JP2958199B2 - Method of coating conductive material surface with chalcogen compound by electrolysis - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production, display and decoration of functional electrodes such as solar cells by coating the surface of a conductive material such as metal with a metal chalcogen compound under moderate conditions. Belong to the way to achieve the purpose.

[0002]

2. Description of the Related Art Conventionally, methods of coating with a chalcogen compound include a method of evaporating a film component in a vacuum or at a high temperature, a method of electrolysis in a molten salt, and a method of electrolytic reduction of chalcogen in an organic solvent containing a metal and simple chalcogen. There has been a way to do that. The conventional method has the following disadvantages.

[0003] Expensive equipment is required. Requires high temperature processing. Poor adhesion of the resulting film. The metal body is eutectoid. A large area object cannot be coated at low cost with good adhesion.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the drawbacks of the conventional methods as described above, and to provide a low-cost coating with good adhesion.

[0005]

In order to achieve the above object, a conductive material is treated in the following order. zinc,
Dissolve soluble salts of silver, copper, lead or cadmium in water. Dissolve thioacetamide, thioacetic acid, thiosulfate, thiourea, thiocarbonate, thioformamide, ammonium thiocarbamate or sodium selenosulfite in water. And mix the solution. The conductive material is immersed in the degreased solution. A cathode current is applied to the conductive material by an external power supply using a platinum or carbon rod as an anode.

[0006] By the above operation, the chalcogen compound can be attached to the surface of the conductive material.

[0007]

According to the above-mentioned reaction of the added reagent, zinc,
It is thought that the chalcogen compound of silver, copper, lead or cadmium can be generated and the chalcogen compound can be attached to the surface by passing a cathodic current, but there is no other explanation, and the principle mechanism Has not yet been fully elucidated. In any case, the conductive material can be firmly coated with the chalcogen compound by the action of both the reaction in the solution and the cathodic current, and this method has not been considered before.

Since a small amount of current may be applied, it is possible to cover not only metal having a small electric resistance but also a conductive material such as glass or resin whose surface is subjected to a conductive treatment. As a result, the conductive substance could be coated with the chalcogen compound in an interference color such as blue, green and red when the coating was thin, and colorless, red or yellow when the coating was thick.

The concentration of each of the chemicals is 1 to 20 kg / m ^3.
The temperature of the reaction bath is from room temperature to about 90 ° C., the pH range is 2 to 4, and the coating can be performed under moderate conditions.

[0010] A simple device which does not require any special device other than the power supply and maintains the temperature is sufficient.

As described above, the reaction solution and the method are simpler than those of the conventional method, and it is possible to cover a large area by enlarging the bathtub. The current density may be small, and there is no fear that the surface of the conductive material reacts and changes, or that the metal body is folded together. The adhesion of the formed film is very good.

Since the coating can be performed with a small current density, non-metals which have been subjected to a conductive treatment such as conductive glass and conductive resin can be coated in addition to metal.

As described above, the processing temperature is low, and a normal polymer such as polystyrene, polymethacrylate, or polyvinyl acetate is applied to completely protect the surface of the non-coated conductive material during the reaction. And can be partially coated.

[0014] The electrode formed by coating has photoresponsiveness,
It has applications as a functional electrode and a colored film, and has a high utility value that can be applied to resins having low heat resistance since the processing temperature is lower than that of the conventional method.

The following is a description of a typical embodiment.

[0016]

Example 1 Example 1 Reaction solution Zinc sulfate 5 kg / m³, Thioacetamide 5Kg / m³  Temperature 70 ° C Metal Metal Titanium Anode Platinum Current density 0.4A / m² As a result of processing with the above configuration, the metal is dried in red in 120 minutes.
It can be tinted and metal coated with zinc sulfide.
Came. 0.2 A / m current density²Even if processed in
The coating is slow but coating is possible. Silver nitrate, copper sulfate, lead chloride
Alternatively, even if cadmium sulfate is used, each sulfide
Could be coated.

Example 2 Reaction solution Zinc chloride 5 kg / m³, Thioacetic acid 5Kg / m³  Temperature 60 ℃ metal metal titanium anode platinum current density 0.4A / m² As a result of processing with the above configuration, the metal is dried in red in 120 minutes.
It can be tinted, and can infect metals with zinc sulfide.
Came. 0.2 A / m current density²Even if processed in
The coating is slow but coating is possible. Hydroxylamine, d
Addition of soluble amines such as tanolamine
The reaction is accelerated and coating is possible at low temperatures. silver nitrate,
Using copper sulfate, lead chloride or cadmium sulfate
Each sulfide could be coated.

Example 3 Reaction solution Zinc chloride 5 kg / m³, Thioacetic acid 5Kg / m³  Temperature 60 ℃ metal conductive glass anode platinum current density 0.4A / m² As a result of processing with the above configuration, the glass is covered with zinc sulfide.
Could be overturned. 0.2 A / m current density²Processed by
Although the coating is slow, coating is possible. silver nitrate,
Using copper sulfate, lead chloride or cadmium sulfate
Each sulfide could be coated.

Example 4 Reaction solution Zinc chloride 5 kg / m³, Thiosulfate 5Kg / m³  Temperature 70 ° C Metal Metal Titanium Anode Platinum Current density 0.4A / m² As a result of processing with the above configuration, the metal turns red in 180 minutes.
It could be colored and the metal could be coated with zinc sulfide. Electric
Flow density 0.2A / m²Coating is slow even when treated with
Can be coated. Silver nitrate, copper sulfate, lead chloride or
Even if using cadmium sulfate, coat with each sulfide
I was able to.

Example 5 Reaction solution Zinc chloride 5 kg / m³, Potassium thiocarbonate 5Kg / m³  Temperature 60 ℃ metal metal titanium anode platinum current density 0.4A / m² As a result of processing with the above configuration, the metal is dried in red in 120 minutes.
It can be tinted and metal coated with zinc sulfide.
Came. 0.2 A / m current density²Even if processed in
The coating is slow but coating is possible. Silver nitrate, copper sulfate, lead chloride
Alternatively, even if cadmium sulfate is used, each sulfide
Could be coated.

Example 6 Reaction solution Zinc sulfate 5 kg / m³, Thiourea 5Kg / m³  Temperature 90 ° C Metal Metal Titanium Anode Platinum Current density 0.4A / m² As a result of processing with the above configuration, the metal is dried in red in 180 minutes.
It can be tinted and metal coated with zinc sulfide.
Came. 0.2 A / m current density²Even if processed in
The coating is slow but coating is possible. Silver nitrate, copper sulfate, lead chloride
Alternatively, even if cadmium sulfate is used, each sulfide
Could be coated.

[0022] Example 7 reaction solution of zinc chloride 5Kg / ^{m 3,} thioformamido 5Kg / ^{m 3} Temperature 70 ° C. metal metal titanium anode platinum current density 0.4 A / ^{m 2} a result of processing in the above configuration, the metal is at 180 minutes The metal was colored to a red interference color and could be coated with zinc sulfide. Even when the treatment is performed at a current density of 0.2 A / m ² , the coating is slow but coating is possible. Even using silver nitrate, copper sulfate, lead chloride or cadmium sulfate, it was possible to coat with each sulfide.

Example 8 Reaction solution Zinc chloride 5 kg / m³, Sodium seleno sulfite 5Kg / m³  Temperature 60 ℃ metal metal titanium anode platinum current density 0.4A / m² As a result of processing with the above configuration, the metal is dried in red in 120 minutes.
Coloring with a matte color and coating the metal with zinc selenide
Was completed. 0.2 A / m current density²If processed in
Coating is also slow, but coating is possible. Silver nitrate, copper sulfate, salt
Even if lead oxide or cadmium sulfate is used,
It could be coated with the renides.

Example 9 Reaction solution Zinc chloride 5 kg / m³Ammonium thiocarbamate 5Kg / m³  Temperature 60 ℃ metal metal titanium anode platinum current density 0.4A / m² As a result of processing with the above configuration, the metal is dried in red in 120 minutes.
It can be tinted and metal coated with zinc sulfide.
Came. 0.2 A / m current density²Even if processed in
The coating is slow but coating is possible. Silver nitrate, copper sulfate, lead chloride
Alternatively, even if cadmium sulfate is used, each sulfide
Could be coated.

Example 10 A polycinnamic acid-based photoresist was replaced with titanium metal.
Light is applied by applying the film to the plate surface in close contact with the coating surface
I do. Unexposed polymer by developer
Dissolve and exfoliate. Parts not covered by the operation of
Metal titanium with a resist film formed on
And process for 150 minutes. Reaction liquid Zinc sulfate 5Kg / m³Thioacetamide 5Kg / m³  Temperature 70 ° C Anode Platinum Potential applied to metal -700 mV (vs. SCE)
The metal titanium is washed with water. For stripper (toluene)
The resist film is further removed. With the above operation, the metal titani
1A / m for um²About cathode current flows and good adhesion
Partially covered.

In the case of using polymethacrylate, the toluene solution is applied to the metal surface and the above operations are repeated to partially cover the metal surface. The same applies to other polymers.

When soluble silver, copper, lead or cadmium salts are used instead of zinc salts, they can be coated with the sulfides of the respective metals.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C25D 9/08 C25D 13/04 C25D 3/00

Claims (1)

(57) [Claims] 1. A metal ion such as zinc ion, silver ion, copper ion, lead ion or cadmium ion and thioacetamide, thioacetate, thiosulfate, thiourea, thiocarbonate, thioformamide, ammonium thiocarbamate or selenosulfite. A method in which a conductive substance is immersed in an aqueous solution containing a reagent, an electric current is applied to the conductive substance, and the conductive substance is cathode-polarized, whereby the chalcogen compound of each metal is attached.