WO2008010409A1

WO2008010409A1 - Polyimide film

Info

Publication number: WO2008010409A1
Application number: PCT/JP2007/063272
Authority: WO
Inventors: Shogo Fujimoto; Hisayasu Kaneshiro; Takashi Kikuchi; Shimizu Masayoshi
Original assignee: Kaneka Corporation
Priority date: 2006-07-18
Filing date: 2007-07-03
Publication date: 2008-01-24
Also published as: TW200827387A

Abstract

A polyimide film suitable for use as, e.g., a base film for the TAB technique. The polyimide film is obtained from a polyamic acid solution as a precursor, and is characterized in that the polyamic acid is obtained by (1) forming a block from at least one flexible aromatic diamine (1-a), at least one linear aromatic diamine (1-b), and at least one aromatic acid dianhydride (1-c) and (2) subsequently adding at least one flexible aromatic diamine (2-a) and at least one aromatic acid dianhydride (2-c) so that the molar amount of the diamine ingredients added in all steps is substantially equal to that of the acid dianhydride ingredients added in all steps to thereby form a block.

Description

Specification

Polyimide film

Technical field

TECHNICAL FIELD [0001] The present invention relates to a polyimide film that has been widely used as an insulating material in accordance with the reduction in weight and size of various electronic devices. More specifically, the present invention relates to a polyimide film that can be suitably used as a flexible printed circuit board, particularly a TAB (Tape Automated Bonding) type base film, in various uses of polyimide films.

Background art

Conventionally, flexible printed wiring boards (hereinafter referred to as FPCs) have been used by being folded mainly in a narrow space inside the camera, taking advantage of their flexibility. In recent years, however, it has come to be used in drive units of flexible disk drives, hard disk drives, copiers, printers, etc., and further improvements in sliding and bending characteristics have been demanded. In order to increase the flexibility of the base film, a film made of a polyimide having a high chemical structural flexibility is generally used. However, since the flexibility is generally high, polyimide has a large linear expansion coefficient. A flexible printed circuit board using a film as an insulating material has a drawback that it tends to be warped and curled. On the other hand, if a polyimide with a small linear expansion coefficient is selected, the flexibility of the film itself is lost and the film becomes very fragile, and the flexibility of the resulting FPC also decreases! .

[0003] In recent years, as a technology that can cope with the increase in the number of pins, miniaturization, and high-density mounting of semiconductor devices, holes (device holes) for mounting semiconductor chips such as LSIs on long insulating films have been provided. Attention has been focused on the TAB technology in which a very thin copper foil lead is formed on top of this and the LSI is connected to a printed wiring board via this lead. In general, TAB technology uses a film carrier tape (FC tape) that has a three-layer structure of a protective layer, an adhesive layer, and an organic insulating film layer (base film layer). The processing steps until the LSI is mounted on the TAB tape that has been processed are as follows.

[0004] That is, the process of processing the TAB tape includes (1) a process of forming sprocket holes and device holes by punching, and (2) removing the protective layer and laminating the copper foil, and then applying the adhesive. Curing process, (3) arrangement pattern formation process (resist coating, copper etching, resist stripping), (4) plating process, (5) inner lead bonding process, (6) grease sealing process, (7) This is done in 8 steps: punching process, (8) outer lead bonding process, and LSI is mounted through the above processing steps.

[0005] In these cache processes, one of the biggest causes of mounting defects is warping and curling of flexible copper clad laminates (FCCL) and TAB tape. Warpage and curl cause defective formation of the arrangement pattern and poor bonding of the semiconductor chip in processes that require dimensional accuracy such as formation of the arrangement pattern, inner lead bonding, and outer lead bonding. In addition, the actual process is performed with a reel reel, and tension is applied in the longitudinal direction of the TAB tape, so that warping and curling in the longitudinal direction can be corrected, but warping and curling in the tape width direction are corrected. I can't do it. In order to prevent such inconvenience, specifically, a base film having a designed linear expansion coefficient and elastic modulus is required in the processing of TAB tape.

[0006] Up to now, the suppression of warping and the control of the linear expansion coefficient have attracted attention as the characteristics of TAB tape, and polyimide films having an appropriate linear expansion coefficient as a base material for TAB tape and polyimide films with less warpage Has been proposed. In addition, it is disclosed that a polyimide film using 3, 3 ′, 4, 4 ′ monobenzophenone tetracarboxylic dianhydride is used as a base film for TAB (see Patent Documents 1 and 2).

[0007] However, from the viewpoint of industrial production of TAB tape, few approaches have been made, and the variation in warpage in industrial production has been recognized.

[0008] In addition, for the improvement of thermal dimensional stability, water absorption characteristics, and mechanical characteristics, for example, a block component of rigid non-thermoplastic polyimide is included by p-phenol-diamine and pyromellitic dianhydride. A technique for achieving these characteristics by using a polyimide film is disclosed (see Patent Documents 3 to 5). However, it has been difficult to stably industrially produce these unless the storage stability is improved by controlling the molecular weight of the polyamic acid solution, which is a polyimide precursor solution, which has poor storage stability.

[0009] On the other hand, in the manufacturing process of TAB tape, there is a process of gold plating, and a process of immersing in an alkaline plating solution is performed. Therefore, when polyimide film is used for TAB applications, linear expansion Needless to say, the material must be able to withstand basic characteristics such as modulus and warpage, even when immersed in an alkaline solution.

[0010] However, in the past, polyimide films have never been designed by focusing on such characteristics, and in reality, when immersed in an alkaline plating solution that has insufficient alkali resistance, copper There was a problem that reliability was lowered such as a decrease in adhesive strength with the foil and a change in dimensions.

Patent Document 1: Japanese Patent Laid-Open No. 9-328544

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-124091

Patent Document 3: Japanese Patent Laid-Open No. 2000-80178

Patent Document 4: Japanese Unexamined Patent Publication No. 2000-119521

Patent Document 5: Japanese Unexamined Patent Publication No. 2006-96919

Disclosure of the invention

Problems to be solved by the invention

[0011] An object of the present invention is to provide a polyimide film that can be used for, for example, a flexible printed circuit board, in particular, a TAB-type base film, and in which warpage and curling are suppressed without causing problematic elongation. In particular, it is to obtain a polyimide film using a polyamic acid having excellent storage stability, which enables stable continuous production in the polymerization of polyamic acid, which is a polyimide precursor. It is another object of the present invention to provide a polyimide film that can be suitably used for a TAB base film that does not cause a decrease in adhesive strength or dimensional change while being exposed to an alkaline plating solution.

Means for solving the problem

In view of the above situation, as a result of intensive studies, the present inventors have found that the following problems can solve the problems of the present invention, and have completed the present invention.

[0013] That is, the present invention is a polyimide film obtained using a polyamic acid solution as a precursor, wherein the polyamic acid comprises (1) at least one flexible aromatic diamine (1-a) and at least After forming a block composed of one kind of linear aromatic diamine (1 b) and at least one kind of aromatic dianhydride (1 c), (2) at least one kind of flexibility Aromatic diamine (2—a) and at least one aromatic dianhydride ( A polyimide film characterized by being obtained by forming a block by adding 2-c) so that the diamine component and the acid dianhydride component in all steps are substantially equimolar.

[0014] In a preferred embodiment, the number of the flexible groups contained in the flexible aromatic diamine (1a) is greater than the number of the flexible groups contained in the flexible aromatic diamine (2-a). It is related with the said polyimide film characterized by few.

[0015] Preferably, the embodiment is characterized in that the flexible aromatic diamine (1a) has one flexible group, and the flexible aromatic diamine (2-a) has two or more flexible groups. And relates to the polyimide film.

[0016] A preferred embodiment relates to the polyimide film, characterized in that it comprises the flexible aromatic diamine (1a) force 4, 4'-diaminodiphenyl ether.

[0017] A preferred embodiment relates to the polyimide film, wherein the flexible aromatic diamine (1-a) is in the range of 10 to 50 mol% based on the total diamine component.

[0018] A preferred embodiment relates to the polyimide film, characterized in that it comprises the flexible aromatic diamine (2-a) force 2, 2 bis (4-aminophenoxyphenyl) propane.

[0019] A preferred embodiment relates to the polyimide film, wherein the flexible aromatic diamine (2-a) is in the range of 10 to 40 mol% based on the total diamine component.

[0020] In a preferred embodiment, the aromatic dianhydride (2-c) includes 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride, Related to polyimide film.

In a preferred embodiment, the polyimide film is characterized in that the aromatic acid dianhydride (2-c) is in a range of 15 to 60 mol% based on the total acid dianhydride component. Concerning.

[0022] A preferred embodiment relates to the polyimide film, wherein the blocking force obtained by (1) is in the range of 40 to 90 mol% based on the total polyamic acid. [0023] Preferably, the embodiment relates to the polyimide film described above, which is used as a base material for a TAB tape.

[0024] A preferred embodiment relates to the polyimide film described above, wherein the polyimide film is obtained by chemically converting polyamic acid.

[0025] In a preferred embodiment, the average linear expansion coefficient at 100 to 200 ° C is 18 to 25 X 10 " ⁶ cm.

The present invention relates to the polyimide film, characterized by being ZcmZ ° C.

[0026] A preferred embodiment relates to the polyimide film, wherein the elastic modulus is 4. OGPa or more.

[0027] A preferred embodiment relates to the above polyimide film, characterized in that the amount of change in thickness when immersed in a 20 ° C IN sodium hydroxide aqueous solution for 6 hours is 5% or less.

[0028] A preferred embodiment relates to the above polyimide film, characterized in that the amount of change in thickness when immersed in an aqueous solution of sodium hydroxide and sodium hydroxide at 60 ° C for 2 minutes is 5% or less.

[0029] In a preferred embodiment, the dimensional change rate when immersed in an aqueous solution of sodium hydroxide and sodium hydroxide at 20 ° C IN for 6 hours is the film flow direction (MD direction) and the direction perpendicular to the MD direction (TD direction). Both are 0.05% or less of the above polyimide film.

The invention's effect

[0030] According to the present invention, a polyamic acid excellent in storage stability can be obtained, which enables stable continuous production while polymerization of polyamic acid which is a precursor of polyimide. When the polyimide film according to the present invention obtained using the polyamic acid is used as a flexible printed circuit board, particularly as a TAB-type base film, the occurrence of warpage and curling can be suppressed without causing problematic elongation. Furthermore, even when exposed to an alkaline plating solution, it is possible to suppress a decrease in adhesive strength, dimensional change, and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

[0031] The polyimide film of the present invention is obtained using a specific polyamic acid solution as a precursor, and the polyamic acid comprises (1) at least one flexible aromatic diamine (1-a ) And at least one linear aromatic diamine (1-b) and at least one aromatic dianhydride (1-c), and (2) at least one One kind of flexible aromatic diamine (2-a) and at least one kind of aromatic acid The water product (2-c) is obtained by adding the diamine component and the acid dianhydride component in all steps so as to be substantially equimolar to form a block.

[0032] The polyamic acid has good storage stability, and the polyimide film obtained using the polyamic acid as a precursor suppresses the occurrence of warpage and curling. It is characterized by being able to produce.

Hereinafter, an embodiment of the present invention will be specifically described.

[0034] (Synthesis of polyamic acid)

In the present invention, a monomer and the like used in producing a polyamic acid that can be used as a precursor of a polyimide film will be described.

[0035] In the production of the polyamic acid, first, in step (1), at least one kind of flexible aromatic diamine (1a), at least one kind of linear aromatic diamine (1b) and at least one kind are used. It is necessary to form a block composed of the aromatic dianhydride (1c).

Here, the flexible aromatic diamine (1-a) in the present invention means an ether group, a methylene group, a propargyl group, a hexafluoropropargyl group, a carbonyl group, a sulfone group, a sulfide group, Diamine containing a flexible group such as an ester group in the main chain, or if the main chain does not contain a flexible group, the nitrogen atoms of the two amino groups and the carbon atom bonded to them are aligned. A diamine compound having no structure.

[0037] More specifically, for example, 2, 2 bis (4-aminophenoxyphenol) propane, 4, 4, —diaminodiphenyl ether, 1, 3 bis (4 aminophenoxy) benzene, 1, 3 Bis (3-aminophenoxy) benzene, 4,4,1bis (3-aminophenoxy) biphenyl, 4,4,1bis (4 aminophenoxy) biphenyl, bis (4 (4aminophenoxy) phenyl) sulfone, Bis (4- (3-aminophenoxy) phenyl) sulfone, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3, 3,- Diaminodiphenyl sulfone, 4, 4'-diaminodiphenyl sulfone, 3, 3, oxydianiline, 3, 4 'oxydianiline, 2, 4' oxydianiline, 4, 4'-diaminodiphenyl dijetylsilane, 4, 4'- Aminojifu Nirushiran, 4, 4 'Jiamino diphenyl E chill phosphine O dimethylsulfoxide, 4, 4' over diamino diphenyl N- Mechiruamin, 4 , 4, -Diaminodiphenyl N-phenylamine, 1,3 diaminobenzene, 1,2 diaminobenzene, 1,5-diaminonaphthalene, 5 amino-2— (p aminophenol) benzoxazole, 6 amino-2— (p Aminoamino) benzoxazole, 5 amino-2- (m-aminophenol) benzoxazole, 6-amino-2- (m-aminophenol) benzoxazole, 2,2,1-p-phenolenebis ( 5-Aminobenzoxazole), 2, 2, —p Huerenbis (6-Aminobenzoxazolone), 1— (5-Aminobenzoxazo mouth) 4 1 (6-Aminobenzoxazo mouth) Benzene , 2, 6- (4, 4, Diaminodiphenol) benzo [1, 2-d: 5, 4 d '] bisoxazole, 2, 6- (4, 4' Diaminodiphenol) Benzo [1, 2 — D: 4, 5— d,] bisoxazole, 2, 6— (3, 4, monodiam Diphenyl) benzo [1,2-d: 5,4-d '] bisoxazole, 2,6-(3,4' diaminodiphenyl) benzo [1,2-d: 4,5-d,] bisoxazole , 2, 6- (3, 3, 1-daminodiphenyl) benzo [1, 2- d: 5, 4-d,] bisoxazole, 2, 6- (3, 3, 1-daminodiphenyl) benzo [1, 2—d: 4, 5—d ′] bisoxazole, and the like. These can be used alone or in combination of two or more.

[0038] Among these flexible aromatic diamines (1a), 4, 4'-diaminodiphenyl ether is used in order to improve the storage stability of the polyamic acid and to develop the desired physical properties. 3, 4 'oxydianiline, 3, 4' oxydianiline, 2,4 'oxydianiline are preferred. Furthermore, in the present invention, it is more preferable to use 4,4′-diaminodiphenyl ether because the final polyimide film can be suitably obtained in addition to the above.

[0039] The number of the flexible groups contained in the flexible aromatic diamine (1a) used in the step (1) in the synthesis of the polyamic acid is the same as that of the flexible aromatic diamine used in the step (2) described later. The number is preferably smaller than the number of flexible groups contained in (2-a). Furthermore, it is more preferable that the number of the flexible groups contained in the flexible aromatic diamine (1-a) is one U.

[0040] The amount of the flexible aromatic diamine (1a) used is the total amount used for synthesizing the polyamic acid from the viewpoint of the storage stability of the polyamic acid and the linear expansion coefficient of the finally obtained polyimide film. The range of 10 to 50 mol% based on the diamine component is preferred, and the range of 20 to 40 mol% is more preferred. In the present invention, the linear aromatic diamine (l-b) used in the step (1) is an ether group, a methylene group, a propargyl group, a hexafluoropropargyl group, or a carbo group. In addition, the main chain does not contain a flexible group such as a sulfone group, a sulfide group, or an ester group, and the nitrogen atom of two amino groups and the carbon atom to which they are bonded are aligned. This means the Jiaming compound.

More specifically, for example, p-phenylenediamine and its nuclear substitution compound, benzidine and its nuclear substitution compound and the like can be mentioned. These can be used alone or in combination of two or more. Among these linear aromatic diamines (1-b), it is particularly preferred to use p-phenylenediamine in terms of processability, handleability, and the balance of properties of the final polyimide film.

[0043] The amount of the linear aromatic diamine (1b) used is preferably in the range of 25 to 60 mol% based on the total diamine components used in the synthesis of the polyamic acid, and more preferably 30 to 50 m. It is more preferable to use in the range of ol%. If the amount of linear aromatic diamine (1-b) used is out of the above range, the linear expansion coefficient of the final polyimide film is preferred and may deviate from the range. In some cases, it is impossible to continuously obtain a film with stable warping.

[0044] In addition, the use ratio of the flexible diamine (1a) and the linear diamine (1b) in the step (1) can be appropriately set. Storage stability of the polyamic acid and finally obtained polyimide film From the standpoint of the linear expansion coefficient, the flexible diamine should be used in the range of 20-50 mol%, preferably 30-40 mol% with respect to the sum of the flexible diamine (1-a) and linear diamine (1-b). Is preferred.

Next, the aromatic dianhydride (1-c) that can be used in the step (1) will be described.

Examples of the acid dianhydride that can be used as the aromatic dianhydride (1c) include pyromellitic dianhydride, 2, 3, 6, 7 naphthalene tetracarboxylic dianhydride, 3, 3 ', 4, 4, -biphenyl tetracarboxylic dianhydride, 1, 2, 5, 6 naphthalene tetracarboxylic dianhydride, 2, 2 ', 3, 3, -biphenyl tetracarboxylic dianhydride, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic dianhydride, 2, 2', 3, 3, monobenzophenone tetracarboxylic dianhydride, 4, 4'-oxydiphthalic dianhydride 3, 4'-oxydiphthalic dianhydride, 2, 2 Bis (3,4 dicarboxyphenyl) propane dianhydride, 3, 4, 9, 10 Perylenetetracarboxylic dianhydride, Bis (3,4 dicarboxyphenyl) propane dianhydride, 1, 1-bis (2,3 dicarboxyphenol) ethane anhydride, 1,1-bis (3,4 carbonate diphenyl) ethane anhydride, bis (2,3 dicarboxyphenyl) methane dianhydride Bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), Examples include tylene bis (trimellitic acid monoester acid anhydride), bisphenol A bis (trimellitic acid monoester acid anhydride), and the like. These may be used as appropriate, alone or mixed at any ratio.

[0046] Among these aromatic acid dianhydrides (1c), pyromellitic acid dianhydride, 2, 2 ', 3, 3,-, from the viewpoint of controlling the linear expansion coefficient within the set range. Biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic dianhydride, 2, 2', 3, 3, monobenzophenone tetracarboxylic dianhydride A thing can illustrate more preferably. Furthermore, pyromellitic dianhydride is particularly preferred.

[0047] The amount of the aromatic dianhydride (1c) used is 40 to 85 mol%, more preferably 50 to 70 mol% based on the total acid dianhydride component. Control within the range is preferable from two viewpoints.

[0048] The present invention is characterized by a method for polymerizing a polyamic acid, which is a polyimide precursor, and in particular in step (1), a flexible aromatic diamine (1-a) and a linear aromatic diamine ( It is characterized by forming blocks using 1-b) and aromatic dianhydride (1c). For example, when polyamic acid is synthesized by polymerizing linear aromatic diamine (1 b) and aromatic dianhydride (1 c), the linear expansion coefficient of the resulting polyimide film is higher than the target value. Although there is an advantage that it is possible to suppress the occurrence of being too much, there is a problem that the storage stability of the polyamic acid obtained with this two-component system alone is low. However, the present inventors copolymerized the flexible aromatic diamine (1a), which is a highly flexible diamine, which is more flexible than the linear aromatic diamine (1-b), into the above system, The inventors have found a surprising finding that it is possible to obtain a polyamic acid that can suppress the linear expansion coefficient of the film from becoming too high than the target value and has good storage stability. [0049] Next, the flexible aromatic diamine (2-a) in the step (2) will be described. Examples of the flexible aromatic diamine (2-a) include the same compounds as the diamine compounds exemplified as the flexible aromatic diamine (1-a). These can be used alone or in combination of two or more. Among these, 2, 2 bis (4 aminophenoxyphenol) propane and 4, 4, 1-diaminodiphenol propane are more preferred from the viewpoint of achieving the target alkali resistance. 4-aminophenol) propane is particularly preferably used.

[0050] From the viewpoint of improving the alkali resistance as described above, the number of the flexible groups in the flexible aromatic diamine (2-a) used in the step (2) is used in the step (1). The number is preferably larger than the number of flexible groups in the flexible aromatic diamine (1a). In particular, the number of flexible groups in the flexible aromatic diamine (2-a) is more preferably 2 or more.

[0051] The amount of the flexible aromatic diamine (2-a) used is 10% on the basis of all diamine components used in the synthesis of polyamic acid from the viewpoint of suppression of breakage during film formation and linear expansion coefficient. Preferably it is in the range of ~ 40 mol%, more preferably in the range of 20-30 mol%.

[0052] The aromatic acid dianhydride (2-c) in the step (2) is exemplified by the same acid dianhydride compounds exemplified as the aromatic acid dianhydride (1c). it can. These can be used singly or in combination of two or more. Among these, pyromellitic dianhydride, 2, 2 ', 3, 3' -biphenyltetracarboxylic dianhydride, 3, 3 ', 4 from the viewpoint of achieving the target linear expansion coefficient , 4, 1-benzozoenone tetracarboxylic dianhydride, 2, 2 ', 3, 3'-benzozoenone tetracarboxylic dianhydride is more preferred, especially 3, 3', 4, 4 ' Acid dianhydrides including benzophenone tetracarboxylic dianhydride can be preferably used.

[0053] The amount of the aromatic dianhydride (2-c) used is preferably 15 to 60 mol% based on the total acid dianhydride component used in the synthesis of the polyamic acid. More preferred is 50mol%. If the amount of aromatic dianhydride (2-c) used is less than 15 mol%, the storage modulus of the film in the high temperature region may become too low, making film formation difficult, and conversely exceeding 60 mol%. And the linear expansion coefficient of the film deviates from the preferred range. In some cases, it takes time to reach a saturated moisture absorption state.

[0054] The flexible aromatic diamine (2-a) and the aromatic dianhydride (2-c) in the step (2) are the diamine component and acid dianhydride used in all steps of the polyamic acid synthesis. It is necessary to add the physical components so as to be substantially equimolar to form a block. Here, “substantially equimolar” means that the total diamine component is used in the range of 49.5 to 50.5 mol% with respect to the sum of the total diamine component and the total acid dianhydride component. If the total amount of diamine components is less than 49.5 mol%, it may be difficult to produce stably, and if it exceeds 50.5 mol%, the viscosity of the polyamic acid becomes too high, resulting in defects in the polyimide film. Tend to be easier to make.

[0055] In the present invention, the meanings of step (1) and step (2) performed in the synthesis of polyamic acid will be described.

[0056] First, in the step (1), a flexible aromatic diamine (1-a), a linear aromatic diamine (1 b), and an aromatic acid dianhydride (1 c) are compared. A rigid, non-thermoplastic polyimide block is formed to prevent the final polyimide film from having an excessively high linear expansion coefficient. However, since the coefficient of linear expansion is too low with this non-thermoplastic polyimide block alone, bending is further bent in step (2) than in the flexible aromatic diamine used in step (1). Block obtained by copolymerizing the aromatic aromatic diamine (2-a) and aromatic acid dianhydride (2-c) to form a relatively soft block. The coexistence of can achieve the target linear expansion coefficient of the polyimide film.

[0057] In the polyamic acid according to the present invention, the blocking force obtained by the step (1) is preferably in the range of 40 to 90 mol% based on the total polyamic acid, and in the range of 50 to 80 mol%. It is more preferable. If the block obtained by the step (1) is less than 40 mol%, the desired physical properties may not be stably expressed. Conversely, if it exceeds 90 mol%, the polyamic acid is stably produced in continuous production. It may be difficult to get

[0058] As a method for producing the polyamic acid used in the present invention, any known method can be used. Usually, an aromatic dianhydride and an aromatic diamine are dissolved in an organic solvent, The obtained polyamic acid solution can be produced by stirring under controlled temperature conditions until the polymerization of the acid dianhydride and diamine is completed. These polyamic acid solutions are usually obtained at a concentration of 5 to 35% by weight, preferably 10 to 30% by weight. Generally, when the concentration is in the above range, a polyamic acid solution having an appropriate molecular weight and solution viscosity can be obtained.

[0059] As the polymerization method, any known method can be used.

[0060] As the solvent for synthesizing the polyamic acid, any solvent that dissolves the resulting polyamic acid can be used. Among them, amide solvents, that is, N, N-dimethylformamide, N, N N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferably used, such as —dimethylacetamide and N-methyl-2-pyrrolidone.

[0061] In addition, a filler can be added to the polyamic acid solution for the purpose of improving various properties of the film such as slidability, thermal conductivity, conductivity, and corona resistance. Any material may be used as the filler, but preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica and the like.

[0062] The particle diameter of the filler is not particularly limited because it is determined by the film characteristics to be modified and the type of filler to be added, but generally the average particle diameter is 0.05. To 100 μm, preferably 0.1 to 75 μm, more preferably 0.1 to 50 μm, and particularly preferably 0.1 to 25 / ζ πι. If the particle diameter is below this range, the effect of improving the film properties is hardly exhibited. Conversely, if it exceeds this range, the surface properties may be greatly impaired or the mechanical properties may be greatly deteriorated.

[0063] Further, the number of added parts of the filler is not particularly limited because the film characteristics to be modified are determined by the filler particle size and the like. In general, the amount of filler added is from 0.01 to 100 parts by weight of LEO, preferably from 0.01 to 90 parts by weight, and more preferably from 0.02 to 80 parts by weight per 100 parts by weight of positive imide. If the amount of filler added is below this range, the effect of reforming by the filler becomes difficult to be exhibited. Conversely, if it exceeds this range, the mechanical properties of the film may be greatly impaired.

[0064] The filler may be added by (1) adding a reaction solution before or during the polymerization of polyamic acid. How to add, (2) After polymerization is completed, a method of kneading filler using three rolls, etc., (3) A method of preparing a dispersion containing filler and mixing it with a polyamic acid solution, etc. Although a method may be used, the method of mixing the dispersion containing the filler with the polyamic acid solution, particularly the method of mixing just before the film formation is preferable because the contamination by the filler in the production line is minimized. When preparing a dispersion containing a filler, it is preferable to use the same solvent as the polymerization solvent for the polyamic acid. Further, in order to disperse the filler satisfactorily and stabilize the dispersion state, it is possible to use a dispersant, a thickener, etc. within a range that does not affect the film properties.

[0065] (Method for producing polyimide film)

As a method for producing a polyimide film using the polyamic acid solution as a precursor, a conventionally known method can be used without any particular limitation. Examples of this method include a thermal imidization method and a chemical imidization method, but imidization by a chemical imidation method is preferable in terms of thermal dimensional stability and mechanical strength.

[0066] Further, in the present invention, it is particularly preferable that the method for producing a polyimide film includes the following steps.

a) A process of obtaining a polyamic acid solution by reacting an aromatic diamine and an aromatic dianhydride in an organic solvent.

b) A step of casting a film-forming dope containing the polyamic acid solution on a support

c) After heating on the support, a step of peeling off the gel film from the strength of the support

d) Step of further heating to imidize and dry the polyamic acid unit remaining in the gel film

[0067] Taking a preferred embodiment of the present invention as an example, a process for producing a polyimide film will be described.

In the chemical imidization method, a polyamic acid solution is mixed with a dehydrating agent typified by an acid anhydride such as acetic anhydride, and an imidic acid catalyst typified by a tertiary amine such as isoquinoline, β-picoline, and pyridine. It is a method of acting. A thermal imidization method may be used in combination with the chemical imidization method. The heating conditions can vary depending on the type of polyamic acid, the thickness of the film, and the like.

[0068] A film-forming dope can be obtained by mixing the dehydrating agent and the imido catalyst at a low temperature in a polyamic acid solution. Subsequently, this dope is applied to a glass plate, aluminum foil, endless stainless steel. Casting in the form of a film on a support such as a les belt or stainless drum, and heating on the support in a temperature range of 80 ° C to 200 ° C, preferably 100 ° C to 180 ° C. After partially curing and Z or drying by activating the imidization catalyst, the support force can be peeled off to obtain a polyamic acid film (hereinafter referred to as gel film! /).

[0069] The gel film is in an intermediate stage of curing to polyamic acid polyimide and has a self-supporting property. (Equation 1) The calculated volatile content is in the range of 5 to 500%. Preferably it is 5 to 100%, more preferably 10 to 80%, and most preferably 30 to 60%. It is preferable to use a film in this range, and if it is removed, the mechanical strength of the polyimide film may be lowered.

(A— B) Χ 100ΖΒ (Equation 1)

In (Formula 1), A and B represent the following.

A: Gel film weight

B: Weight after heating the gel film at 450 ° C for 20 minutes

[0070] The end of the gel film is fixed and dried while avoiding shrinkage during curing, water, residual solvent, residual dehydrating agent and imidization catalyst are removed, and the remaining amic acid unit is completely removed. The polyimide film of the present invention can be obtained by imidization.

[0071] At this time, in order to completely imidize the polyamic acid to obtain a polyimide film, it is preferable to finally heat the film at a temperature of 400 to 580 ° C for 5 to 400 seconds! /. Above this temperature and Z or long heating time may cause thermal degradation of the film and cause problems. On the other hand, if the temperature is lower than this temperature and Z or the heating time is short, the resulting polyimide film may be deteriorated in mechanical strength.

[0072] Further, in order to relieve the internal stress remaining in the film, the heat treatment can be performed under the minimum tension necessary for transporting the film. This heat treatment may be performed in the film manufacturing process, or may be provided separately. The heating conditions vary depending on the film characteristics and the equipment used, and therefore cannot be determined in general.Generally 200 ° C to 500 ° C, preferably 250 ° C to 500 ° C, particularly preferred Alternatively, the internal stress can be relieved by heat treatment at a temperature of 300 ° C. or higher and 450 ° C. or lower for 1 to 300 seconds, preferably 2 to 250 seconds, and particularly preferably 5 to 200 seconds. [0073] Further, the film can be stretched before and after fixing the gel film. At this time, preferred! / ヽ The volatile content is 30 to 200%, preferably 50 to 150%. If the volatile content is below this range, it may be difficult to stretch, and if it exceeds this range, the self-supporting property of the film is poor, and the stretching operation itself may be difficult.

[0074] Stretching may be performed using a well-known and well-known method such as a method using a differential roll or a method of widening the fixing interval of the tenter.

[0075] (Physical properties of polyimide film)

As described above, (1) the average linear expansion coefficient of force preferably ^{18~ 25 X 10- 6 cm / cm} / ° range C in 100 to 200 ° C, more preferably 20~23 X 10- ⁶ cm / (2) Elastic modulus is preferably 4.0-10. OGPa, more preferably 4.5-7. OGPa, and (3) Thickness is 10-125 m, preferably ί. A polyimide film of 35 to: LOO m, more preferably 50 to 75 m, can be suitably obtained.

[0076] When these various characteristics satisfy the above range, the above-mentioned problems in the process of processing a TAB tape or a flexible printed circuit board can be solved, and it can be suitably used. If it is out of the range, there is a possibility that curling will not be able to be carried in the sprocket hole when CCL (copper clad laminate) is used.

[0077] It is important that the polyimide film of the present invention is non-thermoplastic. Non-thermoplastic refers to a material that melts and maintains the shape of the film when it is heated to about 450-500 ° C. Therefore, the polyimide film should be designed so that it becomes non-thermoplastic by the above-mentioned yarn formation.

Furthermore, the polyimide film of the present invention is suitably used as a base material for TAB tape.

When a flexible printed circuit board or a TAB tape is made using the polyimide film obtained by the present invention, the adhesive is completely dried after being completely cured, and humidity is adjusted at 60% RH and a temperature of 23 ° C. Saturated moisture absorption when the amount of warpage no longer changes If the amount of warpage in the dry state Xi force Warp change time until the amount of warpage Xe in the saturated moisture absorption state (time from XI to Xe) is within 6 hours Preferably, it is within 5 hours, particularly preferably within 4 hours. When the warpage change time exceeds the above range, a photomask exposure failure or etching failure occurs during notching due to a dimensional change due to warpage change during the processing process. There is a tendency for defects due to warping to occur, such as good and poor alignment during semiconductor mounting.

[0079] Also, according to the present invention, a polyimide film having a thickness change of 5% or less when immersed in a 20 ° C IN sodium hydroxide aqueous solution for 6 hours can be obtained. A polyimide film having a thickness change of 5% or less when immersed in an aqueous sodium hydroxide solution for 30 minutes can be obtained. Furthermore, the dimensional change rate when immersed in an aqueous solution of sodium hydroxide and sodium hydroxide at 20 ° C IN for 6 hours is 0.05% or less in both the film flow direction (MD direction) and the MD direction (TD direction). A certain polyimide film can be obtained. As a result, it is possible to achieve an effect that does not cause a decrease in adhesive strength or a dimensional change while being exposed to an alkaline plating solution.

Example

Hereinafter, the ability to specifically explain the present invention by way of examples. The present invention is not limited to these examples. The linear expansion coefficient, elastic modulus, warpage measurement, and storage stability evaluation method in the synthesis examples, examples, and comparative examples are as follows.

[0081] (Linear expansion coefficient)

The linear expansion coefficient at 100 to 200 ° C was measured using a TMA120C manufactured by Seiko Electronics Co., Ltd. (sample size width 3 mm, length 10 mm), 10 ° C to 400 ° at 10 ° C / min with a load of 3 g. The temperature is raised to C once, then cooled to 10 ° C, further heated at 10 ° C / min, and the average value is determined from the coefficient of thermal expansion at 100 ° C and 200 ° C during the second temperature increase. As calculated.

[0082] (Elastic modulus)

The elastic modulus was measured according to ASTM D882.

[0083] (Evaluation of storage stability)

The resulting polyamic acid is allowed to stand at 15 ° C for 4 hours, and then subjected to a leaf filter (leaf diameter: 15 inches, number of leaves: 100 sheets, opening size: 3 m). The storage stability when the filtration time twice as long as the initial filtration time was required was evaluated as NG, and the others were evaluated as good (OK).

[0084] (TAB tape creation and warpage measurement)

The value of warpage is 40mm in length X 35mm in width for TAB tape created by the following procedure. The cut and vacuum dried (0. lMPa, 2 hours) state was completely dried, left on a flat surface, and the height of the four corners was measured. The amount of warping is Xi). In addition, the amount of warpage was measured while adjusting the humidity of a vacuum-dried sample at a humidity of 60% RH and a temperature of 23 ° C, and the point when the amount of warpage stopped changing was regarded as a saturated moisture absorption state. To do).

[0085] Further, a TAB tape was prepared as follows.

1. Polyamide resin (Platabond M1276 from Nippon Rilsan) 50 parts by weight, Bisphenol A type epoxy resin (Epicoat 828 from Yuka Shell Epoxy) 30 parts by weight, Cresol novolac epoxy resin 10 parts by weight, toluene An adhesive solution was prepared by mixing 150 parts by weight of a 1Z1 mixed solution of Z isopropyl alcohol with 45 parts by weight of a 20% by weight methylceosolve solution of diaminodiphenylsulfone Z dicyandiamide 4Z1.

2. The adhesive solution was applied on a 25 μm thick PET film to a thickness of 11 m after drying, and dried at 120 ° C. for 2 minutes. This PET film with B-stage adhesive was slit to a width of 26 mm.

3. B-stage adhesive PET film with the center portion of the polyimide film of 35mm width combined Zhang is, and pressed at a pressure of LkgZcm ² at 90 ° C. The PET film was peeled off, and this was bonded to a copper foil (Mitsui Metals, VLP 18 m thickness) by roll lamination. Temperature of bonding at this time is 120 ° C, the pressure was found to be 2kgZcm ^2.

4. The above copper bonded product is heated in steps of 60 ° C for 3 hours, 80 ° C for 3 hours, 120 ° C for 3 hours, 140 ° C for 3 hours, 160 ° C for 4 hours, and then slowly cooled. The adhesive was cured.

[0086] (Alkali resistance (thickness change rate))

The 5 × 5 cm sample was obtained from the following formula from the thickness before and after immersing the sample in a sodium hydroxide aqueous solution.

(Thickness change rate) = I T (after) — T (before) | / T (before) X 100

T (after): Film thickness after immersion in aqueous sodium hydroxide solution

T (before): film thickness before immersion in sodium hydroxide aqueous solution

[0087] (Alkali resistance (dimensional change rate)) A lmm hole was made in each corner of a 20 x 20cm film sample so that the distance between the holes was approximately 15cm, and the distance force between the holes before and after immersion in the aqueous sodium hydroxide solution was determined by the following formula. (Dimensional change rate) = IL (after) — L (before) | / L (before) X 100

L (after): Distance between holes after immersion in aqueous sodium hydroxide solution

L (before): Distance between holes before immersion in aqueous sodium hydroxide solution

In addition, the dimensional change rate in the MD direction and the TD direction for each sample was averaged to obtain the dimensional change rate in each direction.

[0088] The following abbreviations are used in the following Examples and Comparative Examples.

ODA: 4,4'-diaminodiphenyl ether

PDA: p-Phenylenediamine

BAPP: 2, 2-bis (4-aminophenoloxy) propane

BTDA: 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride

PMDA: pyromellitic dianhydride

DMF: N, N-dimethylformamide

[Example 1]

10 ^° C. This was chilled. 225.6 kg of DMF [5. 12 kg of ODA and 6.91 kg of PDA were dissolved and the solution was kept at 15 ° C. 17.55 kg of PMDA was gradually added thereto and stirred for 1 hour to completely dissolve the PMDA. 15.73 kg of BAPP was added to this solution and stirred for 10 minutes, and then Sarako 13.58 kg of BTDA was added and stirred for 30 minutes to dissolve to obtain a prepolymer. This prepolymer was filtered through a 3 μm filter, and PMDA DMF solution (7.2% by weight) was gradually added, and when about 2000 boise was reached, the addition was stopped. The solution was uniformly stirred for 30 minutes to obtain a polyamic acid solution with a solution viscosity of 2700 boise at 23 ° C and a solid content of 20% by weight (ODAZPDAZPMDAZBAPPZBTDAZPMDA = 2

0Z50Z65Z33Z33Z2).

[0090] To this polyamic acid solution, 130.40 kg of acetic anhydride, 54.99 kg of isoquinoline and 14.61 kg of DMF2 were mixed rapidly with a mixer at a weight ratio of 40% with respect to the polyamic acid solution. It was then extruded and cast 10 mm below the die onto a stainless steel endless belt running at a speed of 0.3 m / min. 120 ° CX 900 sec. After drying, peel off from the endless belt and fix to the gripping tool of the tenter furnace, and 130 in the hot air circulating furnace. CX 160 seconds, 250 ° CX 180 seconds, 350 ° CX 210 seconds, 450 ° CX 190 seconds, followed by 460 ° CX 200 seconds, 440 ° CX 150 seconds, 300 ° CX 150 seconds in a far-infrared drying oven A polyimide film having a thickness of 75 m was obtained. Tables 1 and 3 show the film properties. Thereafter, a TAB tape was prepared and evaluated according to a reference example. Table 2 shows the characteristics of TAB tape.

[0091] (Example 2)

Ten. 10.91 kg of ODA and 5.91 g of PDA were dissolved in 228.5 kg of DMF cooled to C, and this solution was kept at 15 ° C. 17.88 kg of PMDA was gradually added thereto and stirred for 1 hour to completely dissolve the PMDA. 11. Add 22 kg of BAPP and stir for 10 minutes, then add 6.60 kg of BTDA and 6.56 kg of PMDA, stir for 30 minutes and dissolve to dissolve the prepolymer. Obtained. After filtering the prepolymer filter 3 m, it was stopped adding PMDA in DMF solution (7.2 wt ^_0/0) gradually and rollers reaches添Ka卩to approximately 2000 Boyes. The solution was uniformly stirred for 30 minutes to obtain a polyamic acid solution with a solution viscosity of 2700 boise at 23 ° C and a solid concentration of 20% by weight (ODAZPDAZPMDAZBAPPZB TDA / PMDA / PMDA = 40/40/60/20/15/23/2 ).

[0092] To this polyamic acid solution, 130.40 kg of acetic anhydride, 54.99 kg of isoquinoline and 14.61 kg of DMF2 were mixed rapidly with a mixer at a weight ratio of 40% with respect to the polyamic acid solution. It was then extruded and cast 10 mm below the die onto a stainless steel endless belt running at a speed of 0.3 m / min. The resin film is dried at 120 ° C for 900 seconds, then peeled off from the endless belt and fixed to the gripper of the tenter furnace, and 130 in a hot air circulating furnace. CX 160 seconds, 250 ° CX 180 seconds, 350 ° CX 210 seconds, 450 ° CX 190 seconds, followed by 460 ° CX 200 seconds, 440 ° CX 150 seconds, 300 ° CX 150 seconds in a far-infrared drying oven A polyimide film having a thickness of 75 m was obtained. Tables 1 and 3 show the film properties.

[0093] (Comparative Example 1)

23. 8 kg of DMF that had been cooled to 10 ° C and 7.01 kg of PDA were dissolved and the solution was kept at 15 ° C. To this, gradually add 10.70 kg of PMDA, stir for 1 hour and add PMDA. It was completely dissolved. Add 9. Olkg of ODA and 7.92 kg of BAPP to this solution and stir for 10 minutes, then add 24.94 kg of BTDA and stir for 30 minutes to dissolve the prepolymer. Obtained. The prepolymer was filtered through a 3 m filter, PMDA DMF solution (7.2 wt%) was gradually added, and the addition was stopped when it reached about 2000 boise. The solution was uniformly stirred for 30 minutes to obtain a polyamic acid solution with a solution viscosity at 23 ° C of 2700 boise and a solid concentration of 20% by weight (PDAZPMDAZODAZBAPPZBTDAZPMDA = 50

Z38Z35Z15Z60Z2).

[0094] To this polyamic acid solution, 130.40 kg of acetic anhydride, 54.99 kg of isoquinoline and 14.61 kg of DMF2 were mixed rapidly with a mixer at a weight ratio of 40% with respect to the polyamic acid solution. It was then extruded and cast 10 mm below the die onto a stainless steel endless belt running at a speed of 0.3 m / min. The resin film is dried at 120 ° C for 900 seconds, then peeled off from the endless belt and fixed to the gripper of the tenter furnace, and 130 in a hot air circulating furnace. CX 160 seconds, 250 ° CX 180 seconds, 350 ° CX 210 seconds, 450 ° CX 190 seconds, followed by 460 ° CX 200 seconds, 440 ° CX 150 seconds, 300 ° CX 150 seconds in a far-infrared drying oven A polyimide film having a thickness of 75 μm was obtained.

[0095] Table 1 shows the results of evaluating film physical properties and storage stability.

[0096] (Comparative Example 2)

10 ^o C [this cooled P was 233. 48 kg of DMF [this 17. 28 kg of BAPP, and dissolve the ODA of 7. 00kg, keeping this solution 15 ° C. After gradually adding 11.2 lkg of BTD A and dissolving, 5.06 kg of PMDA was gradually added and stirred for 1 hour to completely dissolve PMDA. After adding 5.02 kg of PDA to this solution and stirring for 10 minutes, 12.65 kg of PMDA was further added and stirred for 30 minutes to dissolve, thereby obtaining a prepolymer. After filtration the Pureborima a filter of 3 mu m, was stopped hydrogenated mosquitoes卩Upon reaching PMDA in DMF solution (7.2 wt ^_0/0) gradually添Ka卩to approximately 2000 Boyes. The solution was uniformly stirred for 30 minutes to obtain a polyamic acid solution having a solution viscosity of 2700 boise at 23 ° C and a solid concentration of 20% by weight (BAPPZOD A / BTDA / PMDA / PDA / PMDA / PMDA = 30/30/30/18 / 40/50 Z2).

[0097] Acetic anhydride 130.40 kg, isoquinoline 54.99 kg and DMF2 14. 61 kg of hardener is rapidly stirred and mixed with a mixer at a weight ratio of 40% with respect to the polyamic acid solution, extruded from the T-Dieker, and run 10 mm below the die at a speed of 0.3 m / min. Cast on a stainless steel endless belt. The resin film is dried at 120 ° C for 900 seconds, then peeled off from the endless belt and fixed to the gripper of the tenter furnace, and 130 in a hot air circulating furnace. CX 160 seconds, 250 ° CX 180 seconds, 350 ° CX 210 seconds, 450 ° CX 190 seconds, followed by 460 ° CX 200 seconds, 440 ° CX 150 seconds, 300 ° CX 150 seconds in a far-infrared drying oven A polyimide film having a thickness of 75 μm was obtained.

[0098] Table 1 shows the results of evaluating film physical properties and storage stability.

[0099] (Comparative Example 3)

Using UPILEX 50S (polyimide film; Ube Industries, Ltd.), a TAB tape was prepared according to the reference example. Table 2 shows the characteristics of TAB tape.

[0100] (Example 3)

227. 14.55 kg of ODA and 6.28 kg of PDA were dissolved in 8 kg of DMF and the solution was kept at 15 ° C. To this, 25.35 kg of PMDA was gradually added and stirred for 1 hour to completely dissolve the PMDA. To this solution, 5.96 kg of BAPP was added and stirred for 10 minutes. Then, Sarakako 4.68 kg of BTDA and 2.22 kg of PMDA were added and stirred for 30 minutes. Here it was added PMDA in DMF solution (7.2 wt ^_0/0) gradually stopped added was reached approximately 2000 Boyes. The solution was uniformly stirred for 30 minutes to obtain a polyamic acid solution having a solution viscosity of 2700 boise at 23 ° C and a solid concentration of 20% by weight (ODAZPDAZPMDAZBAPP / BTDA / PMDA / PMDA = 50/40/80 / 10/10/8/2 ). Using this polyamic acid solution, a film was formed in the same manner as in Example 1, but the film was brittle and fractured in the tenter furnace. Table 3 shows the characteristics of the polyimide film evaluated at the part where the film was formed.

[0101] (Comparative Example 4)

227. 23.68 kg of ODA was dissolved in 9 kg of DMF and the solution was kept at 15 ° C. To this, 36.84 kg of PMDA was gradually added and stirred for 1 hour to completely dissolve the PMDA. 4. After dissolving by添Ka卩the PDA of 75 kg, was stopped adding PDA of DMF solution (4 wt ^_0/0) was reached added to approximately 2000 Boise gradually. Stir uniformly for 30 minutes to obtain a polyamic acid solution with a solution viscosity of 2700 boise at 23 ° C and a solid content of 20 wt% (ODAZPMDAZPDA = 70/100/30). Using this polyamic acid solution, a polyimide film having a thickness of 75 μm was obtained in the same manner as in Example 1. Table 3 shows the properties of this polyimide film.

[table 1]

[0103] [Table 2]

[0104] [Table 3]

Claims

Claims [1] A polyimide film obtained using a polyamic acid solution as a precursor, wherein the polyamic acid is

(1) Use at least one flexible aromatic diamine (1 a), at least one linear aromatic diamine (1 b) and at least one aromatic dianhydride (1 c). After forming the block composed,

(2) At least one type of flexible aromatic diamine (2-a) and at least one type of aromatic dianhydride (2-c) are substantially divided into diamine component and acid dianhydride component in all steps. A polyimide film, which is obtained by adding an equimolar amount to form a block.

[2] The number of the flexible groups contained in the flexible aromatic diamine (1a) is smaller than the number of the flexible groups contained in the flexible aromatic diamine (2-a). The polyimide film according to claim 1.

[3] The flexible aromatic diamine (1a) has one flexible group, and is a flexible aromatic diamine.

3. The polyimide phenolic according to claim 2, wherein (2-a) has two or more flexible groups.

[4] The polyimide film according to claim 1, comprising the flexible aromatic diamine (1-a) 1S 4,4′-diaminodiphenyl ether.

[5] The polyimide film according to claim 1, wherein the flexible aromatic diamine (1-a) force is in the range of 10 to 50 mol% based on the total diamine component.

[6] The polyimide film according to [1], which comprises the flexible aromatic diamine (2-a) force 2, 2 bis (4-aminophenoxyphenol) plug pan.

[7] The polyimide film as described in [1], which is in the range of 10 to 40 mol% based on the total diamine component, wherein the flexible aromatic diamine (2-a) force is used.

[8] The aromatic acid dianhydride (2-c) includes 3, 3 ′, 4, 4′-benzophenone tetracarboxylic dianhydride, according to claim 1, Polyimide film.

[9] The polyimide film according to claim 1, wherein the aromatic acid dianhydride (2-c) force is in the range of 15 to 60 mol% based on the total acid dianhydride component.

[10] The polyimide film according to claim 1, wherein the blocking force obtained by (1) is in the range of 40 to 90 mol% based on the total polyamic acid.

[11] The polyimide film according to claim 1, wherein the polyimide film is used as a base material for a TAB tape.

[12] The polyimide film according to [1], which is obtained by chemically converting polyamic acid.

[13] The average linear expansion coefficient at 100 to 200 ° C is characterized in that it is a ^{18~25 X 10- 6 cm / cm /} ° C, a polyimide film in the range 11 according claims.

[14] The polyimide phenol of claim 11, wherein the elastic modulus is 4. OGPa or more.

[15] The polyimide film according to claim 11, wherein the thickness change when immersed in a 20 ° C. IN aqueous solution of sodium hydroxide and sodium hydroxide for 6 hours is 5% or less.

[16] The polyimide film according to claim 11, wherein the thickness change when immersed in an aqueous solution of sodium hydroxide and sodium hydroxide at 60 ° C. for 30 minutes is 5% or less.

[17] Dimensional change rate power when immersed in an aqueous solution of sodium hydroxide and sodium hydroxide at 20 ° C IN for 0.05 hours in both the film flow direction (MD direction) and MD direction (TD direction) The polyimide film according to claim 11, wherein: