JP2008050635A - Cu-Ni-ORGANIC ELECTRODEPOSITED THIN FILM STACKED STRUCTURE AND METHOD FOR FORMING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a Cu-Ni-organic electrodeposited thin film stacked structure in which an organic electrodeposited thin film such as an electrodeposited polyimide thin film having excellent adherability is deposited on a Cu-base material. <P>SOLUTION: In the Cu-Ni-organic electrodeposited thin film stacked structure, an organic electrodeposited thin film is deposited on the Cu-base material through a Ni-layer having a thickness of ≥1 μm. A method for forming the Cu-Ni-organic electrodeposited thin film stacked structure comprises: forming a Ni-layer having a thickness of ≥1 μm on the Cu-base material; then bringing the Ni-layer into contact with an electrodeposition solution of an anionic material; and electrodepositing the anionic material on the Ni-layer by using the Cu-base material, on which the Ni-layer is formed, as an anode to deposit the organic electrodeposited thin film. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a Cu—Ni—organic electrodeposition thin film laminated structure in which an organic electrodeposition thin film having excellent adhesion on Cu, particularly an electrodeposited polyimide thin film, and a method for forming the same.

  In the electrodeposition coating method (electrodeposition method), a charged material compound is migrated in a solution by applying a voltage, and the material compound is precipitated by electrolysis of water at an electrode (adhered material). Polyimide resin, which is known as a resin material used in electrodeposition liquids (electrodeposition compositions), is a film formed by agglomerating material compounds on top. Heat resistance, electrical insulation, abrasion resistance It is widely used in a wide range of applications, from space and aviation materials to electrical and electronic parts because of its excellent properties and chemical resistance.

  For example, this electrodeposition method can form a film only on an exposed portion of a conductive portion such as Cu on a substrate having a complicated shape in which a conductive portion and a non-conductive portion are mixed. In particular, polyimide resin is useful as an insulating film for a conductor because it can form a uniform film without pinholes on various conductors.

In addition, the following is mentioned as prior art document information relevant to this invention.
Japanese Patent Laid-Open No. 49-52252 JP 52-32943 A JP-A-63-1111199 JP-A-9-104839 JP 2002-299836 A JP 2003-327905 A JP 2003-327907 A JP 2004-266199 A JP 2005-336559 A JP 2000-8196 A JP 2000-68627 A Japanese Patent Laid-Open No. 8-120496 JP 2002-167694 A Japanese Patent Laid-Open No. 11-269696 Takayuki Uemura and 4 others, “Formation of polyimide film by electrodeposition coating”, Journal of Japan Institute of Electronics Packaging, Vol. 5, No. 3, p. 233-240

  However, when a polyimide thin film formed by an electrodeposition method as an insulating film on a conductive metal was examined, when the most useful Cu as a conductive material was used as an adherend, the formed polyimide thin film and the adherend It was confirmed that there was a case where the adhesion of was not sufficient.

  The present invention has been made in view of the above circumstances, and a Cu-Ni-organic electrodeposited thin film laminated structure in which an organic electrodeposited thin film such as an electrodeposited polyimide thin film having excellent adhesion is formed on Cu and a method for forming the same. The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventor does not decrease the conductivity when forming a polyimide thin film by electrodeposition on Cu, which is the most general-purpose conductor (for example, integration). In a fine Cu wiring pattern or the like in a circuit, it is necessary to keep the Cu surface of the wiring pattern clean so as not to deteriorate the conductive performance of the wiring.), And the interface (attachment surface) with the polyimide thin film as the insulating film It is necessary to form a polyimide thin film while avoiding oxidation and maintaining a clean state. However, when the polyimide thin film was formed by electrodeposition while maintaining the cleanness of the Cu surface, a decrease in adhesion was confirmed. .

  Therefore, further examination revealed that Cu as an electrode to be an electrode in electrodeposition is dissolved into an electrodeposition liquid by an electrode reaction when the electrodeposition is energized, and this dissolved Cu is formed into a film. As a result, it was found that the adhesion of the polyimide thin film was deteriorated.

  And when forming an organic electrodeposition thin film such as a polyimide thin film on a Cu base material by electrodeposition, if the organic electrodeposition thin film is formed through a Ni layer having a thickness of 1 μm or more, the surface of the Cu base material It was discovered that while maintaining the cleanliness, it was possible to avoid the dissolution of Cu in the electrodeposition solution and avoid the deterioration of the adhesion of the organic electrodeposition thin film, and the present invention was made.

That is, this invention provides the formation method of the following Cu-Ni-organic electrodeposition thin film laminated structure and Cu-Ni-organic electrodeposition thin film laminated structure.
[1] A Cu—Ni—organic electrodeposited thin film laminated structure, wherein an organic electrodeposited thin film is formed on a Cu substrate via a Ni layer having a thickness of 1 μm or more.
[2] The Cu—Ni— organic electrodeposited thin film laminated structure according to [1], wherein the organic electrodeposited thin film is a polyimide thin film.
[3] The electrodeposited polyimide thin film is formed by electrodeposition from a polyimide electrodeposition solution which is a mixed solvent solution of an anionic polyimide having a carboxyl group in its molecular structure and water and an organic solvent. The Cu—Ni—organic electrodeposited thin film laminated structure according to [2].
[4] The Cu—Ni— organic electrodeposited thin film laminated structure according to [3], wherein the anionic polyimide is a block copolymerized anionic polyimide.
[5] A Ni layer having a thickness of 1 μm or more is formed on a Cu substrate, and then the Ni layer is brought into contact with an anionic material electrodeposition solution, and the Ni layer is formed on the Ni layer. A method for forming a Cu-Ni-organic electrodeposited thin film laminated structure, wherein an organic electrodeposited thin film is formed by electrodeposition using the prepared Cu substrate as an anode.
[6] An Ni layer having a thickness of 1 μm or more is formed on a Cu substrate, and then the above-mentioned Ni is applied to the electrodeposition liquid which is a mixed solvent solution of an anionic polyimide having a carboxyl group in the molecular structure and water and an organic solvent. Cu— according to [5], wherein a layer is brought into contact, and the polyimide film is formed by electrodeposition of the anionic polyimide on the Ni layer using the Cu base material on which the Ni layer is formed as an anode. A method for forming a Ni-organic electrodeposited thin film laminated structure.
[7] The method for forming a Cu—Ni— organic electrodeposited thin film laminated structure according to [6], wherein the anionic polyimide is a block copolymerized anionic polyimide.

  ADVANTAGE OF THE INVENTION According to this invention, the Cu-Ni-organic electrodeposition thin film laminated structure which formed the organic electrodeposition thin film, such as an electrodeposition polyimide thin film excellent in adhesiveness, on Cu base material can be provided.

Hereinafter, the present invention will be described in more detail.
The Cu—Ni—organic electrodeposition thin film laminated structure of the present invention has a structure in which an organic electrodeposition thin film is laminated on a Cu substrate via a Ni layer having a thickness of 1 μm or more. A Ni layer having a thickness of 1 μm or more is formed, and then the Ni layer is brought into contact with the anionic material electrodeposition solution, and the anionic material is electrodeposited on the Ni layer with the Ni layer formed on the Ni layer as an anode. It can be formed by forming an electro-deposition thin film.

  As this Cu—Ni—organic electrodeposited thin film laminated structure, for example, a structure in which the organic electrodeposited thin film 1 is formed on the upper surface of the Cu base 3 via the Ni layer 2 as shown in FIG. For example, a film obtained by forming an organic electrodeposition thin film on a copper layer such as a flexible printed board or a copper layer such as a copper foil or a circuit copper wiring is applicable.

  In the present invention, even if the Cu base material that becomes an electrode in electrodeposition is a metal that is ionized by an electrode reaction and dissolves in the electrodeposition liquid when the electrodeposition is energized, such as Cu. Due to the Ni layer having a thickness of 1 μm or more formed above, Cu constituting the base material is not dissolved in the electrodeposition liquid, and Cu is hardly taken into the organic electrodeposition thin film. Therefore, this organic electrodeposition thin film does not deteriorate in adhesion, and is excellent as an organic electrodeposition thin film formed on a substrate made of Cu, particularly as an insulating film for electric / electronic materials. A Cu-Ni-organic electrodeposition thin film laminated structure comprising an organic electrodeposition thin film is a laminated structure comprising a Cu base material that ensures electrical conduction and an organic electrodeposition thin film as an insulator thereof. Useful as.

  In the present invention, the organic electrodeposition thin film is a thin film formed by an anode electrodeposition method known as an electrodeposition coating method, and a polyimide thin film is suitable as the organic electrodeposition thin film. This electrodeposited polyimide thin film can be formed by electrodeposition using a mixed solvent solution of an anionic polyimide having a carboxyl group in the molecular structure and an organic solvent as an electrodeposition solution (electrodeposition composition). Moreover, an acrylic electrodeposition thin film can also be mentioned as an organic electrodeposition thin film.

  The Cu-Ni-electrodeposited polyimide thin film laminated structure in which the organic electrodeposited thin film is a polyimide thin film has, for example, a Ni layer having a thickness of 1 μm or more formed on a Cu substrate, and then has a carboxyl group in the molecular structure. The Ni layer is brought into contact with an electrodeposition solution that is a mixed solvent solution of an anionic polyimide water and an organic solvent, the anionic polyimide is electrodeposited on the Ni layer, and the Cu base material on which the Ni layer is formed is electrodeposited. It can be formed by forming a polyimide thin film.

  In the present invention, the polyimide thin film can be formed as an electrodeposition liquid (electrodeposition composition) by using a mixed solvent solution of an anionic polyimide having a carboxyl group in the molecular structure and an organic solvent. As a suitable electrodeposition solution, a known electrodeposition solution used for forming a polyimide thin film by electrodeposition can be used.

  As the polyimide electrodeposition solution, an anionic polyimide, for example, a random copolymerized anionic polyimide described in JP-A-9-104839 (Patent Document 4), JP-A 2003-327905 (Patent) Reference 6), an electrodeposition liquid using a block copolymerized polyimide described in JP-A No. 2003-327907 (Patent Document 7) and the like can be mentioned, but the adhesion of the obtained electrodeposition polyimide film is good. From this point of view, those using block copolymerized anionic polyimide are particularly preferred.

  As this electrodeposition liquid, what contains the random copolymerization anionic polyimide or the block copolymerization anionic polyimide which consists of a reaction product of diamine and an acid dianhydride is mentioned.

  The diamine preferably includes an aromatic diamine, and examples of the aromatic diamine include o-, m-, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, and 2,4-diamino. Xylene, diaminodurene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, benzidine, 4,4′-diaminoterphenyl, 4,4′-diaminoquaterphenyl, 4,4′-diaminodiphenylmethane, 1, 2-bis (anilino) ethane, 4,4′-diaminodiphenyl ether, diaminodiphenyl sulfone, 2,2-bis (p-aminophenyl) propane, 3,3′-dimethylbenzidine, 3,3′-dimethyl-4, 4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl Tan, diaminotoluene, 1,4-bis (p-aminophenoxy) benzene, 4,4′-bis- (p-aminophenoxy) biphenyl, 2,2-bis {4- (p-aminophenoxy) phenyl} propane 4,4′-bis (3-aminophenoxyphenyl) diphenylsulfone, 2,2-bis {4- (p-aminophenoxy) phenyl} hexafluoropropane, and the like. Further, it may contain a diamine other than an aromatic diamine such as 2,6-diaminopyridine. Polyimide containing 2,6-diaminopyridine has an acid group and a base in the molecule, and forms a good polyimide thin film by polymer interaction. Furthermore, there is an advantage that the affinity for water is increased, the water-soluble electrodeposition solution is stabilized, and the obtained electrodeposition film is smooth and dense.

  Examples of the acid dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxy) Phenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone 4,4 ′-{2,2,2-trifluoro-1- (trifluoromethyl) ethylidene} bis (1,2-benzenedicarboxylic anhydride), 9,9-bis {4- (3 4-dicarboxyphenoxy) phenyl} fluorene dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5 , 8-Naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, bicyclo [2.2.2 And aromatic tetracarboxylic dianhydrides such as octo-7-ene-2,3,5,6-tetracarboxylic dianhydride.

  Random copolymerized anionic polyimide and block copolymerized anionic polyimide can be obtained by heating and dehydrating using approximately equal amounts of these diamines and acid dianhydrides. In the case of a block copolymerized anionic polyimide, it is produced by a sequential addition reaction. In the first stage, a polyimide oligomer is formed from acid dianhydride and diamine, and in the second stage, acid dianhydride and / or diamine is further added. Then, polycondensation is performed to obtain a block copolymerized anionic polyimide. In the present invention, the molecular weight of the random copolymerized anionic polyimide and the block copolymerized anionic polyimide (polystyrene conversion value by gel permeation chromatography (GPC)) is 50,000 to 100,000, particularly 60,000 to 80,000. Is preferred.

  This random copolymerized anionic polyimide and block copolymerized anionic polyimide are usually used in an electrodeposition solution as neutralized with a basic compound. As the basic compound, N-dimethylethanol, triethylamine, triethanolamine, N-dimethylbenzylamine, and N-methylmorpholine are used, and N-dimethylethanol and N-methylmorpholine are preferable. The amount of the neutralizing agent (basic compound) used is such that the polyimide is dissolved or stably dispersed in the solution, and is usually 30 mol% or more, particularly 30 to 200 mol% of the stoichiometric neutralization amount. It is preferable. Moreover, it is preferable that the solid content density | concentration of the neutralized polyimide in an electrodeposition liquid is 5-15 mass%.

  On the other hand, water and an organic solvent are used as the solvent for the electrodeposition solution, and the organic solvent is a water-soluble polar organic solvent that dissolves the random copolymerized anionic polyimide and the block copolymerized anionic polyimide, for example, N -Methylpyrrolidone, N, N'-dimethylacetamide, N, N'-dimethylformamide, dimethyl sulfoxide, tetramethylurea, tetrahydrothiophene-1,1-oxide, etc. are used. N-methylpyrrolidone and tetrahydrothiophene-1,1-oxide, which are less toxic, are preferred. These water-soluble polar organic solvents may be those used as a reaction solvent when the above-described block copolymerized anionic polyimide is produced.

  Moreover, as the organic solvent contained in the electrodeposition liquid, an oil-soluble solvent that dissolves the random copolymerized anionic polyimide and the block copolymerized anionic polyimide may be used. The oil-soluble solvent is effective in that it improves the flowability of the polyimide resin deposited on the adherend after electrodeposition and improves the smoothness of the coating film. As a result, the storage stability of the electrodeposition liquid can be enhanced. Here, the oil-soluble solvent means an organic solvent that is substantially insoluble or hardly soluble in water. Examples of oil-soluble solvents for dissolving random copolymerized anionic polyimide and block copolymerized anionic polyimide include 1-acetonaphthone, acetophenone, benzylacetone, methylacetophenone, dimethylacetophenone, propiophenone, valerophenone, anisole, methyl benzoate, benzoic acid Examples include benzyl acid.

  Further, as the organic solvent contained in the electrodeposition liquid, it is preferable to use a poor solvent for polyimide such as an alcohol having a phenyl group, a furfuryl group or a naphthyl group, and examples thereof include benzyl alcohol and substituted benzyl. Examples thereof include alcohol and furfuryl alcohol.

  Although the concentration of the solvent in the electrodeposition liquid is 85 to 95% by mass, the concentration of the organic solvent is 15 to 85% by mass, particularly 20 to 70% by mass. The balance with the solid content concentration of the neutralized polyimide is the concentration of water. In addition, when using the said oil-soluble solvent, it is preferable that the density | concentration of the oil-soluble solvent in an electrodeposition liquid is 10-30 mass%, and when using the poor solvent with respect to the said polyimide, the poor solvent in an electrodeposition liquid The concentration of is preferably 5 to 15% by mass. It is preferable that the pH of the electrodeposition liquid is approximately neutral to weakly basic (for example, pH = 7 to 9, preferably 7.5 to 8).

  As the electrodeposition liquid described above, a commercially available product such as a soluble block copolymerized polyimide electrodeposition liquid Q-ED series (for example, Q-ED-21-129, etc.) manufactured by PI Engineering Laboratory Co., Ltd. may be used. it can.

  Conventionally known conditions can be adopted as electrodeposition conditions. For example, when using a random copolymerized anionic polyimide or a block copolymerized anionic polyimide, the conductive adherend is immersed in an electrodeposition solution at a temperature of 15 to 35 ° C., and an electrode such as Cu or Pt is used as a cathode. A polyimide thin film containing a solvent is formed on the surface of the conductive deposit by energizing at 20 to 400 V, preferably 50 to 200 V, and energizing time 30 seconds to 10 minutes, preferably 1 to 5 minutes.

  Furthermore, after washing and air drying, the polyimide thin film is dried and solidified by heating at 120 to 220 ° C. for 30 minutes to 1 hour to volatilize the solvent. In addition, since the electrodeposited thin film is already a polyimide, heating is sufficient at a temperature sufficient to disperse the solvent, and depending on the type of the solvent, the heating is performed at a temperature of about 80 to 150 ° C. by infrared heating. Minutes to 1 hour may be sufficient. Although the film thickness of an electrodeposition polyimide thin film is not specifically limited, Usually, it is 1-100 micrometers.

  In the present invention, the Cu substrate on which the organic electrodeposition thin film is formed serves as an anode during electrodeposition. The Ni layer formed on the Cu substrate can be formed by, for example, electrolytic plating, electroless plating, dry plating such as sputtering, and the thickness is 1 μm or more. Although the upper limit of thickness is not specifically limited, Usually, it is preferable to set it as 5 micrometers or less. The Ni layer on the Cu substrate may be formed at a desired portion where the organic electrodeposition thin film is formed, but the portion other than the portion where the organic electrodeposition thin film is formed on the Cu substrate. The part immersed in the electrodeposition liquid needs to be in an electrically insulated state without exposing the Cu base material.

  In addition, this invention is suitable as a structure which laminated | stacked the organic electrodeposition thin film as an insulating film on copper layers, such as a copper plate of a flexible printed circuit board, copper foil, etc., and its formation method, for example. In particular, in the flexible printed circuit board, there is a demand for thinning the organic electrodeposition thin film in order to reduce the size and weight, and to maintain the flexibility of the rolled copper foil. A Cu-Ni-organic electrodeposition thin film laminated structure comprising an organic electrodeposition thin film that is significantly thinner than a conventional 25 to 75 μm, for example 1 to 20 μm, particularly 5 to 10 μm, on a copper foil. It can be obtained without reducing the adhesion of the thin film.

  In addition, when the electrodeposition liquid using the random copolymerized anionic polyimide or the block copolymerized anionic polyimide described above is used, high-temperature heat treatment after electrodeposition for imidization is not necessary, Recrystallization is suppressed and high folding resistance can be maintained. Furthermore, the present invention is also suitable as a structure in which an organic electrodeposition thin film is formed on a Cu wiring pattern, a Cu three-dimensional structure, etc. on an uneven substrate, and a method for forming the structure.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example.

[Example 1]
The following pretreatment 1 (electrolytic degreasing, acid cleaning 1, acid cleaning 2) was applied to a Cu foil having a size of 3 cm × 5 cm and a thickness of 36 μm.
Pretreatment 1
Electrolytic degreasing: Immerse in a 3% NaOH aqueous solution containing a surfactant and treat at a current density of 10 A / dm ² for 60 seconds.
Acid cleaning 1: immersed for 60 seconds in a 10% phosphoric acid aqueous solution while rocking.
Acid cleaning 2: immersed for 60 seconds while rocking in 10% sulfuric acid aqueous solution.

  Next, the Cu foil subjected to the pretreatment 1 was washed with water, an Ni layer (thickness: 1 μm) was formed on the Cu foil by electroplating, washed with water, and then dried in the atmosphere at room temperature.

Next, the following pretreatment 2 (pre-dip 1 and pre-dip 2) was applied to the Cu foil on which the Ni layer was formed.
Pretreatment 2
Pre-dip 1: Immersion for 15 seconds while rocking in a commercially available diluent for electrodeposition (made by PI Engineering Laboratory Co., Ltd.).
Pre-dip 2: Immersion for 15 seconds while rocking in a commercially available electrodeposition solution (Q-ED-21-129 manufactured by PI Engineering Laboratory Co., Ltd.).

  Next, the Cu foil on which the Ni layer subjected to the pretreatment 2 was formed was immersed in a commercially available electrodeposition solution (Q-ED-21-129, manufactured by PI Engineering Laboratory Co., Ltd.) at room temperature, and the counter electrode was used as a Pt wire. Then, an applied voltage of 60 V and an energization time of 5 minutes were used for electrodeposition of a polyimide thin film on a Cu foil via a Ni layer. After electrodeposition, a Cu foil on which a polyimide thin film was formed was used as a commercially available diluent for electrodeposition liquid ( It is immersed for 15 seconds while swinging in PIA Research Laboratory Co., Ltd., then heated and dried at 90 ° C. for 30 minutes in the atmosphere, and a polyimide thin film (thickness 50 μm) through a Ni layer on Cu foil. Cu-Ni-electrodeposited polyimide thin film laminated structure was obtained.

  Then, it heated in air | atmosphere for 30 minutes at 220 degreeC for 30 minutes at 180 degreeC.

  The adhesion of the obtained polyimide thin film was evaluated by the following peel test.

  Peeling test: After putting slits at 1 mm intervals using a cutter knife and scratching with tweezers, those that did not peel off were good and those that were peeled off were considered bad.

  As a result, both the withstand voltage test and the peel test were good. Further, neither Cu nor Ni was detected in either the polyimide thin film or the electrodeposition solution.

[Comparative Example 1]
A polyimide thin film was directly formed on the Cu foil in the same manner as in Example 1 except that water washing after the pretreatment 1, formation of the Ni layer and subsequent water washing and drying were not performed. The adhesion of the obtained polyimide thin film was evaluated in the same manner as in Example 1.

  As a result, the peel test was poor.

It is sectional drawing which shows an example of the Cu-Ni-organic electrodeposition thin film laminated structure of this invention.

Explanation of symbols

1 Organic Electrodeposition Thin Film 2 Ni Layer 3 Cu Base

Claims (7)

  A Cu-Ni-organic electrodeposited thin film laminated structure, wherein an organic electrodeposited thin film is formed on a Cu substrate through a Ni layer having a thickness of 1 μm or more.   The Cu-Ni-organic electrodeposition thin film laminated structure according to claim 1, wherein the organic electrodeposition thin film is a polyimide thin film.   The electrodeposited polyimide thin film is formed by electrodeposition from a polyimide electrodeposition solution which is a mixed solvent solution of water and an organic solvent of an anionic polyimide having a carboxyl group in a molecular structure. Item 3. A Cu-Ni-organic electrodeposited thin film laminated structure according to Item 2.   The Cu-Ni-organic electrodeposition thin film laminated structure according to claim 3, wherein the anionic polyimide is a block copolymerized anionic polyimide.   A Cu layer in which a Ni layer having a thickness of 1 μm or more is formed on a Cu substrate, the Ni layer is then brought into contact with an anionic material electrodeposition solution, and the Ni layer is formed on the Ni layer. A method for forming a Cu-Ni-organic electrodeposited thin film laminate structure, wherein an organic electrodeposited thin film is formed by electrodeposition using a substrate as an anode.   A Ni layer having a thickness of 1 μm or more is formed on a Cu substrate, and then the Ni layer is brought into contact with an electrodeposition solution that is a mixed solvent solution of an anionic polyimide having a carboxyl group in the molecular structure and an organic solvent. 6. A Cu-Ni-existent film according to claim 5, wherein the anionic polyimide is electrodeposited on the Ni layer and the Cu base material on which the Ni layer is formed is electrodeposited to form a polyimide thin film. A method for forming an electro-deposition thin film laminated structure. The said anionic polyimide is block copolymerization anionic polyimide, The formation method of the Cu-Ni-organic electrodeposition thin film laminated structure of Claim 6 characterized by the above-mentioned.

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