JPH05310935A - Polyimide, its precursor polymer and resin solution composition - Google Patents

Abstract

PURPOSE:To provide a polyimide composed of respective specific recurring units, etc., at specific ratios, having an intrinsic viscosity higher than a specific level, easily soluble in solvents, having excellent heat-resistance and useful as a coating agent, etc. CONSTITUTION:The objective polyimide is composed of 1-100mol% of a recurring unit of formula I [Ar is bivalent organic group; R is (substituted) alkyl or (substituted) phenyl; m and n are integers of >=1] and 0-99mol% of a recurring unit of formula II (Ar' is tetravalent organic group) and has an intrinsic viscosity of >=0.1dl/g. A precursor polymer of the polyimide and a resin solution composition produced by dissolving the polyimide in a solvent are also useful.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polyimide excellent in solvent solubility in a low boiling point solvent, its precursor polymer, and a polyimide excellent in solvent solubility in a low boiling point solvent, or a precursor polymer thereof in a soluble solvent. The present invention relates to a resin solution composition which is useful as a dissolved coating agent and the like.

[0002]

2. Description of the Related Art Conventionally, when a polyimide having excellent heat resistance is used as a coating agent for electronic parts, etc., since the polyimide is insoluble except for some high boiling point solvents,
In addition to applying a polar solvent solution of polyamic acid, which is a precursor polymer of polyimide, to the substrate and drying the solvent,
It was necessary to perform heat treatment for a long time at a high temperature of 00 ° C. or higher to imidize.

However, in such a method, the generation of stress due to heat treatment and the corrosiveness due to polyamic acid have been problems. (Journal of the Institute of Electronics, Information and Communication Engineers, C, Vol. J71
-C, No. 11. pp1510 (1988), IEICE Transactions C, Vol. J71-C, No. 1
1. pp1516 (1988))

In order to solve these problems, a specific tetracarboxylic dianhydride and a specific diamine are used to form N-
A method for obtaining a polyimide soluble in a polar solvent such as methyl-2-pyrrolidone has been proposed. (Japanese Patent Publication No. 52-303
19, Japanese Patent Publication No. 61-83228, Japanese Patent Publication No. 6
2-18426 publication)

[0005]

However, in the case of this method, the boiling point of a polar solvent such as N-methyl-2-pyrrolidone is high, and therefore, heat treatment conditions at high temperature for a long time are required for complete removal of the solvent. And, there was a problem in its workability.

The present invention solves the above problems and is suitable for coating agents for electronic parts and the like, and has excellent solvent solubility in low boiling point solvents, its precursor polymer, and polyimide having excellent solvent solubility in low boiling point solvents. It is an object of the present invention to provide a resin solution composition which is useful as a coating agent or the like, which is obtained by dissolving a precursor polymer thereof in a soluble solvent.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the inventors of the present invention have made extensive studies on imparting solvent solubility to a low boiling point solvent, and as a result, have completed the present invention. ..

That is, the present invention comprises 1 to 100 mol% of repeating units represented by the following general formula (I) and the following general formula (I)
I) consisting of 0 to 99 mol% of the repeating unit,
It is a polyimide having an intrinsic viscosity of 0.1 dl / g or more.

General formula (I)

[0010]

[Chemical 10]

General formula (II)

[0012]

[Chemical 11]

(In the formula, Ar is a divalent organic group and Ar 'is 4
A valent organic group, R is an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m and n are integers of 1 or more. However, Ar, Ar ', R, m, and n may be different for each repeating unit. )

The present invention also provides the following general formula (III)
Of 1 to 100 mol% of the repeating unit represented by the following formula and 0 to 99 mol% of the repeating unit represented by the following general formula (IV), and the intrinsic viscosity is 0.1 dl / g or more. It is a polyamic acid that is a precursor polymer.

Formula (III)

[0016]

[Chemical formula 12]

General formula (IV)

[0018]

[Chemical 13]

(In the formula, Ar is a divalent organic group and Ar 'is 4
A valent organic group, R is an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m and n are integers of 1 or more. However, Ar, Ar ', R, m, and n may be different for each repeating unit. )

Further, the present invention comprises 1 to 100 mol% of repeating units represented by the following general formula (V) and 0 to 99 mol% of repeating units represented by the following general formula (VI), and has an intrinsic viscosity. Is 0.1 dl / g or more, which is the thermoplastic resin which is the polyimide precursor polymer according to claim 1.

General formula (V)

[0022]

[Chemical 14]

General formula (VI)

[0024]

[Chemical 15]

(In the formula, R'and R "are the formulas (VII) and (V
Structures III) and (IX) are 0 in any order.
To 99%, 0 to 99%, 0 to 100% in molar ratio, Ar is a divalent organic group, Ar 'is a tetravalent organic group, R is an alkyl group, a substituted alkyl group, phenyl A group or a substituted phenyl group, m and n are integers of 1 or more. However, Ar, Ar ', R, m, and n may be different for each repeating unit. )

Formula (VII)

[0027]

[Chemical 16]

Formula (VIII)

[0029]

[Chemical 17]

Formula (IX)

[0031]

[Chemical 18]

Further, the present invention is characterized in that the above-mentioned polyimide is dissolved in a soluble solvent, and that the above-mentioned polyamic acid is dissolved in a soluble solvent. And a resin solution composition comprising the above-mentioned thermoplastic resin dissolved in a soluble solvent.

The present invention will be described in more detail below. The polyimide of the present invention has 1 to 100 mol% of repeating units represented by the following general formula (I), preferably 10 to 100 mol%, more preferably 30 to 100 mol%, and most preferably 50 to 100 mol%. And 0 to 99 mol% of the repeating unit represented by the following general formula (II), preferably 0 to
It preferably comprises 90 mol%, more preferably 0 to 70 mol%, and most preferably 0 to 50 mol%. When the repeating unit represented by the general formula (I) is less than 1 mol% and the repeating unit represented by the general formula (II) exceeds 99 mol%, the solubility in a low boiling point solvent is poor.

General formula (I)

[0035]

[Chemical 19]

General formula (II)

[0037]

[Chemical 20]

The polyamic acid of the present invention comprises 1 to 100 mol% of repeating units represented by the following general formula (III):
Preferably 10 to 100 mol%, more preferably 30
~ 100 mol%, most preferably 50-100 mol%
And a repeating unit represented by the following general formula (IV) 0 to
It is desirable to comprise 99 mol%, preferably 0 to 90 mol%, more preferably 0 to 70 mol%, and most preferably 0 to 50 mol%. When the repeating unit represented by the general formula (III) is less than 1 mol% and the repeating unit represented by the general formula (IV) exceeds 99 mol%, the obtained polyimide has poor solubility in a solvent having a low boiling point. Get scarce.

General formula (III)

[0040]

[Chemical 21]

General formula (IV)

[0042]

[Chemical formula 22]

The thermoplastic resin which is the precursor polymer of the polyimide of the present invention has 1 to 100 mol% of repeating units represented by the following general formula (V), preferably 10 to 100 mol%, more preferably 30 to 100 mol%, most preferably 50 to 100 mol%, and 0 to 99 mol% of repeating units represented by the following general formula (VI), preferably 0 to 9
Desirably, it comprises 0 mol%, more preferably 0 to 70 mol%, and most preferably 0 to 50 mol%. When the repeating unit represented by the general formula (V) is less than 1 mol% and the repeating unit represented by the general formula (VI) exceeds 99 mol%, the obtained polyimide has poor solubility in a solvent having a low boiling point. Get scarce.

General formula (V)

[0045]

[Chemical formula 23]

General formula (VI)

[0047]

[Chemical formula 24]

(In the formula, R ′ and R ″ are represented by formulas (VII) and (V
Structures III) and (IX) are 0 in any order.
~ 99%, 0-99%, 0-100% represents that it contains at a molar ratio. )

Formula (VII)

[0050]

[Chemical 25]

Formula (VIII)

[0052]

[Chemical formula 26]

Formula (IX)

[0054]

[Chemical 27]

Formulas (VII) and (VII) in the present invention
The structures represented by I) and formula (IX) are called an imide structure, an amic acid structure, and an isoimide structure, respectively, and the amic acid structure becomes an imide structure by dehydration ring closure. In this dehydration ring closure, the amic acid structure can be directly made into an imide structure by selecting the reaction conditions, or all or part of it can be once made into an isoimide structure and then made into an imide structure. Accordingly, the polyamic acid having only the structure (amide acid structure) represented by the formula (VIII) reaches the polyimide having the structure (amide structure) represented by the formula (VII) in the process of reaching the formula (V
II), (VIII), and the structure represented by (IX) are 0-99%, 0-99%, 0-100, respectively in arbitrary order.
It is possible to pass through a thermoplastic resin containing it in a molar ratio of%.

General formula (I), general formula (II) of the present invention,
In the general formula (III), the general formula (IV), the general formula (V) and the general formula (VI), Ar is at least one kind of divalent organic group, and the structure of the monomer as the base has the following structure. There is a structure represented by the general formula (X) or the general formula (XI), but it is not limited thereto.

General formula (X)

[0058]

Embedded image H ₂ N—Ar—NH ₂

General formula (XI)

[0060]

[Image Omitted] OCN-Ar-NCO Further, suitable monomers for use in the present invention as the source of Ar include the following, but not limited thereto.

M-phenylenediamine, p-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6
-Diaminonaphthalene, 2,7-diaminonaphthalene,
2,6-diaminoanthracene, 2,7-diaminoanthracene, 1,8-diaminoanthracene, 2,4-diaminotoluene, 2,5-diamino (m-xylene),
2,5-diaminopyridine, 2,6-diaminopyridine, 3,5-diaminopyridine, 2,4-diaminotoluenebenzidine, 3,3'-diaminobiphenyl, 3,
3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenyl ether, 4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,
4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl thioether, 4,4'-diamino-3,3 ', 5,5' -Tetramethyldiphenyl ether, 4,4'-diamino-
3,3 ', 5,5'-tetraethyldiphenyl ether, 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylmethane, 1,3-bis (3-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy)
Benzene, 2,6-bis (3-aminophenoxy) pyridine, 1,4-bis (3-aminophenylsulfonyl)
Benzene, 1,4-bis (4-aminophenylsulfonyl) benzene, 1,4-bis (3-aminophenylsulthioether) benzene, 1,4-bis (4-aminophenylthioether) benzene, 4,4'- Screw (3-
Aminophenoxy) diphenyl sulfone, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, bis (4-aminophenyl) amine, bis (4-aminophenyl) -N-methylamine, bis (4-aminophenyl) -N-phenylamine, bis (4-aminophenyl) phosphine oxide, bis (4-aminophenyl)
Dimethylsilane, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) methylphenylsilane, bis (4-aminophenyl) diphenylsilane,
1,1-bis (3-aminophenyl) ethane, 1,1-
Bis (4-aminophenyl) ethane, 2,2-bis (3
-Aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-amino-
3,5-Dimethylphenyl) propane, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3
-Aminophenoxy) phenyl] sulfone, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether,
Bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy)
Phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-Aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-
Aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4-
(4-Aminophenoxy) phenyl] ethane, 2,2-
Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4 -Aminophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4
-(4-aminophenoxy) phenyl] butane, 2,2
-Bis [3-methyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dimethyl-4
-(4-aminophenoxy) phenyl] butane, 2,2
-Bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 1 , 1,1,3,3,3-hexafluoro-2,
2-bis [3-methyl-4- (4-aminophenoxy)
Phenyl] propane, bis (3-aminophenyl)-
1,1,3,3-tetramethyldisiloxane, bis (4
-Aminophenyl) -1,1,3,3-tetramethyldisiloxane, bis (3-aminophenoxy) -1,1,
3,3-tetramethyldisiloxane, bis (4-aminophenoxy) -1,1,3,3-tetramethyldisiloxane, bis (3-aminophenyl) tetramethyldisilane, bis (4-aminophenyl) tetramethyl Disilane, bis (3-methyl-4-aminophenyl) tetramethyldisilane, bis (3-aminophenoxy) tetramethyldisilane, bis (4-aminophenoxy) tetramethyldisilane, p-phenylene diisocyanic acid, 4,
4-Diisocyanic acid diphenyl ether.

The general formula (II) and the general formula (I
V) and in the general formula (VI), Ar ′ is at least one tetravalent organic group, and the structure of the monomer as the base is represented by the following general formula (XII) or general formula (XIII). There is a structure shown, but not limited to this.

General formula (XII)

[0064]

[Chemical 30]

General formula (XIII)

[0066]

[Chemical 31]

(Wherein X is at least one kind of hydroxyl group or halogen group, Y is at least one kind of alkyl group,
It is a substituted alkyl group, a phenyl group, a substituted phenyl group or a proton. ) Suitable monomers to be used in the present invention include, but are not limited to, the following monomers from which Ar ′ is derived. Pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 2,3,4,5-thiophenetetracarboxylic acid Acid dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3', 3,4 '
-Benzophenone tetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -p-terphenyltetracarboxylic dianhydride, 2,2 ″, 3,
3 ″ -p-terphenyltetracarboxylic dianhydride,
2,3,3 ", 4" -p-terphenyltetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride Anhydride, 1,2,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 1,2,6,7-phenanthrene tetracarboxylic dianhydride , 1, 2, 7, 8
-Phenanthrene tetracarboxylic dianhydride, 1,2,
9,10-phenanthrene tetracarboxylic acid dianhydride,
3,4,9,10-berylenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4 5,8-tetracarboxylic dianhydride, 2,
3,6,7-Tetrachloronaphthalene-1,4,5,8
-Tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, Bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,3
4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1, 1-bis (3,4-
Dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,6-bis (3,4-dicarboxyphenoxy) pyridine dianhydride, 1,1,1,3,3,3-
Hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloquirane dianhydride, Pyromellitic acid, pyromellitic acid tetrachloride, pyromellitic acid dimethyl ester, pyromellitic acid diethyl ester, pyromellitic acid diphenyl ester.

General formula (I) and general formula (III) of the present invention
In the general formula (V), m is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and most preferably an integer of 1 to 5. n is an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. R is at least one kind of an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and includes the following, but not limited thereto.

Methyl group, ethyl group, propyl group, isopropyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, phenyl group, p-toluyl group, m-toluyl group.

The monomers that are the basis of these structures include bis (3,4-dicarboxyphenyl) methyl (3,3,3-trifluoro-n-propyl) silane dianhydride and bis (3,3). 4-dicarboxyphenyl) methyl (3,3,4,4,5,5,6,6,6-nonafluoro-n-hexyl) silane dianhydride, bis (3,4-dicarboxyphenyl) methyl (3 , 3, 4, 4, 5, 5,
6,6,7,7,8,8,8-tridecafluoro-n-
Octyl) silane dianhydride, but not limited to this.

In order to synthesize the above silicon-containing fluorine-containing monomer, first, 4-chloro-o-xylene or the like 4-
A Grignard reagent was synthesized using halo-o-xylene, and this was used as a 3,3,3-trifluoro-n-propyl group, 3,3,4,4,5,5,6,6,6-nonafluoro- n-hexyl group, or 3,3,4,4,5,5,
6,6,7,7,8,8,8-tridecafluoro-n-
React with a dihalosilicon compound containing an octyl group. Then, bis (3,4-dimethylphenyl) methyl (3,3,3-trifluoro-n-propyl) silane and bis (3,4-dimethylphenyl) methyl (3,3,4,) thus obtained. 4,5,5,6,6,6-nonafluoro-n-hexyl) silane, or bis (3,4-dimethylphenyl) methyl (3,3,4,5,5,6,6)
The silicon-containing fluorine-containing monomer is synthesized by oxidizing 6,7,7,8,8,8-tridecafluoro-n-octyl) silane.

Generally, the specific viscosity of a solution is measured at two or more points,
The value obtained by dividing them by the concentration is called the intrinsic viscosity. And
A value obtained by extrapolating this intrinsic viscosity to a concentration of 0.0 g / dl is called intrinsic viscosity. This intrinsic viscosity means the apparent effective volume occupied by one molecule in a solution, and is a value that depends on the type of polymer, the molecular weight, the type of solvent, and the temperature. It is possible to define the magnitude relationship of molecular weights under a constant condition.

On the other hand, in the solution, the effective volume occupied by one molecule of the polymer changes greatly depending on the affinity with the solvent. That is, in a solvent having a good affinity with itself, the effective volume becomes large, which makes it easy to compare the molecular weights.

Therefore, in the present invention, the molecular weight of polyimide, polyamic acid, and thermoplastic resin is at least one solvent selected from tetrahydrofuran, dichloromethane, N, N-dimethylformamide, N-methyl-2-pyrrolidone, and concentrated sulfuric acid. Medium, an intrinsic viscosity at 30 ° C. of at least 0.1 dl / g or more, preferably 0.5 d
It is desirable that it is 1 / g or more, and more preferably 1.0 dl / g or more. If the intrinsic viscosity is less than 0.1 dl / g, a polyimide having sufficient strength cannot be obtained.

In the present invention, the polyimide, its precursor polymer, polyamic acid, and the thermoplastic resin are excellent in solvent solubility in a solvent having a low boiling point. Examples of the solvent having a low boiling point are as follows. There is, but not limited to this.

Chloroform, dichloromethane (CH ₂ C
l ₂ ), 1,1,1-trichloroethane, 1,1,2-
Organic halides such as trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene and tetrachloroethylene. Pyridine, 2-picoline, 3-picoline, 4-picoline, 2,3-lutidine, 2,4-lutidine, 2,5-
Lutidine, 2,6-lutidine, 3,4-lutidine, 3,
Heteroaromatic compounds such as 5-lutidine and 2,6-lutidine. Aprotic polar solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. Cyclic ethers such as tetrahydrofuran (THF) and dioxane.

These solvents can be used as they are or as a mixture. The term “soluble in a low boiling point solvent” as used in the present invention means that it is soluble in at least one kind of low boiling point solvent at room temperature in an amount of 10 g / 1 or more.

The resin solution composition of the present invention can be obtained by dissolving the above polyimide, its precursor polymer, polyamic acid, and the thermoplastic resin in the above low boiling point solvent. Further, the polyimide of the present invention, a polyamic acid that is a precursor polymer thereof, and a thermoplastic resin,
In the case of using each of them, a solvent having good solubility may be appropriately selected and used from the above low boiling point solvents.

In particular, the polyimide of the present invention is excellent in solvent solubility in a low boiling point solvent such as tetrahydrofuran (boiling point 65 ° C.) or dichloromethane (boiling point 40 ° C.), and is dissolved in such a low boiling point solvent. To obtain a resin solution composition. Therefore, it is excellent in workability as a coating agent, and specifically, it can be used in a wide range of applications such as an insulating protective film for electronic parts, a printed circuit board, a flexible printed circuit board, an electrical insulating material such as various laminated plates, and the like. ..

[0080]

The present invention will be described in detail below with reference to examples.

Example 1 4,4'-diaminodiphenyl ether (ODA) 0.
840 g (4.195 mmol) was dissolved in 19.528 g of N, N-dimethylformamide (DMF). To this solution was added bis (3,4-dicarboxyphenyl) methyl (3,3,3-trifluoro-n-propyl) silane dianhydride (MFPSI) 1.822 g (4.194 mmo).
l) was added to obtain a solution of polyamic acid in N, N-dimethylformamide (DMF).

The obtained polyamic acid DMF solution was formed into a film by a casting method (film thickness: 4 μm).
m), a film having a composition of 0% imide, 0% isoimide, and 100% amic acid in molar ratio was obtained. The results of measuring the physical properties are shown in Table 1.

Example 2 A part of the film obtained in Example 1 was heat-treated in an electric furnace (1 mmHg, 250 ° C., 5 hours) to give a molar ratio of 100% imide, 0% isoimide and 0% amic acid. A film having a composition consisting of The results of measuring the physical properties are shown in Table 1, and the results of the infrared absorption spectrum are shown in FIG.

Example 3 4,4'-diaminodiphenyl ether (ODA) 0.
801 g (4,000 mmol) and 0.005 g (0.041 mmol) of p-anisidine as a molecular weight regulator were added to N, N-dimethylformamide (DMF) 18.698.
g. To this solution was added bis (3,4-dicarboxyphenyl) methyl (3,3,3-trifluoro-n-
Propyl) silane dianhydride (MFPSI) 1.746 g
(4.019 mmol) was added, and N, N of polyamic acid was added.
A dimethylformamide (DMF) solution was obtained.

0.5 m of the obtained polyamic acid DMF solution
1 m was added dropwise to 20 ml of dichloromethane (CH ₂ Cl ₂ ) to obtain a precipitate, and 1 m of tetrahydrofuran (THF) was added.
It was dissolved in 1 and 20 ml of dichloromethane was added to this to obtain a white powder. The obtained powder was dissolved in 0.5 ml of THF, and then a film was formed by a casting method (film thickness: 4 μm).
%, And a film having a composition of 100% amic acid was obtained.
The results of measuring the physical properties are shown in Table 1, and the results of the infrared absorption spectrum are shown in FIG.

Example 4 A part of the film obtained in Example 3 was heat-treated (1 mmHg, 100 ° C., 1 hour) in an electric furnace to give a molar ratio of 22% imide, 0% isoimide and 78% amic acid. A film having a composition of was obtained. The results of measuring the physical properties are shown in Table 1.

Example 5 A portion of the film obtained in Example 3 was heat-treated in an electric furnace (1 mmHg, 150 ° C., 1 hour) to give a molar ratio of imide 59%, isoimide 0%, and amic acid 41%. A film having a composition of was obtained. The results of measuring the physical properties are shown in Table 1.

Example 6 A part of the film obtained in Example 3 was heat-treated (1 mmHg, 200 ° C., 1 hour) in an electric furnace to give a molar ratio of 100% imide, 0% isoimide and 0% amic acid. A film having a composition of was obtained. The results of measuring the physical properties are shown in Table 1.

Example 7 A part of the film obtained in Example 1 was treated with toluene 18.4.
g (0.2 mol), acetic anhydride 2.0 g (0.02 mo
It was dipped for 1 hour in a mixed solvent consisting of 1) and 1.6 g (0.02 mol) of pyridine. It was dried under vacuum at 60 ° C. to obtain a film having a composition of 15% imide, 25% isoimide, and 60% amic acid in molar ratio. The results of measuring the physical properties are shown in Table 1, and the results of the infrared absorption spectrum are shown in FIG.

Example 8 A part of the film obtained in Example 7 was heat-treated in an electric furnace (1 mmHg, 235 ° C., 5 hours) to give a molar ratio of 75% imide, 25% isoimide, and 0% amic acid. A film having a composition of was obtained. The results of measuring the physical properties are shown in Table 1.

Example 9 Part of the film heat-treated in Example 8 was further heat-treated in an electric furnace (1 mmHg, 360 ° C., 5 hours).
Then, it was confirmed in the infrared absorption spectrum that the absorption of isoimide disappeared. The results of measuring the physical properties are shown in Table 1.

Comparative Example 1 4,4'-diaminodiphenyl ether (ODA)
996 g (4.975 mmol) and 0.006 g (0.049 mmol) of p-anisidine as a molecular weight regulator were added to N, N-dimethylformamide (DMF) 15.339.
g. To this solution, 1.091 g (5.002 mmol) of pyromellitic dianhydride (PMDA) was added, and N, N-dimethylformamide (D) of polyamic acid was added.
An MF) solution was obtained.

The obtained polyamic acid DMF solution was formed into a film by a casting method (film thickness: 4 μm).
m). The obtained film is heat-treated in an electric furnace (1 mmH
g, 400 ° C., 5 hours) and then the imide 100 in molar ratio
%, Isoimide 0%, and amic acid 0% to obtain a film. The results of measuring the physical properties are shown in Table 1.

Comparative Example 2 4,4'-diaminodiphenyl ether (ODA) 3.
004 g (15.002 mmol) was dissolved in N, N-dimethylformamide (DMF) 54.387 g.
To this solution, 4.414 g (15.00) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added.
2 mmol) was added to obtain a N, N-dimethylformamide (DMF) solution of polyamic acid.

The obtained polyamic acid DMF solution was formed into a film by a casting method (film thickness: 4 μm).
m). The obtained film is heat-treated in an electric furnace (1 mmH
g, 250 ° C., 5 hours), and then the imide 100 in a molar ratio.
%, Isoimide 0%, and amic acid 0% to obtain a film. The results of measuring the physical properties are shown in Table 1.

Comparative Example 3 4,4'-diaminodiphenyl ether (ODA) 1.
001 g (4.999 mmol) was dissolved in N, N-dimethylformamide (DMF) 19.158 g. To this solution, 1.611 g (5.00) of 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA) was added.
0 mmol) was added to obtain a N, N-dimethylformamide (DMF) solution of polyamic acid.

The obtained polyamic acid DMF solution was formed into a film by a casting method (film thickness: 4 μm).
m). The obtained film is heat-treated in an electric furnace (1 mmH
g, 250 ° C., 5 hours), and then the imide 100 in a molar ratio.
%, Isoimide 0%, and amic acid 0% to obtain a film. The results of measuring the physical properties are shown in Table 1.

[0098]

[Table 1]

(Note) (1) Intrinsic viscosity: N, N-dimethylformamide (DM
F), dichloromethane (CH ₂ Cl ₂ ), tetrahydrofuran (THF), or concentrated sulfuric acid (H ₂ SO ₄ ) as a solvent, measured at 30 ° C. using an Ubbelohde viscometer.

(2) Composition ratio of imide, isoimide, amic acid: Infrared absorption spectrum was measured to be 1500 cm.
^-1 (benzene nucleus) as internal standard, 1775cm
^-1 (imide), 1800 cm ^-1 (isoimide), and 1650 cm ^-1 (amide acid) calculated from the absorbance of such.

(3) Glass transition temperature (Tg): Calculated by differential scanning calorimetry (DSC). The measurement conditions are a nitrogen atmosphere, a temperature rising rate of 10 ° C./min, and a temperature range of 50 to 400.
° C.

(4) Solubility: 10 mg of the test piece was dipped in 1 ml of dichloromethane (CH ₂ Cl ₂ ) or tetrahydrofuran (THF) and visually determined. Those dissolved at room temperature are indicated by ◯, and those that did not change are indicated by x.

[0103]

Industrial Applicability As described above, the polyimide according to the present invention is excellent in solvent solubility in a solvent having a low boiling point, and can be dissolved in a solvent having a low boiling point to obtain a resin solution composition having excellent workability. The effect of the present invention is enormous.

[Brief description of drawings]

FIG. 1 is a graph showing an infrared absorption spectrum of Example 2.

FIG. 2 is a graph showing an infrared absorption spectrum of Example 3.

FIG. 3 is a graph showing an infrared absorption spectrum of Example 7.

Claims (6)

[Claims] 1. A recurring unit of 1 to 100 mol% represented by the following general formula (I) and a recurring unit of 0 to 99 mol% represented by the following general formula (II) having an intrinsic viscosity of 0.
A polyimide having a content of 1 dl / g or more. General formula (I): General formula (II): (In the formula, Ar is a divalent organic group, Ar 'is a tetravalent organic group,
R is an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m and n are integers of 1 or more. However, Ar, Ar ', R, m, and n may be different for each repeating unit. ) 2. A repeating unit of 1 to 100 mol% represented by the following general formula (III) and a repeating unit of 0 to 99 mol% represented by the following general formula (IV), and an intrinsic viscosity of 0.1 dl. / G or more, polyamic acid which is the precursor polymer of the polyimide according to claim 1. General formula (III): General formula (IV): (In the formula, Ar is a divalent organic group, Ar 'is a tetravalent organic group,
R is an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m and n are integers of 1 or more. However, Ar, Ar ', R, m, and n may be different for each repeating unit. ) 3. A repeating unit of 1 to 100 mol% represented by the following general formula (V) and 0 to 99 mol% of a repeating unit represented by the following general formula (VI), and an intrinsic viscosity of 0.
The thermoplastic resin, which is a precursor polymer of polyimide according to claim 1, having a content of 1 dl / g or more. General formula (V) General formula (VI): (In the formula, R ′ and R ″ are formulas (VII), (VIII),
The structure of (IX) is 0 to 99% in any order,
Ar represents a divalent organic group, Ar 'represents a tetravalent organic group, R represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. The groups, m and n are integers of 1 or more. However,
Ar, Ar ', R, m, and n may be different for each repeating unit. ) Formula (VII): Formula (VIII): Formula (IX): 4. A resin solution composition comprising the polyimide according to claim 1 dissolved in a soluble solvent. 5. A resin solution composition comprising the polyamic acid according to claim 2 dissolved in a soluble solvent. 6. A resin solution composition comprising the thermoplastic resin according to claim 3 dissolved in a soluble solvent.