CA1231670A - Electrically conducting polymer film and method of manufacturing the same - Google Patents

Abstract

Abstract of the Disclosure A conducting polymer film has an insulating polymer film as a base, and a conducting aromatic polymer compound is contained by electrochemical polymerization in at least part of the insulating polymer film.

Description

Specification Title of the Invention Electrically Conducting Polymer Film and Method of Manufacturing the Same Background of the Invention The present invention relates to an electrically conducting polymer film and a method of manufacturing toe same.
Conventional electrically conducting polymer films are classified into the following two types:
One is a general-purpose polymer material containing carbon Black or a metal such as aluminum or stainless steel as a conductive filler A resultant electrically conducting polymer films have an electrical conductivity of 1 to 10 13 I cm and is used as an antistatic agent, an electromagnetic interference preventing material or the like. This film is prepare such that a polymer is fused and a filler is added Thor, and a resultant material is kneaded and molded. Therefore, a complicated, high-precision process must be used with high reliability of control, resulting in high cost. In addition it is difficult for this film to obtain an electrical conductivity higher than 1 /Q-cm. In order to achieve a high electrical conductivity, the amount of filler must be increased. These excess amount of filler reduces the mechanical strength of the resultant film.

.,`~ -1 23~L$'~) s because of this poor mechanical property, a thin film cannot be easily prepared.
The other conventional electrically conducting polymer comprises a polymer material with electrical conductivity. This type of polymer has been developed as a material for various functional elements, polymeric superconductors and molecular device materials which are receiving a great deal of attention these days. For example, the conventional electrically conducting polymer comprises polyacetylene, polyphenylene-sulfide, polyparaphenylene or the like. The main feature of these films lies in the fact that the polymer chains are consisted of conjugated double bonds, so that carriers are easily mobile along a molecular chain. When a prover impurity is doped, a high electrical conductivity of morn than 10 /Q-cm can ye achieved. However, this class of materials is generally unstable in air, and workability of the film is also degraded.
In addition to these conventional films, it was reported that some aromatic compounds are electrochemicali-y polymerized in its solution containing an electrolyte forming an electrically conducting polymer film on an electrode substrate. Aromatic compounds of this type comprise heterocyclic compounds (e.g., purl and thiophene) or polyaromatic compounds such as azulene, porn and triphenylene (erg., J. Baron, S. Mohmand and I

R~J. Walt man, Is Journal of Research & Development, Vol. 27, No. 4, P. 330, 1983).
However, a conventional electrically conducting polymer film formed by electrochemical polymerization on 5 the electrode substrate has the following disadvantages:
(1) Since the mechanical strength of the film is weak, the films on the substrate or separated from the substrate are relatively fragile. Moldability of this film becomes poor.

(2) adhesion between film and substrate is weak, so that the film tends to peel from the substrate during film formation or cleaning.

(3) The film surface is very coarse, and tends to lose gloss.

(4) The resultant film is insoluble and cannot be fused, resulting in poor moldability.
(C) When an e;ectrGde substrate Scull as Nose glass which has a high electrical resistance as competed with those of electrolytic solution and resultant polymer film is used, the film thickness becomes nonuniform to) Since impurity doping occurs at the same time with the polymerization, it is difficult to control the electrical conductivity of film.
(7) Even a film having low electrical I conductivity becomes black and has low transmittance of visible light. The resultant film cannot be colored.

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Sumacs of the Invention Y
According to an aspect of the invention there is provided an electrically conducting polymer film, comprising an insulating polymer film having an electrically conducting aromatic polymer compound formed by electrolytic polymerize-lion on at least one surface and inside thereof, at least one surface of the electrically conducting polymer film being electrically conducting.
According to a further aspect of the invention there is provided a method of manufacturing an electrically conducting polymer film, comprising the steps of providing an insulating polymer film on the surface of an electrode;
causing an electrolyte solution and an aromatic polymer to reach the electrode surface through the insulating polymer film; electrolytically polymerizing the aromatic polymer at the interface between the electrode and the insulating polymer film; and forming an electrically conducting aromatic compound area from the interface of the insulating polymer film toward the inner side of the insulating polymer film.

Jo 7 Brief Description of the Drawings Fig. 1 is a representation for explaining a method of manufacturing an electrically conducting polymer film according to the present invention;
Figs. PA, 2B and 2C are respectively sectional views showing the basic structures of electrically conducting polymer films prepared by the present invention;
Fig. 3 is a graph showing the relationship between polymerization time and conductivity of a typical electrically conducting polymer film obtained by the present invention, Fig. 4 it a graph showing the relationship between conductivity and transmittance of the typical electrically conducting polymer film obtained by the present invention;
Figs. 5 and 6 are, respectively, sectional views for explaining steps in manufacturing two- and three-layer electrically conducting polymer films on corresponding electrode substrates by means of electrochemical polymerization according to the present invention;
Fig. 7 is a sectional view showing an electrically conducting polymer film according to another embodiment of the present invention;
Fig. 8 shows the steps in manufacturing the polymer film shown in Fig. 7;

, I 3 to Fig. 9 shows an apparatus for manufacturing an electrically conducting polymer film by using a cylindrical electrode in accordance with electrochemical polymerization;
Figs 10 and 11 are, respectively, representations showing plate-like and cylindrical (Fig. 9 electrochemical polymerization electrodes used for manufacturing an electrically conducting polymer film according to the present invention;
Fig. 12 is a graph showing the relationship between surface resistance of electrically conducting polymer film and charge density in polymerization according to the present invention; and Figs. AYE and 13B are graphs each showing the relationship between intensity and etching time in Auger Electronic Spectrascopy of the films.
Discretion of the Preferred ~mbcdiments An electrically conducting polymer film accordions to the present invention is manufactured by the principle of the method shown in Fig. 1. Referring to Fig. 1, one of the electrodes dipped in a solution 11 containing an aromatic compound subjected to electrochemical polymerization, a solvent and an electrolyte has a conducting layer 13 such as a conducting metal oxide film serving as an electrode on a substrate 12. An insulating polymer film 14 is formed on the conducting layer 13. The electrode having the construction described above is dipped it in the solution 11 together with another counter electrode 15. A voltage E is applied between two electrodes.
In this case, since the electrode substrate is coated with the insulating polymer film, a current does not flow through the insulating polymer film. As a result, a conducting film will not be formed on the substrate However, the present inventors have conducted an experiment by using the arrangement described above and found that an electrochemical polymerization occurred even on the insulated electrode surface and that a conducting polymer layer was formed in the insulating polymer film.
Many aromatic compounds can be used as monomer if this invention, but purl is mainly used to explain the details of the present invention. Since polymer films I coated on the surface of the electrode are almost insulator having an electrical conductivity of less than 10 10 I cm, pol~.eri~atlon of purl is not considered to occur.
however, when a solvent and an electrolyte are properly selected with respect to the insulating polymer film, purl molecules, and electrolyte anion diffuse in the polymer film and polymerization occurs. The structure of resultant film varies in accordance with the type of insulating polymer film employed as the base and composition of a solution subjected to the polymerization reaction. As a result of this process, roughly three types of structures can be obtained, as shown in Figs. PA, 2B aye 2C, respectively.

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Purl electrochemical polymerization on the electrode covered with the insulating polymer film is initiated on the electrode surface by purl be no diffused in the film and the electrolyte, so that conducting polypyrrole is produced at an interface button the electrode and film. When the produced polypyrrole grows within the insulating polymer film, the surface (to be referred to as an electrode side hereinafter) of the film which is in contact with the electrode becomes conductive. This state is illustrated in Fig. PA, wherein the opposing surface (to be referred to as a surface side hereinafter) of the film is kept insulative. When electrochemical polymerization continues, the conducting portion in the film is increased. Finally, polypyrrole grows to reach the surface, and the film becomes entirely conductive. This state is illustrated in Fig. 2B.
Normally, two states shown in Figs. PA and 2B are obtained.
However, when miscibility between the conducting aromatic polymer and the insulating polymer film is poor, or adhesion between the insulating polymer film and the electrode is not sufficient, a conducting polymer layer having a multi layer structure shown in Fig. 2C is formed between the electrode and the polymer film. II1 this case, the resultant multi layer film often shows a weak adhesion between the insulating polymer film and the conducting polymer layer, and two layers tend to separate from each other. These films causes a problem in practice However, foe when two or more insulating polymer films are laminated as will be described later, this multi layer structure is effective.
The structures adopted in the present invention will be mainly those illustrated in Figs. PA and 2B.
The features of the electrically conducting polymer films thus prepared are summarized as follows.
However, effects of the films are not limited to these, as will be apparent from the following description.
(1) The electrical conductivity can vary from a low conductivity of the insulating materiel to a high conductivity of about 102 /Q-cm. The electrical conductivity can change by the polymerization time, as shown in Fig. 3. In this case, electrical conductivity is low at the very beginning of polymerization and it gradually increased, thereby obtaining a film of uniform thickness.
(2) Since the electrically conducting polymer film is obtained in the insulating polymer film employed as a base, the resultant conducting polymer film can be thin.
In addition, by selecting a suitable insulating polymer film, the resultant film can have high mechanical strength.
I The present invention can be applied to almost all insulating polymer films.
(4) The manufacturing method is simple, and a low-cost electrically conducting polymer film can be obtained.

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(5) When an insulating polymer film having high adhesion with the electrode surface is used, or a noble metal substrate is used as electrode, an electrically conducting polymer film having good adhesion with the substrate can be obtained

(6) Even if a transparent electrode such as mesa glass (trade mark) or indium tin oxide (IT) having a relatively high surface resistance is used, polymerization can be performed uniformly, thereby obtaining a film having uniform electrical conductivity.

(7) Although a conventional electrically conducting polymer has a color close to black, a film having a high transmittance can be obtained by adjusting the electrochemical polymerization time according to the present invention.
Fig. 4 shows the relationship between optical density and conductivity of polypyrrole polyvinylcarba~ole composite film prepared by this invention.
Typical examples of the-various materials used in the present invention will be described hereinafter An insulating polymer film used in the present invention may comprise: polystyrene; a polystyrene derivative such as chloromethylated polystyrene and polychlorostyrene; a copolymer between styrenes and a monomer (e.g., various vinyl esters, vinyl ethers, acrylic acids and their esters, met acrylic acids and their esters, malefic acid and its esters, fumaric acid and its esters, .

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malefic android, halogenovinylidene compounds, vinyl chloride acrylonitrile, methacrylonitrile and propylene); or a copolymer of styrenes with any aromatic vinyl polymer such as polyvinyl carbazole. Furthermore, the insulating polymer film may comprise a polyvinyl chloride resin (i.e., polyvinyl chloride and a copolymer of vinyl chloride with a monomer descried above). The insulating polymer film may also comprise a copolymer between vinylidene chloride and one of various vinyl esters, vinyl ethers, acrylonitrile, methacrylonitrile and vinyl chloride; polyvinylidene fluoride or a copolymer of vinylidene fluoride with monomer described above, or polyvinyl acetate or copolymer of vinyl acetate with monomer described above. The insulating polymer film may comprise polyethylene, a copolymer of ethylene with a monomer as described above, polyethylene telephthalate, any nylon, polycarbonate, any cellulose 9 polyvinyl alcohol, rubber or the like.
The insulating polymer film may also comprise a thermosetting resin such as epoxy resin, phenol resin, mailmen resin, urea resin, acutely resin, polyamide resin, REV silicone resin.
The insulating polymer film may comprise a polymer film obtained by plasma polymerization.
Additives such as a plasticizer, a pigment, a plastic, a conductive filler, a defogging agent and a just inhibitor may he used. In this case, it is desired to use I I

the additives which hardly dissolve in the electrolytic solution.
An aromatic compound subjected to electrochemical polymerization can be selected from purl, S 3-methylpyrrole, N-methylpyrrole, N-phenylpyrrole, thiophene, 3-methylthiophene, aniline, Furman, phenol, thiophenol, selenophene, tellurophene, biphenyl, azulene, p-terphenyl, o-terphenyl, 2-hydroxybiphenyl, diphenylsulfide, I thienyl)thiophene, 2-(~-thienyl)furan, 2-(2-pyrrolyl)pyrrole, 2-(2-pyrrolyl)thiophene, 2-phenylthiophene, u-thienylphenyl ether, ~-furanyl-~-thienylselenide, 2-(2-pyrrolyl)selenophene, 2-(2-seleninyl)tellurophene, N-vinylcarbazole, N-ethynylcarbazole, methylazulene and porn.
An electrically conducting polymer solution must have a proper composition adjusted for the type of insulating polymer film used. The solution must satisfy at least the following conditions:
(1) The solution does not dissolve the insulating polymer film.
(2) The solution dissolves an aromatic compound which can be electrochemica]ly polymerized with the electrolyte.
(3) The solution has an affinity with the insulating polymer so that an aromatic compound which can :

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be subjected to electrochemical polymerization can be dozed in the insulating polymer film.
n electrolyte for electrochemical polymerization comprises any compound such as organic qua ternary ammonium salts, inorganic salts, or strong acids of proton acid.
An acetonitrile solvent is normally used. However, any solvent can be used when the solvent allows the aromatic compound to perform electrochemica~ polymerization and dissolves a proper electrolyte. For example, the solvent is selected from a nitrobenzene-based solvent, a propylene carbonate-based solvent, an ethylene ylycol-based solvent, an aqueous solvent, an N,N-dimethylformamide-based solvent, and a dimethylsul~o~ide-based solvent. However, any other solvent may, if necessary, be used.
An electrochemical polymerization substrate comprises a noble metal such as gold, platinum and palladium; a base metal such as nickel, chromium and stainless steel; a conducting metal oxide such as, stunk oxide, indium oxide and IT (indium tin oxide); an inorganic semiconductor such as silicon and amorphous silicon; or a material obtained by depositing one of the above materials on a proper substrate, by means of evaporation, sputtering, CUD, plating, or coating. The electrochemical polymerization substrate may comprise a laminate obtained by stacking at least two layers of 'he above-mentioned electrode materials. An electrode la~lina~Q
may be formed into a drum to produce films continuously.

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The resultant electrically conducting polymer film can be used as an electromagnetic interference preventing film, an antistatic film, a photosensitive image sensor film, a solar battery film, and so on.
In addition, the present inventors found that at least two different insulating films can be layered in the electrochemical polymerization, and that a resultant layered film had often superior film quality to that of a single conducting film.
As shown in Fig. 5, a first insulating polymer film 14 is coated on a substrate 12 having an electrode 13.
A second insulating polymer film 21 is formed on the first insulating polymer film 14 in a state (a. The electrochemical polymerization of aromatic compounds by using this electrode produces a two-layer composite electrically conducting polymer film.
In this case, the aromatic polymer is mixed in the two layers 14 and 21 as shown in state by or is mixed only in the layer 14 as shown in state (c).
Even an insulating polymer film having at least three layers can be a composite electrically conducting polymer film having a multi-layer structure by properly selecting the type and thickness of the polymer film and the type of solvent.
when a polymer compound containing an epoxy group such as polyglycidyl methacrylate, or a polymer compound containing an OH group such as novolak resin is used as the 3L~3~ I
insulating polymer film, a resultant conducting film is strongly adhered to the electrode surface.
On the other hand, when an aromatic polymer such as polystyrene, chloromethylated polystyrene, polyvinylphthalate, or polyvinylcarbazole is used to Lore the insulating polymer film, a relatively uniform composite electrically conducting polymer film having a controlled electrical conductivity is obtained. However, this polymer film has weak adhesion to the substrate and can be easily peeled therefrom When an aromatic polymer layer is laminated on a polymer layer having good adhesion with electrode surface, the electrochemical polymerization produces a uniform composite electrically conducting film which has good adhesion and uniform and controllable conductivity.
When a polymer film, which has poor miscibility with electrically polymerized conductive polymer, such as polyethylene or polypropylene type polymer is used as top layer of two-layer insulating film, a two-layer structure having a composite layer of conductive polymer with bottom insulating film and top polymer -film which is still insulated can be easily obtained. This insulating film can be used as protective layer of electrically conducting film.
In the case of combination of an aromatic polymer film as bottom layer and a polymer film with poor miscibility as top layer the electrochemical polymerization ~3~7~

produces uniform, conductivity-controlled composite electrically conducting polymer covered with an insulating polymer film.
When three kinds of polymer film are larminatecl, a multi layer composite conducting polymer film having a combination of respective layers can be obtained. As shown in Fig. 6, a polymer film (first layer) 14 having good adhesion with a substrate 12 is formed on the substrate 12 having a conductive surface (an electrode 13 thereon. Pun aromatic polymer film (second layer) 21 for controlling electrical conductivity is formed on the first layer 14. A
polymer film (third layer) 23 with poor miscibility is formed on the second layer 21. The resultant substrate a is electrochemically polymerized to obtain a form, lo conductivity-controlled composite electrically conducting polymer film having good adhesion, which are covered with insulating polymer film.
According to the conducting polymer film of the present invention, the transparency of film is improved, as previously described.
The present inventors found that when the insulating poller film was made conductive and the electrochemical polymerization time was shortened, the electrical conductivity could not be greatly increased, but the resultant semi conducting film had high transmittance to visible fight: However, when a film has a practical thickness such as, more cyan 20 em, short pol~merizatiGn I

time cannot make the whole film conductive and only the -film surface which us in contact with the electrode surface becomes conductive. When the resultant film is used as a semiconductor film having a high transmittance to visible light, only one conductive surface is utilized.
On the other hand, when both surfaces of the film having the thickness described above are made conductive, the electrochemical polymerization time must be prolonged, thereby decreasing the transmittance.

According to the present invention, a conducting polymer film with electrochemical polymers mixed in the surface and electrode side layers of the film can be provided although the entire film is not made conductive.
Fig. 7 shows a typical example of the above case.
Referring to Fig. 7, upper and lower surface layers 32 and 33 of an insulating polymer film 31 comprise a composite structure obtained by e~ectrochem.ically polymerizing the aromatic compound in the polymer film.
Thickness of the composite conducting surface I layer greatly depends on electrochemical polymerization conditions OX the aromatic compound, especially, electrochemical polymerization time. When the polymerization time is increased, the thickness of the conductive composite layer is increased. As a result, the entire film is made conductive, and no insulating part will appear.

Fig 8 shows steps of a method of manufacturing a conducting polymer film according to the present invention.
Reference numerals 31 to 33 in Fig 8 denote the same parts in Fig. JO Reference numerals 30 and 30' denote electrodes. An insulating polymer film 31 is adhered to an electrode 30 (step A). The electrode 30 is used as a positive electrode, and electrochemical polymerization OX
an aromatic compound is performed in an electrochemical polymerization solution. An electrochemical polymer is formed in a surface layer 32 of the polymer film which is in contact with the electrode 30 (step B). The resultant film is peeled from the electrode, and the opposite surface is adhered to the electrode 30' (step C). This electrode is used as the positive electrode, and electrochemical polymerization of an aromatic compound is performed in the electrochemical polymerization solution. A composite electrochemical polymer is formed in the surface layer 33 adhered to the surface thereof which is in contact with the electrode 30' (step D). A conducting polymer film having upper and lower conducting layers is prepared (step E).
In the above process, the electrodes 30 and 30' may be the same or different in respective steps. In - addition, the electrochemical polymerization solution used in step B may be the same as or different from that in step D. In other words, electrochemical polymers of different types of aromatic compounds may be used.

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In order to manufacture an electrically conducting polymer film according to the present invention, a continuous manufacturing apparatus using a cylindrical electrode can be used to improve productivity and decrease manufacturing cost. Fig. 9 is a side view of a conducting film forming apparatus using the cylindrical electrode in accordance with electrochemical polymerization. Referring to Fig. 9, reference numeral 81 denotes a cylindrical electrode; 82, a film; 83, a thermal transfer roller; 84, an electrochemical polymerization solution; 85, an electrochemical polymerization tank; 86, a counter electrode; 87, a terminal; 88, a guide roller; and 89, a power source.
An insulating polymer film is adhered by the thermal transfer roller 83 to the cylindrical electrode 81.
The thermal transfer roller 83 is slowly rotated to dip the firm ill Ike electrolytic solution. A voltage is applied between the counter electrode 86 and the terminal 87 so as to perform electrochemical polymerization. Polymerization continues for a time period during which the film is being dipped in the solution. The polymerized film is peeled from the cylindrical electrode and washed and dried. Tile dried film is then wound.
Instead of adhering the film by the thermal transfer roller, the film can be directly formed by cozen-Jon the roller, thereby continuously forming the conducting film. In addition, an electrode materiel is proposed ~%3~3~7~) according to the present invention which allows Formation of a conducting polymer film of large area. When electrochemical polymerization is performed, the polymer film must be adhered to the electrode and must be easily peeled from the electrode so as to obtain a uniform conducting film of large area when polymerization is completed. However, when a noble metal substrate as previously mentioned is used, the substrate has uniformity but is expensive. In addition, it is often difficult Jo peel the film from the substrate. When a base metal is used, it has uniformity but the film cannot easily be peeled off. When electrochemical polymerization reaction is repeatedly performed, the surface of the base metal electrode is often degraded by a side reaction. When a metal oxide such as IT is used, it has a higher resistaIlce than that of a metal substrate. As a result, a slight resistance distribution of the conducting film occurs.
In order to overcome these problems, a conducting metal oxide layer or a doped semiconductor layer is laminated on the base metal layer so as to constitute the most suitable electrode.
Fig. 10 shows a laminate obtained such that a base metal layer 42 is formed on an insulating substrate 41; and such that an electrically conducting metal old layer or a doped inorganic semiconductor layer I is formed. The base metal layer comprises aluminum, chromium nickel, stainless steel or copper and is formed by ~23~6~) evaporation, sputtering or the like. The thickness of the hose metal layer may slightly vary in accordance with electrical conductivity, but must be more than 500 A so as to obtain a uniform electrically conducting electrochemical polymer.
The electrically conducting metal oxide layer or doped inorganic semiconductor layer is laminated on this hose metal layer. The conducting metal oxide comprising tin oxide, indium oxide, indium tin oxide (IT) or the like is normal formed by evaporation or sputtering.
An inorganic semiconductor may be used as a laminate layer in addition to the metal oxide. In this case, a substantial amount of impurity is doped in a semiconductor layer so as to effectively decrease electrical resistance. Amorphous or polysilicon is the best material for such a uniform semiconductor layer without pinholes. However, germanium or gallium arsenide may be used in place of amorphous silicon. The laminate is formed by CUD, sputtering or the like. An impurity it doped in a corresponding semiconductor material.
Fig. 11 shows a cylindrical electrode for continuously forming an electrically conducting polymer film. In order to continuously form a conducting film by electrochemical polymerization, it is preferable to form an electrode in a drum-like shape Referring to Fig. 11, when an electrically conducting metal oxide layer or a doped inorganic semiconductor layer 53 is formed on a base metal drum 51, a base metal layer 52 is formed on the surface of a drum made of any material, and the electrically conducting metal oxide layer or the doped inorganic semiconductor layer 53 is laminated on the base metal layer 52. A film is formed on the drumlike electrode, and electrochemical polymerization is performed in the electrochemical polymerization tank while the drum is being rotated. The resultant conducting polymer film is peeled from the drum and washed. Thus, a uniform film can be continuously formed, and repeated use of the electrode can be obtained.
In order to make the diffusion of aromatic compound to be polymerized and electrolyte anion in the insulating polymer film muon easier, the film may comprise a porous material. In this porous film the electrolyte and the aromatic compound tend to be diffused, and polymerization is accelerated, thereby obtaining a uniform conducting film for a shorter polymerization time.
A method of preparing a porous polymer film is known wherein a gel of a polymer solution is prepared and a solvent or the like is removed or any foaming agent is used. A porous material prepared by a solvent extraction method or neutron radiation method is commercially available.
Such a porous material can be used as a film which will be made conductive according to the present invention. However, in this case, a porous film must be 6~7~:3 adhered to the electrode. For this reason, various methods may be proposed. Utilizing a simplest method, a porous film is adhered to the electrode through a thin phenol or epoxy adhesive layer. In this case, the phenol or epoxy resin layer is also made conductive.
According to the present invention, when thickness of an electrically conducting film is small, it is uniform and has high electrical conductivity. However, when thickness is increased, the film becomes nonuniform.
In order to solve this problem, a conductivity filler nay be used.
Examples of the filler may include: a carbon material such as carbon powder, carbon fiber and acetylene black; powder or flake of a metal such as aluminum, copper I and stainless steel; a powder or flake of a conducting metal compound such as indium oxide and titanium oxide; a powder or flake of a noble metal such as gold, platinum, rhodium and palladium; and a powder or flake of a base metal such as nickel, stainless steel, and brass. However, a metal such as aluminum and copper is partially subjected to a side reaction when electrochemical polymerization of an aromatic compound is performed. Therefore, these metals are not preferred.
When thickness is increased or miscibility battalion the insulating polymer film and the aromatic polymer material obtained by electrochemical polymerization is poor, a uniform conducting film cannot ye formed. In I

order to improve this, a removable material is premixed in a polymer film when the polymer film is coated on the electrode substrate.
This material is removed before and during the 5 reaction, and a number of small voids are formed in the polymer film. For this reason, the electrolyte and the aromatic compound tend to be diffused in the film, and polymerization is accelerated. As a result, a uniform electrically conducting polymer film is prepared.
The removable material is preferably mixed with the polymer film for the above reason so as to form a uniform film. The removable material may comprise a material ego., low-melting point halogenated hydrocarbon, phthalic android and camphor) which is volatile by heat lo Andre reduced pressure; a material (e.g., an aromatic compound as a raw material for purl, an electrolyte, or an electrolyte-soluble material such as dialkylphthalate) soluble in an electrolytic solution; or a combination of the solvent-soluble material and a solvent (i.e., a combination of sodium chloride and water). The removable material is then removed before and during the reaction The present invention will now be described by way of examples. However, the present invention will not he limited to these examples.
Example 1 As shown in fig. 1, chloromethylated polystyrene to be referred to as a CAMS hereinafter; molecular weight:

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300,000) was coated by spin coating on a substrate 12 having Nose glass to form a film 13. The substrate coaled with the film 13 was illuminated by an Ye lamp for 10 minutes so as to perform CAMS cross linking. This substrate was used as a cathode, and a platinum mesh was used as an anode. The substrate was dipped in the electrolytic solution, and a constant voltage of 1.3 V was applied between two electrodes, thereby electrochernically polymerizing purl.

The electrolytic solution was prepared such that 1 Milwaukee of purl and 0.3 Milwaukee of electrolytic salt (tetraethylammonium tetrafluoroborate) were dissolved in acetonitrile. The electrochemical polymerization was carried out for 10 minutes. Although the Nose glass substrate is covered with the insulating film (CAMS) having a thickness of 1 micron, black polypyrrole was produced on the substrate when electrolysis was completed The insulating film was rinsed with acetonitrile and dried under a reduced pressure for 24 hours.
Thereafter, the insulating film was kept in a dark place.
The resultant CMS/polypyrrole composite film had good adhesion with the substrate and good mechanical strength, as compared with the case wherein polypyrrole was directly precipitated on the Nose glass substrate.

The CMS/polypyrrole film was peeled from the Nose glass substrate. The electrical conductivity of the resultant film was measured. This measurement was performed as follows. Gold was deposited on the CMS/polypyrrole film by using a metal mask so as to constitute a gold electrode having a predetermined area.
Lead wires were connected to the gold electrode, and the electrical conductivity was measured in accordance with a 4-terminal method. The electrical conductivity of the CMS/polypyrrole film was determined to be 5.2 I cm.
Examples 2 to 8 In the same manner as in Example 1, novolak resin examples 2 and 3), resole resin (Example 4), AZ-1350 (Example 5) available from Shipley, REV (room temperature vulcanizing) silicone rubber (Example 6), polyglycidylmethacrylate (Example 7), and butadiene rubber example 8) were spin coated on corresponding conducting substrates. The coated materials were cross linked by heat or high-energy radiation. On the resultant substrates, purl was electrochemically polymerized in accordance with the same technique as in Example 1, thereby obtaining cross-linked polymer/polypyrrole composite films. The thicknesses and conductivities of the resultant films ore s~marized in Table 1. In either case, the film had high electrical conductivity. Reference symbol ERG denotes .
ethylene glyco].

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In particular, the conducting films ox Examples 5 and 8 could be elongated or stretched by over 50~, and the mechanical strength thereof were be greatly improved.
Examples 9 to 15 In the same manner as in Example 1, CAMS was spin-coated on Nose glass and cross linked upon light radiation. This substrate was used as the cathode. The respective substrates are dipped in solutions of thiophene (Example 9), 3-methylpyrrole (Example 10), N-methylpyrrole (Example 11), azulene (Example 12), methyl azulene example 13), porn example ]~) and carbazole (Example 15). A
counter electrode comprised a platinum electrode. As a result, CMS/conducting polymer films were prepared by electrochemical polymerization. These films had higher mechanical strength than the single polypyrrole film in the same manner as in Example 1. The thicknesses and conducti~ities of the resultant films are summarized in table 2. The substrate comprised Nose glass, the cross linking polymer was CAMS, the electrolytic salt was rluoroborate, per chlorate, sulfate or the like.

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Example 16 Chloromethylated polystyrene (to be referred to as CAMS; molecular weight: 300,000) was spin-coated on a Nose glass substrate to a thickness of 1 em. The substrate 5 coated with this film was used as a cathode, and a net-like platinum electrode was used as an anode. The substrate was dipped in the electrolytic solution, and purl was electrochemically polymerized at a constant voltage of 0.9 to 1.5 V. The electrolochemical solution was prepared such 10 that 1 Milwaukee of purl and 0.3 Milwaukee of tetraethylammonium tetrafluoroborate as the electrolytic salt were dissolved in a solution of acetonitrile-water-ethylene glycol (90 : 5 : 5). Electrochemical reaction (polymerization time varied from 5 to 60 minutes. Although the Nose glass 15 substrate was covered with the insulating film, black polypyrrole was precipitated upon application of an electric field, and its thickness was increased. Fig 3 shows the relationship between the polymerization time minutes) of purl and the electrical conductivity pa) of on the resultant film. According to this graph, it was found that when polymerization time changed, electrical conductivity of the film can be changed about 109 Tulsa and that film hurrying a desired conductivity was prepared Example 17 Polyvinyl chloride film was formed by casting on a Nose glass substrate to a thickness or 1.2 em. On the substrate with polyvinyl chloride film, pvrrole was ~3~'7~

electrochemica].ly polymerized in an electrolytic solution for 20 minutes at a voltage of 1.2 V. The electrolytic solution was obtained such that 1 Milwaukee of purl and 0.3 Molly of tetraethylammoniurn per chlorate were dissolved S in a solvent mixture of acetonitrile-tetrahydrofuran-water-ethylene glycol ~58 : 40 : 1 : 1). As a result, polypyrrole was formed. The electrical conductivities of the upper and lower surfaces of the single layer were 8 /Q-cm and 3 /Q-cm.
10 Comparative Example Even if the same fume as in Example 17 was electrochemically polymerized in a solution of acetoni-trile/ethanol (1 : I, the formation of polypyrrole was not observed.
As is apparent from Example 17 and the Comparative Example, the electrochemical polymerization solvent must be optiniized for each resin so as to prepare ?.
uniform illume In other words, the monomer must be sufficiently diffused in an insulating polymer film and 20 must reach the electrode surface. In this Comparative Example, it is suggested that no diffusion occurs since ethanol does not serve as a solvent to cause swilling of polyvinyl chloride film. In the ahove-mentioned exa~llples, electrochemically oxidized polypyrrole can grow in the film 25 when a sufficient space is produced in the insulating polymer film key swelling, thereby obtaining composite films.

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Examples 18 - 58 Thermoplastic resin films shown in Table 3 Lowry coated by spin coating or casting on corresponding Nose glass substrates to a thickness of 1 micron. 1 Milwaukee of S purl and 0.3 Milwaukee of tetraethylammonium tetrafluorobora~e were dissolved in each of the solvents shown in Table 3. On the resultant substrates With the respective resin films purl was electrochemically polymerized in the corresponding solvents for 20 minutes at a voltage of 1.2 V. As a result, black polypyrrole was formed on each of the films. The resultant films were uniform in the same manner as in Example 16.
The thicknesses of the composite films and the electrical conductivities thereof were measured, as shown lo in Table I
Referring to Table 3, the substrate comprised the Lucy glass substrate, polyIilerization was carried out for I
minutes at room temperature. Reference symbol ME denotes methyl ethyl kitten; EGO ethylene glycol; and 3MF, ~,N-dimethylformamide.

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As is apparent from Table 3, it was found that any type of film had high electrical conductivity. Irk thy 5 manner, any thermoplastic resin film coated as a thin film on the substrate can be properly converted to an electrically conducting polymer film by properly selecting composition of an electrochemical polymerization solution.
Therefore, the thermoplastic resin films used in the present invention are not limited to those described with reference to the Examples, but may be extended to arty thermoplastic film.
Example 59 - 83 Thermoplastic resin films shown in Table were coated by spin coating or casting on corresponding Nose glass substrates to a thickness of 1 micron. 1 mop of purl and 0.3 Milwaukee of tetraethylammonium per chlorate or - tetraethylammonium p-toluenesulfonate were dissolved in each of the solvents shown in Table 4. On the resultant substrates with the respective resin films, purl was electrochemically polymerized in the corresponding solvents MU for 20 minutes at a voltage of 1.2 V. As a result, hack po]ypyrrole was formed on each of the films. The resultant films were uniform in the same manner as in example 16.
Thicknesses of the composite films and the electrical conductivities thereof were measured, as shorn in Table 4.
Referring to Table 4, the substrate comprised the Nose glass substrate, polymerization time was 20 minutes 3LZ~'~6~

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Symbols used for the solvents denote the same as in Table 3.

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I 7~3 Examples 84 - 89 Polyvinyl chloride film was costed Nose glass substrates to a thickness of about 1.2 micron in the same manner as in Example 17. These substrates were used as positive electrodes, respectively. 3-methylpyrrole example 84), N-methylpyrrole (Example 85), thiophene (Example 86), azulene (Example 87), methylazulene (Example 88) and porn (Example 89) were dissolved in the respective solvents shown in Table 4. A platinum electrode served as the counter electrode in each of the solvents.
On the substrates each monomer was electrochemically polymerized for 20 minutes. the thicknesses of the resultant films were increased, and the electrical conductivities thereof were also increased. The test results are summarized in Table 5.
Referring to Table 5, the substrate comprise the Nose glass substrate, polyvinyl chloride thickness was about 1 micron, polymerization time was 20 minutes and polymerization temperature was room temperature. The 20 electrolyte in each of the Examples 84 to 87 was 0.3 Milwaukee of tetraetnylammonium per chlorate.

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Examples 90 and 91 1.2 em tuck polyvinyl chloride film was cashed on a glass substrate (Example 90) deposited with micron thick gold, or on an n-type phosphorus-doped silicon substrate (Example 91) having a resisti~-ity of 15 Q.cm.
These substrates were dipped together with the corresponding counter electrodes in a solution obtained such that 3 mollusk of purl and 0.3 Milwaukee of tetraethylammonium p-toluenesulfonate were dissolved in acetonitrile. The substrate was electrochemically polymerized at a voltage of 1.2 V for 20 minutes. As a result, a film was formed on the gold-deposited substrate to a thickness of 1.8 microns, and a film was formed on the n-type silicon substrate to a thickness of 1.65 microns.
The electrical conductivities of these films were 6.0 /Q~cm and 3.2 I cm, respectively. In this manner, union electrically conducting polymers were formed on the metal substrate and on the semiconductor substrate, respectively.
Example 92 A Nose glass substrate was placed in a reaction chamber to which styrenes was introduced at a vapor pressure of 2.5 x 10 Torn. An RF power having a frequency of 13.56 Issue was applied to the reaction chamber. The substrate w-as exposed at a discharge power of 10 W, a gas flow rate of 10 cc~minute, and a substrate temperature of 40C for 15 minutes. A plasma polymerized polystyrene film having a thickness of about 1.0 micron was obtained. This Jo - 45 -~2~l6~

substrate with the film was used as a cathode, and a net-like platinum electrode was used as an anode. These electrodes were dipped in an electrochemical polymerization solution, and purl was electrochemically polymerized at a constant voltage of 1.3 V.
The electrochemical polymerization solution was prepared such that 1 Milwaukee of purl and 0.3 Milwaukee of tetraethylammonium tetra,luoroborate as an electrolytic salt were dissolved in acetonitrile. By applying owlet, polypyrrole was formed on the substrate. A thickness of the composite film was increased. After 5 minutes polymerization, the film was washed and dried. The thickness of the composite film was measured to be about 1.2 microns. The electrical conductivity along -the direction of the film thickness was less than 1 I cam Tune electrical conductivity along the direction of the thickness before polymerization was 10 9 I cm. Therefore, by 5-minute polymerization, conductivity was increased by more than 108 times. However, the resultant film was strongly adhered to the Nose glass substrate, so an accurate electrical conductivity of the conducting film could not be measured.
Example 93 In the same manner as in Example go, a Nose lass substrate coated with a plasma polymerized polystyrene film was electrochem'calll7 polymerized in the same electrolytic solution as in Example 92 for one hour. A a result, a - I -I

black polymer film having a thickness of 2.5 microns was obtained. This film could be peeled from the substrate and had a high electrical conductivity of 35 /Q~cm.
Example 94 A Nose glass substrate was placed in a reaction chamber to which methylmethacrylate was introduced at a vapor pressure of 4 x 10 2 Torn. An RF voltage having a frequency of 13.56 MHz was applied to the reaction chamber.
The substrate was exposed at a discharge power of 10 W, a lo gas flow rate of 20 cc/minute, and a substrate temperature of 20~C for 3 and 15 minutes. Plasma polymerized polymethylmethacrylate films having thicknesses of about I micron and 1.1 microns were obtained. Electrochemical polymerizatioIl was performed for 20 minutes under the same conditions as in Example 92. No polypyrrole was grown on the omicron thick film. However, polypyrxole was uniformly grown on the 0.4-mierorl thick film. This film could be peeled from the substrate. Therefore, the polypyrrole film was deposited on only the electrode side of the substrate, thereby obtaining a two-layer structure.
Electric conductivity of the polypyrrole surface WAS about 50 I em.
Example 95 A Nose glass substrate was placed in a reaction error to which methylmethaerylate was introduced at a vapor pressure of 4 x 10 2 Torn. An RF voltage having a frequency of 13.56 MHz was applied to the reaction chamber.

, - I -The substrate was exposed at a discharge power of 10 W, a gas flow rate of 20 cc/minute, a substrate temperature of 20C. In this case, a cycle consisting of a discharge time of 10 seconds and a non discharge time of 90 seconds was repeated for 60 minutes. A plasma polymerized polymethylmethacrylate film having a thickness of about 1.1 microns was obtained. This substrate was dipped in an electrolytic solution prepared such that 1 Milwaukee of purl and 0.3 Milwaukee of tetraethylammonium tetrafluoroborate were 10 dissolve in a solvent mixture of acetonitrile :
dimethylsulfoxide (95 : 5). On the substrate, purl was electrochemically polymerized at a voltage of 1.2 V for 20 minutes. A black polypyrrole-plasma polymerized polymethylmetacrylate composite film having a thickness of 15 104 microns was obtained. Resistance of this film along its thickness was very small, and the film had good adhesion. The film was partially cut from the substrate, and its electrical conductivity was 2.5 /Q-cm.
Example 96 Nose glass substrate coated with the same film as in Example 95 was dipped in a solution of acetonitrile-dimethylsulfoxi.de (95 : 5) dissolved with 1.5 mollusk of thiophene and 0.3 Milwaukee of Axle and was electrochemically polymerized at a voltage of 1.5 V for 20 minutes. As a result, a grown film having a thickness of 1.85 microns was owned. This film had good adulation of with the substrate. The film was partially cut from the substrate, and its electrical conductivity was 1.2 I cm.
In the above example, the film was entirely changed conductive. However, when polymerization time is properly set, the film has only one conducting Sirius.
This example will be described below.
Example 97 A polyvinyl chloride film (molecular weight or 70,000) was coated by casting on a Nose glass substrate to a thickness of about 3 microns. This substrate was dipped together with a platinum counter electrode in an electrolytic solution obtained such that 0.3 Milwaukee of tetraethylammonium p-toluenesul~Eonate and 1 Molly of purl were dissolved in a solvent mixture of acetonitrile : nitrobenzene (3 : 1). On the substrate purl was electrochemically polymerized at a voltage of 1.5 V for 30 minutes, thereby precipitating black polypyrrole. The resultant film could be easily peeled from the Nose glass substrate and was soft, mechanically strong, smooth and glossy. The resultant film was partially cut from lie substrate, and the electrical conductivities of the suffix side contacting with the electrolytic solution) and the electrode side (contacting with the Nose glass substrate) of the elm were measured by the 4-terminal method The conductlvities of the surface and electrode sides were 10 10 /Q-cm and 12 /Q-cm, respectively. This -film could be 'Lo -o elongated. foe separation between conduction layer and insulating layer was observed.
Example 98 A vinylchloride-vinylidene copolymer 182 : 18) was coated by casting on a Nose glass substrate to a thickness of 2.5 microns. The substrate coated with this film was dipped together with a platinum counter electrode in an acetonitrile solution dissolved with 0.3 Milwaukee of tetraethylammonium per chlorate and 1 Milwaukee of purl. On the substrate purl was electrochemically polymerized at a voltage of 1.6 V for 30 minutes. A glossy black film was obtained and could be easily peeled from the substrate.
The electrical conductivity of the surface side was less than 10 10 I cm, and the electrical conductivity of electrode side was 8 /Q-cm. Even if this film was elongated to 200~, phase separation did not occur, nor dip the polypyrrole layer peel off Example 99 A polyvinylidenefluoride film was coated on a Nose glass substrate to a thickness of 1.8 microns. This substrate was dipped together with a platinum electrode in an acetonitrile-ethylene glycol solvent mixture (9 : 1) dissolved with 0.3 Milwaukee of tetraethyleneammonium p toluenesulfonate and 1 Milwaukee of purl. On the substrate, purl was electrochemically polymerized at a voltage of 1.8 V for 30 minutes, thereby precipitating black polypyrrole. The black film could be easily peeled from the substrate and had high mechanical strength.
- The electrical conductivity of the surface side was less than lo lo /Q-cm, and the electrical conductivity S of the electrode side was 4.5 I cm. The resultant film could be elongated to at least 200~, but no film separation could be observed.
As shown in these second examples, the film of which conductivities of both sides greatly differ from each lo other can be obtained.
Example lo Polyvinyl chloride molecular weight of 100,000) was cast from a methyl ethyl ketone-tetrahydrofuran (l l) on an IT substrate, thereby obtaining six samples lo polyvinyl chloride films each having a thickness of about lo microns.
The respective substrates were dipped in a solution obtained by dissolving l Milwaukee of purl and 0.3 Milwaukee of tetraethylammonium p-toluenesulfonate in acetonitrile and purl was electrochemically polymerized at a voltage of lo V for 2 minutes, I minutes, 6 minutes, 8 minutes, lo minutes and lo minutes, respectively. The resultant films were washed with ,acétcnitrile and dried. Resistances of the both film surface were measured. The results are illustrated in Fig. 12. The electrode side shows high conductivity only by 2 minutes polymerization. The surface resistance was ~L~3~7~3 decreased in accordance with a decrease in polymerization time. On the other hand, the surface side remained insulative at the beginning. However, by 4 to 5 minutes polymerization, the surfaces showed conductivity. In other words, two-minute polymerization produced the structure shown in Fig. PA, and four- or five-minute polymerization produced the structure shown in Fig 2B. In practice, the structures shown in Figs. PA and 2B were confirmed by Augur electron spec~roscopy of the film.
Fig. AYE shows the thickness profile of a polyvinyl chloride-polypyrrole film having a conducting electrode side and an insulating surface side. Carbon and chlorine were Imiformly distributed along the thickness of the film, while nitrogen contained in polypyrrole was detected from an intermediate portion of the film. Lucy result confirms that this film has a structure shown in Fig. I On the other Rand, referring to Fig. 13B, carton, chlorine and nitrogen were uniformly distributed along the thickness of a polyvinyl chloride-polypyrrole film in which both sides are conductive. Therefore, two polymers were combined to constitute an electrically conducting polymer film.
These films could be easily peeled from the IT
substrates. The surfaces of these films were smooth and had high mechanical strength. Each of these films could be elongated by about 1.2 times.

I ~316 I
example 101 This example shows that a PVC film having a thickness of 30 microns was made conductive.
Polyvinyl chloride (PVC) was costed on an IT
substrate to form a film having a thickness of 30 em. This substrate was dipped in an acetonitrile-nitrobenzene (4 13 solution containing 1 Milwaukee of purl and 0.3 Milwaukee of tetraethyl ammonium p-toluenesulfonate. On the substrate purl was electrochemically polymerized at a voltage of 5 V for 20 minutes. The resultant film was cleaned and dried. The dried film was peeled from the electrode and was subjected to resistance measurement in accordance with the 4-terminal method. A resistance of the electrode side was 250 Q, and that of the surface side was ~80 Q. This film was entirely conductive.
Example 102 This example shows that a polyvinylidene fluoride film having a practical thickness was used to obtain an electrically conducting polymer film.
Chromium and gold were deposited on a glass substrate to thickrlesses of 100 A and 1,000 A to constitute chromium and gold electrodes, respectively. An N,N-dimethylformamide solution of poiyvinyliderle fluoride was coated to form a polyvinylidene fluoride film having a thickness of 15 microns. The electrode with the film assay dipped in an acetonitrile-ethanol (1 1) solution containing 1 Milwaukee of purl and 0.3 Milwaukee of i I I

tetraethylammonium tetrafluoroborate for 5 minutes. On the electrode pyxrole was e]ectrochemically polymerized at a voltage of 5 V and a charge density of 0.03 C/cm2 to obtain a composite polyvinylidene fluoride film. The resultant film was washed, dried and peeled from the substrate. This film had a thickness of 18 microns. Only the electrode side was conductive (surface resistance of 420 Q), and the surface side was insulative and had a resistance of more than 10 MY. Since glass transition point of polyvinylidene fluoride was lower than room temperature, the film had flexibility and was glossy.
In order to test that the mechanical strength of this film was improved, elongation and the Young's modulus were measured. Results are summarized in Table 6 below.

lo Table 6 Young's Modulus and Elongation Young's modulus (dyn/cm2) Elongation I%) _ __ Polyvinylidene 10 fluoride film 1.7 x 10 65%

Polypyrrole/ 10 BF4 film 1.2 x 10 5%
_ _ Hybrid con 10 20 dueling film 3.2 x 10 60%
(0.03 C/cm _ _ _ .
Note: Film thickness of each film was 18 microns.
The Young's modulus of the composite conducting film was about twice that of the polyvin~liden~ fluoride film and about two and half times that of the polypyrrole/BF4 film. The elongation of the composite film was 60% which was almost the same as that of the PVDF film and much greater than that I of the polypyrrole film As is apparent from -the above description, when a high quality film such as the polyvinylidene fluoride film was used, a highly conducting film having high mecharlical strength was obtained.
Example 103 This example shows that a thick conducting polymer film was obtained by using polyvinylidene fluoride.
Chromium and gold were deposited on an IT
substrate having a sheet resistance of 20 Q/O to O O
thicknesses of 100 A and 500 A. The IT substrate deposited with chromium and gold was used as an electrode.
A polyvinylidene fluoride film having a thickness of 150 microns was cast on the substrate.
This film was prepared such that the substrate was dipper in an acetonitrile-ethanol (3 : 2) solution containing 1 Milwaukee of purl and 0.5 Milwaukee of tetraethyla~nonium p-toluenesulfonate for 10 minutes and was electrochemically polymerized at a voltage of 7 V and a charge density of 0.24 C/cm2.
The resultant film was washed, dried and peeled off from the substrate. Only the electrode side was conductive, and a surface resistance was 620 Q.

Comparative Example Even i' a voltage of 2 V was applied to the same film as in Example 95, a current did not substantially flow ~3~'7~

there through. the surface resistance of the electrode side was more than 50 kQ. In this manner, when the film thickness was increased, the voltage is better to be slightly increased.
The following Example shows the case wherein two types of insulating polymer films were laminated, and the resultant laminate is changed conductive by an electrochemical polymerization, thereby preparing a composite two-layer conducting polymer film.
Example 104 Chloromethylated polystyrene (to be referred to as a CAMS hereinafter; molecular weight: 300,000) was coated on a Nose glass substrate to a thickness of 1.5 microns.
Light from a 500-W Ye lamp irradiated the film to cross link the CAMS film. A cyclohexane~chlorobenzene (2 : 1) mixtllre of ethylene-vinylacetate 188 : 12) copolymer was spin-coated on the film to form a film having a thickness of 1.0 micron. The resultant substrate was dipped together with a platinum mesh electrode as the counter electrode n I an acetonitrile-tetrahydrofuran-chlorobenzene (8G : 10 : 10) solvent mixture added with 1 Milwaukee of purl and 0.3 Molly of tetraammonium tetrafluoroborate as an electrolyte. On the substrate, purl was electrochemically polymerized at a voltage of 2.0 V for 20 minutes to precipitate black polypyrrole on the substrate.
The resultant film had a thickness of 2.9 microns and killed be easily peeled from the Nose glass substrate. The film I

structure had a two-layer structure wherein a hack conducting film obtained by mixing CAMS and po]ypyrrole and an EVA film were laminated. The EVA film had high mechanical strength, so that the resultant two-layer structure also had high mechanical strength. An electrical conductivity of the composite CMS-polypyrrole film was 4.3 cam and the EVA film was insulative and had an electrical conductivity less than 10 7 I ant. In the two-layer film, since cross linked CAMS was slightly swelled in the casting EVA solvent, CAMS and EVA were slightly mixed at an interface thereof. As a result, adhesion between these two layers was good r nor would the layers peel from each other at their interface.
Example 105 jive Nose glass substrates each coated with two films consisting of a CAMS -film (thickness of 1.5 microns) and an EVA film (thickness of lo microns) in the same manner as in Example 104 were prepared These substrates were dipped in the same electrochemical polymerization solution as in Example 104 and purl was electrochemically polymerized at a voltage of 2.0 V for 10 seconds, 30 seconds, 2 minutes, 10 minutes and 60 minutes, respectively. When the polymerization time was increased, the film thickness was increased. The respective substrates were covered with uniform, smooth EVA films.
Each resultant film comprised a composite CMS-polvpyrrole film and was peeled from tile corresponding substrate. The I I

electrical conductivities of the CMS-polypyrrole surfaces of the respective composite films were 2 x 10 4, 4 x 10 2, 1 x 10 1, 3~2 x 10 1 and 9.2 crown. The electrical conductities of these films were found to be controlled ill accordance with the polymerization time.
Example 106 Polyglycidyl methacrylate (to be referred to as EGMA hereinafter; molecular weight: 85,000) was coated 'o a thickness of 0.2 micron on an n-type silicon substrate having a resistivity of 5 I cm. The PUMA film was baked at a temperature of 200C for 30 minutes. polyvinyl carbazole (to be referred to as PVCZ hereinafter; molecular weight: 450,000) was coated on the PUG film to a thickness of 1.0 micron. The resultant substrate was used as a positive electrode and was dipped together with a platinum mesh electrode as a counter electrode in an acetonltrile solution dissolved with 1 Milwaukee of thiophene and 0.2 Milwaukee of tetraethylammonium per chlorate. On the substrate thiophene was electrochemically polymerized in a nitrogen gas atmosphere at a voltage of 3.0 V for 20 minutes, thereby precipitating bluish black polythiophene on the substrate. This film had a substantially uniform thickness of 1.5 microns and had good adhesion with the substrate.
The film was cut from the substrate and subjected to measurement of electrical conductivity from the surface thereof. An electrical conductivity was 0.75 cam Polythiophene was hybridized in two layers of the PAM and PVCZ layers.
Example 107 In the same manner as in Example 106, PEA and S PVCZ were coated on an n-type silicon substrate to thicknesses of 0.8 micron and 0.2 micron, respeCtiJe]y.
EVA was then coated to a surface of the PVCZ layer to a thickness of 1.2 microns. The resultant substrate was dipped together with a platinum mesh electrode as a counter electrode in an acetonitrile-tetrahydrofuran-chlorobenzene rug : 1 : 1) solvent containing 1 Milwaukee of purl and 0.4 Milwaukee of tetraethylammonium per chlorate. On the substrate purl was electrochemically polymerized at a voltage of 2.0 V for 35 minutes. Polypyrrole was precipitated on the substrate and the composite film had a thickness of 2.6 microns. The resultant film had good adhesion Will the substrate. The surface of tile film was glossy in the same manner as in the state before electrochemical polymerization was performed. The film was ED cut off from ache substrate, and the structure and electrical conductivity of the film were examiIledO The EVA
layer was laminated on a composite PGMA/PVCZ layer mixed with polypyrrole. The PGMA/PVCZ surface and the EVA
surface had electrical conductivities of 16 /Q~cm and 2 x 10 8 I cm, respectively. When the laminate film formed on this substrate and the phlegm without the EVA film of Example 105 were exposed to air for 30 days, electrical I

conductivity of the film in Example 105 was decreased by 10~, while the film conductivity of Example 106 was decreased by only 2%. This indicated that the EVA film served as a protective film, and that the stability of the electrically conducting polymer could be improved by the laminate structure.
Example 108 Novolak resin (molecular weight of 8,000) was coated on a Nose glass substrate to a thickness of 0.2 micron and was baked at a temperature of 200C for 30 minutes. Poly-2-vinylnaphthalene (molecular weight of 18,000) was coated on the novolak resin film to a thickness of 1.1 microns. The resultant substrate was dipped in an acetonitrile-water-ethylene glycol (98 : 1 : 1) solution added with 1 Milwaukee of 3-methy,pyrrole and 0.4 Milwaukee of tetraethylammonium p-toluenesulfonale. On the substrate, 3-methylpyrrole was electrochemically polymerized at a voltage of 1.4 V for 20 minutes to precipitate bluish black poly-3-methylpyrrole. The resultant film had good adhesion with the substrate and was entirely mixed with conducting poly-3-methylpyrrole. The film was peeled from the substrate, and its electrical conductivity was 0.5 I cm.
Example 109 Chromium and gold were deposited on a glass O
25 substrate to thicknesses of 100 A and 500 A. A polyvinyl carbazole film having a thickness of 5 microns was prepared by casting from a tetrallydrofuran solution of polyvinyl -- I --I

carbazole (molecular weight of 4~0,000). The resultant substrate was dipped together with a platinum-plated titanium mesh electrode as a counter electrode in an acetonitrile solution containing 1 mollusk of purl and 0.3 Milwaukee of tetraethylammonium tetrafluoroborate. The purl was electrochemically polymerized at a voltage of 3.0 V for a predetermined period of time. The polymerized film was washed, dried and peeled from the substrate. The visible light absorption spectrum of the film was measured by a double beam spectrophotometer W IDEC-505 available from JASCO. The surface resistivity was measured by 4-terminal method. The surface resistivities to cam of various films were plotted along the abscissa, and to transmittances (~) thereof were plotted along the ordinate in Fig. 4. In the films prepared in Example 109, the transmittance was more than 50~, and the electrical conductivity was up to a high conductivity of 1 AYE cm.
In this manner, an electrically conducting film with a high transmittance could be prepared and could be used as a transparent antistatic film.
However, it is difficult to obtain a highly conductive polymer film with a high transmittance When such a film has a large thickness, only one surface can be changed electrically conductive.
Example 110 A cyclohexanone solution of vinylidene ~3~6~

chloride-vinylchloride copolymer (80 : 20) was cast on an IT substrate to prepare a 35-micron film. The substrate with the film was dipped in an acetonitrile-nitrobenzene (4 : 1) solution containing 1 Milwaukee of purl and 0.3 rnol/g~
5 of tetraethylammonium per chlorate and purl was electrochemically polymerized at a voltage of 2 V for 1.5 minutes (0.02 C/cm2~. The resultant film was washed, dried and peeled from the substrate and subjected to measurement of a surface resistance and a transmittance. The electrode side of the film was conductive to a surface resistance of 2,500 Q, and the film surface side was insulative to a surface resistance of more than 10 Q. A transmittance of the film was 72~. In this manner, a film having a large thickness, one conducting surface and a high transmittance 15 was obtained.
Example 111 Chromium was deposited on a glass substrate to a thickness of ~00 A. An indium tin oxide (IT) layer was sputtered on the chromium film to a thickness of lg500 A
20 These layers were used as the electrode side for electrochemical polymerization. A tetrahydrofuran solution of polyvinyl chloride was cast on the surface of' the resultant substrate to form a polyvinyl chloride film hazing a thickness of 35 microns.
I On the other hand, an acetonitrile-nitrobenzene I : Jo solution was prepared as an electrochemical ~231~

polymerization solution containing 1.5 mollusk or purl and 0.4 Milwaukee of tetraethylammonium p-toluenesulfon~te~
The electrode with the polyvinyl chloride film was dipped together with a platinum-plated titanium mesh electrode as a counter electrode in the electrochemical polymerization solution. A voltage of 2.0 V was applied between two electrodes, and electrochemical polymerization was performed for 2 minutes. A resultant film was washed, dried and peeled from the electrode. At this stage, the electrode side of film was conductive. Then, the surface side of the film was thermally slicked to the electrode surface at a temperature of 60C. Again, the electrode with the film was dipped together with the platinum-plated titanium mesh electrode in the electrochemical I polymerization solution and the electrochemical polymerization was carried out at a voltage of 2.0 V for 2 minutes. thus, both sides Ox film was changed conductive - A resultant Film was washed, dried and peeled from the electrode. The electrical resistance and transmittance of the film were measured. The results are summarized in Table 7.

'~3~7~

Table 7 Thickness 35.2 to 35.5 microns .
Sheet resistance of 4.2 to 5.0 cry]
upper surface *l Sheet resistance of 4.5 to 5.3 kQ/
S lower surface *l Resistance along thickness 108 Q
__ ._ __ Transmittance t633 no) 52%
__ *l The surface of the film which contacts the electrode in the first elec~rochemical polymerization is defined as the upper surface, and the surface which contacts the electrode in the second ele¢trochemical polymerization is defined as the lower surface. (A square indicates 1 cm Jo As is apparent from Table 7, the conductive property was attributed to the surface and electrode sides of the film and the portion along the direction of thickness of the film indicated a high resistance. The film had a high transmittance of more than 50 Example 112 An N,N-dimethylformamide solution of polyvinylidene fluoride was cast on the same electrode as in Example 111 to form a film hazing a thickness of 15 microns.
on the other hand, a nltroben~ene-ethanol (5 lo solution containing 1 Milwaukee of 3-methylthiophene and 0.3 Mohawk of tetraethylar~-nonium per chlorate was prepared.

I I

The electrode with the polyvinylidene fluoride film was dipped in the electrochemical polymerization solution. A voltage of 4.0 V was applied between the electrode with the polyvinylidene fluoride film and the platinum-plated titanium mesh electrode, and polymerization was performed for one minute to prepare a 3-methylthiophene film. This film was washed, dried and peeled from the electrode.
Then, the surface side of this film was thermally slicked to the electrode surface. The electrode was dipper in an electrochemical polymerization solution of 3-methylthiophene and electrochemical polymerization was carried out at a voltage of 4.0 V for one minute, thereby polymerizing methylthiophene. The resultant film was washed, dried and peeled from the electrode. The electrical resistance and transmittance of the film were measured. The results are summarized in Table 8.
Table 8 .
Thickness 15.5 to 15.8 microns ___ 20 Sheet resistance of 7.4 to 8.6 kiwi upper surface __ Sheet resistance of 7.5 to 8.6 kiwi lower surface *l Resistance along thickness > 108 Q
, Transmittance ~633 no) ¦ 43%
As is apparent from Table 8, electrical conduction was attributed to the surface and electrode sides of the film A portion along the direction of I

thickness of the film indicated a high resistance. The film had a high transmittance of more than 62~.
The following example will be suitable for continuous formation of an electrically conducting polymer film.
Example 113 A polyvinylidene fluoride film having a thickness of 12 microns was set in the manufacturing apparatus shown in Fig. 9. The stainless steel thermal transfer roller 88 was housed to a temperature of 50C. A film was transferred to a drum-like electrode trade of a platinum-plated titanium drum An electrochemical polymerization solution comprised an acetonitrile-ethanol to : 1) solution containing 2.0 molslQ of purl and 1.0 Molly of tetraethylammonium per chlorate. The film coated on the drum-like electrode was subjected to electrochem-cal polymerization at a voltage of 3.5 V for 10 minutes. The resultant film was washed with water, air dried, and wound The surface side of the resulcar.'c film had a resistance of 800 Q, and the electrode side thereof had a low resistance ox 350 Q.
Example 11~
Chromium and indium tin oxide (IT) were deposited on a glass substrate to thicknesses of 100 A and 500 P., thereby constituting an electrochemical polymerization electrode. A cyclohexanone solution containing 15 parts b weight of polyvinylidene fluoride I 76~

and heated at a temperature of 130C was cast on the electrode. The electrode with film was dipped in ethanol and dried to obtain a translucent porous film having a thickness of 0.5 mm. A porosity of this film was 45%.
On the other hand, an acetonitrile-N,N~dimethylformamide (9 : 1) containing 1 Molly of purl and 0.3 Milwaukee of tetraethylammonium tetrafluoroborate was prepared as an electrochemical polymerization solution. The electrode with the film was 10 dipped in this solution. A voltage of 2.5 V was applied between this electrode and a platinum mesh electrode as a counter electrode for 30 minutes, thereby polymerizing purl.
Black conducting polypyrrole was precipitated on 15 the electrode. The film was removed from the electrode, and electrical conductivities of the portion along the direction of thickness, the lower surface and the upper surface were measured to be 4.2 I cm, 6.5 I cm and 3.4 /Q~cm. In this manner, the film was entirely 20 conductive.
Example 115 A methylisobutylketone solution of polyglycldyl methacrylate was spin-coated on an electrode substrate prepared in the same manner as in Example 114 to form a 25 polyglycidyl methacrylate film having a thickness of 2 microns. A porous polycarbona-te film NUCLEPORE (trade name available from NUCLEPORE Corp. and having a thickness of 1 mm was bonded by thermocompression on the pellucidly methacrylate film. The resultant substrate was heated in a nitrogen atmosphere at a temperature of 150C for 30 minutes.
On the other hand, an acetonitride solution containing 1 Milwaukee of thiopherle and 0.4 Molly of tetraethylarNmoniurn per chlorate was prepared ho an electrochemical polymerization solution. The electrode substrate with the film was dipped together with a platinum mesh electrode as a counter electrode in this solution A
voltage of 4.0 V was applied between these two electrodes to form polythiophene. The resultant film was peeled from the substrate, and its electrical conductivity was measured. An electrical conductivity along the direction Of thickness o, the film was 0.8 cam an electrode side thereof was 0.4 /Q-cm, and a surface side thereof was 0.25 /Q~cm~ A substantially uniform electrically conducting polymer film was obtained.
Example 116 A tetrahydrofuran solution was prepared by mixillg polyvinyl chloride resin and carbon black powder having a particle size of 0.2 to 3 microns at a volume ratio of 3 : 1. Chromium and gold were deposited on a glass O O
substrate to thicknesses of 100 A and 1,000 A, and indium tin oxide was sputtered thereon to a thickness ox 2,000 Al thereby preparing an electrochemical polymerization electrode. The tetrahydrofuran solution was coated on the ~l~3~6~7~

electrode by a doctor blade to obtain a carbon blaek-containing polyvinyl chloride film to a thickness of 50 microns and was oven dried at a temperature of 80C for 15 minutes.
On the other hand, an aeetonitrile-tetrahydrofuran (2 : 1) solution containing 1 Milwaukee of purl and 0.4 Milwaukee of tetraethylammonium p-toluenesulfonate was prepared as an eleetrochemical polymerization solution. A voltage of 3.5 V was applied to the electrode with the film and the counter electrode in the eleetroehemieal polymerization solution for 15 minutes, thereby polymerizing purl. The resultant film was obtained such that carbon black and polypyrrole were dispersed in polyvinyl chloride and could be easily peeled lo from the electrode.
The film had an electrical conductivity of 5 x 10 3 /Q-cm before eleetroehcmical polymerization However, when ele~troehemical polymerization was performed, an electrical conductivity of the electrode side was 25 I em, and the surface side had an electrical conductivity of 22 I em. As a result, a highly conductive uniform polymer film before polymerization was prepared.
Although the film before polymerization was brittle, the polymerized film dispersed with polypyrrole had high mechanical strength.
Comparative Example - A polyvinyl chloride film was coated on the same _ I _ Lo 3~6 electrode as in Example 116 to a thickness of 50 microns and was dried at a temperature of ~0C for 15 minutes.
Purl was electrochemical]y polymerized on the electrode with the film in the same manner as in Example 115. The resultant film was obtained such thwack polypyrr~le was dispersed in polyvinyl chloride. The film was peeled from the substrate. An electrical conductivity of the electrode side was 12 I cm, and that of the surface side was 3.5 /Q-cm.
When carton black was not contained in the resultant polymer film, the electrical conductivity was decreased to half, and a difference between the electrical conductivities of the two surfaces was great.
Example 117 A methyl ethyl kitten solution was prepared by mixing polystyrene resin and tin oxide powder having a particle size of 0.2 to 0.5 micron at a volume ratio of 3 : 1. The solution was coated by a doctor blade on the same electrode as in Example 115 to form a tin oxide-containing polystyrene film having a thickness of I
microns. This film was dried in an oven at a temperature of 100C for 15 minutes. On the other hand, an acetonitrile-methyl ethyl kitten containing 1.2 mollusk or thiophene and 0.4 Milwaukee of tetrabutylammonium p-toluenesulfonate (2 : 1) was prepared as an electrochemical polymerization solution. The electrode with the film was dipped in this solution for 15 muons.

A voltage of 4.0 V was applied between the electrode with the film and a platinum-plated titanium mesh electrode as a counter electrode for 20 minutes to electrochemically polymerize thiophene. The resultant film was obtained such S that tin oxide and polythiophene were dispersed in polystyrene and the film could be easily peeled Loom the electrode. An electrical conductivity of the film before polymerization was 2 x 10 5 I cm, However, after polymerization the electrical conductivity was increased to 3.2 I cm. In addition, the mechanical strength of the film was also improved.
example 118 A solution obtained by mixing nickel powder in an ethylene vinyl acetate resin at a volume ratio of 3 as bonded by thermocompression using a thermal transfer roller to form a film having a thickness of 60 microns on the same electrode as ill Example 115.
On the other hand, an acetonitrile-tetrahydrofuran-chlorobenzene I
containing 1 Milwaukee of purl and 0.4 Milwaukee of tetraethylammonium per chlorate was prepared as an electrochemical polymerization solution. A voltage of 3.3 V was applied between the electrode with the film and a platinum-plated titanium mesh electrode as a counter electrode in the electrochemical polymerization solution for 20 minutes, thereby polymerizing purl. The resultant film was obtained such that nickel powder and I

polypyrrole were dispersed in an ethylene-vinylacetate copolymer and could be easily peeled from the electrode.
An electrical conductivity of the film before electrochemical polymerization was 4.5 x 10 5 I cm.
However, after electrochemica] polymerization a conductivity of the electrode side was 18 Jo cm, and that of the surface side was 12.5 /Q-cm. A highly conduct uniform polymer film was obtained.
The mechanical strength of the film was greatly improved.
Example 119 A methyl ethyl kitten solution obtained by mixing I by weight of CBr4 in polyvinyl chloride (molecular weight of 70,000) was cast on a glass substrate deposited with gold having a thickness of 500 A to form a film having a thickness of about 50 microns. The substrate with the realm was heated at a temperature of 100C for 20 minutes to remove CBr4. Thereafter, the substrate was dipped in an acetonitrile solution containing OWE Milwaukee of I tetraethylammonium per chlorate and 1 Milwaukee of purl. The deposited gold film was used as a cathode, and a platinum mesh electrode was used as a counter electrode. A voltage of 3.0 V was applied between the two electrodes fox 10 minutes to perform electrochemical polymerization. As a result, black polypyrrole was formed on the substrate. The resultant film was washed, dried and peeled from the substrate. The electrical conductivities of the electrode 67~

and surface sides were measured by the terminal method.
An electrical conductivity of the electrode side was 12 /Q~cm, and that of the surface side was 7.5 /Q-cm. In this manner, the entire film was made conductive.
Comparative Example A methyl ethyl kitten solution was cast on a glass substrate deposited with gold having a thickness of 500 A to form a polyvinyl chloride (molecular weight of 70,000) film having a thickness of 50 microns. This film lo was subjected to electrochemical polymerization in the same manner as in Example 111, and polypyrrole was precipitated on the substrate. An electrical conductivity ox the electrode side was 5.0 /Q-cm, and that of the surface side was 10 12 /Q-cm which represented insulative property.
This indicated that polypyrrole was not grown to the surface of the film.
Example 120 A chlorobenzene solution obtained by adding 12 by weight of phthalic android in an ethylene-vinyl acetate I : 18) copolymer was cast on a glass substrate deposited with gold having a thickness of 500 A in a thermostat kept at 50C, thereby obtaining a film having a thickness ox 25 microns. The substrate with the film was - placed in a vacuum oven at a reduced pressure of 1 In fur 15 minutes to remove phthalic android. Then the substrate was dipped in an acetonitrile-chlorobenzene-cyclohexane (98 : 1.5 : 0.5) ~LZ~6~7~

containing 0.3 Molly of tetraethylammonium per chlorate end 1 Milwaukee of purl. The deposited gold layer was used do a cathode, and a platinum mesh was used as an anode. Purl was electrochemically polymerized at a voltage of 3.5 V 'ox 10 minutes. The resultant film was washed, dried and peeled from the substrate. The electrical conductivities of the films were measured in accordance with the 4-terminal method. The electrical conductivity of the electrode side was 12 I cm, and that of the surface size was 8 I cm. In this manner, the resultant film had a high electrical conductivity This indicated that polypyrrole was grown throughout the film and had reached its surface.
Comparative Example In the same manner as in Example 120, by using a chlorobenzene solution of an ethylene-vinyl acetate (82 : 18) polymer, a film having a thickness of 22 microns was formed on a gold-deposited glass substrate. Purl was electrochemically polymerized in the same manner as in Example 112. No polypyrrole was formed, and two surfaces of the film were insulative.
Example 121 A methyl ethyl kitten solution obtained by adding 10% by weight of camphor to polystyrene (molecular weight of 350,000) was cast on a glass substrate deposited with platinum hazing a thickness of 5Q0 A, thereby obtaining a film having a thickness ox 85 microns. The substrate with I I

the film was exposed in a vacuum oven at a reduced pressure of 1 mmHg and a temperature ox 70C for 5 minutes to remove camphor. Thereafter, the substrate was dipped in an acetonitrile solution containing 0.5 Milwaukee of tetraethylammonium p-toluenesulfonate and 1.2 mollusk of thiophene. The deposited platinum layer was used as a cathode, and a platinum mesh electrode as a counter electrode was used as an anode. Thiophene was electrochemica~ly polymerized at a voltage ox 4.0 V for lo minutes to precipitate blue polythiophene. The resultant film was washed, dried and peeled from the substrate. The electrical conductivities of the electrode and surface sides of the film were measured in accordance with the terminal method. An electrical conductivity OX the electrode side was 1.5 I cm, and that of the surface side was 0.95 /Q-cm. The entire film was made highly conductive.
Comparative Example A methyl ethyl kitten solution of polystyrene 20 (molecular weight of 350,000) was cast on a substrate deposited with platinum having a thickness of 50G A, thereby obtaining a polystyrene film having a thickness of 80 microns. The film was electrochemically polymerized in toe same manner as in Example 113, and polythiophene was precipitated on the substrate. The electrical conductivities of this film were measured in the same manner as in Example 1]3. A conductivity of the electrode ~3~:3'7~

side was 1.3 /Q-cm, and that of the surface side thereof was insulative and less than 10 lo I cm.
Example 122 An acetone solution obtained by adding 15 parts by weight of purl to 100 parts by weight of a polyvinyl chloride was costed on a glass substrate deposited with gold having a thickness of 700 A, thereby obtaining a pyrrole-containing polyvinyl chloride copolymer film having a thickness of 45 microns.
The substrate with the film was dipped in an acetonitrile solution containing 1 Milwaukee of purl and 0~4 Milwaukee or tetrabutylammonium per chlorate for 10 minutes.
Electrochemical polymerization was then performed at a voltage ox 2.5 V for 10 minutes, thereby precipitating polypvrrole.
The electrical conductivities of the film w no measured. An electrical conductivity of the electrode side was 8 I cm, and that o, the surface side assay 6.5 I cm.
In this manner, a substantially uniform conducting film was obtained.
Example 123 A tetrahydrofuran-cyclohexanone (1 : 1) solution containing 18 parts by weight of tetrabutyla~onium per chlorate with respect to 100 parts by weight of a vinylidene chloride-vinylchloride (70 : 30) polymer was cast on a glass substrate deposited with gold having a thickness or 700 A, so that a film containing >~7(3 tetrabutylammonium per chlorate and having a thickness of 45 microns was obtained.
When purl was elec-trochemically polymerized on the substrate with this film in the same manner as in Example 111, black polypyrrole was obtained.
Electrical conductivities of this film were measured. A highly conductive film was obtained wherein electrical conductivity of the electrode side was 5.5 /Q-cm, and that of the surface side was 4.8 /~cm.
In the vinlylidene chloride-vinyl chloride copolymer film which did not contain tetrabutylammonium per chlorate, an electrical conductivity of the surface side was less than 10 12 cam In Examples 114 and 115, since the electrochemical polymerization solution consisted of purl an tetrabutylammonium per chlorate, the electrochemical polymerization solution would not be contaminated even if purl or tetrabutylammonium per chlorate was contained in the film. However, even if other materials dissolved in the electrochemical polymerization solution were mixed in the film, the save effect could be obtained.
example 124 An aqueous solution containing 20 parts by weight of sodium chloride with respect to 100 parts by weight of polyvinyl alcohol (molecular weight of 120,000) was cast on a glass substrate deposited with platinum having a I

thickness of 1,000 A to obtain a polyvinyl alcohol film containing sodium chloride and having a thic]clless ox 20 microns. The substrate with this film was heated at a room temperature for 10 minutes and was dipped in water at a room temperature for 10 minutes to remove sodium chloride.
Thereafter, the substrate was dipped in an acetonitrile-water-ethylene glycol (70 : 10 : 203 solution containing 1 Milwaukee of purl and 0.4 Milwaukee of tetrabutylammonium chloride. A voltage of 3.2 V was applied between the electrodes to electrochemically polymerize purl for 10 minutes. Electrical conductivities of the resultant film were measured. A
substantially uniform highly conductive polymer film was prepared wherein an electrical conductivity of the lo electrode side was 12~0 /Q~cm, and that of the surface side was 8.5 /Q-cm.
Po~.ymerizatlon was performed lo polyvinyl alcohol which did not contain sodium chloride under the same conditions. In this case, polypyrrole was slightly precipitated on the electrode side, and the surface side was kept insulative.
Example 125 A tetrahydrofuran solution obtained by adding lo.
by weight of dioctylphthalate to polyvinyl chloride 25 (molecular weight of 70,000) was costed on a substrate deposited with gold having a thickness of about 500 A, thereby obtaining a film having a thickness of about 5 ~3~i7~
microns. The substrate with this film was dipped in an acetonitrile solution containing 0.3 Milwaukee of tetraethylammonium p toluenesulfonate and 1 Milwaukee OX
purl. The substrate was used as a cathode, and a platinum mesh electrode was used as an anode.
Polymerization was performed at a voltage of 3.0 V for 10 minutes. As a result, black polypyrrole was precipitated on the substrate. The resultant film was washed, dried and peeled from the substrate. Electrical conductivities of the electrode and surface sides of the film were measured in accordance with the 4-terminal method. The film was changed entirely conductive such that an electrical conductivity of the electrode side was 2G /Q~cm, all that of the surface side was 16 /Q-cm.
example 1~6 A chlorobenzene solution obtained by adding 12%
by weigh of ~ib~ltylphthalate to an ~thylene-vinyl septet 182 : 18) copolymer was cast on a glass substrate deposited with gold having a thickness of about 500 A in a thermostat heated at a temperature of 50C, thereby obtaining a film having a thickness of 25 microns. The substrate with this film was dipped in an acetonitrile-chlorobenzene-cyclohexane (80 : 15 : 5) solution containing 0.3 Milwaukee of tetraethylammonium per chlorate and 1 Mohawk of purl. The substrate served as a cathode, and a platinum mesh electrode served as an anode. Electrochemical polymerization was performed at a I

voltage o. 3.5 V for 10 minutes. The resultant film WAS
washed, dried and peeled from the substrate. Electrical conductivities of the film were measured in accordance 'it'll the 4-terminal method. A highly conc1uctive polymer film was obtained such that an electrical conductivity of the electrode side was 6 I cm and that of the surface side was 3.5 /Q-cm. This indicated that polypyrrole was formed throughout the film and had reached the surface thereof.
In the above two examples, dialkylphthalate was lo partially dissolved in the electrochemical polymerization solution. Therefore, as compared with the corresponding Comparative Example, it was assumed that the electrochemlcal polymerization progressed slowly and that the entire film was made highly conductive.
Example 127 A Nickel was sputtered on a 300-mm square glass substrate to a thickness of 700 A. Indium tin oxide VITO) was laminated by evaporation on the nickel surface lo a thickness of 1,000 A.
This substrate was used as a cathode for eleetrochemical polymerization to render a polyvinyl chloride film conductive. A methyl ethyl kitten solution of polyvinyl chloride (molecular weight of 70,000) was cast on the substrate to form a polyvinyl chloride film having a US thickness of 1.5 microns. The polyvinyl chloride film at a corner of the substrate was peeled so as to connect to a DC
power terminal.

G~70 On the other hand, an acetonitrile-tetrahydrofuran (3 : 1) solution containing 1.5 mollusk of purl and 0.45 Milwaukee of tetxaethylammonium p-toluenesulfonate was prepared as an electrochemical polymerization solution. The substrate with the above film was dipped together with a platinum-plated titanium mesh electrode as a counter electrode in this solution. A
voltage of 3.5 V was applied between these two electrodes for 3 minutes, thereby precipitating hack polypyrrole on the substrate.
A composite polyvinyl chloride-polypy~role film had formed to a thickness of 1.8 microns. This film could be easily peeled from the electrode substrate. The film neither curled nor wrinkled. After the film was peeled off, defects did not form on the surface of the electrode and the electrode could be repeatedly used In order to test the uniformity of electrical conductivity of the film, portions spaced apart by 50 mm, 150 Mel and 250 mm from the power terminal were cut off and were subjected to measurement of electrical conductivities in accordance with the 4-terminal method. The results are shown in Table 9. The surface of the film which contacted the electrode was defined as the electrode side.

~3~t76) Table 9 __ _ _______ Distance from Surface side Electrode side terminal gem) ( to Cm) _ 50 mm10.5 to 12.0 12.5 to 13.5 150 mm10.2 to 13~0 10.8 to 12.8 250 mm10.5 to 13.3 11.2 to 12.5 As is apparent from Table 9, the electrical conductivities throughout the electrode side were substantially uniform.

When electrochemical polymerization was performed on a platinum-plated substrate, a composite polyvinyl chloxide-polypyrrole film having a thickness of 1.9 mirrors was obtained. The resultant film could not be peeled from the substrate without defects. When an IT electrode was deposited on a substrate having a sheet resistance or SO Al a composite film having an average thickness of 1.75 Microns However, the surface resistances of the surface side 50 mm and 250 mm apart from the terminal varied by about 3 times, and the corresponding electrode side portions were subject to a 50~ difference of electrical conductivities, resulting in nonuniform electrical conductivity distribution.
Example 128 Chromium was sputtered on a 300-mm square glass substrate to a thickness of 600 A. A phosphorus-doped amorphous silicon layer was deposited by CUD on the chromium film Jo a thickness OX 2.5 microns. A sheet Lo resistance of the substrate was 2.3 Q/0. The substrate was heated at a temperature of 80C and a polyvinylidene fluoride film having a thickness of 5 microns was thermocompressively bonded thereto by a thermal transfer 5 roller.
On the other hand, an acetonitrile solution containing 1.6 mollusk of thiophene and 0.4 Milwaukee of tetraethylammonium tetrafluoroborate was prepared. The substrate with the film was dipped together with a platinum-plated titanium electrode in the solution. A film portion was peeled off at a corner of the substrate to provide an electrode terminal. Thiophene was electrochemically polymerized at a voltage of 4 for 5 minutes. The resultant film was obtained as a composite film of polyvinylidene fluoride and polythiophene and had a thickness of 5.8 microns. The film could be easily peeled from the substrate and would neither curl nor wrinkle After the film was peeled from the substrate, defects had not formed on the electrode surface. As a result the substrate electrode could be repeatedly used.
Electrical conductivities of the film were measured in the same manner as in Example 122 and were substantially uniform as shown in Table 10.

~L~3~jt7~) Table 10 . .
Distance from Surface side Electrode side terminal I cm) (/Q~cm) 50 mm 12.5 to 13~2 13.7 to 16.5 150 mm 13.0 to 14.1 13.5 to 15.5 250 mm 10.2 to 12.7 13.2 to 15.0 Example 129 The manufacturing apparatus shown in Fig. 9 is used.

Chromium was sputtered to a thickness of 600 A on a surface of an aluminum drum having a diameter of 200 mm and a height of 200 mm. Indium tin oxide (IT) was deposited by evaporation on the outer surface to a thickness of 1.5 microns. In order to uniformly deposit the IT film, the drum was rotated while the evaporation was performed. Mylar sheets were adhered to the upper and lower surfaces of the drum to insulating the upper and lower surfaces. Each Mylar sheet had a thickness of 0.5 mm and a hole of a diameter of 10 mm.
The cylindrical electrode 81 was set, as shown in Fig. 9. An ethylene-vinyl acetate (80 : 20~ copolymer film 32 having a thickness of 20 microns was thermocompressively bonded by the thermal transfer roller 83 on the electrode 81. On the other hand, an acetonitrile-chlorobenzene-N,Ndimethylformamide (3 containing 1.5 mollusk of purl and 0.5 Milwaukee of tetraethylammonium per chlorate was used as the .

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* trade mark .

~23~6 7~3 electrochemical polymerization solution 84. 35% of the electrode was dipped in this solution in the electrochemical polymerization tank 85. A platinum-plated titanium mesh electrode was used as the counter electrode 5 86, and the terminal 87 was connected to the center of the side surface of the electrode, and a voltage was applied between the terminal 87 and the counter electrode 86 to perform electrochemical polymerization. The drum electrode was rotated so that the polymerization time for each part of film corresponds to 10 minutes. The resultant black film was easily peeled from the electrode, and was washed and dried. The dried film was wound.
The electrical conductivity of this film was found to be substantially uniform 8.0 I cm 20-~.
The present invention is not limited to the above-mentioned examples. Various changes and modifications may be made within the spirit and scope of the invention.

Claims (41)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An electrically conducting polymer film, comprising an insulating polymer film having an electrically conducting aromatic polymer compound formed by electrolytic polymeriza-tion on at least one surface and inside thereof, at least one surface of the electrically conducting polymer film being electrically conducting.

2. A film according to claim 1, wherein the insulating polymer film comprises a crosslinked polymer material.

3. A film according to claim 1, wherein the insulating polymer film comprises a thermoplastic resin.

4. A film according to claim 1, wherein the insulating polymer film comprises a polymer material polymerized by plasma polymerization.

5. A film according to claim 1, wherein the insulating polymer film comprises a polymer film having at least two laminated layers.

6. A film according to claim 1, wherein the insulating polymer film is porous.

7. A film according to claim 1, wherein the insulating polymer film contains a conductive filler.

8. A film according to claim 1, wherein the insulating polymer film is formed on an electrode substrate.

9. A film according to claim 8, wherein the electrode substrate includes an electrode comprising a material selected from the group consisting of a noble metal, a base metal, a conducting metal oxide and an inorganic semiconductor.

10. A film according to claim 8, wherein the electrode substrate includes an electrode comprising a base metal layer and a conducting metal oxide layer formed thereon.

11. A film according to claim 8, wherein the electrode substrate includes an electrode comprising a base metal layer and a doped inorganic semiconductor layer formed thereon.

12. A film according to claim 8, wherein the electrode substrate has a drum-like shape.

13. A film according to claim 1, wherein the conducting aromatic polymer compound is formed on each of two surfaces of the insulating polymer film.

14. A film according to claim 1, wherein the insulating polymer film contains at least one additive selected from the group consisting of a plasticizer, a pigment and a dyestuff.

15. A method of manufacturing an electrically conducting polymer film, comprising the steps of providing an insulating polymer film on the surface of an electrode; causing an electrolyte solution and an aromatic polymer to reach said electrode surface through the insulating polymer film;
electrolytically polymerizing said aromatic polymer at the interface between said electrode and the insulating polymer film; and forming an electrically conducting aromatic compound area from said interface of the insulating polymer film toward the inner side of the insulating polymer film.

16. A method according to claim 15, wherein the electrolytically polymerizing step includes the step wherein an electrode on the electrode substrate is used as a cathode, a counter electrode is used as an anode, both electrodes are dipped in an electrochemical polymerization solution, and a voltage is applied between the two electrodes to perform electrochemical polymerization.

17. A method according to claim 15, wherein the insulating polymer film comprises a crosslinked polymer material.

18. A method according to claim 15, wherein the insulating polymer film comprises a thermoplastic resin.

19. A method according to claim 15, wherein the insulating polymer film comprises a polymer material polymerized by plasma polymerization.

20. A method according to claim 15, wherein the insulating polymer film comprises a polymer film having at least two laminated layers.

21. A method according to claim 15, wherein the insulating polymer film is porous.

22. A method according to claim 15, wherein the insulating polymer film contains a conductive filler.

23. A method according to claim 15, wherein the insulating polymer film is provided on an electrode substrate.

24. A method according to claim 23, wherein the electrode substrate includes an electrode comprising a material selected from the group consisting of a noble metal, a base metal, a conducting metal oxide and an inorganic semiconductor.

25. A method according to claim 23, wherein the substrate includes an electrode comprising a base metal layer and a conducting metal oxide layer formed thereon.

26. A method according to claim 23, wherein the substrate includes an electrode comprising a base metal layer and a doped inorganic semiconductor layer formed thereon.

27. A method according to claim 23, wherein the substrate has a drum-like shape.

28. A method according to claim 15, wherein the conducting aromatic compound area is formed on each of two surfaces of the insulating polymer film.

29. A method according to claim 15, wherein the insulating polymer film contains at least one additive selected from the group consisting of a plasticizer, a pigment and a dyestuff.

30. A method according to claim 15, wherein the insulating polymer film comprises a cross linking polymer material, and the electrolytically polymerizing step includes the step of cross linking the insulating polymer film.

31. A method according to claim 23, wherein the electrolytically polymerizing step includes the steps of:
forming an electrochemical polymer by electrochemical polymerization from a surface of the insulating polymer film which contacts the substrate along a direction of thickness, thereby forming a first conducting aromatic polymer compound layer;
peeling the insulating polymer film from the electrode substrate;
bringing a surface of the insulating polymer film which opposes a surface having the first conducting aromatic polymer layer into contact with the electrode substrate; and forming a second conducting aromatic polymer compound layer by electrochemical polymerization performed from the surface contacted by the electrode substrate along a direction toward the first conducting aromatic polymer compound layer.

32. A method according to claim 23, wherein the step of providing the insulating polymer film on the surface of an electrode includes the step of adding a removable material in the insulating polymer film, and the electrolytically polymerizing step includes the step of removing the removable material before and/or during electrochemical polymerization.

33. A method according to claim 32, wherein the step of removing the removable material comprises a heat treatment.

34. A method according to claim 32, wherein the step of removing the removable material comprises a reduced pressure treatment.

35. A method according to claim 32, wherein the step of removing the removable material comprises a combination of a heat treatment and a reduced pressure treatment.

36. A method according to claim 32, wherein the removable material is a material soluble in an electrochemical polymerization solution.

37. A method according to claim 32, wherein the removable material comprises a material soluble in a solvent.

38. A method according to claim 32, wherein the step of forming the insulating polymer film includes the step of adding a conducting filler in the insulating polymer film.

39. A method according to claim 38, wherein the conducting filler comprises a material selected from the group consisting of a carbon material, a metal oxide and a metal.

40. A method according to claim 15, wherein the insulating polymer film contains at least one additive selected from the group consisting of a plasticizer, a pigment and a dyestuff.

41. A method according to claim 15, wherein the step of providing the insulating polymer film includes the step of coating an adhesive on the electrode and the step of thermocompressively bonding the insulating polymer film to the adhesive.