JP2006321219A - Thin laminated polyimide film, thin laminated polyimide film roll and utilization of them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin laminated polyimide film which holds heat resistance and flexibility at a higher level and can be used as a dielectric layer laminated capacitor excellent in heat-resistant plane holdability, a photoelectric conversion layer laminated solar cell or display, a heat-resistant gas barrier film, etc., all of which use a polyimide film not warped by heat as a base material. <P>SOLUTION: The thin laminated polyimide film is constituted by forming a nonmetal thin film layer by dry plating on a polyimide film used as a base material which is composed of a polyimide having at least a biphenyltetracarboxylic acid residue as a residue of an aromatic tetracarboxylic acid and a phenylenediamine residue as a residue of an aromatic diamine, and characterized in that a degree of curling after heat treatment at 300°C is 10% or below. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  In the present invention, various thin films are formed on a flexible base material such as a polymer film by a so-called dry plating method such as sputtering, vapor deposition, ion plating, and CVD, so that a solar cell, a capacitor, a display, and other flexible functions are formed. TECHNICAL FIELD The present invention relates to a thin film laminated polyimide film thin film laminated polyimide film roll used as a flexible functional material used for applications such as materials and the use thereof. More specifically, when a polyimide film having specific physical properties is used as a base film when creating these flexible functional materials, high-temperature treatment during dry plating and when incorporating into a final product as a flexible functional material In the high-temperature treatment or chemical treatment, the thin film-laminated polyimide film is excellent in maintaining the flatness of the resulting flexible functional material by maintaining the high-temperature flatness resistance of the base film and maintaining the flatness in the subsequent processing. About.

Used for bonding type flexible printed wiring board using a method that does not use relatively high temperature for lamination of so-called film and thin film by bonding metal foil such as copper foil and aluminum foil to polyimide film with adhesive Metallized polyimide films are known. This has the following problems considered to be caused by the adhesive used.
First, there are drawbacks in that the dimensional accuracy is lowered due to inferior thermal performance than the film, and the electrical characteristics are deteriorated due to impurity ion contamination, and there is a limit to high density wiring. In addition, there is a disadvantage that the workability such as the thickness of the adhesive layer and the drilling of a double-sided hole is lowered. Therefore, it can be said that there are many inconvenient points for reducing the size and weight.
On the other hand, a method of laminating a thin film using a high temperature for laminating a film and a thin film, that is, a dry plating method using a dry plating method such as vacuum deposition, sputtering, ion plating, and CVD on a polyimide film. There has been proposed a conductive (metallized) polyimide film for a flexible printed wiring board having a metal layer and without a so-called thin film type adhesive layer.
In recent years, using flexible functional materials that are these thin film laminates, all devices represented by electronic devices and the like are in the direction of miniaturization and weight reduction, and thinner thin films using the above-described dry plating are used. The method of using came to be used a lot. In dry plating, adhesion of thin film to substrate film and improvement in thin film performance are easier to achieve at higher temperatures, and more heat-resistant polyimide film is used in dry plating and for stacking highly functional thin films. Has been.

For example, a polyimide film having a thickness of 5 to 500 μm is used as a base film, a copper foil is provided on the surface of the film by a copper sputtering method or the like to form an electrode, and this copper foil electrode is used as an external terminal. A flexible film capacitor in which a part is exposed and an electrode protection cover is formed of polyimide or the like (see Patent Document 1). In addition, a metal-film laminate manufacturing method has been proposed in which a metal oxide by plasma is randomly arranged on a polymer film, and then a metal vapor deposition layer and a metal plating layer are provided (see Patent Document 2). Further, a chromium / chromium oxide sputtering layer having a thickness of 25 to 150 angstroms (上) is provided on the electrically insulating support film, and a copper sputtering layer having a thickness of less than 1 micron is provided, and a photoresist is applied to the copper layer. A method for manufacturing a circuit material to which a composition is applied has been proposed (see Patent Document 3). Moreover, there is an example of a metallized film in which a nickel-chromium alloy layer is used as a base layer for a polyimide film and further thickened with copper (for example, see Patent Document 4).
JP 09-017691 A JP 04-290742 A Japanese Patent Application Laid-Open No. Sho 62-293689 JP 2002-252257 A

Further, as a polyimide film, from a polyimide having 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, p-phenylenediamine, and p-diaminodiphenyl ether (4,4′-oxydianiline) in the main chain as acidic components. A polyimide long film is proposed (see Patent Document 5). Obtained by polymerization and dehydration using biphenyltetracarboxylic dianhydride and / or pyromellitic dianhydride as the aromatic tetracarboxylic acid component and p-phenylenediamine and / or diaminodiphenyl ether as the aromatic diamine component. A long polyimide film has also been proposed (see Patent Document 6).
Moreover, the polyimide benzoxazole film which consists of a polyimide which has a benzoxazole ring in a principal chain is proposed as a polyimide long film with a high elasticity modulus (refer patent document 7).
Furthermore, a polyimide long film with little curling at 25 ° C. is proposed by setting the orientation ratio of the polyimide long film to the predetermined value or less (see Patent Document 8).
JP 09-328544 A JP 09-188863 A Japanese Patent Laid-Open No. 06-056792 JP 2000-085007 A

The use of a base film made of a conventionally known polyimide film or polyimide benzoxazole film is inferior to the use of a base material made of ceramic, and warpage or distortion occurs when thin film lamination is performed by dry plating due to physical properties in the film. There was a problem that was likely to occur. In order to eliminate the warp and distortion of the film, measures have been taken to reduce the apparent warp of the film by heat treatment under stretching. However, even if apparent film warpage, that is, manifested warpage of the film, can be eliminated, it is necessary to process at a high temperature particularly when applied as an electronic component or a highly functional material. However, the problem of the occurrence of curl due to the manifestation of potentially existing strain has not been solved. Therefore, even if the film has a small apparent warp, a film that curls when processed is a thin film laminate film, resulting in a decrease in production yield, and it is often difficult to obtain high-quality functional materials and electronic components. It was.
Furthermore, an important issue along with the development of curl due to high-temperature treatment is the problem of the uniformity in the longitudinal direction of the film. That is, even if there is a potential internal strain locally, the production yield of the film is reduced.
The present invention is a thin film laminated film using a polyimide film excellent in flatness and homogeneity suitable as a base material for high-performance materials, and having excellent heat resistance with little warping and curling even when subjected to high-temperature treatment. And it aims at providing a thin film laminated polyimide film roll.

As a result of intensive studies, the present inventors have found that when a polyimide film having a specific degree of curl at 300 ° C. of 10% or less is used as a base film for solar cells, capacitors, displays, antireflection materials, etc., high quality And found that uniform solar cells, capacitors, displays, and antireflection materials can be obtained, and completed the present invention.
That is, this invention consists of the following structures.
1. A polyimide film obtained by reacting an aromatic diamine with an aromatic tetracarboxylic acid, wherein the polyimide is at least a residue of an aromatic tetracarboxylic acid, a biphenyltetracarboxylic acid residue, a residue of an aromatic diamine As a base film, a polyimide film having a phenylenediamine residue and having a curl degree of 10% or less after 300 ° C. heat treatment of the film is formed, and a non-metallic thin film is formed on at least one side of the base film A thin film laminated polyimide film characterized by the above.
2. 2. The thin film laminated polyimide film as described in 1 above, wherein the curl degree after heat treatment at 300 ° C. of the film is 8% or less.
3. 4. The thin film laminated polyimide film as described in any one of 1 to 3 above, wherein a nonmetallic thin film is formed by a dry plating method.
4). 4. The thin film laminated polyimide film according to any one of 1 to 3 above, wherein the nonmetallic thin film is a high dielectric layer.
5. 4. The thin film laminated polyimide film according to any one of 1 to 3 above, wherein the nonmetallic thin film is a transparent conductive layer.
6). 4. The thin film laminated polyimide film according to any one of 1 to 3 above, wherein the nonmetallic thin film is a photoelectric conversion layer.
7). 4. The thin film laminated polyimide film according to any one of the above 1 to 3, wherein the thin film laminated polyimide film has an oxygen permeability of 0.35 cc / m ² · atm · day or less.
8). 5. A capacitor comprising the thin film laminated polyimide film according to 4 above.
9. 6. An EL device comprising the thin film laminated polyimide film described in 5 above.
10. 7. A solar cell comprising the thin film laminated polyimide film described in 6 above.
11. 8. A packaging material comprising the thin film laminated polyimide film according to 7 above.
12 A polyimide film obtained by reacting an aromatic diamine with an aromatic tetracarboxylic acid, wherein the polyimide is at least a residue of an aromatic tetracarboxylic acid, a biphenyltetracarboxylic acid residue, a residue of an aromatic diamine A polyimide film having a phenylenediamine residue as a base film, and a non-metal thin film on at least one side of the base film. A thin film laminated polyimide film roll comprising a layer.
13. 13. The thin film laminated polyimide film roll as described in 12 above, wherein the curl degree after heat treatment at 300 ° C. of the film is 10% or less.
14 14. The thin film laminated polyimide film roll as described in 12 or 13 above, wherein the difference between the maximum value and the minimum value of the degree of warpage at each part is 5% or less.
15. 15. The thin film laminated polyimide film roll according to any one of 12 to 14 above, wherein the nonmetallic thin film layer is formed by a dry plating method.
16. The thin film laminated polyimide film roll according to any one of the above 12 to 15, wherein the nonmetallic thin film is a high dielectric layer.
17. The thin film laminated polyimide film roll according to any one of the above 12 to 16, wherein the nonmetallic thin film is a transparent conductive layer.
18. The thin film laminated polyimide film roll according to any one of the above 12 to 17, wherein the nonmetallic thin film is a photoelectric conversion layer.
19. The thin film laminated polyimide film roll according to any one of 12 to 18 above, wherein the oxygen permeability of the thin film laminated polyimide film is 0.35 cc / m ² · atm · day or less.

The thin film laminated film using the polyimide film in the present invention as a base film is, for example, a solar cell or a capacitor in which a silicon-based photoelectric conversion layer or a high dielectric layer is formed on one or both sides of the polyimide film. The substrate film is subjected to vapor deposition, sputtering, other heat treatments, and chemical treatments during the formation and lamination of the silicon-based photoelectric conversion layer and the high dielectric layer, and one side may first undergo these treatments during the various treatments. Most of the differences in physical properties between the front and back surfaces of the polyimide film, especially when the curl degree after heat treatment at 300 ° C. on the front and back surfaces is below a certain level, the polyimide film is hardly warped or distorted, especially as a result of high temperature treatment. The quality of the solar cells and capacitors obtained is improved, and the yield is improved. And-obtained maintaining flatness against high temperature processing, such as such is subjected high heat treatment or soldering capacitors and the result is improved these products yield.
In this way, the polyimide film as a heat resistant film is often exposed to heat, and the low curl degree after 300 ° C. heat treatment of the film against the heat is extremely important when used as a base material for industrial products. Quality.
The thin film laminated polyimide film using the specific polyimide film of the present invention is used as a flexible solar cell or a flexible capacitor exposed to a high temperature, and the flexible solar cell or the flexible capacitor is used at the time of production. The polyimide film substrate used is not easily warped or distorted, and it is highly industrially significant because it can improve the production productivity and yield of high-quality flexible solar cells and flexible capacitors.

  The base film in the thin film laminated polyimide film of the present invention is a polyimide film obtained by reacting an aromatic diamine and an aromatic tetracarboxylic acid, and the polyimide is biphenyl as a residue of at least the aromatic tetracarboxylic acid. The first characteristic is that the film has a phenylenediamine residue as a residue of a tetracarboxylic acid residue or aromatic diamine, and the curl degree after heat treatment at 300 ° C. of the film is 10% or less.

In the present invention, the degree of curl of a polyimide film at 300 ° C. means the degree of deformation in the thickness direction relative to the surface direction of the film after performing a predetermined heat treatment, and specifically, shown in FIG. As described above, after a 50 mm × 50 mm test piece was treated with hot air at 300 ° C. for 10 minutes, the test piece was left on the plane so as to be concave, and the distances from the four corner planes (h1, h2, h3, h4) : The average value of unit mm) is a curl amount (mm), and is a value expressed as a percentage (%) of the curl amount with respect to the distance (35.36 mm) from each vertex to the center of the test piece.
The sample piece had a length pitch of 1/5 with respect to the polyimide film, and 2 points in the width direction (1/3 and 2/3 points of the width length), with n = 10 in total 10 The points are sampled (when it cannot be taken, sampling is performed with a maximum of n points), and the measured value is an average value of 10 points (or n).
Specifically, it is calculated by the following formula.
Curling amount (mm) = (h1 + h2 + h3 + h4) / 4
Curling degree (%) = 100 × (curl amount) /35.36
In the present invention, the curl degree after the heat treatment at 300 ° C. is more preferably 8% or less, and further preferably 5% or less.
When it exceeds 10%, when manufacturing an electronic component based on the polyimide film according to the present invention (especially, a step of soldering an electronic member to be processed at a high temperature), the distortion inherent in the film is developed and curling occurs. This may cause problems such as misalignment and floating of the electronic member, and may cause problems in assembly with the housing and connector connection.

In the present invention, a biphenyltetracarboxylic acid residue is a bond in a polyamic acid or polyimide formed by a reaction with an aromatic diamine from a functional derivative such as an acid, anhydride, or halide of biphenyltetracarboxylic acid. This is a residue derived from biphenyltetracarboxylic acid. A phenylenediamine residue refers to a residue derived from phenylenediamine in a bond in polyamic acid or polyimide formed by reaction of phenylenediamine with aromatic tetracarboxylic acids from various derivatives thereof.
Hereinafter, in the present invention, other aromatic tetracarboxylic acid residues and other aromatic diamine residues have the same meaning.

The polyimide film as the base material of the present invention comprises a polyimide obtained by reacting an aromatic diamine and an aromatic tetracarboxylic acid, and the polyimide is biphenyltetracarboxylic as a residue of at least the aromatic tetracarboxylic acid. It has a phenylenediamine residue as an acid residue or a residue of an aromatic diamine.
In the above-mentioned “reaction”, first, aromatic diamines and aromatic tetracarboxylic acids are subjected to a ring-opening polyaddition reaction or the like in a solvent to obtain an aromatic polyamic acid solution, and then the aromatic polyamic acid solution. A polyimide precursor film having self-supporting property (hereinafter also referred to as a green film) is formed and then subjected to high-temperature heat treatment or dehydration condensation (imidization).
The aromatic polyamic acid is a substance composed of the above aromatic tetracarboxylic acids (collectively referred to as acids, anhydrides and functional derivatives, hereinafter also referred to as aromatic tetracarboxylic acids) and aromatic diamines (hereinafter also referred to as aromatic diamines). In particular, an equimolar amount is preferably produced by reacting and polymerizing in an inert organic solvent at a polymerization temperature of 90 ° C. or less for 1 minute to several days. The aromatic tetracarboxylic acid and the aromatic diamine may be added to the organic solvent as a mixture or as a solution, or an organic solvent may be added to the above components. The organic solvent may dissolve some or all of the polymerization components and preferably dissolves the copolyamic acid polymer.

Preferred solvents include N, N-dimethylformamide and N, N-dimethylacetamide. Other useful compounds of this type are N, N-diethylformamide and N, N-diethylacetamide. Other solvents that can be used are dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone and the like. Solvents can be used alone or in combination with each other or with poor solvents such as benzene, benzonitrile, dioxane and the like.
The amount of solvent used is preferably in the range of 75-90% by weight of the aromatic polyamic acid solution, since this concentration range gives the optimum molecular weight. The aromatic tetracarboxylic acid and the aromatic diamine component need not be used in absolute equimolar amounts. In order to adjust the molecular weight, the molar ratio of aromatic tetracarboxylic acid: aromatic diamine is in the range of 0.90 to 1.10.
The aromatic polyamic acid solution produced as described above contains 5 to 40% by mass, preferably 10 to 25% by mass of the polyamic acid polymer.

In the present invention, among these aromatic diamines, phenylenediamine is a preferred diamine. Examples thereof include p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, and the like, preferably p-phenylenediamine.
As a preferred embodiment, other aromatic diamines can be preferably used in addition to these phenylenediamines. Furthermore, in addition to these aromatic diamines, diamines may be appropriately selected and used.
In the present invention, among the aromatic tetracarboxylic acids, biphenyltetracarboxylic acids (biphenyltetracarboxylic acid and its dianhydride (PMDA) and their lower alcohol esters) are preferred.
As a preferred embodiment, in addition to biphenyltetracarboxylic acid, other aromatic tetracarboxylic acids, preferably pyromellitic acids can be used. Furthermore, in addition to these aromatic tetracarboxylic acids, other aromatic tetracarboxylic acids may be appropriately selected and used.
In the present invention, the phenylene diamines are 50 to 100 mol% based on the wholly aromatic diamines, and the other aromatic diamines are 0 to 50 mol% based on the wholly aromatic diamines. It is preferable to use 0-50 mol% of diamines with respect to wholly aromatic diamines. When the mole% ratio exceeds this range, the balance as a heat-resistant polyimide film such as flexibility, rigidity, strength, elastic modulus water absorption, hygroscopic expansion coefficient, and elongation is lost.

  In the present invention, biphenyltetracarboxylic acid is 50 to 100 mol% with respect to the wholly aromatic tetracarboxylic acid, pyromellitic acid is 0 to 50 mol% with respect to the wholly aromatic tetracarboxylic acid, and other aromatic tetracarboxylic acids. Is preferably used in an amount of 0 to 50 mol% with respect to the wholly aromatic tetracarboxylic acid. When the mole% ratio exceeds this range, the balance as a heat-resistant polyimide film such as flexibility, rigidity, strength, elastic modulus water absorption, hygroscopic expansion coefficient, and elongation is lost.

Although what can be used other than said aromatic diamines and aromatic tetracarboxylic acids is not specifically limited, For example, it shows as follows.
4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether, 5-amino-2- (p-aminophenyl) benzoxazole, 6-amino-2- (p-aminophenyl) ) Benzoxazole, 5-amino-2- (m-aminophenyl) benzoxazole, 6-amino-2- (m-aminophenyl) benzoxazole, 4,4′-bis (3-aminophenoxy) biphenyl, bis [ 4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3 -Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) pheny ] -1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4 ′ -Diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [ 4- (4-Aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-amino Nophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4 -(4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane.
Some or all of the hydrogen atoms on the aromatic ring in the aromatic diamine are halogen atoms, alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, cyano groups, or some or all of hydrogen atoms of alkyl groups or alkoxyl groups. An aromatic diamine substituted with a halogenated alkyl group having 1 to 3 carbon atoms substituted with a halogen atom or an alkoxyl group is exemplified.
Further, bisphenol A bis (trimellitic acid monoester acid anhydride), 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propanoic acid anhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7 -Naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Examples include acid dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropanoic acid dianhydride, 4,4′-hexafluoroisopropylidenediphthalic anhydride, and the like.

In the present invention, a green film is formed from an aromatic polyamic acid solution and then subjected to high-temperature heat treatment or dehydration condensation (imidization).
As preferred production example, a polyimide precursor film (green film) on one side (A side) of the imidization ratio IM _A and another one side imidization rate IM _B and the formula of the relationship (B side) The polyimide precursor film (green film) which satisfy | fills is manufactured, and then the polyimide precursor film (green film) is imidized.
Formula 1; | IM _A −IM _B | ≦ 5
In the present invention, the imidation ratio of the green film is measured as follows.
<Measurement method of imidization ratio>
The film to be measured is sampled to a size of 2 cm × 2 cm, the measurement object surface is brought into close contact with the ATR crystal, set in an IR measurement apparatus, and the following specific wavelength absorbance is measured. Get a conversion rate.
Adopting ₁₇₇₈ cm ⁻¹ (near) as the specific wavelength of imide and the absorbance of the measurement surface at that wavelength as λ ₁₇₇₈ , adopting the vicinity of specific wavelength 1478 cm ⁻¹ of the aromatic ring as the reference and the absorbance of the measurement surface at that wavelength as λ ₁₄₇₈ To do.
Equipment: FT-IR FTS60A / 896 (Digilab Japan Co., Ltd.)
Measurement conditions: 1-time reflection ATR attachment (SILVER GATE)
ATR crystal Ge
Incident angle 45 °
Detector DTGS
Resolution 4cm ^-1
Accumulation count 128 times Formula 2; IM = {Iλ / I (450)} × 100
In Formula 2, Iλ = (λ ₁₇₇₈ / λ ₁₄₇₈ ), and I (450) was measured in the same manner as a film obtained by thermal ring-closing imidization of a polyimide precursor film having the same composition at 450 ° C. for 15 minutes (λ ₁₇₇₈ / λ ₁₄₇₈ ).
These values can be measured from Equation 2 with the imidization rate IM of the A surface being IM _A and the imidization rate IM of the B surface being IM _B. The difference between IM _A and IM _B is shown with an absolute value.
The measured value is 2 points in the width direction at any point on the film (1/3 and 2/3 of the width), and the measured value is the average value of the two points.

The method for producing the specific green film is not particularly limited, and preferred examples include the following methods.
When the green film is dried to such an extent that self-supporting properties are obtained, the direction of volatilization of the solvent is limited to the surface in contact with air, so the imidization ratio of the surface in contact with air of the green film is in contact with the support. Although it tends to be smaller than the imidation rate of the surface, in order to obtain a polyimide long film having a difference in absorption ratio of the film front and back of 0.35 or less, the imidization rate on the front and back surfaces and the difference are within a predetermined range. It is important to obtain a certain green film. For this purpose, for example, there is a method of controlling the drying conditions when a polyamic acid solution is coated on a support and dried to obtain a self-supporting green film. By this control, it is possible to obtain a green film in which the imidization ratio of the front and back surfaces of the green film and the difference are within a predetermined range.
The difference in the imidization rate between the front and back surfaces of these green films is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. It is better to control to the range.
When the difference in the imidization ratio between the front and back surfaces of the green film exceeds 5, potentially existing strain inside the film remains, curls occur after heat treatment at 300 ° C., and is not suitable for commercialization. It becomes.

In addition, when the green film is dried to such an extent that self-supporting properties are obtained, a green film having a predetermined range of imidization ratios on the front and back surfaces and the difference between them is controlled by controlling the amount of residual solvent with respect to the total mass after drying. Can do. Specifically, it is important that the amount of residual solvent with respect to the total mass after drying is preferably 25 to 50% by mass, more preferably 35 to 50% by mass. When the residual solvent amount is lower than 25% by mass, the imidization rate on one side of the green film becomes relatively high, and it becomes difficult to obtain a green film with a small difference in imidization rate between the front and back surfaces. In addition, the green film tends to become brittle due to a decrease in molecular weight. Moreover, when it exceeds 50 mass%, self-supporting property becomes inadequate and conveyance of a film becomes difficult in many cases.
In order to achieve such conditions, a drying apparatus such as hot air, hot nitrogen, far infrared rays, and high frequency induction heating can be used, but the following temperature control is required as the drying conditions.
When performing hot air drying, when drying the green film to the extent that self-supporting properties are obtained, the constant rate drying conditions should be lengthened in order to keep the imidization rate range and the difference between the green film front and back surfaces within a predetermined range. It is preferable to operate so that the solvent is uniformly volatilized from the entire coating film. Constant rate drying is a drying region in which the coating film surface is a free liquid surface and the volatilization of the solvent is governed by mass transfer in the outside world. Under the drying conditions where the coating surface is dried and solidified and the solvent diffusion within the coating is rate-limiting, the physical property difference between the front and back surfaces is likely to occur. The preferable dry state varies depending on the type and thickness of the support, but the temperature setting, the air flow setting, and the atmospheric temperature above the coating film (green film) on the support (green film side) are usually higher than those described above. The coating film is dried under conditions where the ambient temperature on the opposite side (opposite side of the coating film side) is 1 to 55 ° C. higher. In the description of the atmospheric temperature, the direction is defined with the direction from the coating film toward the support being the downward direction and the opposite being the upward direction. Such a description in the vertical direction is made for concisely expressing the position of the region to be noted, and is not for specifying the absolute direction of the coating film in actual production.

The “atmosphere temperature on the coating film side” is a temperature in a region (usually a space) from directly above the coating film to 30 mm on the coating film side, and a temperature at a position 5 to 30 mm away from the coating film in the upward direction. By measuring with a thermocouple or the like, the ambient temperature on the coating film surface side can be determined.
The “atmospheric temperature on the opposite side” is the temperature in the region (often including the support and the lower part of the support) from directly below the coating (support part) to the lower 30 mm of the coating. By measuring the temperature at a position 5 to 30 mm downward from the membrane with a thermocouple or the like, the atmosphere temperature on the opposite side can be obtained.

  When drying, if the atmospheric temperature on the opposite side is higher by 1 to 55 ° C. than the atmospheric temperature on the coating film side, a high-quality film can be obtained even if the drying temperature is increased and the drying speed of the coating film is increased. be able to. If the atmospheric temperature on the opposite surface side is lower than the atmospheric temperature on the coating surface side, or if the difference between the atmospheric temperature on the coating surface side and the atmospheric temperature on the opposite side is less than 1 ° C., the vicinity of the coating surface is first Then, the film is dried into a film to form a “lid”, and thereafter, the evaporation of the solvent to be evaporated from the vicinity of the support is hindered to cause distortion in the internal structure of the film. It is undesirable for the apparatus and the economy to be disadvantageous in that the atmospheric temperature on the opposite side is higher than the atmospheric temperature on the coating film side and the temperature difference is greater than 55 ° C. Preferably, at the time of drying, the ambient temperature on the opposite side is higher by 10 to 50 ° C., more preferably 15 to 45 ° C. than the ambient temperature on the coating film side.

The setting of the atmospheric temperature as described above may be performed over the entire process of drying the coating film, or may be performed in a part of the process of drying the coating film. When the coating film is dried by a continuous dryer such as a tunnel furnace, the above-mentioned atmospheric temperature may be set in the drying effective length, preferably 10 to 100%, more preferably 15 to 100%. .
The drying time is 10 to 90 minutes in total, desirably 15 to 45 minutes.

The green film that has undergone the drying step is then subjected to an imidization step, but may be either inline or off-line.
When the off-line is adopted, the green film is wound up once. At this time, curling can be reduced by winding the green film on the tubular body so that the green film is on the inner side (the support is on the outer side).
In any case, it is preferable to carry or wind the film so that the radius of curvature does not become 30 mm or less.

The degree of curl after the 300 ° C. heat treatment of the present invention is low by imidizing a green film obtained by such a method with the imidation ratio of the front and back surfaces and the difference thereof controlled within a predetermined range under predetermined conditions. A polyimide long film is obtained.
As a specific imidization method, a conventionally known imidation reaction can be appropriately used. For example, using a polyamic acid solution that does not contain a ring-closing catalyst or a dehydrating agent, the imidization reaction proceeds by subjecting it to a heat treatment (so-called thermal ring-closing method), or the polyamic acid solution contains a ring-closing catalyst and a dehydrating agent. In particular, a chemical ring closing method in which an imidization reaction is performed by the action of the above ring closing catalyst and a dehydrating agent can be used. A polyimide long film having a curl degree of 10% or less after 300 ° C. heat treatment of a polyimide long film is included. In order to obtain a film, the thermal ring closure method is preferred.

100-500 degreeC is illustrated as a heating maximum temperature of a thermal ring closure method, Preferably it is 200-480 degreeC. When the maximum heating temperature is lower than this range, it is difficult to close the ring sufficiently, and when it is higher than this range, deterioration proceeds and the film tends to become brittle. A more preferable embodiment includes a two-stage heat treatment in which treatment is performed at 150 to 250 ° C. for 3 to 20 minutes and then treatment is performed at 350 to 500 ° C. for 3 to 20 minutes.
In the chemical ring closure method, after the polyamic acid solution is applied to a support, the imidization reaction is partially advanced to form a self-supporting film, and then imidization can be performed completely by heating. In this case, the condition for partially proceeding with the imidization reaction is preferably a heat treatment for 3 to 20 minutes at 100 to 200 ° C., and the condition for allowing the imidization reaction to be completely performed is preferably 200 to 400 ° C. For 3 to 20 minutes.

The above-mentioned drying treatment and imidization treatment are carried out by gripping both ends of the film with a pin tenter or clip. At that time, in order to maintain the uniformity of the film, it is desirable to make the tension in the width direction and the longitudinal direction of the film as uniform as possible.
Specifically, just before the film is subjected to a pin tenter, the both ends of the film can be pressed with a brush, and the pins can be pierced uniformly into the film. The brush is preferably a fibrous material having rigidity and heat resistance, and a high-strength, high-modulus monofilament can be adopted.
By satisfying the conditions (temperature, time, tension) of the imidization treatment described above, it is possible to suppress the occurrence of orientation strain inside the film (front and back and plane direction).

The timing for adding the ring-closing catalyst to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylamine, and heterocyclic tertiary amines such as isoquinoline, pyridine, and betapicoline. Among them, heterocyclic tertiary amines are mentioned. At least one amine selected from is preferred. Although the usage-amount of a ring-closing catalyst with respect to 1 mol of polyamic acids does not have limitation in particular, Preferably it is 0.5-8 mol.
The timing of adding the dehydrating agent to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. Among them, acetic anhydride, benzoic anhydride, etc. Acids or mixtures thereof are preferred. Moreover, the usage-amount of the dehydrating agent with respect to 1 mol of polyamic acids is not particularly limited, but is preferably 0.1 to 4 mol. When a dehydrating agent is used, a gelation retarder such as acetylacetone may be used in combination.

Whether it is a thermal cyclization reaction or a chemical cyclization method, the precursor film (green film) of the polyimide long film formed on the support may be peeled off from the support before it is completely imidized. Then, it may be peeled off after imidization.
Although the thickness of a polyimide long film is not specifically limited, When considering using it for the base substrate for printed wiring boards mentioned later, it is 1-150 micrometers normally, Preferably it is 3-50 micrometers. This thickness can be easily controlled by the amount of the polyamic acid solution applied to the support and the concentration of the polyamic acid solution.
The polyimide long film obtained by the production method of the present invention is preferably a polyimide long film having a smaller curl degree by winding the A side in the winding with the absorption ratio tending to be larger than the B side into a tubular product. Can be obtained. When winding on a tubular object with the A-side in the winding, the radius of curvature is preferably in the range of 30 mm to 600 mm. If the radius of curvature exceeds this range, the curl degree of the polyimide long film may increase.
Further, the winding tension is 100N or more, preferably 150N or more and 500N or less.
Therefore, when roll-rolling a polyimide long film, as a preferred embodiment for improving curl, the A side is in the winding, the radius of curvature is relatively large, 30 to 600 mm, preferably 80 to 300 mm, and the winding tension. Can be adopted.
Moreover, in order to reduce the physical property difference between the winding core side (roll inner layer side) and the winding outer side (roll outer layer side) of the wound film as much as possible, the winding tension increases as the curvature radius of the film increases ( It is desirable to decrease the winding tension on the winding core side and increase the winding tension on the winding outer side.
Further, when the green film is imidized offline, a method of winding the green film so that the green film is on the inside (the support is on the outside) can be employed.

In addition, the above-mentioned absorption ratio means the degree of orientation with respect to the film surface of the imide ring surface of the polyimide molecule from the film surface (or back surface, hereinafter the same) to a depth of about 3 μm. Specifically, polarization ATR measurement is performed by FT-IR (measurement apparatus: Digilab, FTS-60A / 896, etc.), single reflection ATR attachment is golden gate MkII (SPECAC), IRE is diamond, incident angle Is 45 °, resolution is 4 cm ⁻¹ , and the absorption coefficient (Kx, Ky, and Kz) in each direction at a peak (aromatic ring vibration) that appears in the vicinity of 1480 cm ⁻¹ when the film surface is measured under the conditions of 128 times of integration. ) And is defined by the following equation. (However, Kx is the MD direction, Ky is the TD direction, and Kz is the thickness direction absorption coefficient.)
Absorption ratio = (Kx + Ky) / 2 × Kz
The measured value is 2 points in the width direction at any point on the film (1/3 and 2/3 of the width), and the measured value is the average value of the two points.
In the present invention, the A surface is the surface having the larger absorption ratio, and the B surface is the surface having the smaller absorption ratio.

The polyimide long film is heat treated in the green film drying process or imidization process. At that time, if there are uneven spots in the width direction of the film, a difference in physical properties in the width direction of the film occurs, which causes curling.
Therefore, in the present invention, it is desirable to control the unevenness in the width direction of the ambient temperature in the dryer within a central temperature of ± 5 ° C., preferably within ± 3 ° C., and more preferably within ± 2 ° C.
Here, the atmospheric temperature refers to a temperature measured with a thermocouple, a thermo label, or the like at a position away from the surface of the support by an equal distance of 5 mm to 30 mm. In the present invention, it is preferable to provide 8 to 64 temperature detection ends in the width direction.
In particular, the interval between the detection end in the width direction is preferably about 5 cm to 10 cm. As the detection end, a known thermocouple such as alumel chromel may be used.
In the present invention, the atmospheric temperature on the opposite side can be set higher by 5 to 55 ° C. than the atmospheric temperature on the coated surface side. In this case as well, it is important that the temperature is within a range of ± 5 ° C. from the center temperature of the temperature on each side of the support. The center temperature is the arithmetic average value of the Celsius temperature measured at each detection end, and the temperature measured at each detection end in the width direction orthogonal to the direction in which the support travels is within ± 5 ° C. Is a range calculated based on the numerical value of the central value.
The polyimide long film manufactured under such conditions has excellent flatness at an extremely high temperature with a curl degree measured under the above conditions of 10% or less.

Although the thickness of the polyimide film as a base material of the present invention is not particularly limited, it is usually from 1 to 150 μm, preferably from 3 to 50 μm in consideration of use for a base material such as a flexible solar cell or a flexible capacitor. is there. This thickness can be easily controlled by the amount of the polyamic acid solution applied to the support and the concentration of the polyamic acid solution.
In the polyimide film as the substrate of the present invention, it is preferable to impart a fine unevenness to the film surface by adding a lubricant to the polyimide, thereby improving the slipping property of the film.
As the lubricant, inorganic or organic fine particles having an average particle diameter of about 0.03 to 3 μm can be used. Specific examples include titanium oxide, alumina, silica, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, Examples include magnesium oxide, calcium oxide, and clay minerals.
The polyimide film of the present invention is usually an unstretched film, but may be stretched uniaxially or biaxially. Here, the unstretched film refers to a film obtained without intentionally applying a mechanical external force in the surface expansion direction of the film by tenter stretching, roll stretching, inflation stretching, or the like.

As described above, it is desirable that the roll on which the polyimide film according to the present invention is wound has a winding tension of 100 N or more and a curvature radius of 30 to 600 mm. The polyimide film obtained by the above method is less warped or distorted and has excellent flatness, but in the present invention, these characteristics are homogeneous with respect to the longitudinal direction of the film. . That is, it is desirable that the variation rate (standard deviation × 100 / average value) (CV%) of the linear expansion coefficient of the film on the winding side and the core side is 25% or less. Preferably, it is 20% or less, more preferably 15% or less.
Here, the method of measuring the linear expansion coefficient is as follows.
For the polyimide film to be measured, the stretch rate in the MD direction and the TD direction is measured under the following conditions, and the stretch rate / temperature at intervals of 30 ° C. to 45 ° C., 45 ° C. to 60 ° C.,. This measurement was performed up to 300 ° C., and the average value of all measured values was calculated as the coefficient of linear expansion (CTE).
Device name: TMA4000S manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere; Argon Sampling of sample pieces was measured at a pitch of 1/5 of the total length in the longitudinal direction with 2 points (1/3 and 2/3 of the width) in the width direction of the polyimide film roll. 10 points.
Then, the fluctuation rate for 10 points is calculated.

Usually, when a film is rolled, a so-called winding occurs in which the film warps in the winding direction at the time of unwinding, and the warpage is different between the film on the winding core side and the film on the winding side. Furthermore, the roll of the polyimide film according to the present invention has a very small difference in physical properties between the winding core side and the winding outer side, and the difference in the degree of warpage of the film in each part is 5% or less, preferably 3% or less. It will be excellent.
In the present invention, the degree of warping of the film (apparent warping degree) is specifically, as shown in FIG. 1, a test piece of 50 mm × 50 mm is taken from a polyimide film test piece released from a roll on a plane. The average value of the distances from the four corner planes (h1, h2, h3, h4: unit mm) is the amount of warpage (mm), and the distance from each vertex of the test piece to the center ( 35.36 mm) is a value expressed as a percentage (%) of the warpage amount.
Specifically, it is calculated by the following formula.
Warpage (mm) = (h1 + h2 + h3 + h4) / 4
Degree of warpage (%) = 100 × (curl amount) /35.36
Sampling of the sample piece was performed at 2 points (1/3 and 2/3 of the width) in the width direction of the polyimide film roll, and a total of 10 points at a length pitch of 1/5 of the entire length in the longitudinal direction. To do.

Next, the laminated polyimide film of the present invention will be described.
The laminating process described below may be performed batch-wise on a piece of film obtained by cutting the above polyimide film roll, or the polyimide film roll is unwound and continuously processed to be wound up as a non-metal thin film forming polyimide film roll. Also good (roll-to-roll).

In the thin film laminated polyimide film of the present invention, the polyimide basically has at least a biphenyltetracarboxylic acid residue as an aromatic tetracarboxylic acid residue and a phenylenediamine residue as an aromatic diamine residue. Using a polyimide film (IF) with a curl degree of 10% or less after heat treatment at 300 ° C. as a base material, a non-metallic thin film layer (dM) formed by a dry plating method, and appropriately formed above and below the non-metallic thin film layer Layer (DM).
In the present invention, the non-metallic thin film layer (dM) may be composed of a plurality of layers instead of a single layer, and at least one of the plurality of layers is a non-metallic layer. Nonmetal layer, IF / nonmetal layer / metal layer, IF / nonmetal layer / nonmetal layer / metal layer, IF / metal layer / nonmetal layer / metal layer, IF / metal layer / nonmetal layer / nonmetal layer / Metal layer, etc. can also be adopted.
The layers (DM) appropriately formed above and below the non-metallic thin film layer further formed on the IF / dM may be formed by dry plating or may be formed by a method other than dry plating.
The non-metal in the present invention is a compound such as carbon, silicon, a metal oxide, or an organic compound, and any compound may be used as long as it has these as a main component. However, it is always formed by a dry plating method.

Specific examples of non-metals include graphite, amorphous carbon, amorphous silicon, polycrystalline silicon, In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (In ₂ O ₃ with Sn added), etc. Rochelle salt ferroelectrics such as Rochelle salt, lithium ammonium tartrate, lithium thallium tartrate, potassium dihydrogen phosphate, potassium dihydrogen arsenate, rubidium dihydrogen phosphate, rubidium dihydrogen arsenate, cesium dihydrogen arsenate Phosphoric acid (arsenate) dihydrogen alkali salt ferroelectrics such as cesium dihydrogen phosphate, barium titanate, lead titanate, sodium niobate, potassium niobate, sodium tantalate, potassium tantalate, gallic acid Perovskite ferroelectrics such as lanthanum, deformed perovskite ferroelectrics such as tungsten trioxide, Nio Pyrochlorite-type ferroelectrics such as cadmium oxide and lead pyroniobate, ilmenite type strong such as cadmium titanate, cobalt titanate, iron titanate, lithium niobate, magnesium titanate, manganese titanate, nickel titanate, lithium titanate Dielectric, Guanidine, Aluminum, Sulfate Hexahydrate, Guanidine, Gallium, Sulfate, Guanidine, Chrome, Sulfate, Guanidine, Vanadium, Sulfate, Guanidine, Chromium, Selenate, Guanidine, Aluminum・ Gelidine-based ferroelectrics such as selenate, guanidine, gallium, selenate, triglycine sulfate, triglycine fluorilate, triglycine selenate, diglycine nitrate, diglycine manganese chloride dihydrate Products, silver glycine nitrate, etc. Glycine-based ferroelectrics, Pb ₂ MgWO ₃ , Pb ₃ Fe ₂ WO ₆ , Pb ₂ FeTaO ₆ , K3Li ₂ Nb ₅ O ₁₅ , Ba ₂ NaNb ₅ O ₁₅ , Pb ₂ KNb ₅ O ₁₅ system, Pb ₅ Ge ₃ O ₁₁ , Gd ₂ (MoO ₄ ) ₃ series, methylammonium / aluminum sulfate / decahydrate, urea chromium sulfate, ammonium sulfate, ammonium sulfate / cadmium, lithium / hydrazine sulfate, ammonium hydrogen sulfate, Other compounds such as lithium, hydroxide, selenic acid, ammonium monochromate, dicalcium, strontium, propionic acid, urea, ammonium beryllium fluoride, and other inorganic ferroelectrics such as perovskite, pyrochlorite, and ilmenite Ceramic-based strong inducer consisting of a mixture of solids and solid solution Body, specifically, PZT-based {lead titanate / lead zirconate solid solution: Pb (Zr, Ti) O 3}, PLT system {lead titanate / lanthanum titanate solid _{solution: (Pb, La) TiO 3} }, PLZT system {(Pb, La) (Zr, Ti) O ₃ }, lead niobate / barium niobate solid solution system, strontium niobate / barium niobate solid solution system, PTS system {Pb (Ti, Sn) O ₃ }, PST system {(Pb, Sr) TiO ₃ }, BPT system {(Ba, Pb) TiO ₃ }, BST system {(Ba, Sr) TiO ₃ }, BMT system {(Ba, Mg) TiO ₃ }, BCT system Examples include {(Ba, Ca) TiO ₃ }, silicon oxide, aluminum oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, lead oxide, boron oxide, and zinc sulfide.

The layer (DM) appropriately formed close to the non-metallic thin film layer in the present invention may be a color material, a polymer compound, and the above-described non-metal and metal, and the formation means is also limited. It is not a thing.
In the present invention, the polyimide has at least a biphenyltetracarboxylic acid residue as an aromatic tetracarboxylic acid residue, a phenylenediamine residue as an aromatic diamine residue, and the curl degree after heat treatment of the film at 300 ° C. After the surface of the polyimide film having a thickness of 10% or less is subjected to plasma treatment, a thin film such as a nonmetal is then deposited by dry plating such as sputtering or vapor deposition, and layers formed appropriately above and below the nonmetal thin film layer. (DM) may be implemented by various means.
When the surface of the polyimide film is subjected to a plasma treatment, the plasma is an inert gas plasma, and nitrogen gas, Ne, Ar, Kr, or Xe is used as the inert gas. There is no particular limitation on the method for generating plasma, and an inert gas may be introduced into the plasma generator to generate plasma. There is no particular limitation on the plasma treatment method, and a plasma treatment apparatus used for forming a metal layer on the base film may be used. The time required for the plasma treatment is not particularly limited, and is usually 1 second to 30 minutes, preferably 10 seconds to 10 minutes. There are no particular restrictions on the frequency and output of the plasma during the plasma processing, the gas pressure for generating the plasma, and the processing temperature as long as they can be handled by the plasma processing apparatus. The frequency is usually 13.56 MHz, the output is usually 50 W to 1000 W, the gas pressure is usually 0.01 Pa to 10 Pa, and the temperature is usually 20 ° C. to 250 ° C., preferably 20 ° C. to 180 ° C. If the output is too high, the substrate film surface may crack. If the gas pressure is too high, the smoothness of the film may be reduced.

The non-metallic thin film (layer) is formed by a so-called dry plating method such as a sputtering method, a vapor deposition method, an ion plating method, or a CVD method, but a sputtering method or a vapor deposition method is preferable. As the vapor deposition method, electron beam vapor deposition is preferable in that the contamination of the crucible material is small.
There is no particular limitation on the sputtering method as a preferred method for forming a non-metallic thin film. Direct current bipolar sputtering, high frequency sputtering, magnetron sputtering, counter target sputtering, ECR sputtering, bias sputtering, plasma controlled sputtering, multi-target Sputtering or the like can be used. Among these, direct current bipolar sputtering or high frequency sputtering is preferable.
There are no particular restrictions on the output during sputtering processing, the gas pressure for generating plasma, and the processing temperature, so long as they can be handled by the sputtering apparatus. The output is usually 10 W to 1000 W, the gas pressure is usually 0.01 Pa to 10 Pa, and the temperature is usually 20 ° C. to 250 ° C., preferably 20 ° C. to 180 ° C. The film forming rate is 0.1 Å / second to 1000 Å / second, preferably 1 Å / second to 100 Å / second. If the film formation rate is too high, the formed thin film may be cracked. Moreover, when gas pressure is too high, there exists a possibility that adhesiveness may fall.
The metal layer is not particularly limited, but silver, copper, gold, platinum, rhodium, nickel, aluminum, iron, zinc, tin, brass, bronze, bronze, monel, tin lead solder, tin copper solder, Tin-silver solder or the like is used.

In dry plating, in a sputtering method or vapor deposition method, the polyimide film as a substrate is maintained at 100 to 400 ° C., preferably 150 to 350 ° C., so that the adhesion between the film and the thin film is more robust. become.
In this invention, you may heat-process the thin film laminated polyimide film which is a composite_body | complex of the polyimide film obtained by the said method, and a nonmetallic thin film at 200-350 degreeC. 220-330 degreeC is preferable and 240-310 degreeC is more preferable.
This heat treatment alleviates the distortion of the base film and the distortion generated in the thin film formation process of the thin film laminated polyimide film, so that the effects of the present invention can be expressed more effectively, improving the quality as a functional material, Durability and reliability can be improved. If it is less than 200 ° C., the effect of alleviating the strain becomes small. Conversely, if it exceeds 350 ° C., the polyimide film of the base material is deteriorated, which is not preferable.

In the present invention, a thin film laminated polyimide film in which the non-metallic thin film is a high dielectric layer is an example of a preferred embodiment. The high dielectric layer is not limited to the high dielectric layer described below.
As a specific example, a polyimide film is plasma-treated, a nickel-chromium alloy thin film having a thickness of 150 mm is formed thereon by a sputtering method, a copper thin film having a thickness of 3000 mm is formed, and a copper plating layer having a thickness of 4 μm is formed thereon. A first electrode layer is formed. On the first electrode layer, a titanium oxide thin film of 50 nm is formed as a barrier layer by sputtering and a Ba _0.5 Sr _0.5 TiO ₃ thin film having a thickness of 2000 nm is formed as a high dielectric layer. Examples include a capacitor made of a high dielectric layer laminated polyimide film in which a nickel thin film having a thickness and a copper thin film having a thickness of 500 nm are formed, a copper plating layer having a thickness of 4 μm is further formed, and a second electrode layer is formed.

In the present invention, a thin film laminated polyimide film in which the non-metallic thin film is a transparent conductive layer is an example of a preferred embodiment. The transparent conductive layer is not limited to the transparent conductive layer described below.
As a specific example, an ITO thin film (transparent conductive layer) and an aluminum layer are formed on a polyimide film by sputtering (first electrode), and an organic layer containing poly (para-phenylene vinylene) as a luminescent material is formed thereon. A green organic EL device comprising a transparent conductive layer laminated polyimide film formed by screen printing, dried and then formed on the ITO thin film by sputtering to form a second electrode, and further a fluororesin coating protective film is formed. Can be mentioned.

In the present invention, a thin film laminated polyimide film in which the non-metallic thin film is a photoelectric conversion layer is an example of a preferred embodiment. The photoelectric conversion layer is not limited to the photoelectric conversion layer described below.
As a specific example, a stainless steel layer having a thickness of 1000 nm is formed on a polyimide film by a sputtering method, an n-type amorphous silicon layer having a thickness of 25 nm is formed, and an i-type amorphous silicon layer having a thickness of 500 nm is laminated, Further, a p-type amorphous silicon layer (thick silicon-based photoelectric conversion layer) having a thickness of 25 nm is formed, an indium tin oxide (ITO) layer having a thickness of 100 nm is deposited, and a palladium layer having a thickness of 100 nm is vacuum-deposited into a comb shape. The film-like solar cell which consists of a photoelectric conversion layer lamination polyimide film which becomes will be mentioned.

In the present invention, a thin film laminated polyimide film in which the non-metallic thin film is a gas barrier layer is an example of a preferred embodiment. The oxygen permeability of the thin film laminated polyimide film is 0.35 cc / m ² · atm · day or less, preferably 0.15 cc / m ² · atm · day or less, and the water vapor permeability is 1.0 g / m 2 · day or less, preferably Has a performance of 0.5 g / m 2 · day or less.
As a specific example thereof, at least one selected from silicon oxide, aluminum oxide, magnesium oxide, and calcium oxide having a thickness of 20 to 1000 nm by sputtering or vapor deposition on a polyimide film, preferably silicon oxide and aluminum oxide. Examples thereof include a gas barrier film having a metal oxide layer made of a mixture. The electron beam evaporation method is particularly preferably used as the thin film forming method. Such a gas barrier layer suppresses the permeation of oxygen and water vapor, and has an effect of preventing deterioration of a metal layer, a resin layer and the like provided in the vicinity of the film. Further, by using a polyimide film having such a gas barrier layer as a packaging material, it has heat resistance and the contents can be shielded from oxygen and water vapor.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. In addition, the evaluation method of the physical property in a following example is as follows, and the curl degree after 300 degreeC heat processing is as above-mentioned method.
1. The thickness of the polyimide film was measured using a micrometer (Finereuf, Millitron (registered trademark) 1245D).
2. Degree of warpage of thin laminated film (apparent degree of warpage)
As shown in FIG. 1 (C), a film test piece of 50 mm × 50 mm was left to be concave on the plane, and the average of distances from the four corner planes (h1, h2, h3, h4: unit mm) The value is a value expressed as a percentage (%) of the warpage amount with respect to the distance (35.36 mm) from each vertex to the center of the test piece, where the value is the warpage amount (mm).
Specifically, it is calculated by the following formula.
Warpage (mm) = (h1 + h2 + h3 + h4) / 4
Degree of warpage (%) = 100 × (warpage amount) /35.36
Sampling of the sample piece is performed at two points in both the width direction and the length direction of the thin-film laminated polyimide film (in principle, the points from 1/3 and 2/3 of the width are taken. ) A total of 4 points shall be represented by the average value.

Abbreviations of compounds used in Examples and the like are described below.
PMDA: pyromellitic dianhydride ODA: 4,4′-diaminodiphenyl ether P-PDA: paraphenylenediamine BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride DMF: dimethylformamide DMAC: dimethyl Acetamide AA: Acetic anhydride IQ: Isoquinoline Abbreviation GF indicates a polyimide precursor film (green film), and abbreviation IF indicates a polyimide film.

(Production Example A; Real-1 to Real-3)
A container equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then P-PDA was added. Next, after DMAC is added and completely dissolved, BPDA is added, and P-PDA and BPDA as monomers are polymerized in DMAC at a molar ratio of 1/1, and the monomer charge concentration becomes 15% by mass. When stirred at 25 ° C. for 5 hours, a brown viscous polyamic acid solution was obtained. 15 parts by mass of AA and 3 parts by mass of IQ are mixed with 100 parts by mass of the obtained polyamic acid solution, and this is mixed with a polyester film (Cosmo Shine A4100 (Toyobo Co., Ltd.) having a thickness of 188 microns and a width of 800 mm. )) Coated on the non-lubricating surface to a width of 740 mm (squeegee / belt gap is 430 μm)
It dried by passing through the continuous drying furnace which has four drying zones. Each zone has three rows of slit-shaped air outlets above and below the film. The hot air temperature between the air outlets can be controlled within a range of plus or minus 1.5 ° C and the air volume difference can be controlled within a range of plus or minus 3%. Has been. The width direction is controlled to be within ± 1 ° C. until a width corresponding to 1.2 times the effective film width.

The setting of the drying oven is as follows.
Drying condition A
Leveling zone temperature 25 ° C, no air volume 1st zone upper temperature 105 ° C, lower temperature 105 ° C
Air volume 20-25 cubic m / min for both top and bottom Zone 2 Upper temperature 100 ° C, Lower temperature 100 ° C
Air volume 30 to 35 cubic m / min in both upper and lower zones Third zone Upper temperature 95 ° C, Lower temperature 100 ° C
Air volume 20-25 cubic m / min on both top and bottom Zone 4 Upper temperature 90 ° C, Lower temperature 100 ° C
Upper air volume 15 cubic m / min, lower air volume 20 cubic m / min The length of each zone is the same, and the total drying time is 18 minutes.
Further, the air volume is the total of the air volumes from the outlets of each zone, and is changed within the above range for Real-1, Real-2, and Real-3.
Under such drying conditions, it has been confirmed that the surface of the coating film does not reach a dry-to-touch state until the third zone, and is almost constant rate drying conditions.
The surface of the coating film was dry to the touch shortly after entering the fourth zone, and thereafter, the drying progressed in a decelerating manner. At this time, the lower temperature and the air volume are set higher than the upper side to promote the diffusion of the solvent in the coating film.
In addition, it is confirmed that the temperature is within ± 1.5 ° C. by monitoring at intervals of 10 cm by a thermocouple supported at a position of 10 mm on the film at the portion directly below the blowout port at the center of each zone.

GF (polyamide acid film) that became self-supporting after drying was peeled from the polyester film to obtain GF (green film), GF real-1, GF real-2, and GF real-3.
Each GF (green film) obtained was passed through a continuous heat treatment furnace purged with nitrogen while holding both ends with a pin tenter, the first stage was 180 ° C. for 5 minutes, and the heating rate was 4 ° C./second. The temperature was raised, and the second stage was heated at 400 ° C. for 5 minutes as a second stage to proceed the imidization reaction. Then, each IF (polyimide film), IF real-1, IF real-2, and IF real-3 which show brown were obtained by cooling to room temperature in 5 minutes.
In addition, when heat-treating GF (green film), a brush made of an aromatic polyamide monofilament strand was provided so as to be in contact with both ends of the film so that both ends of the film pierced uniformly into the pins of the pin tenter.
The obtained polyimide film was rolled up into a roll under the following conditions to obtain a film roll.
Winding method: Inner winding Winding tension: 145 to 155N
Roll curvature radius: 84mm
The thickness and curl degree of each IF (polyimide film) obtained were 25 μm and 1.8% for IF real-1, 25.1 μm and 3.8% for IF real-2, and 25 μm for IF real-3. It was 6.5%.
Moreover, the film characteristics of the roll film of IF Real-1 were as follows.
Fluctuation rate of linear expansion coefficient: 11.3%
Maximum warpage: 2.2%
Minimum warpage: 0.7%

(Production Example B; Real-4 to Real-6)
A container equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then P-PDA was added. Next, after DMAC is added and completely dissolved, BPDA is added, and P-PDA and BPDA as monomers are polymerized in DMAC at a molar ratio of 1/1, and the monomer charge concentration becomes 15% by mass. When stirred at 25 ° C. for 5 hours, a brown viscous polyamic acid solution was obtained. The obtained polyamic acid solution was coated on a stainless steel belt (the gap between the squeegee and the belt was 450 μm), and dried in the same manner as in Production Examples: Example-1 to Example-3. GF that became self-supporting after drying was peeled from the stainless steel belt to obtain GF, GF real-4, GF real-5, and GF real-6.
The obtained GF was passed through a continuous heat treatment furnace purged with nitrogen, the first stage was heated at 180 ° C. for 3 minutes, and the heating rate was 4 ° C./second, and the second stage was at 460 ° C. for 2 minutes. Under the conditions, two-stage heating was performed to advance the imidization reaction. Then, it cooled to room temperature in 5 minutes, and obtained each IF, IF real-4, IF real-5, and IF real-6 of 25 micrometers in thickness which exhibits brown.
In addition, when heat-treating GF, a brush made of an aromatic polyamide monofilament strand is provided so as to be in contact with both ends of the film so that both ends of the film pierce the pins of the pin tenter uniformly, and the temperature of the pin portion is 120 to 180. Pinning was performed after cooling in advance to be in the range of ° C.
The obtained polyimide film was rolled up into a roll under the following conditions to obtain a film roll.
Winding method: Inner winding Winding tension: 140-162N
Roll curvature radius: 84mm
The thickness and curl degree of each IF obtained were 25 μm and 4.5% for IF real-4, 25.1 μm and 5.8% for IF real-5, and 25 μm and 8.5% for IF real-6. Met.
Moreover, the film characteristics of the roll film of IF Real-4 were as follows.
Fluctuation rate of linear expansion coefficient: 10.2%
Maximum degree of warpage: 0.6%
Minimum warpage: 0.1%

(Production Example C; ratio-1 to ratio-3)
15 parts by mass of AA and 3 parts by mass of IQ are mixed with 100 parts by mass of the polyamic acid solution obtained in Production Example A, and this is coated on a stainless steel belt (the gap between the squeegee / belt is 430 μm), and production examples; drying was carried out in the same drying apparatus as in Examples -1 to -3, and the drying conditions (temperature is the set temperature of the drying furnace) are as follows.
Leveling zone 25 ° C, no air flow 1st zone temperature 110 ° C
Air volume 20-25 cubic m / min on both top and bottom Zone 2 Temperature 120 ° C on both top and bottom
Air volume 20-25 cubic m / min for both top and bottom Zone 3 Temperature 120 ° C for both top and bottom
Air volume 20-25 cubic m / min on both top and bottom Zone 4 Temperature 120 ° C on both top and bottom
Airflow 20-25 cubic m / min in both the top and bottom The length of each zone is the same, and the total drying time is 9 minutes.
The air volume is the total of the air volumes from the outlets of each zone, and is changed within the above range by ratio-1, ratio-2, and ratio-3.
Under such drying conditions, it can be inferred that the surface of the coating film is dry to the touch at the center of the second zone, and thereafter drying at a reduced rate is performed.

The GF that became self-supporting after drying was peeled off from the stainless steel belt to obtain each GF3 species, GF ratio-1, GF ratio-2, and GF ratio-3.
Each GF obtained was passed through a continuous heat treatment furnace purged with nitrogen while holding both ends with a pin tenter, and the first stage was heated at 180 ° C. for 5 minutes and at a heating rate of 4 ° C./second. As the second stage, two stages of heating were performed at 400 ° C. for 5 minutes to advance the imidization reaction. Then, each IF which shows brown, IF ratio-1, IF ratio-2, and IF ratio-3 were obtained by cooling to room temperature in 5 minutes.
The thickness and curl of each IF obtained were 25 μm and 10.5% at an IF ratio of −1, 25.1 μm and 13.1% at an IF ratio of −2, and 25 μm and 20.5% at an IF ratio of −3. Met.

(Examples 1-6, Comparative Examples 1-3)
<Manufacture of high dielectric layer laminated polyimide film>
The polyimide film obtained in IF Example-1 of Production Example A and IF Example-4 of Production Example B was rolled up into a roll under various conditions shown in Table 1 to obtain a film roll. Table 1 shows the film characteristics of the roll film.
The obtained film roll was used and set in a vacuum apparatus equipped with an unwinding device, a winding device and a plasma processing device, respectively, and then the plasma treatment of the film surface was performed.
The plasma treatment conditions were a xenon gas, a frequency of 13.56 MHz, an output of 80 W, and a gas pressure of 0.9 Pa. The temperature during the treatment was 24 ° C. and the residence time in the plasma atmosphere was about 45 seconds. Next, the film after the plasma treatment is set in a vacuum apparatus having a winding apparatus, a winding apparatus, and a sputtering area, and the conditions of frequency 13.56 MHz, output 400 W, gas pressure 0.8 Pa, nickel-chromium ( A 150% nickel-chromium alloy film was formed by RF sputtering under a xenon atmosphere using a 7% chromium) target. Next, a copper thin film having a thickness of 3000 μm was formed by sputtering using a copper target, and a thick copper plating layer having a thickness of 4 μm was formed using a copper sulfate plating bath to obtain a first electrode layer.
Subsequently, a substrate temperature is set to 450 ° C., a titanium oxide layer of 50 nm is formed on the first electrode layer, a Ba _0.5 Sr _0.5 TiO ₃ target is used as a dielectric layer, and a 2000 nm thin film is formed by high-frequency sputtering. A high dielectric layer was formed. Further, on the thin film high dielectric layer, nickel of 500 nm and copper of 500 nm are formed by sputtering. Finally, a thick copper plating layer having a thickness of 4 μm is formed by using a copper sulfate plating bath to form the second electrode. A high dielectric laminated film was obtained as a layer.

Each high dielectric layer laminated polyimide film obtained from each film was judged by the average value of the degree of warpage of each five sheets. In each film, the average value of the warp degree exceeds 10%, x, the warp degree exceeding 7% to 10%, Δ, 5-7%, and less than 5%.
As a result, IF real-1, IF real-2, IF real-4 are all ◎, IF real-3, IF real-5, IF real-6 are ◯, IF ratio-1, IF ratio-2, IF ratio -3 was all x.
Moreover, by evaluation of the capacity density and withstand voltage of each obtained high dielectric layer laminated polyimide film,
In each high-dielectric layer laminated polyimide film from IF real-1, IF real-2, IF real-3, IF real-4, IF real-5, and IF real-6, stable capacitance density without variation, respectively. In the high dielectric layer laminated polyimide film from IF ratio-1, IF ratio-2, IF ratio-3, a product having a practical with sufficient withstand voltage (100 kV / m or more) was obtained. In each case, spots were observed in the capacity density, and the withstand voltage was less than 10 kV / m.

(Examples 7-12, Comparative Examples 4-6)
Using each polyimide film obtained in the production example, a 100 nm-thick indium tin oxide (ITO) thin film layer and a 500 nm-thick aluminum layer are formed on the polyimide film using a sputtering apparatus. An electrode was obtained. The first electrode is given a predetermined electrode shape by masking. In addition, an electrode for mounting a drive circuit, which is routed to a portion corresponding to the outside of the element, is also formed. Next, a light emitting layer is formed on the first electrode. Here, an organic layer containing undoped poly (para-phenylene vinylene) as a light-emitting substance was formed by a screen printing method. The drying temperature of the membrane is a maximum of 180 ° C. Finally, an ITO thin film layer was formed as a second electrode by sputtering on the light emitting layer, and a fluororesin coating was applied thereon to form a protective film.
When an alternating voltage of 1000 Hz with a peak-to-peak of 60 V was applied to the organic EL element made of the transparent conductive layer laminated polyimide film made of each polyimide film, each IF real-1, IF real-2, IF real-3, Those from IF Real-4, IF Real-5, and IF Real-6 emitted vivid green light and were effective as EL elements. However, IF ratio-1, IF ratio-2, IF ratio-3 The product from No. 1 had unstable emission.
Each transparent conductive layer-laminated polyimide film obtained from each film polyimide film has a warp degree average value exceeding 10% x, a warp degree exceeding 7% to 10%, and 5-7%. ○ When less than 5% is evaluated as ◎, IF actual-1, IF actual-2, IF actual-4 are all ◎, IF actual-3, IF actual-5, IF actual-6 are all ○ IF ratio-1, IF ratio-2, and IF ratio-3 were all x.

(Examples 13-18, Comparative Examples 7-9)
Each polyimide film obtained in the production example was used, and a stainless steel target having a thickness of 1000 nm was formed on each polyimide film using a stainless steel target with a sputtering apparatus. Next, a film in which a stainless steel layer is formed is placed between the counter electrode and the support electrode in the vacuum reactor, and the inside of the reactor is once evacuated to 1 × 10 ⁻⁵ Torr, and the temperature of the support electrode is increased to 350 ° C. It was. Then, while applying a high frequency voltage of 15 MHz of 15 W to the counter electrode and the support electrode, argon gas was introduced into the reactor, pre-sputtered in an argon atmosphere of 1 Torr, and then SiH ₄ diluted to 10% with hydrogen gas. Similarly, a PH ₃ gas diluted to 1% with hydrogen gas was simultaneously introduced to form a 25 nm n-type amorphous silicon layer on the stainless steel layer in an atmosphere of 1 Torr. Next, only SiH ₄ is introduced, an i-type amorphous silicon layer having a thickness of 500 nm is laminated on the n-type amorphous silicon layer, and further a mixture containing 1% B ₂ H ₆ in SiH ₄ gas. By introducing gas, a p-type amorphous silicon layer having a thickness of 25 nm was formed on the i-type amorphous silicon layer.
Next, the film on which the pin type amorphous silicon layer was formed was mounted in a vacuum deposition apparatus, and an indium tin oxide layer having a thickness of 100 nm was deposited by an electron beam method to form a hetero electrode layer. Finally, a 100 nm palladium layer was vacuum-deposited in a comb shape.
The film-like solar cell which consists of each photoelectric converting layer lamination polyimide film obtained as mentioned above was obtained. In the production process of the film-like solar cell, when the polyimide film substrate of IF -1 to IF -6 is used, there are no problems such as generation of warp or wrinkle due to heat, and excellent flatness. A solar cell was obtained, but when a polyimide film substrate having an IF ratio of −1 to IF ratio of -3 was used, there was a problem that it was deformed by heat or warped, and the sun with excellent flatness It was difficult to obtain a battery.
Each photoelectric conversion layer laminated polyimide film obtained from each polyimide film was judged based on the average value of the five warpage degrees. In each film, the average value of the warp degree exceeds 10%, x, the warp degree exceeding 7% to 10%, Δ, 5-7%, and less than 5%.
As a result, IF real-1, IF real-2, and IF real-4 are all ◎, IF real-3, IF real-5, and IF real-6 are all ◯, IF ratio-1, IF ratio-2, IF All ratios -3 were x.

(Examples 19 and 20, Comparative Examples 10 to 15)
The obtained film roll is used and set in a vacuum apparatus equipped with an unwinding device, a chill roll, and a winding device, respectively, and then a composite metal oxide composed of aluminum oxide and silicon oxide that serve as a gas barrier layer on the film surface by vapor deposition. A thin film layer was formed. More specifically, particulate Al ₂ O ₃ (purity 99.9%) and SiO ₂ (purity 99.9%) having a size of about 3 to 5 mm are used as the vapor deposition material, and the following by electron beam vapor deposition. A silicon aluminum complex oxide thin film (2) was formed under the conditions. The vapor deposition materials were separately mixed in two water-cooled hearths, and each of Al ₂ O ₃ and SiO ₂ was heated in a time-sharing manner using one electron gun as a heating source. At this time, the emission current of the electron gun was set to 1.5 to 3.0 A, and the heating ratio of Al ₂ O ₃ and SiO ₂ was set to 30:10. The back of the film being deposited is cooled by a chill roll. A DC voltage of −100 V is applied to the chill roll, and the temperature of the chill roll is −10 ° C. The obtained composite metal oxide thin film had a thickness of 40 nm. In order to reduce the amount of residual water vapor in the vacuum chamber, the vapor deposition material was preliminarily heated before vapor deposition. The emission current of the electron gun during preheating was 0.5 A, the heating ratio of Al ₂ O ₃ and SiO ₂ was 10:10, and the preheating time was 5 minutes or 10 minutes. As a result, the ultimate vacuum before vapor deposition was 2 × 10 ⁻⁶ Torr or lower, the vacuum during vapor deposition was improved to 4 × 10 ⁻⁴ Torr or lower, and the water vapor partial pressure was 4 × 10 ⁻⁵ Torr. The obtained composite metal oxide thin film-forming film (gas barrier film) was wound into a roll.
The obtained non-metallic thin film laminate film was cut into 25 cm × 25 cm, and the average value of the warp degree for 5 sheets was determined. The results are shown in Table 1.
In each non-metallized film, the average value of warp degree exceeds 10%, ×, the warp degree exceeding 7% to 10%, Δ, 5-7%, ○, less than 5% .
The oxygen permeability of the obtained thin film laminated polyimide film was measured using an oxygen permeability measuring device (manufactured by Modern Controls, OX-TRAN100). Further, the water vapor permeability of the obtained gas barrier film was measured using a water vapor permeability tester (Lissy Corporation, L80-4000 type). The results are shown in Table 1.
The oxygen permeability and water vapor permeability of the laminated films of the examples were lower than those of the comparative examples, and showed excellent gas barrier properties.

(Examples 21 and 22)
The polyimide film obtained in IF Example-1 of Production Example A and IF Example-4 of Production Example B was rolled up into a roll under various conditions shown in Table 1 to obtain a film roll. Next, the polyimide film was unwound from the film roll, and set in a vacuum apparatus equipped with an unwinding device, a chill roll, and a winding device in the same manner as in Example 19, and the film surface was subjected to the same conditions except that the conveyance speed was halved. A composite metal oxide thin film layer having a thickness of 80 nm made of aluminum oxide and silicon oxide serving as a gas barrier layer was formed by vapor deposition.
The evaluation was made in the same manner as in Example 19 below. The results are shown in Table 1.

As described above, the thin film laminated polyimide film using the polyimide film having specific physical properties of the present invention as a base material is excellent in flatness, and is processed into, for example, a solar cell, a capacitor, a display, a heat-resistant gas barrier film, etc. Even if it is a case, it becomes a thing without a curvature and distortion, and it is excellent also in the adhesiveness of a film and a thin film layer not only in the flat surface maintenance property.
It is also useful for various thin film layers formed by sputtering, ion plating, and dry plating for vapor deposition that uses a film exposed to high temperatures as a base material. It is also useful as a film.

It is the schematic diagram which showed the measuring method (and curvature degree measuring method) of the curl degree of a polyimide film. (A) is a top view, (b) is a sectional view indicated by aa in (a) before hot air treatment, and (c) is indicated by aa in (a) after hot air treatment. It is sectional drawing.

Explanation of symbols

1 Test piece such as polyimide film 2 Alumina / Ceramic plate

Claims (19)

  A polyimide film obtained by reacting an aromatic diamine with an aromatic tetracarboxylic acid, wherein the polyimide is at least a residue of an aromatic tetracarboxylic acid, a biphenyltetracarboxylic acid residue, a residue of an aromatic diamine As a base film, a polyimide film having a phenylenediamine residue and having a curl degree of 10% or less after 300 ° C. heat treatment of the film is formed, and a non-metallic thin film is formed on at least one side of the base film A thin film laminated polyimide film characterized by that.   2. The thin film laminated polyimide film according to claim 1, wherein the curl degree of the film after heat treatment at 300 [deg.] C. is 8% or less.   The thin film laminated polyimide film according to claim 1, wherein the nonmetallic thin film is formed by a dry plating method.   The thin film laminated polyimide film according to claim 1, wherein the non-metallic thin film is a high dielectric layer.   The thin film laminated polyimide film according to claim 1, wherein the non-metallic thin film is a transparent conductive layer.   The thin film laminated polyimide film according to claim 1, wherein the non-metallic thin film is a photoelectric conversion layer. The thin film laminated polyimide film according to any one of claims 1 to 3, wherein the thin film laminated polyimide film has an oxygen permeability of 0.35 cc / m ² · atm · day or less.   A capacitor comprising the thin film laminated polyimide film according to claim 4.   An EL device comprising the thin film laminated polyimide film according to claim 5.   A solar cell comprising the thin film laminated polyimide film according to claim 6.   A packaging material comprising the thin film laminated polyimide film according to claim 7.   A polyimide film obtained by reacting an aromatic diamine with an aromatic tetracarboxylic acid, wherein the polyimide is at least a residue of an aromatic tetracarboxylic acid, a biphenyltetracarboxylic acid residue, a residue of an aromatic diamine A polyimide film having a phenylenediamine residue as a base film, and a non-metal thin film on at least one side of the base film. A thin film laminated polyimide film roll comprising a layer.   The thin film laminated polyimide film roll according to claim 12, wherein the curl degree of the film after heat treatment at 300 ° C. is 10% or less.   14. The thin film laminated polyimide film roll according to claim 12, wherein the difference between the maximum value and the minimum value of the degree of warpage at each portion is 5% or less.   The thin film laminated polyimide film roll according to any one of claims 12 to 14, wherein the nonmetal thin film layer is formed by a dry plating method.   The thin film laminated polyimide film roll according to any one of claims 12 to 15, wherein the nonmetallic thin film is a high dielectric layer.   The thin film laminated polyimide film roll according to any one of claims 12 to 16, wherein the nonmetallic thin film is a transparent conductive layer.   The thin film laminated polyimide film roll according to any one of claims 12 to 17, wherein the nonmetallic thin film is a photoelectric conversion layer. 19. The thin film laminated polyimide film roll according to claim 12, wherein the thin film laminated polyimide film has an oxygen permeability of 0.35 cc / m ² · atm · day or less.

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