JP2001123114A - Method for forming polymerized film, method of insulating and coating metal by using the same, and insulated and coated metal conductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem of difficulty in the formation of a polymerized film having a sufficient thickness in the conventional method for forming an insulating polymer thin film by using an electrolytic polymerization because the surface of a conductor is insulated by the growth of the film. SOLUTION: The metal conductor is dipped in an aqueous solution containing a polymerizable monomer, a supporting electrolyte and an alkylamine, and an electroconductive polymer film is formed by the electrolysis by using the metal conductor as an electrode. The dopant is eliminated from the obtained electroconductive polymer film to provide the objective polymerized film excellent in insulation properties on the electrode surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an electrically insulating film on a surface of a metal coil or the like. In particular, the present invention relates to an organic polymer film formed by an electrolytic polymerization method, a method for forming the same, and a method for insulating and coating a metal material using the same and an insulated metal conductor.

[0002]

2. Description of the Related Art In recent years, as electronic equipment has become smaller and more sophisticated, it has been desired that the coil itself, which is a component of the equipment, be made smaller and more efficient. It is becoming. For this reason, the thickness of the insulating coating of the electric wire is very thin, that is, several μm or less.

On the other hand, as an insulated wire having a rectangular cross section, an insulated wire having a relatively thick insulating film of about 8 to 20 μm has been proposed. Such an insulated wire has been manufactured by applying and baking an insulating varnish to a metal conductor stretched in a linear shape. Alternatively, it can also be manufactured by forming an insulating film on a conductor having a round cross section and then rolling it.

[0004] One of the techniques for forming a polymer thin film on a metal electrode is an electrolytic polymerization method. A method for forming an insulating polymer thin film on a conductor by electrolytic polymerization is described in the literature, Electrokimika Actor, Vol. 22, pp. 451-457,
977 (Electrochimica Acta, 22,451-457 (1977))
And Journal of Applied Electrochemistry, Vol. 9, pp. 483-493, 1979 (Journa
l of Applied Electrochemistry, 9,483-493 (1979)).

Further, a method for forming a conductive conjugated polymer film by electrolytic polymerization and thereafter performing an undoping process to obtain an insulating polymer thin film is disclosed in JP-A-63-205.
011 and JP-A-4-259915.

[0006]

As described above, in order to make the coil itself smaller and more efficient, the insulating coating of the electric wire is made thinner. As a result, the insulated electric wire is coated with a needle or the like of an automatic winding machine. Susceptible to damage. For this reason, there is a problem that a rare short circuit and a ground defect are likely to occur in a coil as a product.

Further, among the insulated wires having a rectangular cross section, those having a thickness of an insulating thin film of several μm or less have not been developed. It is difficult to stably form a thin film having a thickness of several μm or less on the end face of a conductor having a rectangular cross section by a coating and baking method of an insulating varnish.
However, on the other hand, in a method of manufacturing a rectangular insulated wire by rolling after forming an insulating film on a round conductor, residual stress remains in the insulating film, when the rolling rate is large, or when the insulating film is an ultra-thin film, There is a problem that damage such as cracks occurs in the film.

As a method for solving the above problems, a method of forming an electrically insulating polymer thin film on the coil by performing electrolytic polymerization using a metal coil as an electrode is considered. However, the methods proposed so far have a problem in that the electropolymerized film has an electrical insulating property, so that the growth of the film on the electrode impairs the conductivity and makes it difficult to obtain a sufficient thickness.

It is also conceivable to form a conductive polymer thin film once on a metal coil by electrolytic polymerization and then to perform insulation by dedoping. When this method is used, since the polymerization product is conductive, a film having a sufficient film thickness can be obtained. However, the methods proposed so far mainly use platinum, iron, glass electrodes, etc. as a conductor, and form a conjugated polymer film having a sufficient film thickness on copper, which is generally used as a conductor. There was no such example.

[0010]

In order to solve these problems, a method of forming a polymer film according to the present invention comprises immersing a metal conductor in an aqueous solution containing a polymerizable monomer, a supporting electrolyte and an alkylamine. Electropolymerization of the polymerizable monomer is performed using a metal conductor as an electrode.

The second method of forming a polymer film according to the present invention is characterized in that pyrrole and its derivatives are used as the polymerizable monomer.

A third method of forming a polymer film according to the present invention is characterized in that aniline and a derivative thereof are used as a polymerizable monomer.

A fourth method of forming a polymer film according to the present invention is characterized in that the metal conductor has copper as a composition.

The fifth method of forming a polymer film according to the present invention is characterized in that an aqueous solution containing a polymerizable monomer, a supporting electrolyte and an alkylamine is basic.

According to a sixth aspect of the present invention, there is provided a method for forming a polymer film, wherein a metal conductor is immersed in an aqueous solution containing a polymerizable monomer, a supporting electrolyte and an alkylamine, and electrolytic polymerization is carried out using the metal conductor as an electrode. Thereafter, the electrical resistance of the polymer film is increased by removing the dopant remaining in the polymer film.

Further, the method of forming the polymer film of the present invention the seventh, the supporting electrolyte, OH as an anion component ^-, Cl ^-, B
_{^{r -, I 3 -, BF}} 4 -, ClO 4 -, SO 4 2-, PF 6 -, AsF 6 -, SbF 6 - , characterized in that it contains an ion selected from.

An eighth method of forming a polymer film according to the present invention is characterized in that an electric field having a polarity different from that during electrolysis is applied between the metal conductor and the counter electrode, as the above-mentioned method of removing the dopant. .

A ninth method of forming a polymer film according to the present invention is characterized in that the metal conductor is immersed in an aqueous solution of an electrolyte or an alcohol solution as a method of desorbing the dopant.

In a tenth aspect of the present invention, the metal conductor is immersed in an aqueous solution of an electrolyte or an alcoholic solution, and an electric field having a polarity different from that during electrolysis is formed. It is characterized in that the voltage is applied between the metal conductor and the counter electrode.

An eleventh aspect of the present invention provides a method for insulating coating a metal material on a metal conductor having an electrically insulating coating portion, by using the above-described method for forming a polymer coating film on defective portions of the coating portion. Is formed.

According to a twelfth aspect of the present invention, there is provided an insulated metal conductor, wherein a polymer film is formed on a part or the entire surface of the metal conductor by the above-described method for forming a polymer film.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for forming a polymer film according to the present invention will be described.

First, a polymerizable monomer according to the first invention,
A method for forming a polymer film, comprising immersing a metal conductor in an aqueous solution containing a supporting electrolyte and an alkylamine, and performing electrolytic polymerization of the polymerizable monomer using the metal conductor as an electrode will be described.

The polymerizable monomer is not particularly limited as long as it can be dissolved in an aqueous solution to form a conductive polymer product by electrolytic polymerization. Examples of the polymerizable monomer include heterocyclic compounds such as pyrrole and triazine thiol; Aromatic compounds having a hetero substituent, such as aniline and phenol, and derivatives thereof can be used. The supporting electrolyte is not particularly limited as long as it dissolves in the aqueous solution to be used and generates ions in the solution.

Examples of the alkylamine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tertiary butylamine, dimethylamine, diethylamine, di (n-propyl) amine and di (isopropyl). ) Amine, di (n-butyl) amine, di (isobutyl) amine, di (tertiarybutyl) amine, trimethylamine, triethylamine, tri (n-propyl) amine,
Tri (isopropyl) amine, tri (n-butyl) amine, tri (isobutyl) amine, tri (tert-butyl) amine, or mono-, di-, or trialkylamine having an alkyl group larger than these, or ethanolamine And substituted alkylamines such as diethanolamine and triethanolamine.

At this time, considering the solubility in an aqueous solution to be described later, a mono- or dialkylamine having a small alkyl chain is suitable, and for example, ethylamine, dimethylamine, and diethylamine can be used. For the same reason, alkylamines having a hydrophilic substituent such as ethanolamine, diethanolamine, and triethanolamine are also preferable.

As the aqueous solution, water is used as a solvent, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butyl alcohol, 2-methoxyethanol, 2-methoxyethanol, An alcohol such as ethoxyethanol, 2-butoxyethanol or ethylene glycol, or a water-soluble polar organic solvent such as acetonitrile, dimethylformamide, dimethylsulfoxide, NMP or propylene carbonate is added as required.

The concentration of the polymerizable monomer is from 0.01 to 10 mol /
l, preferably 0.05 to 2 mol / l. The concentration of the supporting electrolyte is 0.01 to 10 mol / l, preferably 0.05 to 2 mol / l.
It is. The alkylamine concentration is between 0.05 and 1 mol / l.

As the metal conductor, zinc, tin, nickel,
Aluminum, chromium, iron, copper, titanium, silver, palladium, indium, platinum, gold, and the like can be used.
Iron, stainless steel, aluminum,
Various substances such as palladium, platinum, gold, and carbon can be used.

When a metal is used as an electrode during electrolytic polymerization, an oxide film may be formed on the surface and passivated, depending on the hydrogen ion concentration of the electrolytic solution, the electrode potential during electrolysis, and other reaction conditions. When this passivation occurs, the electropolymerization reaction is stopped due to a shortage of current, and it becomes difficult to form a polymer film having a sufficient film thickness.

In the present invention, by adding an alkylamine to the aqueous solution, passivation of the metal conductor is suppressed, and a polymer film having a thickness of 1 μm or more can be formed.

Next, a method of forming a polymer film according to the second invention, which is characterized by using pyrrole and its derivative as the polymerizable monomer, will be described.

It is known that a conductive polymer film is formed on a working electrode by electrolytic oxidation of pyrrole and its derivatives. Conventionally, formation of a pyrrole polymer film by an electrolytic polymerization method has been carried out in a polar organic solvent such as acetonitrile, nitrobenzene, propylene carbonate and the like. Considering the effects on the environment and the human body, it is desirable to reduce the amount of these organic solvents used.

In the present invention, by adding an alkylamine to a solution, an electrolytically polymerized polypyrrole film having a sufficient film thickness can be formed on various metal conductors by using an aqueous solution having a lower environmental load. Became possible.

The type of the pyrrole derivative is not particularly limited as long as it shows solubility in the aqueous solution to be used, but 2-pyrrolecarboxylic acid, 2-pyrrolecarboxylic acid ester, indole and the like can be used.

Next, a method of forming a polymer film according to the third aspect of the present invention, which comprises using aniline or a derivative thereof as a polymerizable monomer, will be described.

It is known that a conductive polymer film is formed on a working electrode by electrolytic oxidation of aniline and its derivatives. The formation of an aniline polymer film by the electrolytic polymerization method has been conventionally carried out in a polar organic solvent such as acetonitrile, nitrobenzene, propylene carbonate and the like, similarly to the electrolytic polymerization of pyrrole.

In the present invention, by adding an alkylamine to a solution, it is possible to form an electropolymerized polyaniline film having a sufficient film thickness on various metal conductors by using an aqueous solution having a small environmental load. It has become possible.

The type of the aniline derivative is not particularly limited as long as it shows solubility in the aqueous solution to be used, but 2-methylaniline, 2-aminobenzoic acid, o-anisidine and the like can be used.

Next, a description will be given of a method of forming a polymer film according to a fourth aspect of the present invention, wherein the metal conductor has copper as a composition.

When electrolysis is carried out using copper as a working electrode under neutral to basic conditions, an oxide film is formed on the copper surface to passivate it. On the other hand, when the same electrolysis is performed under acidic or strong basic conditions, the dissolution of the copper electrode proceeds. For this reason, there has not been an example in which a polymer film having a film thickness of 1 μm or more is formed on copper by the electrolytic polymerization method.

In the present invention, by adding an alkylamine to the aqueous solution, the passivation of the copper electrode was suppressed, and it was possible to form an electropolymerized film having a thickness of 1 μm or more.

Copper is a metal having high reactivity with ammonia and amino compounds, and it is known that copper easily forms a complex with these compounds. Therefore,
When copper is used as the electrode, the effect of suppressing the passivation of the electrode by the alkylamine is considered to be particularly high.

As the metal conductor having copper as a composition,
Copper, metal containing no metal elements other than copper, deoxidized copper, oxygen-free copper, brass containing zinc, free-cutting brass containing zinc and lead, admiralty brass containing zinc and tin, tin and phosphorus Phosphor bronze containing aluminum, aluminum bronze containing aluminum, Corson alloy containing nickel and silicon, Heusler alloy containing manganese and aluminum, nickel silver and nickel white, Cubro nickel containing nickel, etc. , Beryllium copper, nickel copper, silver copper, cadmium copper, chromium copper and the like can be used.

Next, a polymerizable monomer according to the fifth invention,
The method for forming a polymer film according to claim 1, wherein the aqueous solution containing the supporting electrolyte and the alkylamine is basic.

The basic aqueous solution is obtained by using water as a solvent,
Methanol, ethanol, 1-propanol, 2
-Alcohols such as propanol, 1-butanol, 2-butanol, tert-butyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and ethylene glycol, acetonitrile, dimethylformamide, dimethylsulfoxide, NMP, propylene carbonate A polar solvent such as sodium hydroxide, potassium hydroxide, calcium hydroxide, or an alkali metal alcoholate is added thereto as needed.

By adding the alkylamine to the aqueous solution, passivation of the metal conductor is suppressed, and the electrolytic polymerization reaction can be continued for a long time. But copper, zinc,
When a metal such as tin or nickel is used as a conductor, when electrolysis is performed under acidic conditions, the metal itself dissolves instead of the progress of passivation due to the formation of an oxide film of the metal. In a system in which such a dissolution reaction proceeds, it is difficult to form an electropolymerized film on a metal conductor even when an alkylamine is added to an aqueous solution. When such a metal is used as the conductor, dissolution of the metal conductor is suppressed by making the aqueous solution used for the electropolymerization basic, and the formation of the electropolymerized film can be carried out by adding an alkylamine.

In particular, when copper is used as the metal conductor, the aqueous solution used for the electrolytic polymerization preferably has a hydrogen ion concentration index in the range of 7 to 13.

Next, a polymerizable monomer according to the sixth invention,
After immersing the metal conductor in an aqueous solution containing a supporting electrolyte and an alkylamine and performing electrolytic polymerization using the metal conductor as an electrode, by removing the dopant remaining in the polymer film, the electric resistance of the polymer film is reduced. A method for forming a polymer film, which is characterized by increasing the number, is described.

When an insulating film is directly formed by electrolytic polymerization, the conductivity of the electrode is greatly reduced immediately after the start of electrolysis due to the insulating property of the product, and the polymerization reaction is stopped early. For this reason, it was difficult to obtain an insulating film having a thickness of more than 1 μm by electrolytic polymerization.

On the other hand, when the product of the electropolymerization is conductive, the thickness of the polymer film can be easily controlled by the applied voltage and the electrolysis time.

The electric conductivity of a conductive polymer film formed by electrolytic polymerization is generally caused by charge transfer by a dopant component contained in the film. The higher the dopant concentration in the film, the higher the conductivity of the polymer film. Has an increased electrical conductivity. For this reason, by removing the dopant from the conductive polymer film formed by the electrolytic polymerization method, a polymer film excellent in electric insulation can be obtained.

According to the present invention, it has become possible to form an insulating polymer film having an arbitrary thickness of 1 μm or more by an electrolytic polymerization method.

Next, the supporting electrolyte according to the seventh invention is:
OH as an anion component ^{-, Cl -, Br -,} I 3 -, BF 4 -, Cl
A method for forming a polymer film containing ions selected from O ₄ ⁻ , SO ₄ ²⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ will be described.

When an insulating polymer film is formed by desorbing a dopant from the above-described conductive polymer, the mobility of the dopant is high to improve the electrical insulation. Desirably easy to separate.

As an example of the mechanism for introducing the dopant into the electropolymerized film, electrochemical doping of polypyrrole is shown in (Chemical Formula 1). When forming a polymer film in electrolytic oxidation, the film is formed on the anode side. Since the oxidation potential of the polymerization product is lower than the oxidation potential of the monomer, the main chain of the polymerization film undergoes oxidation to generate cation radicals. As a result, the anion component of the supporting electrolyte, which has moved to the anode side due to the application of the voltage, is introduced into the polymer film to maintain the electrical neutrality of the polymer film, and contributes to the development of the electrical conductivity of the film as a dopant. Therefore, in order to form a polymer film having high insulating properties, it is desirable that the mobility of the anion component of the supporting electrolyte be high. From this viewpoint, the anionic component, at least SbF ₆ ^- is preferably a smaller ion.

[0057]

Embedded image

The cation component of the supporting electrolyte is not particularly limited, but metal cations such as K ⁺ , Na ⁺ , Li ⁺ , Ca ²⁺ , Mg ²⁺ , Al ³⁺ , NH ₄ ⁺ and alkylammonium ion A supporting electrolyte containing such as a cation component can be used.

Next, as a method for desorbing the dopant according to the eighth aspect of the present invention, a method of forming a polymer film, wherein an electric field having a polarity different from that during electrolysis is applied between the metal conductor and the counter electrode. Will be described.

As described above, when a polymer film is formed in electrolytic oxidation, the polymer film after the electrolysis is present as a cation radical in which a part of the polymer main chain has been oxidized. An anionic component of the electrolyte is introduced therein as a dopant. Conversely, when a polymer film is formed by electrolytic reduction, the polymer film after electrolysis has an anion radical structure in which part of the polymer main chain has been reduced, and the cation component of the electrolyte is introduced as a dopant into the film. Is done. Generally, such doping is
It is reversible to the electrode potential.

Therefore, by applying an electric field having a polarity different from that during electrolysis to the metal conductor on which the electrolytic polymerized film is formed according to the present invention, the polymer radical is reduced or oxidized to be converted into a neutral molecule, Dopant is eliminated from the coating. As a result, it becomes possible to form an electrolytic polymerized film having excellent insulation properties. At this time, the voltage applied to the electrode is not particularly limited.

Next, as a method of desorbing the above-mentioned dopant according to the ninth aspect of the present invention, a method of forming a polymer film, which comprises immersing the metal conductor in an aqueous solution of an electrolyte or an alcohol solution, will be described.

As described above, the polymer film after electrolysis has a radical structure in which a part of the polymer main chain has undergone oxidation or reduction, and an ionic dopant is introduced into the film. When such an electropolymerized film is immersed in an electrolyte solution, the electrostatic interaction between the polymer radical and the ionic dopant is relatively caused by the occurrence of the electrostatic interaction with the ionic component generated from the electrolyte. Decrease. As a result, the dopant can be eliminated from the polymer film.

Examples of the electrolyte include halides such as potassium chloride, sodium chloride, calcium chloride, ammonium chloride, potassium bromide, and sodium bromide, perchlorates such as sodium perchlorate and lithium perchlorate, alum, and ammonium sulfate. Such as sulfates, potassium nitrate,
Nitrates such as sodium nitrate and ammonium nitrate, and carbonates such as potassium carbonate and sodium carbonate can be used.

Further, by using an electrolyte having a reducing anion as a component, the reduction reaction of the cation radical portion in the polymerized film to neutral molecules proceeds. As a result, desorption of the anion dopant from the polymer film proceeds efficiently.

Examples of the electrolyte having a reducing anion as a component include thiosulfates such as sodium thiosulfate, hyposulfites such as sodium hyposulfite, bisulfites such as sodium bisulfite, and sulfites such as potassium sulfite and sodium sulfite. Salts and the like can be used.

Further, when a metal hydroxide is used as a supporting electrolyte during electrolytic polymerization, an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or an acid such as ammonium chloride or ammonium nitrate may be used as an electrolyte solution when the dopant is eliminated. By using an aqueous solution of an electrolyte or an alcohol solution, the hydroxide ions introduced into the polymerized film can be neutralized and removed.

As the solvent for dissolving the electrolyte, water or alcohol can be used. The type of alcohol is not particularly limited as long as it does not dissolve the electrolyte and does not dissolve the polymer film formed by the electrolytic polymerization, but use methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, or the like. Can be.

Next, as a method for desorbing the dopant according to the tenth aspect of the present invention, the metal conductor is immersed in an aqueous solution of an electrolyte or an alcohol solution, and an electric field having a polarity different from that during electrolysis is applied to the metal conductor and the opposite electrode. A method for forming a polymer film, which is characterized by applying a voltage during the period, will be described.

As described above, an electric field having a polarity different from that during the electropolymerization is applied between the metal conductor and the counter electrode, or the metal conductor having the electropolymerized film formed thereon is immersed in an aqueous solution of an electrolyte or an alcohol solution. This makes it possible to desorb the dopant component introduced into the film and increase the electric resistance of the film. By simultaneously using these two methods, the desorption of the dopant from the polymer film can be more effectively advanced. As a result, a film having excellent electrical insulation can be formed more efficiently. Also in this case, the voltage applied to the electrode is not particularly limited.

Next, according to the eleventh aspect of the present invention, a polymer film is formed on a metal conductor having an electrically insulating coating portion at a defective portion of the coating portion by the above-described method of forming a polymer film. The method of insulating coating of the metal described below will be described.

The metal conductor having an electrically insulating coating portion refers to an enameled wire having an insulating coating formed on the surface thereof by applying or baking a varnish, a metal conductor having a passivated film formed on the surface, or the like. If there is a defect in these insulating coating portions, the portions are electrically connected to the outside, and therefore, these can be used as electrodes to perform electrolytic polymerization. After performing the electrolytic polymerization, the insulating coating can be formed by performing the undoping treatment described above. INDUSTRIAL APPLICABILITY By applying the present invention, it is possible to selectively perform insulation repair of an electronic component such as an insulated wire having an insulation defect, a transformer conductor, or a capacitor.

Next, a description will be given of an insulating coated metal conductor according to the twelfth invention, wherein a polymer film is formed on a part or all of the surface of the metal conductor by the above-described method for forming a polymer film.

According to the above-described method for forming a polymer film, a polymer film having a range from submicron to several μm or several tens μm can be formed on an electric wire as a metal conductor. That is, the insulated wire formed in this way has a smaller thickness of the coating than the conventional insulated wire. For example, when applied as a motor winding, the winding density per unit volume is increased, and the efficiency is increased. Motor with high performance can be obtained.

[0075]

Next, a specific embodiment will be described.

Example 1 A 25 × 60 × 0.1 mm strip-shaped copper electrode and a platinum electrode were immersed in an aqueous solution containing 0.1 mol of pyrrole, 0.1 mol of potassium hydroxide, and 0.6 mol of diethylamine. 3V potential between electrodes
And electrolysis was performed for 10 minutes. After the completion of the electrolysis, the copper electrode was taken out, washed with pure water, and then dried in a thermostat at 50 ° C. for 3 hours. According to the gravimetric method, the film thickness was 3 μm. After depositing a gold electrode on the resulting polymer film, a platinum wire was adhered to the gold electrode with a silver paint, and the platinum wire was connected to a copper plate to measure the volume resistivity.
+ 4Ω · cm.

Example 2 A 25: 60.times.0 aqueous solution of 0.1 mol of pyrrole, 0.1 mol of potassium hydroxide and 0.3 mol of diethylamine in water: methanol = 75: 25% by volume was prepared.
A 1 mm strip-shaped copper electrode and a platinum electrode were immersed, and a voltage was applied so that a potential between both electrodes was 3 V using the copper electrode as an anode, and electrolysis was performed for 10 minutes. After the completion of the electrolysis, the copper electrode was taken out, washed with pure water, and then dried in a thermostat at 50 ° C. for 3 hours. According to the gravimetric method, the film thickness was 3 μm.
After depositing a gold electrode on the resulting polymer film, a platinum wire was adhered to the gold electrode with silver paint, and the platinum wire and a copper plate were connected to measure the volume resistivity of the polymer film.1.5E + 4Ω ·cm
showed that.

Example 3 An aqueous solution of aniline 0.1 mol, potassium hydroxide 0.1 mol, diethylamine 0.3 mol, water: methanol = 75: 25 vol.
A 1 mm strip-shaped copper electrode and a platinum electrode were immersed, and a voltage was applied so that a potential between both electrodes was 3 V using the copper electrode as an anode, and electrolysis was performed for 10 minutes. After the completion of the electrolysis, the copper electrode was taken out, washed with pure water, and then dried in a thermostat at 50 ° C. for 3 hours. According to the gravimetric method, the film thickness was 2.5 μm. After depositing a gold electrode on the resulting polymer film, a platinum wire was adhered to the gold electrode with silver paint, and the platinum wire and a copper plate were connected to measure the volume resistivity of the polymer film.
・ Cm was indicated.

(Example 4) 25 x 60 x 0. 5 aqueous solution of pyrrole 0.1 mole, potassium hydroxide 0.1 mole, diethylamine 0.3 mole, water: methanol = 75: 25% by volume.
A 1 mm strip-shaped copper electrode and a platinum electrode were immersed, and a voltage was applied so that a potential between both electrodes was 3 V using the copper electrode as an anode, and electrolysis was performed for 10 minutes. After the electrolysis was completed, the copper electrode was taken out, washed with a 1 molar sodium chloride aqueous solution, and then dried in a thermostat at 50 ° C. for 3 hours. According to the gravimetric method, the film thickness was 3 μm. After depositing a gold electrode on the resulting polymer film, a platinum wire was adhered to the gold electrode with silver paint, and the platinum wire and the copper plate were connected to measure the volume resistivity.The result was 7.5E + 9Ωcm. Indicated.

(Example 5) 25 x 60 x 0.2% aqueous solution of pyrrole 0.1 mol, potassium hydroxide 0.1 mol, diethylamine 0.3 mol, water: methanol = 75: 25% by volume.
A 1 mm strip-shaped copper electrode and a platinum electrode were immersed, and a voltage was applied so that a potential between both electrodes was 3 V using the copper electrode as an anode, and electrolysis was performed for 10 minutes. After the electrolysis, the copper electrode was taken out, washed with a 0.1 molar sodium dithionite aqueous solution, and dried at 50 ° C. for 3 hours in a thermostat. According to the gravimetric method, the film thickness was 3 μm. After depositing a gold electrode on the resulting polymer film, a platinum wire was adhered to the gold electrode with silver paint, and the platinum wire and a copper plate were connected to measure the volume resistivity.The result was 1.5E + 10Ωcm. Indicated.

(Example 6) A 25 x 60 x 0. 0 aqueous solution of 0.1 mol of pyrrole, 0.1 mol of potassium hydroxide and 0.3 mol of diethylamine in water: methanol = 75: 25% by volume was prepared.
A 1 mm strip-shaped copper electrode and a platinum electrode were immersed, and a voltage was applied so that a potential between both electrodes was 3 V using the copper electrode as an anode, and electrolysis was performed for 10 minutes. After completion of the electrolysis, the copper electrode was taken out, washed with 1N hydrochloric acid, and then dried in a thermostat at 50 ° C. for 3 hours. According to the gravimetric method, the film thickness was 3 μm. After depositing a gold electrode on the resulting polymer film, a platinum wire was adhered to the gold electrode with silver paint, and the platinum wire and a copper plate were connected to measure the volume resistivity.The result was 3.0E + 10Ωcm. Indicated.

(Example 7) 25 x 60 x 0.2% aqueous solution of pyrrole 0.1 mol, potassium hydroxide 0.1 mol, diethylamine 0.3 mol, water: methanol = 75: 25% by volume.
A 1 mm strip-shaped copper electrode and a platinum electrode were immersed, and a voltage was applied so that a potential between both electrodes was 3 V using the copper electrode as an anode, and electrolysis was performed for 10 minutes. After the electrolysis is completed, the copper electrode is taken out, washed with pure water, immersed in a 1 molar sodium perchlorate aqueous solution, and a voltage is applied so that the potential between the copper electrode and the platinum electrode is 2 V with the copper electrode as a cathode. Then, electrolysis was performed for 5 minutes. After the completion of the electrolysis, the copper electrode was taken out, washed with pure water, and then dried in a thermostat at 50 ° C. for 3 hours. According to the gravimetric method, the film thickness was 3 μm. After depositing a gold electrode on the resulting polymer film, a platinum wire was adhered to the gold electrode with silver paint, and the platinum wire and a copper plate were connected to measure the volume resistivity.The result was 5.0E + 10Ωcm. Indicated.

(Example 8) After enamel-coated lead wires having a diameter of 1 mm were wound into a ring shape having a diameter of 2 cm, a part of the enamel coating was removed with sandpaper to prepare an electrode having an insulating defect portion formed thereon. The electrode and a 5 × 60 × 0.1 mm rectangular platinum electrode as a counter electrode were immersed in an aqueous solution of pyrrole 0.1 mol, potassium hydroxide 0.1 mol, diethylamine 0.3 mol, water: methanol = 75: 25% by volume, and enamelled. Electrolysis was performed for 10 minutes by applying a voltage so that the potential between both electrodes was 3 V using the coated conductive wire as an anode. After completion of electrolysis, take out the enamel-coated lead wire, wash it with pure water,
Dipped in an aqueous solution of sodium perchlorate at a molar concentration, and the potential between the platinum electrode and the enamel-coated lead wire as a cathode is 2 V
And electrolysis was performed for 5 minutes. After the electrolysis was completed, the enamel-coated conductor was taken out, washed with pure water, and then dried at 50 ° C. for 3 hours in a constant temperature bath.
An insulating film was selectively formed on the stripped portion of the enameled wire. Immerse this electrode and platinum electrode in saline
When the conduction between both electrodes was examined, the insulation was good.

(Comparative Example 1) 25 x 60 x 0.1 mm
Was immersed in a strip-shaped copper electrode and a platinum electrode, and a voltage was applied such that the potential between the two electrodes was 3 V using the copper electrode as an anode, and electrolysis was performed for 10 minutes. After the completion of the electrolysis, the copper electrode was taken out, washed with pure water, and then dried in a thermostat at 50 ° C. for 3 hours. According to the gravimetric method, the film thickness was 0.1 μm or less.

Comparative Example 2 A 25 × 60 × 0.1 mm strip-shaped copper electrode and a platinum electrode were immersed in an acidic aqueous solution of pyrrole 0.1 mol, 0.1 mol of perchloric acid, and 0.1 mol of lithium perchlorate. The potential between both electrodes is 3 V
And electrolysis was performed for 10 minutes. When the copper electrode and the platinum electrode were taken out after the electrolysis, the copper electrode was dissolved and copper was deposited on the platinum electrode.

Comparative Example 3 25 × 60 × 0.1 was added to a neutral aqueous solution of pyrrole 0.1 mol and sodium perchlorate 0.1 mol.
A strip-shaped copper electrode of mm and a platinum electrode were immersed, and the copper electrode was used as an anode, and a voltage was applied so that a potential between both electrodes became 3 V, and electrolysis was performed for 10 minutes. When the copper electrode and the platinum electrode were taken out after the electrolysis, the copper electrode was dissolved and copper was deposited on the platinum electrode.

[0087]

As described above, according to the present invention, an insulating thin film can be formed on a metal conductor.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 7/02 H01B 7/02 A 13/00 517 13/00 517 13/06 13/06 17/62 17 / 62 F term (reference) 4J038 DJ011 PC02 4J043 PA02 QB02 QB03 RA08 SA05 UA121 XA12 XA15 XA16 XA23 XA26 XB14 XB19 YB05 YB08 YB15 YB22 YB50 ZA46 ZB03 ZB11 ZB48 5G309 MA01 MA15 5G325 AB03

Claims (12)

[Claims] 1. A polymer film, wherein a metal conductor is immersed in an aqueous solution containing a polymerizable monomer, a supporting electrolyte and an alkylamine, and the polymerizable monomer is subjected to electrolytic polymerization using the metal conductor as an electrode. Forming method. 2. The method according to claim 1, wherein pyrrole and a derivative thereof are used as the polymerizable monomer. 3. The method according to claim 1, wherein aniline or a derivative thereof is used as the polymerizable monomer. 4. The method according to claim 1, wherein the metal conductor has copper as a composition. 5. The method according to claim 1, wherein the aqueous solution containing the polymerizable monomer, the supporting electrolyte and the alkylamine is basic. 6. A metal conductor is immersed in an aqueous solution containing a polymerizable monomer, a supporting electrolyte and an alkylamine. Electropolymerization is performed using the metal conductor as an electrode, and then the dopant remaining in the polymer film is eliminated. Thereby increasing the electrical resistance of the polymer film. 7. The method according to claim 7, wherein the supporting electrolyte comprises O as an anionic component.
^{H -, Cl -, Br -} , I 3 -, BF 4 -, ClO 4 -, SO 4 2-, PF 6 -, As
F ₆ ^-, SbF ₆ ^- formation method of polymerization film according to claim 5, characterized in that it contains ions chosen from. 8. The method for forming a polymer film according to claim 6, wherein an electric field having a polarity different from that during electrolysis is applied between the metal conductor and the counter electrode as a method for removing the dopant. 9. The method for forming a polymer film according to claim 6, wherein the metal conductor is immersed in an aqueous solution of an electrolyte or an alcohol solution as a method of desorbing the dopant. 10. A method for desorbing a dopant, wherein the metal conductor is immersed in an aqueous solution of an electrolyte or an alcohol solution, and an electric field having a polarity different from that during electrolysis is applied between the metal conductor and the counter electrode. A method for forming a polymer film according to claim 6. 11. A metal conductor having an electrically insulating coating portion, wherein a defective portion of the coating portion is provided at a defective portion.
A method for forming a polymer film by the method for forming a polymer film according to any one of 4, 5, 6, 7, 8 and 9, wherein the method comprises the steps of: 12. A part or all of a metal conductor surface,
An insulated metal conductor, wherein a polymerized film is formed by the method for forming a polymerized film according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, and 9.