JPH0912719A - Production of polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide having a small linear expansion coefficient and excellent dimensional stability and industrially useful for film, etc., by imidating a specific polyimide precursor in the presence of a specific compound. SOLUTION: The objective polyimide having the recurring structural unit of formula V can be produced by reacting (A) an aromatic diamine compound of formula I [X is direct bond, SO2 , CO, O, S, C(CH3 )2 or C(CF3 )2 ] [e.g. 4,4'-bis(3- aminophenoxy)biphenyl] with (B) a tetracarboxylic acid dianhydride of formula II (Ar is group of formula III, formula IV, etc.) (e.g. pyromellitic dianhydride) in a solvent (e.g. N-methyl-2-pyrrolidone) and imidating the resultant polyimide precursor in the presence of a compound having at least two groups selected from OH, NH2 , COOH, CH2 COOH and SO3 H on the aromatic ring of a molecule (e.g. o-hydroxybenzoic acid).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyimide having excellent dimensional stability.

[0002]

2. Description of the Related Art Conventionally, poiliimide obtained by the reaction of tetracarboxylic dianhydride and diamine has not only high heat resistance but also mechanical strength, chemical resistance, flame retardancy, and electrical insulation. It is used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment, and is expected to be widely used in the fields where heat resistance is required in the future. Various polyimides having excellent properties have been developed. However, even if it has excellent heat resistance, it does not have a clear glass transition temperature, so when it is used as a molding material, it must be processed using a technique such as sintering molding, or it has excellent workability. However, it has a low glass transition temperature, is soluble in halogenated hydrocarbons, and is not satisfactory in terms of heat resistance and solvent resistance. On the other hand, the present inventors previously described the mechanical properties,
As a polyimide having thermal properties, electrical properties, solvent resistance and heat resistance, a general formula (3)

[0003]

Embedded image A polyimide having a repeating structural unit represented by (JP-A-62-205124) The above-mentioned polyimide is a heat resistant resin having many good physical properties, but when the polyimide is used in the form of a film such as an adhesive or a protective film, the film is heated. Since the rate of expansion sometimes is larger than that of the adherend, the film easily peels from the adherend. Therefore, a method for producing a polyimide having a small dimensional change during heating, that is, a small linear expansion coefficient has been desired.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems and found that a polyimide having good dimensional stability can be polymerized by using a specific method. The present invention has been reached. That is, the present invention provides a compound represented by the general formula (3)

[0005]

[Chemical 6] In a method for producing a polyimide having a repeating structural unit represented by, and a polyimide having a polymer molecule terminal having this repeating structural unit:
Polyamic acid, which is a precursor of polyimide, is converted into OH group, N
H ₂ group, COOH group, CH ₂ COOH group and SO ₃ H
A method for producing a polyimide, which comprises thermally or chemically imidizing in the presence of a compound having at least two or more groups on one molecule of an aromatic ring, the polyimide obtained by the method and The polyimide film. More specifically, the general formula (1) (Formula 7)

[0006]

Embedded image (Wherein X is the same as above), and an aromatic diamine compound represented by the general formula (2)

[0007]

Embedded image (In the formula, Ar is the same as above.), And a tetracarboxylic dianhydride represented by the formula is reacted to give a compound represented by the general formula (3)

[0008]

Embedded image In the method for producing a polyimide having a repeating structural unit represented by the formula (X and Ar are the same as above), an aromatic diamine compound represented by the general formula (1),
The tetracarboxylic acid dianhydride represented by the general formula (2) is
After reacting in a solvent to form a polyimide precursor, OH
Group, NH ₂ group, COOH group, CH ₂ COOH group and S
A method for producing a polyimide, which comprises imidizing in the presence of a compound having at least two O ₃ H groups on one molecule of an aromatic ring. Furthermore, this method is used for producing a polyimide having a repeating structural unit represented by the general formula (3).

[0009]

Embedded image (In the formula, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. Is 2
Represents a valence group. ) And / or the general formula (5) V-NH ₂ (5) (wherein V has 6 to 15 carbon atoms, a monocyclic aromatic group, and a condensed polycyclic group). A non-condensed polycyclic aromatic group in which the aromatic group or the aromatic groups are connected to each other directly or by a bridging member 1
Represents a valence group. The same method is applied to a polyimide containing a polymer obtained by allowing an aromatic monoamine represented by the formula (1) to coexist with the end of the polymer. That is, the polyimide in the production method of the present invention has the general formula (3)
1)

[0010]

Embedded image A polyimide having a repeating structural unit represented by the formula (wherein X and Ar are the same as above), and a polyimide including a polymer having a polymer terminal blocked. The aromatic diamine component used when producing a polyimide having this repeating structural unit is represented by the general formula (1)

[0011]

Embedded image A diamine compound represented by the formula (X is the same as above),
Specifically, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) diphenyl sulfide, 4,4'-bis (3-aminophenoxy) benzophenone, 4,4 '-Bis (3-aminophenoxy) diphenyl ether, 4,4'-bis (3
-Aminophenoxy) diphenyl sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane or 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane and the general formula (2)

[0012]

Embedded image (In the formula, Ar is the same as the above.)

The tetracarboxylic dianhydride represented by the following, specifically, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4
4'-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetra Carboxylic dianhydride, 3,3 ', 4,
4'-diphenylmethanetetracarboxylic dianhydride,
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedi Anhydrous, 4,4 '-(p-phenylenedioxy)
Diphthalic dianhydride or 2,2-bis [4- (3,4
-Dicarboxyphenyl) phenoxy] propane dianhydride is reacted in a solvent to form a polyimide precursor,
It can be obtained by imidization in the presence of a compound having at least two or more of OH group, NH ₂ group, COOH group, CH ₂ COOH group and SO ₃ H group on one aromatic ring.

The imidization accelerator used in the present invention,
Examples of the compound having at least two or more of OH group, NH ₂ group, COOH group, CH ₂ COOH group and SO ₃ H group on one molecule of aromatic ring include, for example, o-hydroxybenzoic acid and m-hydroxybenzoic acid. , P-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6
-Dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-sulfanilic acid, m-sulfanilic acid, p -Sulfanilic acid, o-hydroxyphenyl sulfonic acid, m-hydroxyphenyl sulfonic acid, p-hydroxyphenyl sulfonic acid, o-aminophenol, m-aminophenol-
, P-aminophenol, o-hydroxyphenylacetic acid, m-hydroxyphenylacetic acid, p-hydroxyphenylacetic acid, o-aminophenylacetic acid, m-aminophenylacetic acid, p-aminophenylacetic acid, o-sulfophenylacetic acid, They are m-sulfophenylacetic acid and p-sulfophenylacetic acid. Further, an imidization accelerator, OH group, NH
The amount of the compound having at least two or more of 2 groups, COOH group, CH2 COOH group and SO3 H group on one molecule of aromatic ring is 0.05 to 8 per mol of aromatic tetracarboxylic dianhydride. Mol, preferably 0.5-4
Is a mole. If the amount used is less than 0.5 mol, the effect as an imidization promoter is poor, and if it exceeds 8 mol, the imidization promoter remains in the polyimide, possibly affecting the physical properties of the polyimide.

The aromatic diamine compound used in the method for producing a polyimide of the present invention is the diamine compound represented by the above general formula (1), but other diamines can be used within the range not impairing the performance. Examples of diamine compounds that can be used include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, o-aminobenzylamine, 3-chloro-1,2-phenylenediamine, 4-
Chloro-1,2-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 3,5-diaminotoluene , 2-methoxy-1,4-phenylenediamine, 4-methoxy-
1,2-phenylenediamine, 4-methoxy-1,3-
Phenylenediamine, benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3 '
-Dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide,
3,4'-diaminodiphenyl sulfoxide, 4,4 '
-Diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone,

3,3'-diaminobenzophenone, 3,
4'-diaminobenzophenone 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4-
(4-Aminophenoxy) phenyl] ethane, 1,1-
Bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4
-Aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane,
1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) Phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2
-Bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy)
-3,5-Dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 1,3-bis (4-aminophenoxy) benzene, 1,4 -Bis (3-aminophenoxy)
Benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (2-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 3,3'-bis ( 2-aminophenoxy) biphenyl, 3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) diphenyl sulfide, 4,4′-bis (2-aminophenoxy) diphenyl sulfide, 3,3′-bis (2-aminophenoxy) diphenyl sulfide, 3,3′-bis (3-aminophenoxy) diphenyl sulfide, 3,
3'-bis (4-aminophenoxy) diphenyl sulfide, 4,4'-bis (2-aminophenoxy) benzophenone, 4,4'-bis (4-aminophenoxy) benzophenone, 3,3'-bis (2- Aminophenoxy) benzophenone, 3,3′-bis (3-aminophenoxy) benzophenone, 3,3′-bis (4-aminophenoxy) benzophenone,

4,4'-bis (2-aminophenoxy)
Diphenyl ether, 4,4'-bis (4-aminophenoxy) diphenyl ether, 3,3'-bis (2-aminophenoxy) diphenyl ether, 3,3'-bis (3-aminophenoxy ) Diphenyl ether, 3,
3'-bis (4-aminophenoxy) diphenyl ether, 4,4'-bis (2-aminophenoxy) diphenyl sulfone, 4,4'-bis (4-aminophenoxy)
Diphenyl sulfone, 3,3′-bis (2-aminophenoxy) diphenyl sulfone, 3,3′-bis (3-aminophenoxy) diphenyl sulfone, 3,3′-bis (4-aminophenoxy) diphenyl sulfone, 2, Two
-Bis [4- (2-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (2-aminophenoxy) phenyl] propane , 2,2-bis [3-
(3-aminophenoxy) phenyl] propane, 2,2
-Bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (2-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis [4- (4-aminophenoxy)
Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (2-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis [3- (3-aminophenoxy) -1,1,1,3,3,3-hexafluorophenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfoxide, 1,3-bis [4- (4
-Aminophenoxy) benzoyl] benzene, 1,3-
Bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene,

4,4'-bis (3-aminophenoxy)
-3,3'-Dimethylbiphenyl, 4,4'-bis (3
-Aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3', 5,5'-tetrachlorobiphenyl,
4,4′-bis (3-aminophenoxy) -3,3 ′,
5,5'-tetrabromobiphenyl, bis [4- (3-
Aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4-
(3-Aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy)
-3,5-Dimethoxyphenyl] sulfide, 1,1-
Bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy)
Benzene, 4,4'-bis (4-aminobenzoyl) biphenyl, 4,4'-bis (3-aminobenzoyl) biphenyl, 3,3'-bis (4-aminobenzoyl) biphenyl, 3,3'-bis (3-Aminobenzoyl) biphenyl, 4,4'-bis (4-aminobenzoyl) diphenylether, 4,4'-bis (3-aminobenzoyl) diphenylether, 3,3'-bis (4 -Aminobenzoyl) diphenyl ether, 3,3'-bis (3-aminobenzoyl) diphenyl ether, bis [4- (4-aminobenzoyl) phenyl] ketone, bis [4- (3-aminobenzoyl) Phenyl] ketone,
Bis [3- (4-aminobenzoyl) phenyl] ketone, bis [3- (3-aminobenzoyl) phenyl] ketone, bis [4- (4-aminobenzoyl) phenyl]
Sulfide, bis [4- (3-aminobenzoyl) phenyl] sulfide, bis [3- (4-aminobenzoyl) phenyl] sulfide, bis [3- (3-aminobenzoyl) phenyl] sulfide, bis [4- (4 -Aminobenzoyl) phenyl] sulfone, bis [4- (3
-Aminobenzoyl) phenyl] sulfone, bis [3-
(4-aminobenzoyl) phenyl] sulfone, bis [3- (3-aminobenzoyl) phenyl] sulfone,
Bis [4- (4-aminobenzoyl) phenyl] methane, Bis [4- (3-aminobenzoyl) phenyl] methane, Bis [3- (4-aminobenzoyl) phenyl]
Methane, bis [3- (3-aminobenzoyl) phenyl] methane,

2,2-bis [4- (4-aminobenzoyl) phenyl] propane, 2,2-bis [4- (3-aminobenzoyl) phenyl] propane, 2,2-bis [3- (4- Aminobenzoyl) phenyl] propane,
2,2-bis [3- (3-aminobenzoyl) phenyl] propane, 2,2-bis [4- (4-aminobenzoyl) phenyl] -1,1,1,3,3,3-hexafluoropropane 2,2-bis [4- (3-aminobenzoyl) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminobenzoyl) phenyl] -1,1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (3-aminobenzoyl) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenyl sulfone,
4,4'-bis [4- (3-aminophenoxy) phenoxy] diphenyl sulfone, 3,3'-bis [4- (4
-Aminophenoxy) phenoxy] diphenyl sulfone, 3,3'-bis [4- (3-aminophenoxy) phenoxy] diphenyl sulfone, 4,4'-bis [4-
(4-Aminocumyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (3-aminocumyl) phenoxy] diphenylsulfone, 3,3′-bis [4- (4
-Aminocumyl) phenoxy] diphenyl sulfone,
3,3'-bis [4- (3-aminocumyl) phenoxy] diphenylsulfone, 4,4'-bis [4- (4-
Aminophenoxy) benzoyl] diphenyl ether,
4,4'-bis [4- (3-aminophenoxy) benzoyl] diphenyl ether, 3,3'-bis [4- (4
-Aminophenoxy) benzoyl] diphenyl ether, 3,3'-bis [4- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4-
(4-aminophenoxy) phenoxy] biphenyl,
4,4'-bis [4- (3-aminophenoxy) phenoxy] biphenyl, 3,3'-bis [4- (4-aminophenoxy) phenoxy] biphenyl, 3,3'-bis [4- (3- Aminophenoxy) phenoxy] biphenyl, 4,4'-bis [4- (4-aminocumyl) phenoxy] biphenyl, 4,4'-bis [4- (3-aminocumyl) phenoxy] biphenyl, 3,3'-bis [ Four
-(4-aminocumyl) phenoxy] biphenyl, 3,
3'-bis [4- (3-aminocumyl) phenoxy] biphenyl, 4,4'-bis [4- (4-aminophenoxy) benzoyl] biphenyl, 4,4'-bis [4-
(3-aminophenoxy) benzoyl] biphenyl,
3,3'-bis [4- (4-aminophenoxy) benzoyl] biphenyl, 3,3'-bis [4- (3-aminophenoxy) benzoyl] biphenyl and the like can be mentioned.

The aromatic tetracarboxylic dianhydride used in the method for producing a polyimide of the present invention is the aromatic tetracarboxylic dianhydride represented by the above-mentioned general formula (2), but in a range that does not impair the performance. It is also possible to use other tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides that can be used include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 2,2 ′,
3,3′-diphenylmethanetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,2,3,4-benzenetetracarboxylic acid Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride An anhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, etc. are mentioned.

In the method for producing a polyimide of the present invention, a dicarboxylic acid anhydride or a monoamine may be used for the purpose of sealing the polymer molecule ends. Specific examples of these compounds include phthalic anhydride, 2,3
-Benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl sulfide anhydride, 3,4 -Dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,
Examples thereof include 8-naphthalenedicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, and 1,9-anthracene dicarboxylic acid anhydride. These dicarboxylic acid anhydrides may be substituted with a group having no reactivity with amines or dicarboxylic acid anhydrides. These can be used alone or in combination of two or more. Of these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used.

Examples of monoamines include the following. For example, aniline, o-toluidine, m
-Toluidine, p-toluidine, 2,3-xylidine,
2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline,
p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline,
p-nitroaniline, m-nitroaniline, o-aminophenol, p-aminophenol, m-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o -Aminobenzaldehyde, p-aminobenzaldehyde, m-aminobenzaldehyde, o-aminobenznitrile, p-aminobenznitrile, m-aminobenznitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-amino Phenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-
Aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4
-Aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-
Naphthol, 5-amino-1-naphthol, 2-amino-1-naphthol, 4-amino-1-nafrole, 5-
Amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like. Usually, of these aromatic monoamines, derivatives of aniline are preferably used. These can be used alone or in combination of two or more. These monoamines and / or dicarboxylic acid anhydrides may be used alone or in combination of two or more kinds without any problem. The amount of these compounds used is 1 to several times as much as the difference in the number of moles of the diamine and the tetracarboxylic dianhydride used (excess component is tetracarboxylic dianhydride), or dicarboxylic anhydride (excess component is Although it may be a diamine), it is generally used in an amount of about 0.01 mol times at least one component. Specifically, 0.001 to 0.2 mol of dicarboxylic acid anhydride and / or monoamine is used with respect to 1 mol of the total amount of the tetracarboxylic acid dianhydride. It is preferably 0.005 to 0.05 mol.

The polymerization of the polyimide precursor, that is, the polyamic acid in the present invention is usually carried out in an organic solvent. As the organic solvent used in this reaction, any one can be used as long as it can dissolve the polyamic acid that is the precursor of the polyimide, and specifically, an amide solvent, an ether solvent, and a phenol solvent. Examples of the solvent include N, N-dimethylformamide and N, N-.
Dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane- Bis (2-methoxyethyl) ether,
1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide,
Dimethyl sulfone, tetramethyl urea, hexamethyl phosphoramide, phenol, o-cresol, m-cresol, p-cresol, cresylic acid, o-chlorophenol, m-chlorophenol, p-chlorophenol, anisole and the like can be mentioned. These may be used alone or in combination of two or more. Particularly, an amide solvent is preferable from the viewpoint of solution stability and utilization as workability.

In the method for producing a polyimide according to the present invention, it is possible to coexist with an organic base catalyst. As the organic base catalyst, pyridine, α-picoline,
Tertiary amines such as β-picoline, γ-picoline, quinoline, isoquinoline and triethylamine are used, but pyridine and γ-picoline are particularly preferable. The amount of these catalysts used is 0.001 to 0.50 mol per 1 mol of the total amount of tetracarboxylic dianhydride. It is particularly preferably 0.01 to 0.1 mol.

The polymerization concentration (polymer concentration) in the method for producing a polyimide of the present invention is not particularly limited, but it is desirable to carry out the polymerization at a high concentration in view of economical efficiency at the time of production, 10 to 60 wt%, More preferably 15 to 50
wt%. Further, as a method of reacting a diamine component, a tetracarboxylic acid dianhydride component and a dicarboxylic acid anhydride and / or a monoamine in a solvent to obtain a polyamic acid which is a precursor of polyimide, (a) tetracarboxylic acid dianhydride A method in which a dicarboxylic acid anhydride or a monoamine is added after the reaction between the component component and the diamine component and the reaction is continued. (B) A method in which a tetracarboxylic dianhydride component is reacted with a monoamine and then a diamine component is added to continue the reaction. (C) A method of reacting a diamine component and a dicarboxylic acid anhydride, and then adding a tetracarboxylic acid dianhydride component to continue the reaction. (D) tetracarboxylic dianhydride component, diamine component,
Examples thereof include a method in which a dicarboxylic acid anhydride or a monoamine is added and reacted at the same time, and any addition / reaction method may be used.

The reaction temperature for producing the polyamic acid which is the precursor of polyimide is -20 to 60 ° C, preferably 0 to 40 ° C.

The reaction time varies depending on the diamine, the tetracarboxylic dianhydride used, the type of solvent, the reaction temperature and the like, but as a guide, it is 1 to 48 hours, usually several hours to ten and several hours. The polyamic acid thus obtained is imidized with OH group, NH ₂ group, CO
After adding a compound having at least two or more of OH group, CH ₂ COOH group and SO ₃ H group on one molecule of aromatic ring, the mixture is stirred to form a uniform solution. The polyamic acid solution thus obtained is subsequently subjected to imidization by a thermal method, that is, by heating to 100 to 400 ° C. or by imidization using a dehydrating agent such as an organic base catalyst and acetic anhydride. The polyimide of

In the case of thermal imidization, the heating time varies depending on the diamine used, the tetracarboxylic dianhydride, the type of solvent, the reaction temperature and the like.
Distilled water reacts until it reaches a theoretical amount (normally, not all of them are recovered, so the recovery rate is 70 to 90%). Usually, it takes about several hours to 10 hours. is there. In this case, water generated by the imidization reaction is generally and effectively added by adding an azeotropic agent such as toluene to the reaction system and removing the water by azeotropic distillation. Further, when the imidization reaction is carried out using a dehydrating agent such as acetic anhydride, it is not necessary to remove the produced water out of the system. As the reaction time,
This is the same as in the case of the above-mentioned thermal imidization. Polyimide is obtained by the above method.

In the case of producing a polyimide film, a polyamic acid solution in which a polyamic acid and an imidizing agent are mixed is coated on a smooth glass plate or a metal plate and then 40 to 250 ° C., preferably 60 to 200 ° C.
The temperature is raised to and held for a certain period of time. The holding time varies depending on the types of diamine, tetracarboxylic dianhydride and imidizing agent used, but is usually 30 minutes to 20 hours, preferably 1 to 6 hours. After maintaining the imidization temperature at a relatively low temperature, the temperature is further raised to a temperature of 250 to 400 ° C., and the solvent removal and the imidization are completed and the imidizing agent is removed at the same time. The heating time at this time is usually 1 to 1.
It is 0 hours, preferably 2 to 6 hours. The intended polyimide film is obtained by the above method.

[0030]

The present invention will be described below in detail with reference to examples and comparative examples. The physical properties of the polyimide in the examples were measured by the following methods. Linear expansion coefficient: Mac Science Co., thermal analyzer, TM
Measured with A4000. Logarithmic viscosity: 0.5 g / 1 for N-methyl-2-pyrrolidone
Measured at 35 ° C. after dissolving the polyamic acid at a concentration of 00 ml. Glass transition temperature (Tg): measured by Shimadzu Corp. thermal analyzer Shimadzu DT40 series DSC-41M Example 1 4,4′-bis (3-amino) in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. Phenoxy) biphenyl 3
6.84 g (0.100 mol) and N-methyl-2-pyrrolidone 233 g were charged, and pyromellitic dianhydride 20.72 g (0.09) was added while stirring under a nitrogen atmosphere.
(5 mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours to obtain a uniform polyamic acid varnish. The polyamic acid varnish thus obtained had an inherent viscosity of 0.52 dl / g. To this polyamic acid varnish, 13.81 g (0.10 mo of m-hydroxybenzoic acid was added.
1) was added and the mixture was further stirred for 1 hour. Obtained polyamic acid solution, after coating on a glass plate, under a nitrogen stream,
After heating at 100 ° C. for 1 hour, it was further heated at 250 ° C. for 4 hours to obtain a polyimide film having a thickness of 32 μm. When the linear expansion coefficient of the obtained polyimide film at 50 to 150 ° C. was measured, it was 38 ppm / K, and the glass transition temperature was 249 ° C.

Example 2 In Example 1, 1.48 g of phthalic anhydride (0.01
mol) was added in the same manner as in Example 1 except that
A polyimide film of m was obtained. The coefficient of linear expansion of the obtained polyimide film at 50 to 150 ° C. was 36 ppm / K.

Example 3 4,4'-bis (3-aminophenoxy) biphenyl 3 was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
6.84 g (0.100 mol) and 260 g of N-methyl-2-pyrrolidone were charged, and 28.25 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added while stirring under a nitrogen atmosphere. (0.096 mol) was added in portions while paying attention to the increase in solution temperature, and the mixture was stirred at room temperature for about 4 hours, and then 1.18 g (0.008 mol) of phthalic anhydride was added.
l) was added. The mixture was further stirred for 20 hours to obtain a uniform polyamic acid varnish. The polyamic acid varnish thus obtained had an inherent viscosity of 0.49 dl / g. To this polyamic acid varnish, 13.71 g (0.10 mo) of m-aminobenzoic acid was added.
1) was added and the mixture was further stirred for 1 hour. After coating the obtained polyamic acid varnish on a glass plate, under a nitrogen stream,
After heating at 100 ° C. for 1 hour, it was further heated at 250 ° C. for 4 hours to obtain a polyimide film having a thickness of 30 μm. The linear expansion coefficient of the obtained polyimide film at 50 to 150 ° C. was measured and found to be 35 ppm / K, and the glass transition temperature was 223 ° C.

Examples 4 to 11 Using various diamines, acid anhydrides, imidizing agents and sealants, the reaction was carried out in the same manner as in Example 1 to obtain polyimide films. Table 1 shows the reaction conditions and the linear expansion coefficient in that case.

Comparative Example 1 4,4'-bis (3-aminophenoxy) biphenyl 3 was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
6.84 g (0.100 mol) and N-methyl-2-pyrrolidone 233 g were charged, and pyromellitic dianhydride 20.72 g (0.09) was added while stirring under a nitrogen atmosphere.
(5 mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours to obtain a uniform polyamic acid varnish. The polyamic acid varnish thus obtained had an inherent viscosity of 0.51 dl / g. This polyamic acid varnish was coated on a glass plate and then under a nitrogen stream at 250 ° C.
And heated for 4 hours to obtain a polyimide film having a thickness of 35 μm. 50-150 ° C. of the obtained polyimide film
When the linear expansion coefficient in was measured, it was 54 ppm / K,
The glass transition temperature was 250 ° C.

Comparative Examples 2 to 4 Various polyimide films were obtained in the same manner as in Comparative Example 1 without adding an imidizing agent. Table 1 shows the reaction conditions and the linear expansion coefficient of the obtained polyimide film.

As can be seen from the results in Table 1, the imidizing agent was added, the imidization was carried out at a low temperature, and the temperature was further raised. The linear expansion coefficient is about 20 ppm / K smaller than that of the polyimide ferm cured without addition. Compared with the polyimide film of the comparative example, the polyimide film of the present invention having a linear expansion coefficient smaller by about 20 ppm / K has less thermal expansion during heating than the polyimide film of the comparative example, and is excellent in dimensional stability.

[0037]

[Table 1] .

[Table 2] * 1) m-BP: 4,4'-bis (3-aminophenoxy) biphenyl, m-CO: 4,4'-bis (3-aminophenoxy) benzophenone, m-BADE: 4,4'-bis ( 3-aminophenoxy) diphenyl ether, m-BAPS: 4,4'-
Bis (3-aminophenoxy) diphenyl sulfide,
m-BAPP: 2,2-bis [4- (3-aminophenoxy)
Phenyl] propane, 6F-BAPP: 2,2-bis [4-
(3-Aminophenoxyphenyl] -1,1,1,3,3,3-hexafluoropropane, m-BS: m-4,4'-bis (3-
Aminophenoxy) biphenyl sulfone * 2) PMDA: Pyromellitic dianhydride, BPDA: 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, BTDA: 3,3 ',
4,4'-benzophenone tetracarboxylic dianhydride, ODP
A: 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 6FDA: 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane dianhydride, HQDA: 4,4 '(p-phenylenedioxy) diphthalic acid dianhydride, DSDA: 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, * 3) PA : Phthalic anhydride, AN: aniline, NA: 1,8-naphthalenedicarboxylic acid anhydride, * 4) m-HBA: m-hydroxybenzoic acid, m-ABA: m-
Aminobenzoic acid, p-SFA: p-sulfanilic acid, p-HP
S: p-hydroxyphenylsulfonic acid, m-APH: m-aminophenol, p-HPA: p-hydroxyphenylacetic acid, m-APA: m-aminophenylacetic acid, m-SPA: m-sulfenylacetic acid, p- HBA: p-hydroxybenzoic acid * 5) The linear expansion coefficient is measured in the temperature range of 50 to 150 ° C

[0038]

INDUSTRIAL APPLICABILITY Since the polyimide ferm produced by the method of the present invention has a small linear expansion coefficient and excellent dimensional stability, it can be said to be an industrially useful method for producing a polyimide.

Claims (4)

[Claims] 1. A compound of the general formula (1) (Wherein X is _{direct, -SO 2 -, - CO -} , - O -, - S
_{-, - C (CH 3)} 2 - or -C (CF _{3) 2} - represents a. ) And an aromatic diamine compound represented by the general formula (2) By reacting a tetracarboxylic dianhydride represented by the following general formula (3) (Chemical Formula 3) (Wherein X and Ar are the same as those in the general formulas (1) and (2)), the aromatic diamine compound represented by the general formula (1) is used in the method for producing a polyimide having a repeating structural unit. after the general formula (2) the tetracarboxylic acid dianhydride represented by the polyimide precursor was reacted in a solvent, OH groups, NH2 groups, COOH groups, CH ₂ at least 2 COOH groups and SO ₃ H groups A method for producing a polyimide, which comprises imidizing in the presence of a compound having one or more on an aromatic ring of one molecule. 2. When producing a polyimide having a repeating structural unit represented by the general formula (3), the general formula (4)
(Formula 4) (In the formula, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. Is 2
Represents a valence group. ) And / or the general formula (5) V-NH ₂ (5) (wherein V has 6 to 15 carbon atoms, a monocyclic aromatic group, and a condensed polycyclic group). A non-condensed polycyclic aromatic group in which the aromatic group or the aromatic groups are connected to each other directly or by a bridging member 1
Represents a valence group. 3. The method for producing a polyimide according to claim 1, further comprising a polymer obtained by allowing an aromatic monoamine represented by the formula (1) to coexist with the end of the polymer being blocked. 3. A polyimide obtained by the method according to claim 1. 4. A polyimide film obtained from the polyimide of claim 3.