JP2007197696A - Low heat-shrinking and highly adhesive polyimide film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide film that exhibits improved heat shrinkage and enhanced adhesive properties. <P>SOLUTION: The low heat-shrinking and highly adhesive polyimide film is obtained by subjecting a polyimide film formed from p-phenylenediamine, 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride to a discharge treatment and subsequently to a heat treatment while keeping a tension of the film constant in the longitudinal direction and has a surface free energy of at least 80 mN/m as measured by the contact angle method and a heat shrinkage of at most 0.10% at 200°C for 1 hr. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyimide film having improved heat shrinkability and at the same time improved adhesion.

  Polyimide films obtained by polycondensation of aromatic tetracarboxylic dianhydrides and aromatic diamines have been widely used as base films for flexible printed circuit boards because of their excellent heat resistance, insulation and mechanical properties. It was.

  In order to make a flexible printed circuit board using a polyimide film as a base film, it is necessary to laminate a metal foil such as copper on the film via an adhesive, or to attach the metal directly to the film by vacuum deposition, sputtering, etc. However, since considerable heat is applied in these steps, the polyimide film is required to have dimensional stability against heat. Furthermore, as a recent trend, fine pitches are being promoted, and a polyimide film with smaller shrinkage due to heat is required.

  As means for meeting such demands, there has been proposed a method in which a polyimide film is substantially tension free, heat-treated in a heating oven, and then cooled (for example, see Patent Document 1). However, this method of heat treatment under no tension is an effective method because the latent shrinkage stress of the film is alleviated and the subsequent shrinkage to heating is reduced. However, in order to perform the heat treatment under no tension, In any case, a roll of film is allowed to stand in a heating oven or a method of unwinding and continuously processing the film in a continuous heating furnace equipped with a winder. Since the film is processed for a long time under no tension, there is a problem that the resulting film is in a state of waves, which causes a variation in thermal shrinkage. In particular, in the case of continuous processing, there has been a disadvantage that the film meanders and a complete product roll cannot be obtained.

  Furthermore, in applications such as base films for flexible printed wiring boards and carrier tape films for IC tape automated bonding, polyimide films and copper foils are usually bonded using various adhesives. Yes. However, since polyimide often has insufficient adhesion due to its chemical structure and high chemical resistance, a method of chemically treating the film surface with an acid or alkali (see, for example, Patent Document 1), and Attempts have been made to improve adhesiveness by applying a physical processing method such as sandblasting (see, for example, Patent Document 2).

However, since these processes require separate steps such as washing and drying after the process, they have problems in terms of not only productivity, stability and cost but also environmental conservation.
JP 62-41024 JP 2002-294965 A Japanese Patent Laid-Open No. 9-48864

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Accordingly, an object of the present invention is to provide a polyimide film having improved heat shrinkability and at the same time improved adhesion.

  To achieve the above object, according to the present invention, paraphenylenediamine, 4,4′-diaminodiphenyl ether, pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride A polyimide film formed by subjecting a polyimide film formed from a discharge treatment to heat treatment while maintaining a constant tension in the length direction of the film, and having a surface free energy measured based on a contact angle method of 80 mN / There is provided a low heat shrinkage / high adhesion polyimide film characterized by having a heat shrinkage ratio of 0.10% or less at 200 ° C. for 1 hour.

In the low thermal shrinkage / high adhesion polyimide film of the present invention,
The polyimide film comprises 12-30 mol% paraphenylenediamine, 70-88 mol% 4,4'-diaminodiphenyl ether, 50-99.5 mol% pyromellitic dianhydride and 0.5-50 mol. % Copolymerized polyimide formed from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
The elastic modulus of the polyimide film is 4 to 7 GPa, the linear expansion coefficient at 50 to 200 ° C. is 5 to 20 ppm / ° C., the humidity expansion coefficient is 20 ppm /% RH or less, and the water absorption is 2% or less.
The electric discharge treatment is a plasma electric discharge treatment, and the heat treatment is a treatment performed while keeping the tension in the length direction of the film constant within a range of 1 kg / m to 10 kg / m,
Are mentioned as preferable conditions.

  According to the present invention, as will be described below, it is possible to obtain a polyimide film having improved heat shrinkability and at the same time improved adhesion. That is, the low heat shrinkage / high adhesion polyimide film of the present invention is not only excellent in dimensional stability against heat, but also has a small shrinkage due to heat, and its adhesion to copper foil is greatly improved as compared with the prior art.

  Hereinafter, the low thermal shrinkage / high adhesion polyimide film of the present invention will be described in detail.

  First, the polyimide acid that is a precursor for obtaining the polyimide film of the present invention will be described. The polyamic acid used in the present invention comprises paraphenylenediamine and 4,4′-diaminodiphenyl ether as aromatic diamine components, pyromellitic dianhydride and 3,3 ′ as aromatic tetracarboxylic dianhydride components. , 4,4′-biphenyltetracarboxylic dianhydride is obtained by polymerization.

  As a method until the polyimide film of the present invention is formed, any known method such as a method in which polyamic acid is polymerized in advance and then imidized can be used. For example, any known method can be used as a method for producing a polyamic acid, and usually obtained by dissolving substantially equal molar amounts of an aromatic dianhydride and an aromatic diamine in an organic solvent. It is produced by stirring the polyamic acid organic solvent solution under controlled temperature conditions until the polymerization of the acid dianhydride and the diamine is completed. These polyamic acid solutions are usually obtained at a concentration of 5 to 35 wt%, preferably 10 to 30 wt%. When the concentration is in this range, an appropriate molecular weight and solution viscosity can be obtained.

  Any known method can be used as the polymerization method, and the following method is particularly preferable as the polymerization method.

That is,
1) A method in which an aromatic diamine is dissolved in an organic polar solvent and this is reacted with a substantially equimolar amount of an aromatic tetracarboxylic dianhydride for polymerization.
2) An aromatic tetracarboxylic dianhydride is reacted with a small molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Then, the method of superposing | polymerizing using an aromatic diamine compound so that an aromatic tetracarboxylic dianhydride and an aromatic diamine compound may become substantially equimolar in all the processes.
3) An aromatic tetracarboxylic dianhydride is reacted with an excess molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after adding an aromatic diamine compound here, using the aromatic tetracarboxylic dianhydride so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are substantially equimolar in all steps. How to polymerize.
4) A method in which an aromatic tetracarboxylic dianhydride is dissolved and / or dispersed in an organic polar solvent and then polymerized using an aromatic diamine compound so as to be substantially equimolar.
5) A method in which a substantially equimolar mixture of aromatic tetracarboxylic dianhydride and aromatic diamine is reacted in an organic polar solvent for polymerization.
And so on.

  In the present invention, the polyamic acid obtained by any of the above methods may be used, and the polymerization method is not particularly limited. In the present invention, the effect can of course be obtained even if molecular arrangement in the polymer and expensive monomers are used.

  Among these methods, from the viewpoint of stably controlling the process, all of the aromatic diamine components used in all processes are dissolved in an organic solvent, and then aromatic tetracarboxylic dianhydride so as to be substantially equimolar thereafter. It is preferable to use a method in which a physical component is added to conduct a polymerization reaction.

  In the present invention, as the aromatic tetracarboxylic dianhydride component, pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are used in combination. Other aromatic tetracarboxylic dianhydrides can be used in combination as long as they are below.

  Other aromatic tetracarboxylic dianhydrides that can be used in combination include 2,3,6,7-naphthalenetetracarboxylic dianhydride and 2,2′-bis (3,4-dicarboxyphenyl) propane dianhydride. Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-carboxyphenyl) ether dianhydride, naphthalene-1, 2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydro-naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4 , 8-Dimethyl-1,2,3,5,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6, -dichloronaphthalene-1,4,58-tetracarboxylic acid Anhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride Phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxy) Phenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride Benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, or a mixture of two or more thereof.

  As the aromatic diamine component, two kinds of 4,4'-diaminodiphenyl ether and paraphenylene diamine are used, but other aromatic diamines can be used in combination as long as they are 40 mol% or less.

    Other aromatic diamines that can be used in combination include 3,4'-diaminodiphenyl ether, metaphenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 2,6-diaminopyridine, bis- (4-aminophenyl) diethylsilane, bis- (4-aminophenyl) diphenylsilane, 3,3 '-Dichlorobenzidine, bis- (4-aminophenyl) ethylphosphine oxide, bis- (4-aminophenyl) phenylphosphine oxide, bis- (4-aminophenyl) -N-phenylamine, bis- (4-amino) Phenyl) -N-methylamine, 1, -Diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-dimethyl-3 ', 4-diaminobiphenyl, 3,3'-dimethoxybenzidine, 2,4-bis (β -Amino-t-butyl) toluene, bis (p-β-amino-t-butyl-phenyl) ether, p-bis- (2-methyl-4-amino-benzyl) benzene, p-bis- (1,1 -Dimethyl-5-amino-benzyl) benzene, m-xylylenediamine, p-xylylenediamine, 1,3-diaminoadamantane, 3,37-diamino-1,17-diadamantane, 3,3'-diamino- 1,1′-diadamantane, bis (para-amino-cyclohexyl) methane, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, noname Range amine, decamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diamino-dodecane, 1,2-bis- (3-amino-propoxy) ethane, 2,2- Dimethylpropylenediamine, 3-methoxy-hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 5-methylnonamethylenediamine, 5-methylnonamethylenediamine, 1,4-diamino-cyclohexane, 1,12-diamino-octadecane 2,5-diamino-1,3,4-oxadiazole, 2,2-bis (4-aminophenyl) hexafluoropropane, N- (3-aminophenyl) -4-aminobenzamide, 4-aminophenyl -3-aminobenzoate and the like.

  Next, as an organic solvent used for polycondensation of polyimide in the present invention, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N-dimethylmethoxy Examples include acetamide, N-methyl-caprolactam, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylene sulfone, formamide, N-methylformamide and ptyrolactone. . These organic solvents can be used alone or in combination, or in combination with solvents having poor solvent properties such as benzene, benzonitrile, dioxane, ptyrolactone, xylene, toluene and cyclohexane.

  In the present invention, it is possible to carry out polycondensation of polyimide without adding a catalyst, but it may be preferable to add the following catalysts and dehydrating agents.

  As the catalyst, tertiary amines are preferably used. Specific examples of these amines include trimethylamine, triethylamine, triethylenediamine, pyridine, isoquinoline, 2-ethylpyridine, 2-methylpyridine, and N-ethylmorpholine. N-methylmorpholine, diethylcyclohexylamine, N-dimethylcyclohexylamine, 4-benzoylpyridine, 2,4-lutidine, 2,6-lutidine, 2,4,6-collidine, 3,4-lutidine, 3, Examples include 5-lutidine, 4-methylpyridine, 3-methylpyridine, 4-isopropylpyridine, N-dimethylbenzylamine, 4-benzylpyridine, and N-dimethyldodecylamine.

  Examples of the dehydrating agent include organic carboxylic acid anhydrides, N, N-dialkylcarbodiimides, lower fatty acid halides, halogenated lower fatty acid halides, halogenated lower fatty acid anhydrides, arylphosphonic acid dihalides, and thionyl halides. Can be mentioned.

  Here, examples of the organic carboxylic acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, anhydrides mixed with each other, and aromatic monocarboxylic acids such as benzoic acid and naphthoic acid. Examples thereof include a mixture with an anhydride and a mixture of carbonic acid and formic acid and an anhydride of a fatty acid ketene (ketene and dimethyl ketene). Among them, the use of acetic anhydride and ketene is preferable.

  In addition to benzoic anhydride, other usable aromatic anhydrides include o-, m- or p-toluic acid, m- or p-ethylbenzoic acid, p-propylbenzoic acid, p-isopropylbenzoic acid. Acid, anisic acid, o-, m- or p-nitrobenzoic acid, o-, m- or p-halobenzoic acid, various dibromo or dichlorobenzoic acids, tribromo or trichlorobenzoic acid, isomers of dimethylbenzoic acid, for example Hemicylic acid, 3,4-xylyl acid, isoxysilyl acid or mesitylene acid, veratrmic acid, trimethoxybenzoic acid, α or β-naphthoic acid, biphenylcarboxylic acid and other acid anhydrides, mixed anhydrides of the above anhydrides, fatty acid mono Mixture anhydrides with carboxylic acids such as acetic acid, propionic acid and the like, and mixed anhydrides with carbonic acid or formic acid respective anhydrides Can be mentioned.

  N, N′-dialkylcarbodiimides are represented by the formula: R—N═C═N—R, wherein R can be different alkyl groups but are generally the same, preferably R groups Is a lower alkyl group of 1 to 8 carbon atoms.

  Examples of the dehydrating agent containing halogen include acetyl chloride, acetyl bromide, acetyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, n-butyryl chloride, N-butyryl bromide, valeryl chloride, mono-, di- or tri-chloroacetyl chloride, bromoacetyl bromide, chloroacetic anhydride, phenylphosphonic dichloride, thionyl chloride, thionyl bromide, thionyl fluoride, thionyl Examples include chlorofluoride and trifluoroacetic anhydride.

  The method for forming the polyimide film of the present invention is not particularly limited, but it is common to form a film by casting a polyamic acid solution or extruding it into a film, performing drying and heat treatment to advance imidization. is there.

  At this time, the drying / heat treatment is achieved by passing the polyamic acid solution extruded into a cast or film shape through a drying heat treatment zone maintained in a high temperature atmosphere of 200 to 550 ° C., preferably 250 to 500 ° C. Can do.

  In the present invention, it is desirable to adjust the film thickness to be 5 to 150 μm, preferably 7 to 125 μm.

  The polyimide film of the present invention comprises 12-30 mol% paraphenylenediamine, 70-88 mol% 4,4'-diaminodiphenyl ether, 50-99.5 mol% pyromellitic dianhydride, 0.5- Desirably, it is formed from 50 mole percent 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.

  However, the addition ratio of paraphenylenediamine and 4,4′-diaminodiphenyl ether in the diamine component is such that the copolymerized polyimide film becomes soft when the amount of 4,4′-diaminodiphenyl ether increases, and conversely the copolymer polyimide when the amount of paraphenylenediamine increases. Since a film becomes hard, it is preferable to set the addition ratio of both according to the use of a copolymerization polyimide film. In addition, when the obtained copolymerized polyimide film is used for, for example, a flexible printed board, it is preferable that the film properties are not too hard and not too soft. It is preferable that a phenylenediamine is 12-30 mol%.

  And the polyimide film of this invention is characterized by the surface free energy measured based on the contact angle method being 80 mN / m or more.

  Here, when the surface free energy of the polyimide film is less than 80 mN / m, the effect of improving adhesiveness becomes insufficient, which is not preferable. When the surface free energy condition satisfies the above range, a copolymerized polyimide film having excellent adhesion to the copper foil can be obtained.

  In addition, the polyimide film of the present invention preferably has a thermal shrinkage rate of 0.10% or less, more preferably 0.05% or less under heating conditions of 200 ° C./1 hour.

  When the thermal shrinkage rate exceeds 0.10%, the effect of improving the shrinkability to heat is reduced, which is not preferable.

  Furthermore, the polyimide film of the present invention has an elastic modulus of 4 to 7 GPa, a linear expansion coefficient at 50 to 200 ° C. of 5 to 20 ppm / ° C., a humidity expansion coefficient of 20 ppm /% RH or less, and a water absorption of 2% or less. More preferably, the elastic modulus is 5 to 6 GPa, the linear expansion coefficient is 8 to 18 ppm / ° C., the humidity expansion coefficient is 15 ppm / RH% or less, and the water absorption is 1.8% or less.

  The copolymerized polyimide film of the present invention satisfying the above characteristics is obtained by forming a polyimide film having the above composition, then subjecting the copolymerized polyimide film to a discharge treatment, and then maintaining a constant tension in the length direction of the film. It can manufacture by heat-processing.

  As the discharge treatment in the present invention, plasma treatment is typical.

The pressure of the atmosphere in which the plasma treatment is performed is not particularly limited, but is preferably in the range of 100 to 1000 Torr, and more preferably in the pressure range of 600 to 900 Torr. Although it does not specifically limit as a gas composition of the atmosphere which performs the said plasma processing, It is preferable to contain oxygen. Moreover, you may contain a noble gas at least 20 mol%. Examples of the rare gas include He, Ne, Ar, and Xe, and Ar is preferable. A rare gas such as CO ₂ and N ₂ may be mixed and used. The plasma irradiation time for performing the plasma treatment is preferably 1 second to 10 minutes.

  The gas type, gas pressure, and treatment density of the plasma treatment are not particularly limited, but the gas pressure is preferably performed under a pressure in the range of 13300 to 1330,000 Pa. The gas that can be used to form the plasma gas preferably contains 50% or more of an inert gas. Further, it is preferably 80% or more, particularly 90% or more. Specific examples of the inert gas include helium, argon, krypton, xenon, neon, radon, nitrogen and the like, and these can be used alone or in combination of two or more.

  Examples of the gas that can be mixed with the inert gas include oxygen, air, carbon monoxide, carbon dioxide, carbon tetrachloride, chloroform, hydrogen, ammonia, carbon tetrafluoride, trichlorofluoroethane, trifluoromethane, and the like.

Preferred gas mixture combinations are argon / oxygen, argon / ammonia, argon / helium / oxygen, argon / carbon dioxide, argon / nitrogen / carbon dioxide, argon / helium / nitrogen, argon / helium / nitrogen / carbon dioxide, argon / Helium, argon / helium / acetone, helium / acetone, helium / air, argon / helium / silane. The processing power density is preferably ²⁰⁰ w · min / m ² or more. More preferably, the treatment is performed at 500 w · min / m ² or more, more preferably 1000 w · min / m ² .

  As described above, the gas type, gas pressure, and treatment density of the corona treatment are not particularly limited, but are generally performed in the atmosphere.

  Regarding the heat treatment after the discharge treatment in the present invention, the obtained polyimide film is kept at a relatively low temperature and relatively short while maintaining the tension in the length direction of the film at 1 kg / m or more and 10 kg / m or less. Heating in time is an important requirement.

  The smaller the tension during the heat treatment, the lower the heat shrinkable film can be obtained. However, under complete tension, the film meanders, especially during continuous winding, and the film not only wrinkles and wavy, but also heat shrinks. Since the variation in rate tends to increase, the rate needs to be 1 kg / m or more. On the other hand, if the tension exceeds 10 kg / m, it is not preferable because the heat-shrinkable film intended by the present invention cannot be obtained. And the range of a preferable tension | tensile_strength is 2 kg / m-7 kg / m.

  As a heating means during the heat treatment, a method of irradiating far infrared rays or a method of blowing hot air is preferable. The polyimide film has an absorption peak in the far-infrared region, and heat treatment is performed in an extremely short time by irradiating far-infrared rays including this absorption wavelength. In addition to far-infrared irradiation and hot air spraying, a radiation heater can be used in combination, and further, heat treatment can be performed using only the radiation heater.

  Although heat processing temperature is not specifically limited, 300-500 degreeC is preferable, More preferably, it is 350-450 degreeC.

  The heat treatment time is preferably about 1 second to 10 minutes. When the treatment time is longer than this, the characteristics such as poor film flatness are deteriorated, which may cause an undesirable tendency.

  In the present invention, it is preferable to perform a heat treatment after the discharge treatment. By performing the treatment in this order, the film has appropriate slipperiness, and wrinkles and the like when wound are reduced.

  In the present invention, the polyimide film that has been subjected to the discharge treatment and the heat treatment is wound after having a specified width, for example, by slitting the end portion.

  The polyimide film of the present invention thus obtained has not only excellent dimensional stability against heat, but also small shrinkage due to heat, and further improved adhesiveness with copper foil, so these characteristics are improved. Utilizing it as a base insulating film for TAB (Tape Automated Bonding) and COF (Chip On Flex), which are base materials used for flexible printed circuit boards (FPC) such as electronic components, or for LOC, which is a support member in semiconductor devices It can be usefully used as a tape.

  Hereinafter, the present invention will be described specifically by way of examples. Each characteristic of the polyimide film in an Example was evaluated with the following method.

(Surface free energy)
The surface free energy was determined using the FACE CA-W150 of Kyoto Interface Science from the average value of contact angles obtained by measuring n = 5 times each with water, ethylene glycol and methylene iodide on the surface of the film subjected to the surface treatment. A large value means good wettability and generally high adhesion.

(Adhesion evaluation)
An adhesive mixed with an epoxy resin adhesive (trade name Epox AH-357A / AH-357B / AH-357C = 100/5/12 weight ratio) manufactured by Mitsui Chemicals, Inc. is applied to each film with a coater, and 130 ° C. × 4 Pre-drying was performed for 18 minutes, and 18 μm rolled copper foil (BHY-22B-T, manufactured by Japan Energy Co., Ltd.) was layered thereon to obtain a copper-clad laminate by press curing at 170 ° C. for 80 minutes under 2 MPa pressure. A 0.8 mm circuit was cut into the obtained laminate and etched with a ferric chloride solution to prepare a sample for evaluation. The obtained metal foil part with a width of 0.8 mm was peeled off at a peeling angle of 90 ° and 50 mm / min, measured n = 5 times, and the average value was defined as the adhesive strength.

(Measurement of heat shrinkage)
The measurement of the heat shrinkage rate was performed according to IPC-FC-231 Number 2.2.4. Heating conditions of 200 ° C. × 1 hour were used and other conditions were used.

<Example 1>
253.4 g of N, N-dimethylacetamide was placed in a 500 cc glass flask, and 1.947 g of paraphenylenediamine and 3.828 g of pyromellitic dianhydride were added thereto and reacted at room temperature and normal pressure for 1 hour. Next, 26.431 g of 4,4′-diaminodiphenyl ether was added thereto and stirred until uniform, and then 8.826 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added. The reaction was performed for 1 hour. Subsequently, 22.314 g of pyromellitic dianhydride was added thereto and further reacted for 1 hour to obtain a polyamic acid solution.

  Acetic anhydride, isoquinoline, and N, N-dimethylacetamide were added to this polyamic acid solution and stirred, and then the solution was extruded onto a heated support and converted into polyimide to obtain a self-supporting film.

  Next, the above film is peeled off from the support, and further, the conversion reaction to imide is completed, and the film is dried and heat-treated by passing through a 250 to 450 ° C. drying heat treatment zone to roll as a polyimide film having a thickness of 25 μm. Winded up. The obtained film had thermal shrinkage of MD: 0.12 and TD: 0.15.

Next, the polyimide film was subjected to plasma treatment. The plasma treatment is performed between an electrode whose surface is coated with a dielectric and cooled to 25 ° C. in an atmosphere of 750 Toor containing at least 20 mol% of a rare gas, and a dielectric-coated electrode that supports the polyimide film. The surface of the film was continuously treated with a treatment strength of 500 w · min / m ² by a high voltage applied to the film.

  Then, after continuously feeding into a tunnel type infrared irradiation furnace at 400 ° C., heat treatment was performed at a tension of 1.0 kg / m, and cooling to room temperature while winding up outside the furnace. The film tension during the heat treatment was adjusted by the difference in rotation speed between the feed roller and the take-up roller, and the heat treatment time was adjusted by the relative rotation speed of each roller to obtain the target polyimide film.

  Table 1 summarizes the results of the evaluation of adhesiveness and heat shrinkage of this film.

<Example 2>
Table 1 summarizes the results of evaluation of adhesiveness and thermal shrinkage after obtaining a polyimide film by the same method as in Example 1 except that the film thickness was 7.5 μm.

<Example 3>
After adding 248 g of dimethylacetamide, 4.866 g of paraphenylenediamine and 21.215 g of 4,4′-diaminodiphenyl ether, 22.870 g of pyromellitic anhydride was added and reacted for 1 hour. , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride 13.240 g was added, and a polyimide film was obtained in the same manner as in Example except that a polyamic acid solution was obtained by reacting for 1 hour. Table 1 summarizes the results of evaluation of adhesiveness and thermal shrinkage.

<Example 4>
Table 1 summarizes the results of evaluation of adhesiveness and thermal shrinkage after obtaining a polyimide film by the same method as in Example 3 except that the film thickness was 7.5 μm.

<Comparative Example 1>
Table 1 summarizes the results of evaluation of adhesiveness and thermal shrinkage of the polyimide film obtained by the same method as in Example 1 except that the heat treatment at 400 ° C. was not performed.

<Comparative example 2>
Table 1 summarizes the results of evaluation of adhesiveness and thermal shrinkage of the polyimide film obtained by the same method as in Example 1 except that the plasma treatment was not performed.

<Comparative Example 3>
Table 1 summarizes the results of evaluation of adhesiveness and thermal shrinkage of the polyimide film obtained by the same method as in Example 1 except that the heat treatment at 400 ° C. and the plasma treatment were not performed.

  The polyimide film of the present invention is not only excellent in dimensional stability against heat, but also has small shrinkage due to heat, and the adhesiveness with the copper foil is significantly improved than before, making use of these characteristics, As a base insulating film for TAB (Tape Automated Bonding) and COF (Chip On Flex), which are base materials used for flexible printed circuit boards (FPC) such as electronic components, or as a LOC tape as a support member in semiconductor devices It can be usefully used.

Claims (5)

A polyimide film formed from paraphenylenediamine, 4,4′-diaminodiphenyl ether, pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is subjected to discharge treatment, A polyimide film obtained by heat treatment while maintaining a constant tension in the length direction of the film. The surface free energy measured based on the contact angle method is 80 mN / m or more, and heat shrinkage at 200 ° C. for 1 hour. A low heat shrinkage and high adhesion polyimide film characterized by a rate of 0.10% or less. The polyimide film comprises 12-30 mol% paraphenylenediamine, 70-88 mol% 4,4'-diaminodiphenyl ether, 50-99.5 mol% pyromellitic dianhydride and 0.5-50 mol. 2. The low thermal shrinkage and high adhesion polyimide film according to claim 1, comprising a copolymerized polyimide formed from 3% 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. The polyimide film has an elastic modulus of 4 to 7 GPa, a linear expansion coefficient at 50 to 200 ° C. of 5 to 20 ppm / ° C., a humidity expansion coefficient of 20 ppm /% RH or less, and a water absorption of 2% or less. The low thermal shrinkage and high adhesion polyimide film according to claim 1 or 2. The low heat shrinkage / high adhesion polyimide film according to claim 1, wherein the discharge treatment is a plasma discharge treatment. 5. The heat treatment is a treatment performed while keeping the tension in the length direction of the film constant within a range of 1 kg / m to 10 kg / m. 5. Low heat shrink and high adhesion polyimide film.