JP2001006462A - Polymerized film forming method and metal insulation coating method using it and insulation film applied metal conductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable application of good electric insulation film on the surface of a metal coil or the like by forming a polymer having a functional residue by electritic polymerization, and performing hardening of the polymer through addition of a hardener to the polymer during or after the electric treatment. SOLUTION: A thin polymer film can be formed is uniform with respect to various shapes of conductors such as insulation wires having flat angles by the use of electrolytic polymerization method. By adding a hardening agent into the formed polymer with a functional residue, owing to a function of the agent or a reaction between the agent and the residue, the residues perform cross-link reaction with each other to thereby form a three-dimensional net-like structure. As a result, thermal and mechanical characteristics and durability with respect to chemicals such as organic solvent improve, and also an increase of volume resistance rate occurs. Such various characteristics of the polymer are improved. As the polymer having such a functional residue, those having carbon-carbon nonsaturation bonding can be used. Also, as the hardening agent those of inorganic or organic peroxides can be used.

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 insulation coating of the electric wire is extremely thin, that is, several microns 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)).

[0005]

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 microns or less have not been developed. It is difficult to stably form a thin film having a thickness of several microns 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-mentioned problem, 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, in the electrolytic polymerization method, generally, the molecular weight of the generated polymer is about several thousands, and the heat resistance and the mechanical properties are sometimes insufficient. Therefore, if the thermal and mechanical strength of the insulating film and the adhesion to the coil can be further improved, the damage and cracking of the film can be reduced, and these problems can be further improved. However, there has been no example in which a film obtained by electrolytic polymerization is subjected to a curing treatment for increasing thermal and mechanical strength.

[0008]

In order to solve these problems, a method for forming a polymer film according to the present invention comprises forming a polymer having a functional residue by electrolytic polymerization,
Adding a curing agent to the polymer during or after electrolysis,
Thereafter, the polymer is cured.

In a second method of forming a polymer film according to the present invention, the functional residue contained in the polymer is a carbon-carbon unsaturated bond.

In a third aspect of the present invention, there is provided the method for forming a polymer film, wherein the monomer for forming the polymer is unsubstituted at the 4-position and substituted at least one of the 2, 3, 5, and 6-positions. Wherein a phenol derivative having a carbon-carbon unsaturated bond in any of the substituents is used.

A fourth method of forming a polymer film according to the present invention is characterized in that the curing agent is added to the polymer by immersing the electrode having the polymer formed on the surface thereof in a solution containing the curing agent. And

A fifth method of forming a polymer film according to the present invention is characterized in that an organic peroxide is used as the curing agent.

In a sixth aspect of the present invention, there is provided a method for forming a polymer film, wherein water is used as a solvent of the solution containing the curing agent.

In a seventh aspect of the present invention, there is provided a method for forming a polymer film, wherein the polymer film is cured by heating the polymer film under reduced pressure.

An eighth method of forming a polymer film according to the present invention is characterized in that the polymer film thus formed is cured by heating it in an inert gas.

In a ninth aspect of the present invention, there is provided a method for forming a polymer film, wherein the metal conductor having the polymer film formed on the surface is cured by electrically heating the metal conductor.

In a tenth aspect of the present invention, there is provided a metal insulating coating method, wherein a polymer film is formed on a defective portion of the insulating coating of a metal conductor having the insulating coating by the above method. I do.

The eleventh insulation-coated metal conductor is characterized in that a polymer film is formed on the surface of the metal conductor by the above method.

[0019]

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

First, a polymer having a functional residue according to the first invention is formed by electrolytic polymerization, and a curing agent is added to the polymer during or after electrolysis, and then the polymer is cured. A method for forming a polymer film characterized by the following will be described.

By using the electrolytic polymerization method, it is possible to form a uniform polymer thin film on conductors of various shapes such as insulated wires having a rectangular cross section. When a curing agent is added to a polymer having functional residues formed by this electrolytic polymerization method, and if energy such as heating or electron beam irradiation is added in some cases, the action of the added curing agent or The functional residue in the polymer undergoes a cross-linking reaction with another functional residue by reaction with the residue, and the polymer forms a three-dimensional network structure. As a result, improvements in thermal and mechanical properties represented by an increase in the glass transition point and heat deformation temperature,
Improvements in various physical properties of the polymer, such as development of durability against chemicals such as acetone, diethyl ether, and chloroform, and an increase in volume resistivity, are observed.

For polymers having functional residues,
The type of the residue is not particularly limited. For example, carbon-
A polymer having a carbon unsaturated bond, a carboxyl group, an amino group, an epoxy group, a methylol group, an isocyanate group, or the like can be used.

As the curing agent, various compounds can be used depending on the functional residue of the polymer to be formed.

Specifically, when the functional residue is a carbon-carbon unsaturated bond, inorganic peroxides such as aqueous hydrogen peroxide, sodium peroxide and potassium peroxide, benzoyl peroxide, t- Organic peroxides such as butyl perbenzoate, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide and di-t-butyl peroxide; and azo compounds such as azobisisobutyronitrile. A radical initiator can be used as a curing agent.

Further, similarly to rubber, a sulfur-based vulcanizing agent may be used as a curing agent.

When the functional residue is a carboxyl group or an amino group, a polyepoxy compound such as (poly) ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether or bisphenol A diglycidyl ether is used as a curing agent. Can be. Further, inorganic bases such as hydroxides of alkali metals or alkaline earth metals, organic bases such as tertiary amines, and salts and complex compounds thereof may be added to the curing agent and used as a co-catalyst for the curing reaction.

When the functional residue is an epoxy group,
3 such as ethylenediamine and hexamethylenediamine
Non-grade polyamine compounds or polybasic acids such as phthalic acid, maleic acid and adipic acid can be used as curing agents. In the same manner as in the previous example, an inorganic base such as an alkali metal or alkaline earth metal hydroxide, an organic base such as a tertiary amine, and a salt and a complex compound thereof are added and used as a co-catalyst of a curing reaction to a curing agent. Is also good.

When the functional residue is a methylol group, an aldehyde such as formaldehyde or a polyisocyanate compound can be used as a curing agent.

When the functional residue is an isocyanate group, a polyamine, polybasic acid, polyol or the like can be used as a curing agent.

Examples of these curing agents include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids and anhydrides such as carboxylic acid and aromatic sulfonic acid, Lewis acids such as boron trifluoride, metal organic acid salts, amines, and the like. A reaction accelerator represented by an ammonium salt or the like can also be added as a co-catalyst.

Next, a method of forming a polymer film according to the second invention, wherein the functional residue contained in the polymer is a carbon-carbon unsaturated bond, will be described.

When a radical initiator shown above as a curing agent is allowed to act on a polymer containing a carbon-carbon unsaturated bond as a functional residue, the unsaturated bond of the polymer or the unsaturated bond and the unsaturated bond in the system are reacted. Crosslinking is performed between molecules by a radical polymerization reaction or an ionic polymerization reaction with a monomer, and a three-dimensional network structure is formed. As a result, polymer properties such as improvement in thermal and mechanical properties represented by an increase in the glass transition point and heat distortion temperature, development of durability against chemicals such as acetone, diethyl ether, and chloroform, increase in volume resistivity, etc. Of various physical properties are observed.

The type of the polymer having a carbon-carbon unsaturated bond is not particularly limited. In addition to polyenes, polyynes, unsaturated polyesters, unsaturated polyurethanes, etc. having a carbon-carbon unsaturated bond in the main chain, hydrocarbon polymers, poly (meth) acrylates, polyesters having a carbon-carbon unsaturated bond in a side chain , Polyaryl ether, polyaniline, polypyrrole, polythiophene, and the like.

Next, as a monomer for forming the polymer according to the third invention, the 4-position is unsubstituted and 2,
A method for forming a polymer film, wherein one or more of the 3, 5, and 6 positions are substituted and a phenol derivative having a carbon-carbon unsaturated bond in any of the substituents is used will be described.

The 4-position is unsubstituted, and one or more of the 2, 3, 5, and 6-positions are substituted.
In the phenol derivative having a carbon unsaturated bond, the type of the substituent having a carbon-carbon unsaturated bond is not particularly limited. In addition to unsaturated aliphatic or aromatic hydrocarbon groups represented by vinyl group, allyl group, propargyl group, allenyl group, etc., any substituent having a carbon-carbon unsaturated bond should be used. Can be.

In the phenol derivative, the types of substituents other than the substituent having a carbon-carbon unsaturated bond described in the preceding paragraph are not particularly limited. For example, carbon 1 to 12
And a saturated or unsaturated aliphatic or aromatic hydrocarbon group, an alkoxy group, an amino group, an acyl group, a carbonyloxyalkyl group, an amide group and the like.

The 4-position is unsubstituted, and one or more of the 2, 3, 5, and 6-positions are substituted.
The concentration of the phenol derivative having a carbon unsaturated bond is 0.
The amount is from 01 to 10 mol / l, preferably from 0.1 to 2 mol / l.
The concentration of the basic compound is 0.5 to 2 times, preferably 0.5 to 1.2 times the molar amount of the phenol derivative.

The reaction formula of the electrolytic polymerization is represented by the following formulas (1) and (2).
Shown in (Formula 1) is that the 4-position is unsubstituted, and
One or more of the 5- and 6-positions are substituted, and a phenol derivative having a carbon-carbon unsaturated bond in any of the substituents becomes a phenoxide ion in an alkaline aqueous solution and shows a reaction of generating a phenoxide radical by oxidation. .
(Formula 2) shows a reaction in which the phenoxide radical is added to the aromatic ring of the phenol derivative or the polymer, and the polymerization proceeds. There is no particular limitation on the applied voltage.

[0039]

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[0040]

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Next, a polymer film according to a fourth aspect of the present invention, wherein the curing agent is added to the polymer by immersing the electrode formed on the surface of the polymer in a solution containing the curing agent. The method for forming the film will be described.

Depending on the type of the curing agent, the curing agent itself reacts and deteriorates when a voltage is applied during polymerization. Also, for example, when a metal is used as an electrode for forming a polymer, and a peroxide is used as a hardening agent, the electrode and the hardening agent before forming the polymer directly interact with each other, which may hinder polymer formation. . Therefore, after a polymer is formed on an electrode by an electrolytic polymerization method, the electrode is immersed in an aqueous solution or an organic solvent solution containing a curing agent to diffuse and introduce the curing agent into the polymer film. By performing this method, it becomes possible to add a hardening agent having poor stability or a hardening agent that interacts with the electrode to the polymer.

The electrolytic polymerization method is a wet process in which a film is formed in an electrolytic solution, and a step of washing the electrolytic solution attached to the film or the electrode after the film is formed is often performed. Particularly, as a monomer for forming a polymer, the 4-position is unsubstituted and one or more of the 2, 3, 5, and 6-positions are substituted, and carbon-carbon unsaturated is contained in any of the substituents. When a phenol derivative having a bond is used, the polymer formed by electrolytic polymerization swells due to the electrolytic solution and may exhibit a gel state. In this case, the purpose is to remove a solution component contained in the polymerization product. For this purpose, a step of immersing in an aqueous solution other than water or an electrolytic solution or an organic solvent solution is performed. By dissolving the curing agent in water or a solution used in such a washing / immersion step, and immersing the electrode having the polymer formed on the surface in the solution, the curing agent can be efficiently added to the polymer. it can.

As a solvent containing a curing agent, in addition to water,
Any organic solvent that dissolves the curing agent and does not dissolve the polymer formed on the electrode surface can be used. For example, hydrocarbons such as pentane, hexane, benzene, and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, and ethylene glycol Alcohols, such as
Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and diethyl ketone, and polar solvents such as dimethyl sulfoxide, dimethylformamide and acetonitrile can be used.

Preferably, the ability to dissolve the polymer is generally low, such as aliphatic hydrocarbons such as pentane, hexane and heptane; alcohols such as methanol, ethanol and ethylene glycol; lower ethers such as dimethyl ether and diethyl ether; Acetonitrile.

If necessary, these solvents may be used as components other than the curing agent, such as acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid.
Sodium hydroxide, potassium hydroxide, sodium chloride,
Metal salts such as potassium chloride and other compounds may be dissolved. However, if these salts remain in the polymer, they lower the electrical insulation, so they need to be used according to the purpose of the polymer film.

Next, as a curing agent according to the fifth invention,
A method for forming a polymer film using an organic peroxide will be described.

The organic peroxide is mildly decomposed at a relatively low temperature to generate radicals. Particularly when the functional residue contained in the polymer is a carbon-carbon unsaturated bond, a curing reaction of the polymer is started by radicals generated from the organic peroxide. Since the decomposition temperature varies greatly depending on the chemical structure, an organic peroxide having an appropriate decomposition temperature can be selected according to the type of the polymer and the processing conditions.

Organic peroxides are less susceptible to corrosion, ignition and explosion than metal peroxides, and are therefore easier to handle. Furthermore, since the organic peroxide has a higher boiling point than hydrogen peroxide, loss due to volatilization during heating of the polymer described below is reduced, and the curing reaction can proceed more efficiently.

Next, a method of forming a polymer film according to a sixth aspect of the present invention, wherein water is used as a solvent for a solution containing a curing agent, will be described.

Since water has a lower ability to dissolve a polymer than an organic solvent, loss due to dissolution of the polymer in the step of adding a curing agent can be reduced. Also,
When a curing agent is added to the polymer in the washing / immersion step, water has a large dielectric constant, so that generally a highly polar electrolyte component can be effectively removed.

When water is used as the solvent, any water-soluble organic peroxide such as t-butyl hydroperoxide, succinic peroxide, or t-butyl maleic acid may be used as a curing agent. can do.

As described above, acids, metal salts and other compounds may be dissolved as components other than the curing agent, if necessary.

Next, a method of forming a polymer film according to a seventh aspect of the present invention, which comprises curing the formed polymer film by heating it under reduced pressure, will be described.

When a curing reaction is performed on a polymer having a functional residue using a curing agent, heating is often required during curing depending on the types of the polymer and the curing agent. Even when heating is not essential, the curing reaction is usually accelerated by heating. When this heat treatment is performed in the air, oxygen present in the air causes deterioration of the polymer physical properties due to oxidative deterioration and deterioration of the conductivity due to oxidation of the conductor formed on the surface of the polymer.

Therefore, by performing the heat treatment step in a system in which the oxygen concentration has been reduced by reducing the pressure, the progress of these side reactions can be suppressed, and the curing reaction can proceed efficiently. The pressure in the heat treatment system is 100 Pascal or less, preferably 1 to 10 ^-4 Pascal.

Next, a method of forming a polymer film according to the eighth aspect of the invention, which is characterized in that the formed polymer film is cured by heating it in an inert gas, will be described.

As described above, when the polymer is heated in air for the purpose of accelerating the curing reaction, side reactions such as oxidation of the polymer and the electrode proceed. So, polymer and
By performing the heating in an inert gas having low reactivity with the conductor having the polymer formed on the surface, the curing reaction can be efficiently advanced. Heating is about 10 ° C or more higher than the curing temperature of the curing agent used and about 10 ° C above the thermal decomposition temperature of the polymer.
It is desirable to carry out in a temperature range lower by at least ° C.

As the inert gas, helium, neon,
A rare gas such as argon, nitrogen, carbon dioxide, or the like can be used.

Next, a method of forming a polymer film according to a ninth aspect of the present invention, which comprises curing a metal conductor having a polymer film formed on its surface by electrically heating the metal conductor, will be described.

When a good conductor such as a metal is placed in an AC magnetic field, a current flows through the conductor due to electromagnetic induction, and the conductor generates heat due to the Joule heat. By utilizing this induction heating phenomenon, the polymer film formed on the conductor can be heated to accelerate the curing of the polymer. By performing the induction heating, the metal conductor can be heated at a high speed, with high efficiency and uniformly, and the temperature control for electric heating becomes easy.

As the metal conductor for forming the polymer film on the surface, zinc, tin, nickel, aluminum, chromium, iron,
Copper, titanium, silver, palladium, indium, platinum, gold,
And alloys of these metals and the like can be used.

Next, a tenth aspect of the present invention is to provide a metal conductor having an insulating coating, wherein a polymer film is formed on a defective portion of the insulating coating by the above method. The method will be described.

The metal conductor having an insulating coating refers to an enameled wire having an insulating coating formed on the surface by applying and baking a varnish, a metal conductor having a passivated film formed on the surface, and the like. If a defect exists in these surface coating portions, the portion is electrically connected to the outside, so that it can be used as an electrode for electrolytic polymerization. During or after the electrolytic polymerization, a curing agent is added to the polymer and the polymer is cured, whereby the insulation at the defective portion is firmly repaired. 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, an insulating coated metal conductor according to the eleventh aspect of the present invention, which is characterized in that a polymer film is formed on the surface of the metal conductor by the above method, will be described.

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. In addition, since the strength of the film is large, it is possible to reduce defects due to defects in the insulating coating, such as rare shorts and ground defects during product production.

[0067]

Next, a specific embodiment will be described.

Example 1 0.7 mol of 2-allylphenol, 0.7 mol of potassium hydroxide, 0.3 mol of diethylamine
A 25 x 60 x 0.1 mm strip-shaped copper electrode and a platinum electrode are immersed in an aqueous solution of molarity water: methanol = 75: 25% by volume, and the voltage is adjusted so that the potential between both electrodes becomes 3 V using the copper electrode as an anode. Was applied to perform electrolysis for 20 minutes. After the electrolysis, the copper electrode was taken out and immersed in a 30% hydrogen peroxide solution for 2 minutes. The copper electrode was taken out and heated at 180 ° C. for 3 hours in a thermostat to cure the formed polymer film. According to the gravimetric method, the film thickness was 30 μm. The formed film was peeled off, and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Example 2 0.7 mol of 2-allylphenol, 0.7 mol of potassium hydroxide, 0.3 mol of diethylamine
A 25 x 60 x 0.1 mm strip-shaped copper electrode and a platinum electrode are immersed in an aqueous solution of molarity water: methanol = 75: 25% by volume, and the voltage is adjusted so that the potential between both electrodes becomes 3 V using the copper electrode as an anode. Was applied to perform electrolysis for 20 minutes. After the completion of the electrolysis, the copper electrode was taken out and immersed in a 1% t-butyl maleic acid aqueous solution for 30 minutes. Take out the copper electrode and place it in a thermostat
The resulting polymer film was cured by heating at 150 ° C. for 3 hours. According to the gravimetric method, the film thickness was 30 μm. The formed film was peeled off, and the heat deformation temperature was measured by measuring the penetration using a thermomechanical tester.
Above 0 ° C, deformation due to decomposition occurred. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Example 3 A strip-shaped copper electrode of 25 × 60 × 0.1 mm was added to an aqueous solution of water: methanol = 80: 20% by volume having 0.7 mol concentration of hydroxybenzyl alcohol, 0.7 mol concentration of potassium hydroxide and 0.3 mol concentration of diethylamine. And a platinum electrode are immersed, and the potential between both electrodes is 3
Electrolysis was performed for 10 minutes by applying a voltage so as to be V. After the completion of electrolysis, take out the copper electrode, immerse it in formalin for 20 seconds,
After immersion in pure water for 10 seconds, it was taken out. By taking out the copper electrode and heating it at 100 ° C for 1 hour in a thermostat,
The resulting polymer film was cured. According to the gravimetric method, the film thickness was 10 μm. The formed film was peeled off, and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester. As a result, deformation due to decomposition occurred at 200 ° C. or higher. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Example 4 A solution of 25 × 60 × 0.1 mm in an aqueous solution of 0.7 mol of 2- (1-propenyl) phenol, 0.7 mol of potassium hydroxide and 0.3 mol of diethylamine in water: methanol = 75: 25% by volume was used. A copper electrode in the form of a strip and a platinum electrode are immersed, and the potential between the two electrodes is 3 with the copper electrode as the anode.
The voltage was applied so as to be V, and electrolysis was performed for 20 minutes. After the completion of the electrolysis, the copper electrode was taken out and immersed in a methanol solution in which a sulfur-based vulcanizing agent was dissolved at 2% by weight for 30 seconds. The copper electrode was taken out and heated at 180 ° C. for 1 hour in a thermostat to cure the polymer film formed. According to the gravimetric method, the film thickness was 13 μm. The formed film was peeled off, and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester, and it was 160 ° C. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Example 5 0.7 mol of 2-allylphenol, 0.7 mol of potassium hydroxide, 0.3 mol of diethylamine
A 25 x 60 x 0.1 mm strip-shaped copper electrode and a platinum electrode are immersed in an aqueous solution of molarity water: methanol = 75: 25% by volume, and the voltage is adjusted so that the potential between both electrodes becomes 3 V using the copper electrode as an anode. Was applied to perform electrolysis for 20 minutes. After the electrolysis was completed, the copper electrode was taken out and immersed in a 0.1 molar azobisisobutyronitrile methanol solution for 1 minute. Thereafter, the copper electrode was taken out and heated at 120 ° C. for 2 hours in a thermostatic oven to cure the formed polymer film. According to the gravimetric method, the film thickness was 2 μm. The formed film was peeled off, and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Example 6 0.7 molar concentration of hydroxybenzoic acid, 0.7 molar concentration of potassium hydroxide, 0.3 molar concentration of diethylamine
A 25 x 60 x 0.1 mm strip-shaped copper electrode and platinum electrode are immersed in a 50:50 volume% aqueous solution of water: methanol at a molar concentration, and the voltage is adjusted so that the potential between both electrodes is 3 V using the copper electrode as an anode. Was applied to perform electrolysis for 10 minutes. After the electrolysis, the copper electrode was taken out and immersed in methanol containing 5% by weight of ethylene glycol diglycidyl ether for 1 minute. The copper electrode was taken out and heated in a thermostat at 120 ° C. for 3 hours to cure the formed polymer film. According to the gravimetric method, the film thickness was 23 μm. The formed film was peeled off, and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester, and it was 178 ° C. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

(Example 7) Hydroxyethyl methacrylate 2 mol concentration, sodium perchlorate 0.5 mol concentration water:
25x60x0.1mm in aqueous solution of methanol = 90: 10vol%
Was immersed in a strip-shaped copper electrode and a platinum electrode, and electrolysis was performed for 8 minutes by applying a voltage so that the potential between both electrodes was 3 V using the copper electrode as an anode. After the completion of the electrolysis, the copper electrode was taken out and immersed in an aqueous solution of water: methanol = 60: 40 volume% containing 5% by weight of a blocked isocyanate agent for 1 minute. The copper electrode was taken out and heated at 150 ° C. for 1 hour in a thermostat to cure the formed polymer film. According to the gravimetric method, the film thickness was 23 μm. The formed film was peeled off, and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester. As a result, deformation due to decomposition occurred at 200 ° C. or higher. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Example 8 0.7 mol of 2-allylphenol, 0.7 mol of potassium hydroxide, 0.3 mol of diethylamine
A 25 x 60 x 0.1 mm strip-shaped copper electrode and a platinum electrode are immersed in an aqueous solution of molarity water: methanol = 75: 25% by volume, and the voltage is adjusted so that the potential between both electrodes becomes 3 V using the copper electrode as an anode. Was applied to perform electrolysis for 20 minutes. After the electrolysis, the copper electrode was taken out and immersed in a 30% hydrogen peroxide solution for 2 minutes. The copper electrode was taken out, put into a thermostat set at 180 ° C., and the inside of the thermostat was depressurized to 0.1 Pa and heated for 3 hours to cure the formed polymer film. According to the gravimetric method, the film thickness was 30 μm. The formed film was peeled off, and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Example 9 0.7 mol of 2-allylphenol, 0.7 mol of potassium hydroxide, 0.3 mol of diethylamine
A 25 x 60 x 0.1 mm strip-shaped copper electrode and a platinum electrode are immersed in an aqueous solution of molarity water: methanol = 75: 25% by volume, and the voltage is adjusted so that the potential between both electrodes becomes 3 V using the copper electrode as an anode. Was applied to perform electrolysis for 20 minutes. After the electrolysis, the copper electrode was taken out and immersed in a 30% hydrogen peroxide solution for 2 minutes. Remove the copper electrode and place it in a constant temperature bath
The resulting polymer film was cured by heating at 3 ° C. for 3 hours. According to the gravimetric method, the film thickness was 30 μm. The formed film was peeled off, and the heat deformation temperature was measured by measuring the penetration using a thermomechanical tester.
Above ℃, deformation due to decomposition occurred. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Example 10 0.7 mol of 2-allylphenol, 0.7 mol of potassium hydroxide, diethylamine
A 25x60x0.1mm strip-shaped copper electrode and a platinum electrode are immersed in an aqueous solution of 0.3 molar water: methanol = 75: 25% by volume so that the potential between the two electrodes becomes 3V using the copper electrode as an anode. Electrolysis was performed for 20 minutes by applying a voltage. After the electrolysis, the copper electrode was taken out and immersed in a 30% hydrogen peroxide solution for 2 minutes. The copper electrode was taken out and heated for 2 minutes using an induction heating device with a frequency of 50 kHz and an output of 3 kW to cure the polymer film formed. 35 μm thickness by gravimetric method
Met. When the formed film was peeled off and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester,
180 ° C. When the formed film was immersed in acetone, dissolution of the film was not confirmed.

Comparative Example 1 0.7 mol of 2-allylphenol, 0.7 mol of potassium hydroxide, 0.3 mol of diethylamine
A 25 x 60 x 0.1 mm strip-shaped copper electrode and a platinum electrode are immersed in an aqueous solution of molarity water: methanol = 75: 25% by volume, and the voltage is adjusted so that the potential between both electrodes becomes 3 V using the copper electrode as an anode. Was applied to perform electrolysis for 20 minutes. After the electrolysis, the copper electrode was taken out and immersed in water for 2 minutes. The copper electrode was taken out and dried in a thermostat at 50 ° C. for 3 hours. According to the gravimetric method, the film thickness was 30 μm. The formed film was peeled off, and the heating deformation temperature was measured by penetration measurement using a thermomechanical tester. When the formed film was immersed in acetone, the film was dissolved.

Comparative Example 2 A 25 × 60 × 0.1 mm strip-shaped copper electrode was placed in an aqueous solution of 0.7 mol of hydroxybenzyl alcohol, 0.7 mol of potassium hydroxide and 0.3 mol of diethylamine in water: methanol = 80: 20% by volume. And a platinum electrode are immersed, and the potential between both electrodes is 3
Electrolysis was performed for 10 minutes by applying a voltage so as to be V. After the electrolysis, the copper electrode was taken out, immersed in pure water for 10 seconds, and taken out. The copper electrode was taken out and dried at 50 ° C. for 1 hour in a thermostat. According to the gravimetric method, the film thickness was 15 μm.
The formed film was peeled off, and the heat deformation temperature was measured by penetration measurement using a thermomechanical tester. When the formed film was immersed in acetone, the film was dissolved.

[0080]

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) C08J 3/24 CEZ C08J 3/24 CEZZ C25D 9/02 C25D 9/02 H01B 7/02 H01B 7/02 A F 13/00 517 13/00 517 // C08J 5/18 CER C08J 5/18 CER C08L 101: 00

Claims (11)

[Claims] 1. A polymer film, comprising: forming a polymer having a functional residue by electrolytic polymerization, adding a curing agent to the polymer during or after electrolysis, and then curing the polymer. Forming method. 2. The method according to claim 1, wherein the functional residue contained in the polymer is carbon-
The method for forming a polymerized film according to claim 1, wherein the polymerized film is a carbon unsaturated bond. 3. A monomer for forming a polymer,
A phenol derivative wherein the 4-position is unsubstituted and one or more of the 2, 3, 5, and 6 positions are substituted, and a phenol derivative having a carbon-carbon unsaturated bond in any of the substituents is used. Item 3. The method for forming a polymer film according to Item 1 or 2. 4. The method according to claim 1, wherein the curing agent is added to the polymer by immersing the electrode having the polymer formed on the surface in a solution containing the curing agent.
The method for forming a polymer film according to the above. 5. The method for forming a polymer film according to claim 1, wherein an organic peroxide is used as a curing agent. 6. The method according to claim 1, wherein water is used as a solvent of the solution containing the curing agent. 7. A method for forming a polymer film, wherein the polymer film formed by the method according to claim 1, 2, 3, 4, 5, or 6 is cured by heating under reduced pressure. 8. A method for forming a polymer film, wherein the polymer film formed by the method according to claim 1, 2, 3, 4, 5, or 6 is cured by heating in an inert gas. 9. The method according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein curing is performed by electrically heating a metal conductor having a polymerized film formed on the surface thereof. Method of forming a polymer film. 10. A metal conductor having an insulating coating, wherein a defective portion of the insulating coating is provided on a defective portion of the insulating coating.
A method for insulating coating of a metal, comprising forming a polymer film by the method according to 6, 7, 8 or 9. 11. The method according to claim 1, wherein the surface of the metal conductor is provided.
An insulated metal conductor, wherein a polymer film is formed by the method described in 3, 4, 5, 6, 7, 8, or 9.