WO2004062873A1

WO2004062873A1 - Process for producing polyimide film

Info

Publication number: WO2004062873A1
Application number: PCT/JP2003/008845
Authority: WO
Inventors: Shinya Tange; Shinichiro Mori; Ryouichi Nagashima; Tsutomu Nakamura; Toyoaki Ishiwata; Toru Sawaki
Original assignee: Teijin Limited
Priority date: 2003-01-08
Filing date: 2003-07-11
Publication date: 2004-07-29
Also published as: AU2003303671A1; TW200412357A; JPWO2004062873A1; JP4373925B2; TWI282802B

Abstract

A polyimide film is produced by adding a dehydrating reagent to a polyamic acid solution; subsequently casting the obtained solution over a support to thereby obtain a film; introducing the film together with the support in a reaction congelation vessel equipped with means for preventing leakage of air from inside the vessel to outside the vessel, and heating them in an atmosphere of 1 to 2000 ppm water content to thereby obtain a gel film having at least portion of the polyamic acid converted to polyimide or polyisoimide; separating the obtained gel film from the support, optionally followed by washing; performing simultaneous biaxial orientation or sequential biaxial orientation to thereby obtain a biaxially oriented film, optionally followed by washing so as to remove solvents; and performing heat treatment thereof, thereby forming a biaxially oriented polyimide film.

Description

Technical field Polyimide film production method Technical field.

The present invention relates to a method for producing a polyimide film with highly improved mechanical properties, and a biaxially oriented polyimide film obtained from the same. Background technology ',

Totally aromatic polyimide is widely used industrially because of its excellent heat resistance and mechanical properties, and in particular its film occupies an important position as a substrate of thin layer electronic parts including electronic mounting applications. There is. In recent years, due to strong demand for miniaturization of electronic parts, demands have been made that thinner polyimide films are required. With the decrease in thickness, high rigidity becomes an indispensable condition for practical or handling of films. . Although the wholly aromatic polyimide film has a rigid structure, for example, the high Young's modulus is not necessarily realized as compared to the wholly aromatic polyamide film, and even the highest Young's modulus polyimide film commercially available The current situation is to stay at the level of 9 GP a at most.

As a method of achieving high Young's modulus with a wholly aromatic polyimide film, (1) making the molecular structure constituting the polyimide into a rigid and highly linear chemical structure, and (2) molecular orientation of the polyimide by a physical method You can think of The chemical structure of (1) includes pyromellitic acid or 3, 3, 4, 4, 1-biphenyl tetracarboxylic acid as the acid component, paradiendiamine as the amine component, benzidine, or various combinations of their nuclear substitutes. Material examination has been made. Among them, polyparaphenylene dimellomeritimide has the highest theoretical yield rate (for example, Tashiro et al., “The Journal of Japan Society of Textile Science 4 3rd Series” 1 8 7 8 7 8). It is the material most expected as a high Young's modulus film material. · However, despite its potential, polyparaphenylene pyromellitic imide film As a result, there were problems such as extremely fragile and not able to obtain a force of 4 and no realization as a high Young's modulus film with well-balanced.

As a method to solve this problem, a method was proposed by chemically cyclizing a polyamic acid solution obtained by the reaction of paradylene dipyramine and pyromellitic acid anhydride. The ring ratio of the pyromellitic imide film was at most 8.5 GP a (Japanese Patent Application Laid-Open No. 1122291). In addition, a dope with a large amount of acetic anhydride added is cast on a polyamic acid solution obtained by the reaction of nucleus-substituted paradiurediamine and pyromellitic anhydride, and dried at a low temperature under reduced pressure and then heat-treated. It is described that a film with a Young's modulus of 2 0. 1 GP a can be obtained, but this method requires several hours of drying at low temperatures, and this is an industrially impractical technology. In addition, it is described that when this technology is applied to polyparaphenylene pyromellitic imide, it is not possible to measure a fragile film that can not even be measured by a machine, and its effect is limited. Japanese Patent Publication No. 6- 1 7 2 5 2 9).

Therefore, the realization technology of high Young's modulus film widely applicable to rigid aromatic polyimide is not completed, and polyparaphenylene pyromellitic imide film having high Young's modulus and practical toughness is not known in particular. As a method to solve these problems, we immersed the cast gel-like film in an isoimidation solution consisting of acetic anhydride which is a dehydration reaction agent, an organic amine compound which is a dehydration reaction catalyst and a solvent, and then in a swollen state. And a so-called wet film forming method were disclosed (WO O 1/8 1 46).

Also disclosed is a manufacturing method in which a gel-like film obtained by casting is solidified by a dry film forming method while removing the solvent on a drum or an endless belt, and then biaxially stretched in a swollen state to be imidized. However, when this dry film forming method is used for a rigid aromatic polyimide, especially polyparaphenylene pyrrole imide film, a brittle film can not be obtained. In addition, problems such as having to mix a large excess of dehydrating reaction agent and dehydrating reaction catalyst into the polyamic acid solution to sufficiently perform the isoimidization reaction remain. There has not been known a dry film forming method which is more industrially advantageous than the wet film forming method which can be widely applied to the production of decal. Disclosure of the invention

An object of the present invention is to provide a method for producing a polyimide film which is widely applicable to rigid polyimide production and industrially advantageous.

Another object of the present invention is to provide a high Young's modulus polyparaphenylene pyromellitic imide film according to the production method.

Other objects and advantages of the present invention will become apparent from the following description. The above objects and advantages of the present invention, (1) a polyamic acid solution was prepared, wherein the polyamic acid is p- phenylenediamine component 4 0 mol% 1 0 0 mole ^_0/0 hereinafter and p- Hue two Ren: an aromatic Jiamin component different aromatic Jiamin component consists of 0 mole ^_0/0 or 6 0 mole ^_0/0 following the Jiamin, pyromellitic acid component exceeds 8 0 mol% and pyromellitic acid The different aromatic tetracarboxylic acid component substantially consists of a tetracarboxylic acid component consisting of 0 mol% or more and less than 20 mol%, and the solvent of the polyamic acid solution is N, N-dimethylformamide, N, N _ Dimethylacetamide, N-methyl-2-pyrrolidone or at least one member selected from the group consisting of 1, 3-dimethylimidazole 'zinone;

(2) A polyamic acid composition prepared by adding acetic anhydride as a dehydration reaction agent and an organic amine compound as a dehydration reaction catalyst to the polyamic acid solution prepared in the above step (1) is cast on a support. Then, by subjecting this to heating and heat treatment, a dewatering reaction is carried out to form a gel film in which at least a part of the polyamic acid is converted to a polyimide or a polyimide.

(3) Separate the obtained gel film from the support, wash it if necessary, and biaxially stretch it;

(4) A method for producing a polyimide film, comprising subjecting the obtained biaxially stretched gel film to a heat treatment to form a biaxially oriented polyimide film, wherein the concentration of water in the reaction atmosphere in step (2) is Polyimide having a concentration of 1 to 200 ppm It is achieved by the method of producing a film. According to the present method, it is possible to provide a dry film-forming manufacturing method which can minimize the use amount of the dehydration reaction agent and the dehydration reaction catalyst at each solidification temperature. Brief description of the drawings

Figure 1

It is the schematic of an example of a reaction coagulation tank.

1. Reaction coagulation tank (shaded area)

2. Sealing tank

3. T die

4. Support

5.

6. Polyimide film

7. Atmospheric pressure dew point <1 ° C 8 ° C. Preferred embodiment of the invention

The method for producing the polyimide of the present invention) prepares a polyamic acid solution, wherein the polyamic acid has a p-phenylidenediamine component in an amount of 40% to 100% by mol and an aroma different from p-phenirendiamine. aromatic Jiamin component family Jiamin component consists 6 0 mole ^_0/0 following 0 mol% or more, pyromellitic acid component exceeds 8 0 mole ^_0/0, and an aromatic tetracarboxylic acid component different from pyromellitic The solvent of the polyamic acid solution is substantially N, N-dimethylformamide, N, N-dimethyl acetoamide, N-methyl-2-pylori, consisting essentially of a tetracarboxylic acid component consisting of at least 0 mol% and at most 20 mol%. At least one member selected from the group consisting of don and 1,3-dimethylimidazolidinone;

(2) The polyamic acid solution prepared in the above step (1) is further added as a dehydration reaction agent A polyamic acid composition formed by adding acetic anhydride and an organic amine compound as a dehydration reaction catalyst is cast on a support, and this is subjected to heating and heat treatment to cause dehydration reaction, resulting in at least one of polyamic acids. Form a gelfi / rem where part is converted to polyimide or polyisoimide;

(4) A method for producing a polyimide film, comprising subjecting the obtained biaxially stretched gel film to a heat treatment to form a biaxially oriented polyimide film, wherein the concentration of water in the reaction atmosphere of step (2) is 1 It is characterized in that it is set to .about.200 ppm.

The diamine component constituting the polyimide of the present invention is p-phenydiamine, an aromatic diamine different from that.

Examples of the aromatic diamine component different from p-phenylenediamine include, for example, m-phenylidenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6 —Diaminonaphthalene, 2,7-Diamino naphthalene, 2,6-Diamino anthracene, 2,7-Diamino anthracene, 1,8-Diamino anthracene, 2,4 Diamino Toluene, 2,5— Diamino (m-xylene), 2,5-diaminopyridine, 2,6-diaminopyridine, 3,5-diaminopyridine, 2, 4-diamino toluene benzidine, 3,3 'diamino biphenyl dinore, 3,3' dichloro benzene di, 3, 3, 1-dimethynolbenzidine, 3, 3,-dimethoxy benzidine, 2, 2, 1-diamino benzophenone, 4, 4 '-diamino benzophenone, 3, 3, 1 di. 4, 4, Diaminodiphenyl dinore ether, 3, 4, Diaminodiphenyle noree tenore, 3, 3, monodiaminodiphenylmethane, 4, 4 'diaminodiphenylmethane, 4, 4, Diaminodiphenyne ^ / methane, 3, 4 'Diaminodiphenynoles nolefon, 4, 4' Diaminodiphenyone ^ / sphone, 3, 3 'Diaminodipheninoles / Reid, 3, 4, dimethylaminodiphenyl sulfide, 4, 4, diaminodiphenyl sulfide, 4, 4, diaminodiphenyl thioether, 4, 4, 4-diamino 3,3,5,5'-tetramethyldiphenyl ether, Four, four, one diami No. 3,3 ', 5,5 -Tetraethinoresiphenone oleate, 4,4, Diamino no 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-aminophenylsulfoninole) benzene, 1,4-bis (4-amino-phenolenoles norefonole) benzene, 1,4-bis- (3-aminophenolenolethioate Nore Benzene, 1,4-bis (4-aminophenol thioether) benzene, 2,4-bis (3-aminophenoxy) diphenenores nolephon, 4,4'-bis (4-aminophenoxy) diphenyls Ruphon, bis (4-aminophenyl) -amine (1-amino-phenyl) -methylamino-bis- (4-amino-phenol-no-le) -'- pheneno-leamine bis (4-amino-phenol-no-le) phosphinoxide, 1, 1- Bis (3-aminophenyl) ethane, 1, 1 bis (4-aminophenol) ethanol, 2, 2- bis (3- aminophorene) propane, 2, 2- bis (4-aminophenyl) propane 2, 2-bis (4-amino-3, 5-dimethynolefinole) propane, 4, 4-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) -phen-2-ol] snolephon, bis [4 4-(4 amino amino phenyl) phenyl] sulfoshi, bis [4 (4 amino amino phenyl) phenyl] ether, bis [4 (4 amino amino phenyl) phenyl] methane, bis [3-Methlyol 4- (4-aminophenoxy) phenoxy] methane, bis [3- cro- 4-(4 _ aminophenoxy) fuel] methane, bis [3, 5- dimethinole 4-(4- aminophenoxy) Phenyl] methane, 1,1-bis [4-amino-phenyloxy] phenyl] ethane, 1,1-bis- [3-methyl-4- (4-amino-phenyloxy) phenyl] ethane, 1,1-bis- [phenyl] methane 3-Black Mouth 1 1 1 (4-amino-phenoxy) phenyl] ethane, 1, 1 bis [3, 5-dimethyl 1 4 1 (4- phaminophenoxy) phenylene] ether, 2, 1 bis [4- ( 4 1-aminophenoxy) phenyl] propane, 2, 2-bis [3- methinolee 4 1 (4-amino-phenoxy) phenone] propane, 2, 2- bis [3- chloro-4 1 (4 amino amino acid) Enoxy) 二 f ノ nore] propane, 2,2-bis [3,5 ジメチル dimethyl-4 ((4-aminophenoxy) 二 finore] propane, 2, 2-bis [4 一 (4-amino phenoxy) phenyl] butane, 2 2, 2-bis [3-methyl-4- (4-amino-phenyloxy) phenyl] putane, 2,2-bis [3,5-dimethynole-4l (4-aminoaminophenoxy) phenyl] butane, 2,2-bis [3 4-(4 amino amino phenoxy) phenyl] butane, 1, 1, 1, 3, 3, 3-Hexafluoro 1 2, 2-bis (4-aminophenol 2) propane, 1, 1 1, 3, 3, 3 1-hexafluoro-2-, 2-bis [3-methyl- 4-(1-aminophenoxy) phenyl] propane, etc. and aromatic ring substitutes with their halogen atoms or alkyl groups. '

The diamine component may consist of p-phenylenediamine alone or in combination with p-phenylenediamine and a combination of aromatic diamines different from those mentioned above. In the latter case, p-phenylenediamine is in a proportion of at least 40 mol%, preferably at least 60 mol%, based on the total diamine component, and 60 mol% of another aromatic diamine different therefrom. % Or less, preferably 40 mol% or less.

Further, the tetracarboxylic acid component constituting the polyimide is pyromellitic acid and an aromatic tetracarboxylic acid different therefrom.

Examples of the aromatic tetracarboxylic acid component different from pyromellitic acid include, for example, 1, 2, 3, 4_ benzenetetracarboxylic acid dianhydride, 2, 3, 5, 6-pyridinetetracarboxylic acid dianhydride, 2, 3 , 4,5-Thiophene tetracarboxylic dianhydride, 2, 2, 3, 3, monobenzophenone tetracarboxylic dianhydride, 2, 3, 3, 4, 4'-benzophenone tetracarboxylic acid Acid dianhydride, 3, 3, 4, 4, 1 -benzophenone tetracarboxylic acid dianhydride, 3, 3, 4, 4, 1-biphenyl tetrabasic rubonic acid dianhydride, 2, 2 ', 3, 3, 1-biphenyl tetracarboxylic dianhydride, 2, 3, 3, 4 '-biphenyl tetracarboxylic dianhydride, 3, 3, 4 4' 1 p-terphenyl tetracarboxylic dianhydride 2, 2, 3, 3, 1 p-terphenyltetracarboxylic acid dianhydride, 2, 3, 3, 4, 1 p-terphenyl Te tetracarboxylic acid dianhydride, 1, 2, 4, 5-naphthalene tetracarboxylic dianhydride , 1,2,5,6-Naphthalenetetracarboxylic dianhydride, 1,2,6,7-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-Naphthalene tetranohydride dianhydride , 2, 3, 6, 7-Naphthalenetetracarboxylic acid dianhydride, 2, 3, 6, 7-Anthracenetetracarboxylic acid dianhydride, 1, 2, 5, 6-Anthracene tetracarboxylic acid dianhydride 1,2,6,7-phenanthrenetetracarbanoic acid dianhydride, 1,2,7,8-phenenthrenetetracarboxylic acid dianhydride, 1,2,9,10-phenanthrenetetra Norebonic acid dianhydride, 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride, 2, 6-dichloronaphthalene 1, 4, 5, 8-tetracarboxylic acid dianhydride, 2, 7- Dichloroethene naphtha-thalene 1 1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene 1,4,5,8-tetracarboxylic acid dianhydride, 1,4,5,8-tetrachloronaphthalenone 2,3,6,7-tetracarboxylic acid dianhydride, bis (2,3-dicarboxylic acid dianhydride Shifenyl) ethenoreny anhydride, bis (3, 4-dicanorexoxie finchone) etheri anhydride, bis (2, 3-dicarpoxyphenyl) methane dianhydride, bis (3, 4- dicarpoxyphenyl) ) Methane dianhydride, bis (2, 3-dicarboxyphenyl) sulfone dianhydride, bis (3, 4- dicarboxyphenyl) sulfone dianhydride, 1, 1- bis (2, 3- dicarboxy) Phenyl) ethane dianhydride, 1,1-bis (3, 4-di kanore boxila e dinore) ethane di anhydride, water, 2, 2- bis (2, 3- dicarboxyphenyl) propane dianhydride 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride 2, 6-bis (3,4-dioroleboxyphenoxy) pyridine dianhydride, 1, 1, 1, 1, 3, 3, 3 _ hexafanololaro 2, 2 1 bis (3, 4-diforce ^ / boxyphee ii Nore) propane dianhydride, bis (3, 4-disulfoxyphenyl) dimethylsilane dianhydride, etc. may be mentioned.

The tetracarboxylic acid component may consist of pyromellitic acid alone or a combination of pyromellitic acid and an aromatic tetrabasic rubber different from that as described above. In the latter case the combination, pyromellitic acid, based on the total tetracarboxylic acid component, the ratio i.e. the aromatic tetracarboxylic acid which is different from that exceeds 8 0 mole ^_0/0 made from less than 20 molar%. Especially p- and phenylene Renjiamin component Jiamin component comprising 1 0 0 mole ^_0/0, the film of the present invention is made of polyimide consisting of pyromellitic acid component 1 0 0 mole ^_0/0, express more preferable Young's modulus . (Polyimide film manufacturing method)

The method for producing the polyimide film of the present invention will be described in detail.

The first production method of the present invention comprises the following steps (1) to (4).

(1) a polyamic acid solution was prepared, wherein the polyamic acid is p- phenylenediamine Amin different aromatic Jiamin component and component 4 0 mol% 1 0 0 mole ^_0/0 or less and p- phenylene Renjiamin is ◦ aromatic di § amine component consisting mol% 6 0 mole ^_0/0 or less, than the pyromellitic acid component 8 0 mole ^_0/0, and an aromatic tetracarboxylic force Rupon acid component different from the pyromellitic 0 And the solvent of the polyamic acid solution is N, N-dimethylformamide, N, N-dimethylacetoamide, N-methynore At least one member selected from the group consisting of 2-piperidine riddon and 1,3-dimethylimidazolidinone;

(2) A polyamic acid composition prepared by adding acetic anhydride as a dehydration reaction agent and an organic amine compound as a dehydration reaction catalyst to the polyamic acid solution prepared in the above step (1) is cast on a support. Then the concentration of water on this:! Dehydration reaction is carried out by heating and heat treatment in a reaction atmosphere of ~ 200 ppm to form a gel film in which at least a portion of the polyamic acid is converted to polyimide or polyimide;

(4) The obtained biaxially stretched gel film is subjected to a heat treatment to form a biaxially oriented polyimide film. '

In step (1), a solution of polyamic acid is first prepared. The polyamic acid comprises the diamine component and the tetracarboxylic acid component as described above. Compose the jammin ingredient Specific examples of the aromatic tetracarboxylic acid different from the aromatic diamine different from p-phenylidenediamine and the aromatic tetracarboxylic acid to be added may include the same specific examples as described above for the polyimide. The diamine component of the polyamic acid may consist of p-ferendiamine alone or in combination with p-phenylidenediamine and an aromatic diamine different from that as described above. In the latter case the combination, p- Hue - Les Njiamin, based on the total Jiamin component 4 0 mol% ratio, preferably the ratio of 6 0 mole ^_0/0 above, aromatic Jiamin 6 0 differs from that It consists of not more than mol%, preferably not more than 40 mol%.

Also, the tetracarboxylic acid component of the polyamic acid consists of pyromellitic acid alone or a combination of pyromellitic acid and an aromatic tetracarboxylic acid different from that as described above. In the case of the latter combination, pyromellitic acid is in a proportion of more than 80 mol%, based on the total tetrabasic acid component, and is composed of less than 20 mol% of different aromatic tetrabasic acids.

Further, when producing a polyamic acid, these diamines and acid anhydrides preferably have a molar ratio of diamine to acid anhydride of 0.90-0.10, more preferably 0.9-1. It is preferable to use at 0 5.

The ends of this polyamic acid are preferably sealed. In the case of using an end capping agent, for example, as the end capping agent, for example, phthalic anhydride and its substitution product, hexahydrophthalic anhydride and its substitution product, succinic anhydride and its substitution, As a body and an ingredient of amin, a-phosphorin and its substitution products are mentioned. ·

As the solvent, at least one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetoamide, N-methylpyrrolidone and 1,3-dimethylimidazolidinone is used. These solvents can be used alone or in combination of two or more. The solvent used is preferably as dry as possible. When the solvent contains a large amount of water, it may be difficult to obtain a polyamic acid having a desired degree of polymerization. Specifically, the water content in the solvent is preferably 0.1 to 100 ppm. Preferably it is 500 ppm or less, More preferably, it is 100 ppm or less, and it is 50 ppm Is particularly preferred. If the water content in the solvent is less than 0.1 ppm, the equipment load will be large to maintain and manage such water content.

According to the step (1), preferably, a solution of a solid concentration of 0.5 to 30% by weight, more preferably 2 to 15% by weight of a polyamic acid in a solvent is prepared.

Next, in the step (2), acetic anhydride as a dehydration reaction agent and an organic amine compound as a dehydration reaction catalyst are continuously or batchwise mixed with the polyamic acid solution prepared in the step (1). Acetic anhydride is used as a dehydrating agent. The organoamine compound acts as a reaction catalyst for the reaction of acetic anhydride and polyamic acid, and examples thereof include tertiary aliphatic amines such as trimethinoleamine, tolytilamine, toribitoleamine, diisopropylethamine, and triethylenediamine; N, N-dimethylamine, aromatic diamine such as bis (N, N- dimethinoleamino) naphthalene, pyridine and derivatives thereof, picoline and derivatives thereof, lutidine, quinolin, isoquinoline, 1, 8-diazabicyclo Heterocyclic compounds such as [5 · 4.0] undecene, N, N-dimethylaminopyridine can be used. Of these, pyridine and picoline are preferred from the economic viewpoint. Also, triethylenediamine and N, N-dimethylaminopyridine are preferably used because a very high imido group fraction can be realized in threading with acetic anhydride and a gel film having high resistance to water can be obtained. . Among these, pyridine is preferred. The order of addition to the polyamic acid solution is not particularly limited, but the order of addition is preferably the order of first adding and mixing an organoamine compound and then adding and mixing acetic anhydride.

It is also preferred to include acetic acid in the polyamic acid composition. The acetic acid contained in the polyamic acid solution forms a complex salt with the organic amine complex and, when present, has the effect of suppressing the volatilization of the organic amine compound. The amount of acetic acid contained in the polyamic acid solution is not particularly limited, but is preferably not less than 0. 0 0 0 1 mol and not more than 4.0 mol, preferably not more than 0. 0 mol, per 1 mol of the organic amine compound. It is more than 0 mole and less than 1.0 mole.

Acetic anhydride is added in an amount of 1 to 30 times per 1 mol of polyamic acid repeating unit. Mol, preferably 1 to 8 times mol, more preferably 2 to 4 times mol, and the organic compound is 0.01 to 25 times mol, preferably 0. 1 to 25 times mol per mol of the polyamic acid repeating unit. The molar ratio is 0 to 1 to 8 moles, more preferably 0.4 to 4 moles. The order of addition is not particularly limited, but it is preferable to carry out in the order of organic amine compound and acetic anhydride.

As the addition method, a method of continuously adding and mixing by a static mixer such as a kneader or a static mixer, or adding and mixing in a batch by an anchor blade, a helicopter ribbon blade or the like in a mixing kettle There is a way. In addition, after mixing of acetic anhydride and organic amine compound, it is preferable to cast it on a support immediately to ensure stable liquid transfer, and piping caused by a marked increase in viscosity due to a ring closure reaction of polyamic acid. It is preferable to keep the solution temperature at room temperature or lower, and more preferably 1 ° C. to 0 ° C., to prevent internal blocking and blocking during casting · casting defects. Then, a polyamic acid composition prepared by adding a dehydration reaction agent is spread on a support to obtain a film. As a film forming method of casting on a support, a method by die extrusion, casting using an applicator, a method using a coater, etc. are exemplified. When casting a polyamic acid, a metallic belt, casting drum, etc. can be used as a support. It can also be cast on an organic polymer film such as polyesterol and polypropylene and sent as it is to a reaction coagulation tank.

It is preferable to carry out these steps under a low humidity atmosphere, and in the casting treatment in the step (2), the polyamic acid composition is placed on a support in an atmosphere with a water concentration of 1 to 400 ppm. It is preferable to cast on .

The temperature of the polyamic acid solution at the time of casting is preferably in the range of 1 to 40 ° C. If the temperature is less than 3 ° C., the viscosity of the polyamic acid becomes extremely high or the solution solidifies, so that the formability may be significantly reduced or the film may not be castable. 4 0. When it is higher than C, the chemical stability of the polyamic acid solution is lost, and some casting occurs before casting, or the molding processability decreases, making casting impossible. There is a case. The temperature is preferably in the range of 25 ° to 30 ° C., and more preferably in the range of 1 ° to 20 ° C. The range of −15 to 15 ° C. is particularly preferred.

The gel film formation of the step (2) is carried out under an atmosphere in which the water concentration is in a specific range to form a gel film in which at least a part of the polyamic acid is converted to a polyimide or a polyisoimide. The concentration of water in this reaction atmosphere is 1 to 200 p p m, more preferably the concentration of water is 1 to 300 p p m. That is, the atmospheric pressure dew point is 18 ° C. or less as the concentration of water is 1 to 200 p p m. That is, the atmospheric pressure dew point is not more than 130 ° C. as the concentration of water is 1 to 300 p p m. If the atmosphere is higher than this, the chemical imidation reaction does not proceed sufficiently, and the resulting film may become brittle.

It is desirable to set the temperature as high as possible from the viewpoint of the activity of the polyisoimidization reaction as the temperature condition in the formation reaction of the gel-like film, but it is preferably 150 ° C. or less, more preferably 110 ° C. C or less. When the temperature is higher than 150 ° C., not only facility load increases, but also acetic anhydride and organic amine compounds may not be able to sufficiently contribute to the reaction due to remarkable evaporation of acetic anhydride and organic amine compounds. The gel film formation temperature in step (2) is preferably 20 to 150 ° C, more preferably 20 to 120 ° C, and still more preferably 3 to 60 ° C.

In the case of forming a gel-like film in a reaction coagulation tank, it is preferable that a reaction coagulation tank has a mechanism for preventing gas in the tank from leaking out of the tank. By using a reaction coagulation tank equipped with a mechanism to prevent leakage to the outside of the gas pressure tank inside the tank, it is possible to solidify the reaction even under high temperature reaction conditions, especially at each solidification temperature. Can be shortened.

In addition, although not particularly limited, the partial pressure of each component which can be volatilized in the reaction coagulating tank, for example, acetic anhydride which is a dehydration reaction agent, organic amine compound or organic solvent in the reaction coagulating tank is saturated It is preferred that the pressure be maintained close to the pressure. In particular, when the formation reaction temperature of the gel-like film is high, the volatilization of the reaction dehydrating agent is minimized, the reduction of the formation reaction efficiency of the gel-like film is prevented, and the reaction rate is stabilized.

As a mechanism for preventing the gas in the reaction coagulation tank from leaking out of the tank, for example, the inside of the tank and the tank There is a method of installing a gas curtain that blows a gas perpendicularly to the film surface between the outside and a method of installing a roll or a plate so as to contact the film upper limit surface. It is preferable to flow a gas having 1 to 2000 ppm into the reaction coagulation tank, and install a seal tank for exhausting the gas in the vicinity where the gas enters the reaction coagulation tank.

Examples of the gas having a concentration of water of 1 to 2000 ppm include dry nitrogen and dry air. The more preferred water concentration of the gas is 1 to 300 ppm.

Further, a gas having a water concentration of 1 to 2000 ppm is made parallel to the film advancing direction toward the reaction coagulation tank 3⁄4, that is, an average flow velocity 0.! It is preferable to use

In addition, it is preferable that the product of the average flow velocity and the blowing distance in the plane perpendicular to the film traveling direction be 10 cm ² / s or more, and more preferably 5000 cm ² / s or less. Here, the blowing distance is the distance between the seal tank outer inlet surface and the surface perpendicular to the flow at the center of the exhaust port. By installing the sealing tank, the inside of the reaction coagulating tank is brought into a state close to or near the saturated vapor pressure of the dehydration reaction agent and the dehydration reaction catalyst. In addition, the film obtained when the average flow rate is out of the above range or the product of the average flow rate and the blowing distance is smaller than 1 O cmVs may become fragile unless it is incorporated with an excess of the imidization solution. If the product of the flow velocity and the blowing distance is larger than 5000 cmVs, it is not preferable because the equipment becomes redundant.

The sealing tank is made to flow gas toward the inside of the reaction coagulation tank. As shown in Figure 1, the sealing tank has an exhaust port above and below the film surface and it is installed by both ends of the reaction coagulation tank. It can be done. When installed at both ends, it is preferable that both end seal tank exhaust port be equal pressure. When a casting drum is used in step (2), unlike in Figure 1, the sealing tank only needs to have the film outlet from the reaction coagulation tank. Similarly, when the casted film is returned within the reaction coagulation tank to make the inlet and outlet sides of the reaction coagulation tank identical, only one seal tank may be used.

Furthermore, it is preferred to minimize the width and height of the reaction coagulation and sealing baths. When the width and height are unnecessarily large, the isoimidation solution is wasted and diffused It will

In addition, in the anticoagulation tank of step (2), it is preferable to install a gas seal that allows a gas having a water concentration of 1 to 2000 ppm to flow toward the outside of the reaction coagulation tank. Such a mechanism makes it possible to prevent the gas in the reaction coagulation tank from leaking out of the tank and to prevent the entry of water from the outside of the tank. A gas having a concentration of water of 1 to 2000 ppm is flowed into the reaction coagulating tank, and a seal tank for exhausting the gas to the vicinity where the gas enters the reaction coagulating tank; It is further preferable to use in combination with a gas seal for flowing a gas of 1 to 2000 ppm toward the outside of the reaction coagulating tank.

The conditions such as the flow velocity at the gas seal may be substantially the same as the gas inflow into the reaction solidification tank. That is, it is preferable to flow a gas having a water concentration of 1 to 2000 ppm toward the inside of the reaction coagulating tank at an average flow velocity of 0.1 to 1.0 m / s with respect to a plane perpendicular to the film traveling direction.

In addition, it is preferable that the product of the average flow velocity and the blowing distance in the plane perpendicular to the film traveling direction be 10 cmVs or more, more preferably 5000 cm ² / s or less. The gas seal is preferably installed at the boundary where the film is exposed to an atmosphere different from the water concentration atmosphere of the reaction tank coagulation tank.

Also, when the isoimido group fraction of the gel-like film obtained in this step is more than 0% and 80% or less, high coverage and a draw ratio are preferably obtained, and more preferably 3% or more and 50% or less. is there. When the isoimide group fraction is 0%, sufficient stretching can not be performed, and when the isoimide group fraction exceeds 80%, the self-supporting property is deteriorated and the orientation effect by the stretching is reduced.

In step (3), the unstretched gel-like film obtained in step (2) is separated from the support and subjected to biaxial stretching. The biaxial stretching may be carried out after separation of the unstretched film from the support and after washing or may be carried out without washing. For the washing, for example, the same solvent as used in the step (1) is used.

Stretching can be performed at a magnification of 1. 1 to 60 in each of the longitudinal and lateral directions. Although the stretching temperature is not particularly limited, it may be a temperature at which the solvent is volatilized and the stretchability is not reduced, and, for example, preferably 120 ° C. to 180 ° C. In addition, there is an extension one after another Or either method of simultaneous biaxial stretching may be used. Stretching may be in a solvent, in air, in an inert atmosphere, or at a low temperature.

It is preferable that the gel-like film subjected to biaxial stretching in step (3) has a swelling degree of 100 to 5,00%. This provides a high draw ratio. If the content is less than 100%, the stretchability is insufficient and the film tends to break in the process of stretching. If the content is more than 5,00%, the strength of the gel decreases and the handling becomes difficult. .

Finally, in step (4), the biaxially stretched film obtained in step (3) is subjected to a heat treatment to form a biaxially oriented polyimide film.

In the step (4), the film may be processed under fixed or tensioned restraint conditions until the end. In addition, it may be processed partially under restraint, and then may be processed under non-restraint, or may be processed partially under restraint in both the vertical and horizontal directions, and then processed under one-sided restraint such as, for example, only vertical restraint. It is good. In such a case, it is preferable to heat-treat under restraint or under one-sided restraint after drying until the amount of solvent remaining in the film under restraint becomes 10% or less with respect to the weight of the polymer.

Also, as a restraining method, it is possible to use a conventionally known method, and there is no particular limitation. For example, for longitudinal restraining, a clawper roll, a nip roll, a vacuum suction type suction roll, and winding There are a method of generating tension by restraining the film by a roll or the like, a method of fixing the film edge portion with a clip, and a method of restraining by piercing a pin for both longitudinal and lateral restraint or lateral restraint. In addition, there is also a method in which the nip pressure is simultaneously and horizontally constrained by a calender roll or the like. When constraining with a calender roll etc., heat treatment is also performed at the roll heating temperature in a very short time simultaneously with the restraint.

Examples of the heat treatment method include hot air heating, vacuum heating, infrared heating, microwave heating, contact using a hot plate, non-contact heating using a hot roll, contact heating using a hot roll, etc. It can also be used in combination at the same time.

The heat treatment temperature is at least two steps, first at 60 to 300 ° C., more preferably at 100 to 250 ° C., and finally at 300 to 50 ° C., more preferably at 45 0 ~ 5 50. The temperature is raised stepwise at a temperature of C. This suppresses the orientation relaxation and gives 95% An imido group fraction can be realized.

In addition, the biaxially stretched film can be washed to remove the solvent before the heat treatment. For washing, the solvent may be dissolved, for example, lower alcohol such as isopronol, higher alcohol such as octyl alcohol, aromatic hydrocarbon such as toluene and xylene, hydrogen, ether solvents such as dioxasan, acetone, methyl Ketone solvents such as ethyl ketone can be mentioned.

In the biaxially oriented polyimide film obtained as described above, the molecular chains are strongly oriented in the film plane, and a high Young's modulus polyimide: film having excellent in-plane balance is obtained. The biaxially oriented polyimide film of the present invention is characterized in that the in-plane two-way perpendicular measurement has a Yang ratio of 5 GPa, preferably 8 GPa, more preferably 1 OGP a, and a special orientation. It is a film whose strength is improved by forming a fine structure. Even if such a high Young's modulus polyimide film is a thin film having a thickness of 10 m or less due to high rigidity, it should be suitably used for electronic applications, for example, a support of an electric wiring board on which a copper thin film is laminated. Can. It can also be used as a support for flexible circuit boards, tapes for tape automated bonding (TAB), and tapes for LOC (lead-on-chip). Moreover, it can be used as a base film of a magnetic recording tape. Example

Hereinafter, the method of the present invention will be described in more detail by way of examples. However, these examples do not limit the scope of the present invention. Analysis method

1) Logarithmic viscosity of polyamic acid

The polymer concentration in NMP was measured at 35 ° C. at a polymer concentration of 0.50 g / 10 0 m 1.

2) Swelling degree

It is calculated from the ratio of the weight in the swollen and dried states. That is, when the dry weight is W 1 and the swelling weight is W 2 The swelling degree was calculated as (W 2 / W 1 1) × 100.

3) Strength and elongation

The measurement was performed using an Orientech UCT-1 T at a tensile speed of 5 mm Zmin using a sample of 5 OmmX 1 Omm.

4) Fraction of isoimide group fraction

It was determined as follows from the peak intensity ratio measured by the absorption method using a Fourier transform infrared spectrometer (Nic o l t Ma g n a 750).

Isoimido groups ratio _{(%) = (A 920 /} A 1024) 3 X 100, A 92. : Absorption intensity of the peak derived from 920 c π ¹ isoimide bond of the sample

_{1024 1024} : Absorption intensity of the peak derived from 1024 cm- ¹ benzene ring of the sample

Imido group fraction (%) = (A ₇₂₀ / A ₁₀₂₄ ) / 5. 1 X 100

A ₇₂ . : Absorption intensity of peak from 720 cm ¹ imide bond of sample

A ₁₀₂₄ : Absorption intensity of the peak derived from 1024 cm- ¹ benzene ring of the sample

'

Example 1

In a reaction vessel cooled to 15 ° C, the moisture content is controlled with a molecular sieve under a nitrogen atmosphere.

After dehydration to 32 ppm, add 20 L of N-methyl-2_pyloridone (NMP), and then completely dissolve and dissolve 276 g of paradiendiamine (water content: 3370 ppm), and then pyromellitic anhydride After 557 g of dianhydride was added and allowed to react for 1 hour, and then allowed to react at about 5 ° C. for 2 hours, 0.76 g of phthalic anhydride was added to complete the reaction. The logarithmic viscosity of the obtained polyamic acid solution was 4.10. Next, the fluid was cooled to 110 ° C. in 28.6 ml Z minutes by the gear pump, and the number of elements installed in the middle of the liquid transfer piping between the reaction vessel and the T die was 48 stages. For the static mixer of 6.5, the reaction vessel side is 0 stage, T die side

As step 48, add pyridine (water content 19 ppm) to the 0th step in 1.1 ml, then add and mix acetic anhydride on the 24th step in 1.9 ml (molar ratio: in the dope) Polyamic acid repeating unit / no vinegar Z-pyridine 1/6/4), — book at 10 ° C The mixed solution was cast on a PET film from a chisel die with a lip opening of 1500 μ and a width of 32 Omm in a casting tank with a nitrogen concentration of 40 ppm, to obtain a film.

Next, this film was introduced into the reaction coagulating tank in 0.05 mZ with PET film. The temperature in the reaction coagulation tank is 40 ° C, and dry nitrogen with a water concentration of 40 ppm (atmospheric pressure dew point-50 ° C) is attached to both ends of the reaction coagulation tank from both ends outside the reaction coagulation tank The same flow rate was applied to the exhaust port with a penetration distance of 7.5 cm, and an average flow rate of 20 cm Z seconds was applied to the vertical surface in the film traveling direction. The product of the dry nitrogen flow rate and the blowing distance is 150 cm ² / s. The reaction time is 30 minutes. The water concentration in the coagulation reaction atmosphere was 40 ppm. The imide group fraction of the obtained gel-like film was 95%, and no imide group could be detected.

Next, both ends of the obtained gel film were fixed by chucks; co-axial stretching was performed biaxially at room temperature (25 ° C.) in a biaxial direction at a rate of 5 mm for Z seconds at a rate of 5 mm. The swelling degree of the gel film at the start of stretching was 1110%.

The stretched gel film was fixed on a frame and dried at 160 ° C. for 30 minutes, and then gradually raised up to 450 ° C. to obtain a polyimide film. The thickness of the obtained polyimide film is 15 μπι, the tensile elastic modulus measured in two directions orthogonal to each other in the plane is 17.9 GPa and 16.0 GPa, the tensile strength is 0.39 GPa and 0.35 GPa, and the elongation is 5 1% and 4.9%. In addition, the refractive index in the thickness direction was η ζ = 1 · 573, and the density was 1. 508 g · cm ³ . The imide group fraction is 100. /. Met. The results are also shown in Table 1. Example 2.

A polyimide film was produced in the same manner as in Example 1 except that the dry nitrogen flowing into the reaction coagulating tank was changed to a dry air having a concentration of 1000 ppm of water. The results are shown in Table 1. Example 3

Dry nitrogen is directed from the outside of both ends of the reaction coagulation tank to the exhaust port attached to both ends of the reaction coagulation tank A polyimide film was obtained in the same manner as in Example 1 except that the flow was performed at 0.5 m / s. The product of the dry nitrogen flow rate and the blowing distance is 3 7 5 cm ² / s. The results are shown in Table 1. Comparative example 1

A polyimide film was produced in the same manner as in Example 1 except that the dry nitrogen flowing into the reaction coagulating tank was changed to air having a water concentration of 370O ppm. However, under these conditions, the film was broken during drying and heat treatment because the reaction in the reaction coagulation tank was insufficient, and a film could not be obtained. Example 4

Before film formation, the inside of the reaction coagulation tank is replaced with nitrogen, and during film formation, dry nitrogen is not flowed from the outside of both ends of the reaction coagulation tank to the exhaust ports attached to both ends of the reaction coagulation tank, that is, substantially. A polyimide film was obtained in the same manner as in Example 1 except that the reaction was coagulated under the absence of conditions. The obtained film was able to measure mechanical strength but was low in elongation and brittle. The results are shown in Table 1. Example 5

A polyimide film was obtained in the same manner as in Example 1 except that dry nitrogen was flowed from the outside of both ends of the reaction coagulation tank to exhaust ports attached to both ends of the reaction coagulation tank at 0.90 m / s. The product of the dry nitrogen flow rate and the blowing distance is 67.5 cm ² / s. The obtained film was capable of measuring mechanical strength but was low in elongation and somewhat brittle. The results are shown in Table 1. Example 6

A polyimide film was obtained in the same manner as in Example 1 except that dry nitrogen was flowed from the outside of both ends of the reaction coagulation tank to exhaust ports attached to both ends of the reaction coagulation tank at a flow rate of 1.2 m / s. The product of the dry nitrogen flow rate and the blowing distance is 900 cm ² / s. Obtained The film was able to measure mechanical strength, but it had low elongation and was brittle. The results are shown in Table 1. Example 7

A polyimide film was obtained in the same manner as in Example 1 except that dry nitrogen was flowed from the outside of both ends of the reaction coagulation tank to the exhaust ports attached to both ends of the reaction coagulation tank at a flow rate of 0.60 m / s. The product of the dry nitrogen flow rate and the blowing distance is 45 cm ² / s. The results are shown in Table 1. Example 8

A polyimide film was manufactured in exactly the same manner as in Example 7 except that the blowing distance of the dry nitrogen attached to both ends of the reaction coagulation tank was 1.5 cm. The product of the blowing distance is 9 cm ² / s. The film obtained under these conditions had a low elongation. The results are shown in Table 2.

'

Example 9

Pyridine is added at 4.4 ml / min and acetic anhydride is added and mixed at 3.8 ml / min (molar ratio: polyamic acid repeating unit in dope Z non-vinegar Z pyridine = 1 1 126). The polyimide film was spread in the same manner as in Example 4. The results are shown in Table 2. Example 1 0

A polyimide colloid was obtained by the same method as Example 1 except that the temperature in the reaction coagulating tank was set to 60 ° C. The results are shown in Table 2. Example 1 1

A polyimide film was obtained in the same manner as in Example 1 except that the opening degree of the lip was changed to 3 5 0 0 5 and the stretching ratio was increased to 1.6 times. The degree of swelling of the gel film at the start of stretching is It was 1 and 150%. The results are shown in Table 2. Example 12

The temperature in the reaction coagulation tank is 90 ° C, the lip opening is 350 / ^, and the transport speed of PET film is 0. lm / min, and the reaction time is 5 minutes. A polyimide film was obtained in the same manner as in Example 1. The results are shown in Table 2. Example 13

The temperature in the reaction coagulation tank is brought to 140 ° C., pyridine is added at 5.4 ml / min, acetic anhydride is added at 8.2 ml / min, and mixed (molar ratio: vinegar without doped Z pyridine = 1/25 / 20 ), And a polyimide film was obtained in the same manner as in Example 1 except that the transfer time of the PET film was 0.5 m / min and the reaction time was 1 minute. The results are shown in Table 2.

3008845

twenty three

* 1: Average flow velocity of gas in the seal tank with respect to the vertical surface

Table 2

* 1: Average flow velocity of the gas in the sealing tank in the plane perpendicular to the film traveling direction Example 1 4

The procedure is exactly the same as in Example 1 except that the gas flowing into the casting tank and the reaction coagulation tank is changed from nitrogen of water concentration 40 ppm to dry air of water concentration 100 ppm. A polyimide film was obtained. The results are shown in Table 3. Example 1 5

A polyimide film was obtained in the same manner as in Example 1 except that the temperature of the polyamic acid solution at the time of casting was set to 20 ° C. by controlling the temperature of the T die. The results are shown in Table 3.

Claims

The scope of the claims

1. (1) A polyamic acid solution is prepared, wherein the polyamic acid contains 40 mol% or more and 100 mol% or less of p-phenylenediamine component and 0 mol of aromatic diamine component different from p-phenylenediamine. / ₀ and more than 60 mole% aromatic Jiamin component consisting, Pirome, slit acid component 80 mol ^_0/0 beyond and different aromatic tetracarboxylic acid component 0 mol% to 20 mol% and pyromellitic And the solvent of the polyamic acid solution is N, N-dimethylformamide, N, N-dimethylacetoamide, N-methyl-2-pyrrolidone and 1, 3-dimethino! And / or at least one member selected from the group consisting of imidazolidinones;

(2) A polyamic acid composition prepared by adding acetic anhydride as a dehydration reaction agent and organic amine as a dehydration reaction catalyst to the polyamic acid solution prepared in the above step (1) is cast on a support, It is subjected to heating and heat treatment to form a gel film in which at least a portion of the polyamic acid is converted to polyimide or polyisoimide by dehydration reaction.

'(3) Separate the obtained gel film from the support, wash it if necessary, and biaxially stretch it;

(4) A method for producing a polyimide film, comprising subjecting the obtained biaxially stretched gel film to a heat treatment to form a biaxially oriented polyimide film, wherein the concentration of water in the reaction atmosphere of step (2) is 1 A method for producing a polyimide film, characterized in that it is set to ~ 2000 pm.

2. The method for producing a polyimide film according to claim 1, wherein a gel-like film is formed at 20 to 150 ° C. in the step (2).

3. When the gel film formation of step (2) is carried out in a reaction coagulating tank, a gas having a concentration of water of 1 to 2000 ppm is flowed into the reaction coagulating tank, and The method for producing a polyimide film according to claim 1, wherein a seal tank for exhausting the gas is installed in the vicinity of the body entering the reaction coagulation tank.

4. The method for producing a polyimide film according to claim 3, wherein the gas is allowed to flow at an average flow velocity of 0.10 to L. 0 m / s with respect to a plane perpendicular to the film traveling direction.

5. The method for producing a polyimide film according to claim 3, wherein the gas is allowed to flow at a product of an average flow velocity and a blowing distance of 10 cm ² / s or more in a plane perpendicular to the film traveling direction.

6. The sealing tank has exhaust ports above and below the film surface and is installed at both ends of the reaction coagulation tank, and the both end sealing tank exhaust ports are maintained at equal pressure. Method.

7. The method for producing a polyimide film according to claim 1, wherein a gas seal is provided to flow a gas having a concentration of water of 1 to 2000 ppm toward the outside of the reaction coagulation tank.

8. The method for producing a polyimide film according to claim 7, wherein the gas seal is installed at a boundary where the film is exposed to an atmosphere different from the reaction coagulation bath.

9. In the casting process in step (2), the concentration of water in the polyamic acid composition:! The method for producing a polyimide film according to claim 1, wherein the film is cast on a support under an atmosphere of 4 to 2000 ppm.

10. A method for producing a polyimide film, wherein the temperature of the solution at the time of casting in step (2) is in the range of 30 to 40 ° C.

11. The water content in the solvent used is in the range of 0.1 to 1000 ppm. The manufacturing method of the polyimide film of Claim 11.

12. After stretching the gel-like film in at least one direction in step (3) and drying until the amount of solvent remaining in the film under restraint in step (4) is 10% or less of the weight of the polymer, The method for producing a polyimide film according to claim 1, wherein the heat treatment is carried out in an unrestrained manner.

13. The method for producing a polyimide film according to claim 1, wherein the organic amine compound used in the step (2) is pyridine.

14. The method for producing a polyimide film according to claim 1, wherein the polyamic acid composition of the step (2) contains acetic acid.

15. a Jiamin component p- phenylene Renjiamin component composed of different aromatic Jiamin component 0 mole ^_0/0 to 60 molar% or less and 40 mol ^_0/0 beyond 100 mol% or less and p- phenylene Renjiamin A polyimide mosquito substantially consisting of a tetracarboxylic acid component comprising pyromellitic acid in an amount of more than 80% by mole and an aromatic tetracarboxylic acid component different from pyromellitic acid in an amount of 0 to 20% by mole; Then, two orthogonal directions, each having a Young's modulus of more than 1 OGP a, exist in the film plane. The polyimide film obtained by the manufacturing method in any one of -14.

16. Poly imide film according to polyimide p- phenylene Renjiamin and components diamines component consisting of 100 mole ^_0/0, pyromellitic acid component 100 mol ^_0/0 and power Ranaru claim 15.

17. A metal wiring circuit board comprising the polyimide film according to claim 15,

18. A tape for LOC comprising the polyimide film according to claim 15.