor composition, deprotection of the carboxyl group of the benzofuran derivative (i.e., detachment of the benzofuran compound from the benzofuran derivative), and utilization of tetracarboxylic acid by heat treatment The hardening of the acid and polyamine oxime imidization (the formation of polyamic acid and the formation of polyimine by dehydration ring closure).

The heat treatment is preferably carried out in two stages, that is, a stage in which the polyimide intermediate precursor composition is dried, a deprotection of a carboxyl group of the benzofuran derivative, and a ruthenium using a tetracarboxylic acid and a polyamine. The stage of hardening of imidization (formation of poly-proline and formation of polyimine by dehydration ring closure), or the following three stages, that is, the stage of drying the composition of the polyimide precursor precursor, The stage of deprotection of the carboxyl group of the benzofuran derivative and the stage of hardening by the ruthenium iodization (dehydration ring closure) of the tetracarboxylic acid and the polyamine.

In the drying stage in which the polyimide intermediate precursor composition is dried, the heating temperature is usually 80 ° C or higher, preferably 80 ° C to 100 ° C. The heating time is preferably from several minutes to one hour, more preferably from 15 minutes to 45 minutes. The formability of the composition can be improved by drying.

In the stage of performing deprotection of the carboxyl group of the benzofuran derivative, the heating temperature is preferably 170 ° C or more and less than 200 ° C. The heating time is preferably from several minutes to one hour, more preferably from 15 minutes to 45 minutes.

Deprotection of a carboxyl group of a benzofuran derivative, and a stage of hardening by ruthenium iodization (dehydration ring closure) of a tetracarboxylic acid and a polyamine, or oxime imidization using a tetracarboxylic acid and a polyamine ( In the hardening stage of the dehydration ring closure, it is preferably from 200 ° C to 400 ° C. The heating time is preferably from several minutes to several hours, more preferably from 10 minutes to 50 minutes.

As the heating method, a suitable method such as extrusion heating, steam heating, oven heating, or hot air heating may be employed. Usually, the reaction is carried out by extrusion heating in a predetermined shape, and then further heated by steam, oven heating, hot air heating, or the like. Carry out the reaction.

The present invention is characterized in that it will be synthesized by benzofuran a hemiacetal ester bond formed by the reaction of a substance with a carboxyl group, a benzofuran derivative having a protective group introduced therein, and a polyamine used as a polyimine raw material, thereby improving storage stability; and heating the same, Thereby, the deprotection of the carboxyl group of the benzofuran derivative (that is, the detachment of the benzofuran compound from the benzofuran derivative), and the ruthenium imidization of the tetracarboxylic acid and the polyamine (dehydration ring closure: ie, The hardening of the polyimine produced by the formation of polyamic acid, and finally the polyimine resin from which the benzofuran compound is detached is obtained.

The polyimide resin produced by the production method of the present invention is, for example, Transportation equipment such as automobiles, general machines. Device, electronics. In a wide range of fields such as electrical and construction, as a sealing material and cushioning. Protective materials, wire covering materials, industrial conveyor belts, hoses, sheets, air bags, etc. are useful.

The present invention will be more specifically described below by way of examples and comparative examples.

Example

[Example 1]

(1) Manufacture of polyimine precursor composition

1,2,4,5-benzenetetracarboxylic acid (11.1 g) and water (45.1 g) were added to a separable flask (200 mL; a cylinder type) equipped with a stirrer, and the mixture was stirred and mixed at 25 ° C for 10 minutes. 2,3-benzofuran (4.9 g) was added, and further stirred and mixed at 25 ° C for 30 minutes to obtain an aqueous dispersion of the benzofuran derivative.

To the aqueous dispersion of the obtained benzofuran derivative, a styrene acrylic polyamine (manufactured by Nippon Shokubai Co., Ltd., POLYMENT ^(R) NK-200PM; a nonvolatile residue of 56% by mass and an amine value of 2.55 mmol was added. /g-solid, m = 60) (71.6 g), stirred and mixed at 25 ° C for 2 hours to obtain an aqueous dispersion of polyimine precursor (polyimine precursor composition).

(2) Viscosity measurement

The viscosity of the obtained polyimide intermediate precursor composition immediately after the production at 22 ° C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model: TV-22).

The measurement results are shown in the column of "initial viscosity (22 ° C)" in Table 1.

(3) Storage stability test

The polyimine precursor composition (30.0 g) immediately after the production was extracted into a glass bottle and immediately allowed to stand in a constant temperature room at 25 °C. The viscosity at 22 ° C was measured after 1 day, 3 days, and 7 days from the standstill, and the appearance was observed by visual observation.

The measurement results of the viscosity are shown in the column of "viscosity (22 ° C)" in "Storage Stability (25 ° C)" in Table 2, and the observation results of the appearance are shown in Table 2, "Storage Stability (25 ° C)". In the "Appearance (Visual)" column.

(4) Solvent resistance test

The polyimine precursor composition immediately after the production was extracted into a glass bottle and immediately allowed to stand in a constant temperature room at 25 °C. The polyimide substrate having a cured film was produced by the following procedure using a polyimide polyimide precursor composition after one day, three days, and seven days from the standstill, and the solvent resistance test was performed.

The polyimide precursor composition was applied onto one surface of the glass substrate in such a manner that the thickness of the dried coating film became 40 μm. After coating, the mixture was heated at 90 ° C for 30 minutes using a hot plate, and then heat-treated at 250 ° C for 30 minutes in a constant temperature drying oven to form a polyfluorene on one surface of the glass substrate. A cured film of an amine resin.

The surface of the cured film was rubbed with a cloth containing N-methyl-2-pyrrolidone (NMP), and the solvent resistance of the cured film was evaluated in accordance with the following evaluation criteria. The evaluation results are shown in the column of "solvent resistance test" in Table 3.

(evaluation benchmark)

A: No change

B: Swelling or erosion in the cured film

C: at least a part of the glass substrate is exposed or poorly coated

(5) Water resistance test (hot water impregnation test)

The newly prepared polyimide precursor precursor composition is extracted into a glass bottle and stood upright That is, it was allowed to stand in a constant temperature room at 25 °C. A glass substrate having a cured film was prepared by the following procedure using a polyimide composition having a polyimine precursor after one day, three days, and seven days from the standstill, and a water resistance test was performed.

The polyimide precursor composition was applied onto one surface of the glass substrate in such a manner that the thickness of the dried coating film became 40 μm. After coating, the mixture was heated at 90 ° C for 30 minutes using a hot plate, and then heat-treated at 250 ° C for 30 minutes in a constant temperature drying oven to form a polyfluorene on one surface of the glass substrate. A cured film of an amine resin.

The glass substrate on which the cured film was formed was immersed in hot water at 90° C. and left for 10 minutes, and then the cured film was visually observed, and the water resistance of the cured film was evaluated based on the following evaluation criteria. The evaluation results are shown in the column of "water resistance test" in Table 3.

(evaluation benchmark)

A: No change

B: whitening or swelling in the cured film

C: at least a part of the glass substrate is exposed or poorly coated

[Embodiment 2]

(1) Manufacture of polyimine precursor composition

1,2,4,5-benzenetetracarboxylic acid (11.1 g) and water (44.5 g) were added to a separable flask (200 mL; a cylinder type) equipped with a stirrer, and the mixture was stirred and mixed at 25 ° C for 10 minutes. 3-methylbenzofuran (5.5 g) was added, and further stirred and mixed at 25 ° C for 30 minutes to obtain an aqueous dispersion of the benzofuran derivative.

To the aqueous dispersion of the obtained benzofuran derivative, a styrene acrylic polyamine (manufactured by Nippon Shokubai Co., Ltd., POLYMENT ^(R) NK-200PM; a nonvolatile residue of 56% by mass and an amine value of 2.55 mmol was added. /g-solid, m = 60) (71.6 g), stirred and mixed at 25 ° C for 2 hours to obtain an aqueous dispersion of polyimine precursor (polyimine precursor composition).

(2) Viscosity measurement, storage stability test, solvent resistance test, water resistance test

The viscosity measurement, the storage stability test, the solvent resistance test, and the water resistance test were carried out in the same manner as in Example 1. The results are shown in Table 1, Table 2 and Table 3.

[Comparative Example 1]

(1) Manufacture of polyimine precursor composition

1,2,4,5-benzenetetracarboxylic acid (11.1 g) and water (50.0 g) were added to a separable flask (200 mL; a cylinder type) equipped with a stirrer, and the mixture was stirred and mixed at 25 ° C for 10 minutes. A styrene-acrylic polyamine (manufactured by Nippon Shokubai Co., Ltd., POLYMENT ^(R) NK-200PM; a nonvolatile residue of 56% by mass, an amine value of 2.55 mmol/g-solid, m=60) (71.6 g), The mixture was stirred and mixed at 25 ° C for 2 hours to obtain an aqueous dispersion of polyimine precursor (polyimine precursor composition).

(2) Viscosity measurement, storage stability test, solvent resistance test, water resistance test

Since the obtained polyimide intermediate precursor composition lost fluidity, it was not subjected to any of the viscosity measurement, the storage stability test, the solvent resistance test, and the water resistance test.

[Comparative Example 2]

(1) Manufacture of polyimine precursor composition

1,2,4,5-benzenetetracarboxylic acid (11.1 g) and water (45.9 g) were added to a separable flask (200 mL; a cylinder type) equipped with a stirrer, and the mixture was stirred and mixed at 25 ° C for 10 minutes. Butyl vinyl ether (4.1 g) was added, and further stirred and mixed at 25 ° C for 30 minutes to obtain an aqueous dispersion of a butyl vinyl ether derivative.

To the aqueous dispersion of the obtained butyl vinyl ether derivative, a styrene acrylic polyamine (manufactured by Nippon Shokubai Co., Ltd., POLYMENT ^(R) NK-200PM; a nonvolatile residue of 56% by mass, an amine value was added. 2.55 mmol/g-solid, m=60) (71.6 g) was stirred and mixed at 25 ° C for 2 hours to obtain an aqueous dispersion of polyimine precursor (polyimine precursor composition).

(2) Viscosity measurement and storage stability test

The viscosity measurement and the storage stability test were carried out in the same manner as in Example 1 using the obtained polyimide intermediate precursor composition. However, on the 7th day after the standing in the constant temperature chamber of the storage stability test, the composition of the polyimide precursor was gelled, and thus the viscosity measurement could not be performed.

The measurement results of the viscosity immediately after the production of the obtained polyimide intermediate precursor composition are shown in the column of "initial viscosity (22 ° C)" in Table 1, and the measurement results of the viscosity in the storage stability test are shown in In the column of "Viscosity (22 °C)" in "Storage Stability (25 °C)" in Table 2, the observation of the appearance is shown in "Appearance (Visual) of "Storage Stability (25 °C)" in Table 2. In the column.

(3) Solvent resistance test and water resistance test

The obtained polyimide intermediate precursor composition was used in the same manner as in Example 1. The solvent resistance test and the water resistance test were carried out in the manner.

The evaluation results of the solvent resistance are shown in the column of "solvent resistance test" in Table 3, and the evaluation results of the water resistance are shown in the column of "water resistance test" in Table 3.

[Comparative Example 3]

(1) Manufacture of polyimine precursor composition

Add 1,2,4,5-benzenetetracarboxylic acid (11.1 g) and N-methyl-2-pyrrolidone (50.0 g) to a separable flask (200 mL; cartridge) equipped with a stirrer at 25 After stirring and mixing for 10 minutes at ° C, a styrene acrylic polyamine (POLYMENT ^(R) NK-200PM, manufactured by Nippon Shokubai Co., Ltd.; a nonvolatile residue of 56% by mass and an amine value of 2.55 mmol/g-solid, was added. m = 60) (71.6 g), which was stirred and mixed at 25 ° C for 2 hours to obtain a solution of a polyimine precursor (polyimine precursor composition).

(2) Viscosity measurement, storage stability test, solvent resistance test, water resistance test

The viscosity measurement, the storage stability test, the solvent resistance test, and the water resistance test were carried out in the same manner as in Example 1.

The obtained polyimide intermediate precursor composition showed a solution state on the first day of the blending, but crystallized after the third day, and thus the test for the coating film was not carried out. The results are shown in Table 1, Table 2 and Table 3.

The polyimine precursor compositions of Examples 1 and 2 have low viscosity and excellent coatability.

The polyimide polyimide precursor composition of Comparative Example 2 containing a polyimide intermediate having a vinyl ether compound instead of a benzofuran compound has a low viscosity and excellent coatability.

The polyimine precursor composition of the aqueous dispersion of the N-methyl-2-pyrrolidone solution of Comparative Example 3, which was not a polyimine precursor, had a low initial viscosity and excellent coating properties. However, the environmental load is high, and it is also disadvantageous in terms of cost.

The polyimide intermediate precursor compositions of Examples 1 and 2 had a low viscosity and a coating property were not damaged even after a certain period of time after the production.

On the other hand, the polyimine precursor composition containing the polyethylenimine precursor to which the vinyl ether compound but the benzofuran compound was added in Comparative Example 2 had a low initial viscosity and excellent coating properties. If a certain period of time elapses after manufacture, the appearance changes, the viscosity increases, and the coatability is impaired.

Further, the polyimine precursor composition of the aqueous dispersion of the N-methyl-2-pyrrolidone solution of Comparative Example 3 which was produced instead of the polyimine precursor was low in initial viscosity and excellent in coating property. However, it crystallized out after 3 days without being durable.

The polyimide intermediate precursor compositions of Examples 1 and 2 were produced even The polyimide resin obtained by heat treatment after a certain period of time is excellent in solvent resistance and water resistance.

On the other hand, the polyimine precursor composition of the polyimine precursor containing the vinyl ether compound but not the benzofuran compound of Comparative Example 2 was subjected to heat treatment after a certain period of time after the production. The solvent resistance and water resistance of the obtained polyimide resin are deteriorated.

In addition, the polyimine precursor composition of the aqueous dispersion of Comparative Example 3 which was made into an N-methyl-2-pyrrolidone solution rather than a polyimine precursor was crystallized after 3 days of preparation, and was not durable. However, the polyimide resin obtained by heat-treating the composition after one day of preparation is excellent in solvent resistance and water resistance.

Claims (4)

A benzofuran derivative composition comprising a benzofuran derivative represented by the following formula (1) and an aqueous medium, In the formula (1), X is a tetravalent organic group (excluding a group having reactivity with an amine group), and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen. An atom, a halogen atom or a monovalent organic group (except for those having reactivity with an amine group or a carboxyl group); R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to represent a cyclic structure]. A polyimine precursor composition comprising a benzofuran derivative represented by the following formula (1), a polyamine represented by the following formula (C), and an aqueous medium, In the formula (1), X is a tetravalent organic group (excluding a group having reactivity with an amine group), and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen. An atom, a halogen atom or a monovalent organic group (except for those having reactivity with an amine group or a carboxyl group); R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to represent a cyclic structure; in the formula (C) Y is an m-valent organic group (excluding a group having reactivity with a carboxyl group), and m is an integer of 2 or more]. A method for producing a polyimine resin, comprising: a step of producing a composition of a benzofuran derivative, a benzofuran compound represented by the following formula (A), and a tetracarboxylic acid represented by the following formula (B) Mixing and stirring the acid and the aqueous medium; preparing the polyimine precursor composition, and preparing the benzofuran derivative obtained in the step of producing the benzofuran derivative by the following formula (C) a polyamine and an aqueous medium are mixed and stirred; and a polyimine resin production step, the polyimine-containing precursor obtained in the production step of the polyimide intermediate composition and The polyimine precursor composition of the aqueous medium is subjected to heat treatment to harden it; [In the formula (A), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a monovalent organic group (except for those having reactivity with an amine group or a carboxyl group) And R ³ , R ⁴ , R ⁵ and R ⁶ may each be bonded to each other to represent a cyclic structure; in the formula (B), X is a tetravalent organic group (except for a group having reactivity with an amine group) In the formula (C), Y is an m-valent organic group (excluding a group having reactivity with a carboxyl group), and m is an integer of 2 or more]. A polyimine resin obtained by the method for producing a polyimide resin according to claim 3 of the patent application.