JP2003321798A - Method and apparatus for electrical treatment such as electroplating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and apparatus for electrical treatment such as electroplating which is suitably used for example, for the electrical treatment such as electroplating and in which each process is safely and reasonably performed using super critical or subcritical carbon dioxide, and carbon dioxide, a treating liquid and the like after being used are safely, reasonably and rapidly treated, the quantity of a pickling solution, a plating solution or the like to be used is reduced, the waste water produced by the plating is decreased and recycled to prevent the environmental pollution to improve the working environment and the productivity, the throwing power of the plating is remarkably improved and fine finish is attained. <P>SOLUTION: A super critical or subcritical state is formed in a reaction vessel 1 housing electrolytic materials and an electrolyte solution. An electrode material 3 is electrolyzed under the critical state or subcritical state or the electrolyzed electrode material and/or the electrolytic materials contained in the electrolyte solution are deposited and stuck on the other electrode material 4. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is suitable for electrochemical treatment such as electroplating, and can perform each treatment step safely, rationally and promptly by using supercritical or subcritical carbon dioxide, and after use. Reasonably and promptly treats carbon dioxide and treatment solution, etc., suppresses the amount of pickling solution, plating solution, etc. used, and further reduces the amount of waste solution generated from plating work to prevent environmental pollution, In addition to improving the work environment to improve productivity, we plan to reuse them, and also dramatically improve the plating distribution, resulting in a beautiful finish and the denseness on the back surface and recesses of the workpiece. In addition, the uniform plating can be realized easily and its productivity can be improved, while the bath required for each treatment can be omitted and the size and weight can be reduced to reduce the equipment cost and the installation space. etc Electrochemical processing method and its electrochemical reactor.

[0002]

2. Description of the Related Art The conventional electroplating process is roughly divided into a pretreatment process, a plating process, and a posttreatment process. Of these, the pretreatment process involves degreasing and pickling, and these are usually performed by immersing the prescribed treatment liquid in a dedicated bath and heating it, and immersing the object to be treated in this treatment liquid for a prescribed time. There is.
Therefore, a plurality of baths and their work spaces are required, and the equipment cost is high, and the work environment is bad because the work is forced to be performed in a situation where the processing liquid is scattered and harmful gas is generated. There was a problem that it took a long time to soak and productivity was poor.

For conventional degreasing cleaning, alkali heating,
Various cleaning methods such as electrolytic cleaning, solvent cleaning, and emulsion cleaning have been proposed, but all require chemical injection and special equipment. Furthermore, the object to be processed is immersed in each processing solution, or the processing solution vapor is vaporized. Since it is exposed to the inside, there is a problem that it takes time to drain the water thereafter.

In order to solve such a problem, for example, in Japanese Unexamined Patent Publication No. 2000-63891, carbon dioxide in a supercritical state is supplied to and brought into contact with a small-volume chamber for containing an object to be cleaned, and at the same time, the object to be cleaned is contacted. The cleaning object is heated or vibrated to dissolve and remove the PCB adhering to the cleaning object.

However, in this conventional cleaning device, after cleaning,
Since all the carbon dioxide in the supercritical state is discharged to the atmosphere, the consumption of carbon dioxide increases and the cost becomes high for cleaning the electroplating product having a larger volume than the chamber.
Further, deterioration of the working environment due to the emission of carbon dioxide is expected, and therefore it cannot be adopted.

Further, in the conventional plating process, a plurality of washings are required adjacent to the plating tank, and water is constantly supplied to the main washing tank, so that the equipment cost becomes high and the water usage fee increases. There is. Further, the recovery of the plating solution when taking out the object to be plated from the plating tank, so-called pumping back, is very complicated and troublesome, and the recovered solution needs to be concentrated, so that the productivity is very low.

On the other hand, in the conventional electroplating, the plating is generally poor in distribution, and almost no plating is applied to the back surface or the concave portion of the object having a low current density. Since it is troublesome to change the plating or dispose the auxiliary electrode on the relevant part, it is difficult to cope with the plating of the object having a different shape. Further, in the conventional post-treatment process, after plating, it was washed with water, washed with hot water, and dried, but it took time and productivity was poor.

Furthermore, the wastewater discharged from the plating plant is
Although the quality of water is regulated by law, of the wastewater generated from plating work, cleaning wastewater is generally treated with a specified chemical to detoxify it, and then PH adjustment is used to remove heavy metals as hydroxides. Was treated by adding it to the wash drainage little by little, or treating it separately, and mixing the treatment liquid with a thin wash drainage for treatment. However, the conventional wastewater treatment requires expensive equipment, various chemicals, a large amount of water, and a lot of time, and the productivity is very poor.

[0009]

The present invention solves such a problem and is suitable for electrochemical treatments such as electroplating, and uses supercritical or subcritical carbon dioxide to safely perform each treatment step. It can be done reasonably and promptly, and it can process the carbon dioxide and treatment solution after use reasonably and promptly, and can control the amount of pickling solution and plating solution used, and further reduce the amount of waste solution generated from plating work. In addition to preventing environmental pollution and improving the work environment to improve productivity, they can be reused and the plating distribution can be dramatically improved to achieve a beautiful finish and It facilitates precise and uniform plating on the back surface and recesses of the object to be processed, improving its productivity, while omitting the bathtub required for each process and making it smaller and lighter, reducing equipment costs and installation space.
It is an object of the present invention to provide an electrochemical treatment method such as electroplating and an electrochemical reaction apparatus for the same, which can achieve a compact size.

[0010]

Therefore, according to the invention of claim 1, the cathode and anode electrode materials are contained in a reaction bath capable of containing the electrolyte material, and one of the electrode materials is electrolyzed, or the electrolysis is performed. In an electrochemical treatment method such as electroplating in which an electrolytic substance contained in the electrode substance and / or the electrolytic solution is deposited and adhered to the other electrode substance, a reaction bath containing the electrolytic substance and the electrolytic solution is placed in a supercritical state. Alternatively, it is formed in a subcritical state, and the electrode substance is electrolyzed under the state, or the electrolytic substance contained in the electrolyzed electrode substance and / or the electrolyte solution is deposited and adhered to the other electrode substance, and, for example, electric Suitable for electrochemical treatment such as plating, supercritical or subcritical carbon dioxide can be used to perform each treatment step safely, rationally and promptly Reasonably and swiftly process the raw materials and processing solutions, reduce the amount of pickling solution and plating solution used, and reduce the amount of waste liquid generated from plating work to prevent environmental pollution and work environment. In addition to improving productivity and reusing them, the plating distribution is dramatically improved to achieve a beautiful finish, and the back surface and recesses of the object to be processed are also minute and uniform. Such plating can be easily realized and its productivity can be improved, and it can be applied to electroforming, anodic oxide film forming, and electrolytic polishing to improve its productivity and obtain a good finished state. I am trying.

According to a second aspect of the present invention, an electrode material for a cathode and an anode is housed in a reaction bath capable of housing an electrolytic material, the electrolytic material is electrolyzed, and the electrolyzed material is collected on the side of the other electrode material. In electrochemical treatment methods such as plating,
A reaction bath containing an electrolytic substance is formed in a supercritical state or a subcritical state, the electrolytic substance is electrolyzed under the state, and is collected on the other electrode substance side, and electrolytic extraction of metal is performed, It is applicable to the refining method to improve productivity and obtain a good finished state. The invention according to claim 3, wherein an object to be treated is contained in a reaction bath capable of accommodating an electrolytic substance, and an electrolytic treatment method such as electroplating in which the electrolytic substance contained in an electrolyte solution is deposited and adhered to the object to be treated. In, a reaction bath containing an electrolytic substance is formed in a supercritical state or a subcritical state, and under the state, the electrolytic substance is deposited and adhered to an object to be treated, and electroless plating that does not require an external electric field or It is applicable to the chemical conversion treatment method to improve its productivity and obtain a good finished state.

According to a fourth aspect of the present invention, the electrode material is electrolyzed, or the electrolyzed electrode material and / or the electrolytic material contained in the electrolyte solution is deposited and adhered to the other electrode material, or the electrolytic material is electrolyzed. After collecting on the other electrode material side, the reaction bath is transferred from the supercritical state or subcritical state to the state below the critical point, the electrolyte solution and the supercritical or subcritical material are returned to a two-layer state, and those At the same time as discharging, a rapid flow is formed in the system such as the reaction bath at the time of the above-mentioned transition to promote cleaning and drying of the object to be treated. According to a fifth aspect of the invention, after electrolysis of the electrode substance or the electrolytic substance, a substance in a supercritical state or a substance in a subcritical state is introduced into the reaction bath to wash the electrode substance or remove an oxide film. Therefore, the treatment is carried out reasonably and promptly to promote the drying.

According to a sixth aspect of the present invention, after electrolysis of the electrode substance or electrolytic substance, a substance in a supercritical state or a substance in a subcritical state is introduced into the reaction bath to wash the electrode substance or the electrolyte substance collecting side. Or, it is dried so that the treatment can be performed reasonably and quickly to promote the drying. The invention of claim 7 introduces a substance in a supercritical state or a substance in a subcritical state, an electrolytic substance and a surfactant into the reaction bath at the time of electrolysis of the electrode substance, so that the inside of the reaction bath is in a supercritical state or a subcritical state. By emulsifying at a critical level, the deposition and deposition of electrode materials or electrolytes can be performed uniformly, quickly and with high density. For example, the plating coverage can be dramatically improved, and a beautiful finish can be obtained, and the back surface of the object to be treated can be obtained. Dense and uniform plating can be easily realized on the and concave portions to improve the productivity.

According to the invention of claim 8, before the electrolysis of the electrode substance or the electrolytic substance, the substance in the supercritical state or the substance in the subcritical state, the oxide film removing solution and the surfactant are introduced into the reaction bath, The reaction bath is emulsified in a supercritical state or a subcritical state so that the treatments can be performed reasonably, rapidly and with high density. According to the invention of claim 9, a storage tank is provided outside the reaction bath which can communicate with the reaction bath, and the used supercritical substance or subcritical substance, electrolytic substance or cleaning or oxide film removing substance is stored in the storage bath. To stop their emissions,
We try to recycle and use it reasonably and effectively. The invention according to claim 10 regenerates the used supercritical substance or subcritical substance stored in the storage tank and recirculates it to the reaction bath, or the used electrolytic substance or cleaning or oxide film removal stored in the storage tank. The substances are regenerated and refluxed in each solution tank, so that the supercritical substances or subcritical substances after use, the electrolytic substances after use, the cleaning or oxide film removing substances, etc. are effectively utilized. .

According to an eleventh aspect of the present invention, the deposition and deposition of the electrode material and the pretreatment step thereof, or the electrolysis and collection of the electrolytic material and the pretreatment step thereof are carried out in a single reaction bath, and each treatment step is performed. The bath tub is abolished, the facility cost is reduced and the installation space is made compact, the complexity of moving the object to be treated for each bath is improved, and the work efficiency is improved. According to the invention of claim 12, at least two reaction baths capable of carrying out the deposition and deposition of the electrode substance and the treatment process before and after it or the electrolysis and collection of the electrolytic substance and the treatment process before and after it are provided. A series of treatments in a plurality of reaction baths such that some of the treatments are performed, the other of the treatments is performed in the other reaction bath, and these treatments are performed alternately between the reaction baths. The process is divided into two and the processes are alternately performed so that a series of processing operations can be performed reasonably and quickly. The invention of claim 13 electrolyzes an electrode material,
Alternatively, after the electrolyzed electrode substance is deposited and adhered to the other electrode substance, the reaction bath is used to deposit and attach a plurality of layers of electrode substances to the other electrode substance, and the object to be treated is carried out from the reaction bath. Without doing so, pretreatment of the electrode material of the next layer, deposition and adhesion can be continued, and workability and productivity are improved.

According to a fourteenth aspect of the present invention, a cathode and an anode electrode materials are contained in a reaction bath capable of containing an electrolyte material, one of the electrode materials is electrolyzed, or the electrolyzed electrode material and / or the electrolyte solution is contained. In an electrochemical reaction device such as electroplating in which an electrolytic substance to be deposited and adhered to the other electrode substance is formed, a reaction bath containing the electrolytic substance is formed in a supercritical state or a subcritical state, and under the state, It is suitable for electrochemical treatment such as electroplating, for example, by electrolyzing the electrode material, or by depositing and depositing the electrolyzed electrode material and / or the electrolytic material contained in the electrolyte solution on the other electrode material, and it is supercritical. Or, by using subcritical carbon dioxide, each treatment step can be performed safely, rationally and promptly, and the carbon dioxide and treatment solution after use can be treated rationally and promptly. At the same time, it suppresses the amount of pickling solution and plating solution used, further reduces the amount of waste solution generated from plating work, prevents environmental pollution, improves the work environment and improves productivity, and In addition to reusing and dramatically improving the plating distribution, a beautiful finish can be obtained, and precise and uniform plating can be easily achieved on the back surface and recesses of the object to be processed, which improves productivity. While improving, it is applicable to the electroforming method, the anodic oxide film forming method, and the electrolytic polishing method, so that the productivity can be improved and a good finished state can be obtained.

According to a fifteenth aspect of the present invention, the cathode and anode electrode materials are contained in a reaction bath capable of containing the electrolyte material, the electrolyte material is electrolyzed, and the other electrode material side is collected. In an electrochemical reaction device such as plating, a reaction bath containing an electrolytic substance is formed in a supercritical state or a subcritical state, the electrolytic substance is electrolyzed under the state, and this is collected on the other electrode substance side. In this way, it can be applied to the electrolytic extraction and refining methods of metals so that the productivity is improved and a good finished state is obtained. According to a sixteenth aspect of the invention, an electrochemical reaction such as electroplating in which an object to be treated is contained in a reaction bath capable of accommodating an electrolytic substance and the electrolytic substance contained in an electrolyte solution is deposited and adhered to the object to be treated. In the apparatus, electroless plating that does not require an external electric field by forming a reaction bath containing an electrolytic substance in a supercritical state or a subcritical state and depositing and depositing the electrolytic substance on an object to be treated under the state. It is also applicable to chemical conversion treatment methods to improve its productivity and obtain a good finished state.

According to a seventeenth aspect of the present invention, the electrode material is electrolyzed,
Alternatively, after depositing and adhering the electrolyzed electrode substance and / or the electrolytic substance contained in the electrolyte solution to the other electrode substance, or after electrolyzing the electrolytic substance and collecting this on the other electrode substance side, the reaction bath is supercritical. From the state or subcritical state to the low pressure side, the electrolyte solution and the supercritical or subcritical substance are returned to the two-layer state, and their discharge is realized, and at the time of the transition, it is rapidly changed into the system such as the reaction bath. A stream is formed to facilitate cleaning and drying of the material to be processed. According to the invention of claim 18, a storage tank, which can communicate with the reaction bath, is provided outside the reaction bath, and a substance in a supercritical state, a substance in a subcritical state or an electrolytic substance, or a cleaning or oxide film is used in the storage bath. The removed substances are stored so that their emission can be controlled, and they can be regenerated or used reasonably and effectively.

According to a nineteenth aspect of the present invention, the used supercritical substance or subcritical substance stored in the storage tank is regenerated and returned to the reaction bath, or the used electrolytic material or cleaning or stored in the storage tank is used. Regenerate the oxide film removal substance and reflux it to the reaction bath so that the supercritical substance or subcritical substance after use, the electrolytic substance after use or the cleaning or oxide film removal substance etc. can be effectively utilized. There is. According to the invention of claim 20, the deposition / adhesion of the electrode material and the pretreatment step thereof or the electrolysis and collection of the electrolytic material and the pretreatment step thereof can be processed in a single reaction bath, and a bath for each of the treatment steps can be provided. It is abolished, the facility cost is reduced, the installation space is made compact, the complexity of moving the object to be treated for each bath is improved, and the work efficiency is improved.

According to a twenty-first aspect of the present invention, at least two reaction baths are provided, which are capable of carrying out the deposition and deposition of the electrode material and the processing steps before and after it, or the electrolysis and collection of the electrolytic material and the processing steps before and after it, one of which is provided. A reaction bath carries out a part of the treatment steps, the other reaction bath carries out the rest of the treatment steps, and these treatments can be carried out alternately between the reaction baths, with a series of reaction baths The treatment process is divided into two and the treatments are alternately performed so that a series of treatment work can be performed reasonably and quickly. In the invention of claim 22, the electrode material is electrolyzed, or the electrolyzed electrode material is deposited and adhered to the other electrode material, and then the reaction bath is used to deposit a plurality of layers of electrode material on the other electrode material. By adhering, it is possible to continue the pretreatment and deposition adhesion of the electrode material of the next layer without carrying out the object to be treated from the reaction bath, thereby improving workability and productivity.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a preferred embodiment in which the present invention is applied to electroplating (nickel plating) which is an electrochemical treatment method will be described.
Is a stainless steel plating bath that is an electrochemical reaction bath, the inner surface of which is lined with vinyl chloride or hard rubber, and the lid (not shown) is airtight and removable in the upper opening. It is installed.

A direct current power source 2 which is an external electric field is provided outside the plating tank 1, and an anode 3 which is an electrode material which conducts to the positive electrode side thereof and an electrode material which conducts to the negative electrode side and which is an object to be treated. The cathode 4 and the plating tank 1 can be housed. In the embodiment, a pure nickel plate is used for the anode 3 and a brass plate for Hull cell test is used for the cathode 4.

In the figure, reference numeral 5 is a switch inserted in the power supply circuit of the power source 2, and is turned on only during an electrochemical reaction, that is, during electroplating, so that the anode 3 and the cathode 4 can be energized. Reference numeral 6 is a stirrer 2 such as a stirrer provided at the bottom of the plating tank 1 for introducing carbon dioxide, which will be described later, which is a supercritical substance introduced into the plating tank 1, and an electrolyte solution or an acid solution containing a surfactant. It is possible to stir.

A gas container 8 in which carbon dioxide 7 as a supercritical substance is pressurized and stored in a high pressure outside the plating tank 1
, Electrolyte solution tanks 11 and 12 containing electrolyte solutions 9 and 10 of different kinds, and an acid solution 1 of PH7 and below
Acid solution tank 14 containing 3 and carbon dioxide 15 after use
And a gas reservoir 16 for storing the used acid solution 17 containing a surfactant after use, or liquid reservoirs 20 to 22 as a plurality of reservoirs containing the electrolyte solutions 18 and 19 containing a surfactant after use. It is arranged.

Return pipes 49 to communicating with the solution tanks 11, 12 and 14 are connected to the liquid reservoirs 20 to 22.
51 is connected, and each of the used solutions 17 to 19 is separated from the surfactant or is prepared to have a slightly high concentration without being separated and is regenerated, and then the solution is refluxed to each of the solution tanks 9, 10 and 13. There is.

The gas container 8 communicates with the upper part of the plating tank 1 via a conduit 23, and a compression pump 24 and a valve 25 are inserted in the pipe 23. The compression pump 24 is capable of pressurizing carbon dioxide 7 to a predetermined pressure, in the embodiment, carbon dioxide 7 to 10.0 MPa, which is a critical pressure of 7.38 MPa or more. In this case, the carbon dioxide 7 is not limited to supercritical,
It is also possible to pressurize to a subcritical state and execute the subsequent processing.

The valve 25 is for cleaning the cathode 4 which is carried out between each processing step of the plating operation, that is, before each processing such as degreasing processing, oxide film removal, so-called pickling processing, plating processing and drying. During the process, the valve is opened for a certain period of time so that carbon dioxide 7 in a supercritical state can be introduced into the plating tank 1. A heating means 26 such as a heater is arranged on the downstream side of the conduit 23 to remove the carbon dioxide 7 from the critical temperature 31.1 ° C.
It is possible to heat above.

Each of the tanks 11 to 13 communicates with the lower portion of the plating tank 1 via conduits 27 to 29, and valves 30 to 32 and a common liquid feed pump 33 are inserted in the tubes 27 to 29. . Among them, the valves 30 and 31 are opened for a certain period of time before the plating process, and the electrolyte solutions 9 and 10 containing a predetermined surfactant can be introduced into the plating tank 1 via the liquid feed pump 33. .

The valve 32 is opened for a certain period of time before pickling so that the acid solution 13 containing a predetermined surfactant can be introduced into the plating tank 1 via the liquid feed pump 33. In the figure,
34 to 36 are the electrolyte solutions 9 and 10 and the acid solution 13
The surface active agent added to the solution can be introduced through a pump (not shown) when the solutions 9, 10, and 13 are supplied.

The gas reservoir 15 communicates with the upper portion of the plating tank 1 via a conduit 37, and a valve 38 is inserted in the pipe 37. The valve 38 is opened for a certain period of time before degreasing treatment, pickling treatment, plating treatment, and drying treatment, and before washing the object 4 to be performed therebetween, and the carbon dioxide 15 after use is stored in the gas storage tank 15. It is possible to introduce.

In the figure, 39 is a return pipe having one end connected to the gas reservoir 15, the other end is connected to the compression pump 24, and a column 40 capable of absorbing water and fats and oils is inserted into the pipe 39. There is. When a predetermined amount of carbon dioxide 15 is stored in the gas storage tank 15, the carbon dioxide 1
5 is introduced into the column 40 to be regenerated to the initial state, which can be returned to the compressor 24.

The liquid storage tanks 20 to 22 communicate with the lower part of the plating tank 1 via conduits 41 to 43, and the pipes 41 to 41
Valves 44 to 46 are inserted in 43. this house,
After the pickling of the cathode 4, the valve 44 is opened for a certain period of time,
The pickling solution 17 after use can be introduced into the liquid reservoir 20 together with the surfactant 36. In addition, the valve 45,
The valve 46 is opened for a certain period of time after each plating process so that the used electrolyte solutions 18 and 19 can be introduced into the liquid reservoirs 21 and 22 together with the surfactants 34 and 35.

In addition, reference numeral 47 in the drawing denotes a washing water tank which is inserted in parallel with the liquid feeding pump 33 and the conduits 27 to 29, and after feeding the respective solutions 9, 10, 13 to the plating tank 1, the pump 3
The inside of 3 can be washed. Reference numeral 48 is an entrainer made of an organic solvent such as alcohol, which is a gas container 8 and a compressor 24.
It is selectively introduced into the conduit 23 between and to allow the persistent oil and fat component to be degreased.

The electrochemical reaction apparatus for electroplating or the like thus constructed has a pretreatment for plating, that is, degreasing, pickling,
Since each process of cleaning, plating, and post-plating, that is, multiple steps of collecting and drying the object 4 is performed in a single plating tank 1, a conventional plating process that requires a dedicated bath for each process Easy to configure and installation space
The space becomes compact and the equipment cost can be reduced.

In addition, the device of the present invention, the degreasing, pickling,
Various kinds of wastes discharged from each work of cleaning and plating treatment, that is, a pickling solution containing carbon dioxide and a surfactant and an electrolyte solution are discharged to the gas storage tank 16 and a plurality of liquid storage tanks 20 to 22 to be discharged to the outside. Since the waste is avoided and it is reasonably treated, it does not require expensive and large-scale wastewater treatment facilities as in the past.

Moreover, since each of the above treatments is carried out using supercritical carbon dioxide having a very good diffusivity, compared with the conventional plating method in which the object to be treated is immersed in the plating solution, an acid solution or A very small amount of the electrolyte solution is sufficient, so that the amount of the electrolyte solution used can be reduced and the emission treatment facility can be made compact and lightweight. Furthermore, since each of the treatments is performed using supercritical carbon dioxide and the use of the solution or water is suppressed as much as possible, the wastewater treatment facility can be omitted, and the cleaning, recovery, and drying of the object to be treated can be achieved. The electrolyte solution can be easily and quickly recovered.

Further, since the apparatus of the present invention uses carbon dioxide having a critical point at a relatively low temperature and a low pressure as a supercritical substance, a supercritical state can be easily and quickly obtained with a relatively small energy. The cost of use can be reduced and the pressure resistance of the plating tank 1 can be relaxed, which can be manufactured at low cost.

When electroplating is carried out using such an electrochemical reaction apparatus, the negative electrode side of the plating tank 1 is first polished, for example, the surface is finished under the condition where the electrodes 3 and 4 are not energized. The object 4 to be treated is attached, the lid (not shown) is closed, and the plating tank 1 is sealed. Next, the compression pump 24 is driven, the heating means 26 is operated to open the gas container 8, the carbon dioxide inside is guided to the compression pump 24, and the carbon dioxide is pressurized to a pressure higher than the critical pressure. At a temperature above the critical temperature to generate supercritical carbon dioxide,
It is introduced into the plating tank 1 through the opening valve of No. 5.

The supercritical carbon dioxide diffuses into the plating tank 1 at a high speed, and the carbon dioxide in the tank 1 is brought into a supercritical state to come into contact with the object 4 to be processed and to the object 4 and the anode 3. High-speed and efficient cleaning of adhering oils and fats, water and foreign substances. At this time, if the stirrer 6 is operated to stir the supercritical carbon dioxide, the diffusion is made uniform and the cleaning efficiency is improved. Moreover, since the use of water and solution as in the conventional emulsion cleaning is abolished, the drying of the object 4 is promoted accordingly.

As described above, according to the present invention, since the object 4 to be processed is degreased and washed under the supercritical state, the use of harmful degreasing agent is more difficult than the conventional method of immersing the object 4 in the degreasing liquid. Eliminates the need to improve the working environment, and can do this safely, quickly and easily, and because degreasing cleaning is performed in the plating tank 1, there is no need for a dedicated degreasing tank as in the past, and the equipment costs correspondingly. Can be reduced.

After washing for a predetermined time, the valve 38 is opened, and instead the valve 25 is closed to stop the drive of the compression pump 24. By doing so, the carbon dioxide is decompressed and moves to a state below the critical point, and is rapidly vaporized or liquefied to move upward in the plating tank 1, and is guided to the conduit 37 and moved to the gas reservoir 16. . This situation is as shown in FIG.

Therefore, the fats and oils, the water content, the foreign matters and the like collected in the carbon dioxide move to the gas reservoir 16 and a flow is generated in the system when the carbon dioxide moves, so that the anode 3 and the object to be treated 4 are processed. To improve the cleaning accuracy in combination with the above cleaning. In this way, after the used carbon dioxide 15 is discharged to the gas storage tank 16, the valve 38 is closed.

After the cleaning, the object 4 to be processed is pickled. At the time of this pickling, the valve 32 is opened under the condition where the energization is stopped and the plating tank 1 is hermetically sealed, and the acid solution tank 1
The acid solution 13 in 4 is sent to the liquid feed pump 33, and at the same time, a predetermined surfactant 36 is added to the acid solution 13 and these are sent into the plating tank 1.

The acid solution 13 and the surfactant 36 are shown in FIG.
As shown in (a), two layers are formed in the plating tank 1. Under this circumstance, the compression pump 24 is driven, the heating means 26 is operated to open the gas container 8, and the carbon dioxide inside is guided to the compression pump 24, and this is pressurized to a pressure higher than the critical pressure. The carbon dioxide is heated to a critical temperature or higher by the heating means 26 to generate supercritical carbon dioxide, which is introduced into the plating tank 1 by opening the valve 25.

Thus, the supercritical carbon dioxide is added to the plating tank 1
When it is introduced into the plating tank 1, it diffuses into the plating tank 1 at a high speed, and is rapidly mixed with the acid solution 13 and the surfactant 36 to make it emulsify. Rust on the surface of the object 4 is removed and the oxide film is removed to activate the surface. This situation is as shown in Fig. 3 (b), in which case the stirring bar 6
When the emulsion substance is stirred and the emulsion substance is stirred, the diffusion is made uniform, the oxide film is uniformly and efficiently removed, and the pickling efficiency is improved.

When the valve 44 is opened after pickling for a predetermined time, the critical carbon dioxide is decompressed to a state below the critical point, and the acid solution 13 and the surfactant 36 used in the plating tank 1 are used. The two-layer state with is restored. This situation is as shown in FIG. During that time, high-pressure carbon dioxide is introduced into the plating tank 1 through the valve 25, and the pressure causes the used acid solution 13 and the surfactant 36 to be extruded, which is guided to the conduit 41 and moved to the liquid reservoir 20. Be accommodated. This situation is as shown in FIG.

As described above, according to the present invention, since the oxide film of the object 4 to be processed is removed under the supercritical condition, the acid solution of the acid solution is more easily compared with the conventional pickling method in which the object is immersed in the acid solution. The amount used can be reduced and this can be performed quickly and easily, and since the pickling tank 1 performs pickling, a dedicated pickling tank as in the conventional case is not required, and the equipment cost can be reduced accordingly.

Thus, when the acid solution 17 is completely discharged, the valve 44 is closed and the valve 38 is opened instead, so that the used carbon dioxide in the plating tank 1 is replaced with the carbon dioxide under the introduction. Is pushed out, and this is guided to the conduit 37, moved to the gas storage tank 15, and accommodated. At that time, a flow is generated in the system during the movement of the carbon dioxide, and the anode 3 and the object to be treated 4 are washed. This situation is as shown in FIG. In this case, the order of discharging the acid solution 17 and the carbon dioxide after use may be reversed from the above order, but if both are done as described above, both can be discharged efficiently and precisely.

Then, after the used carbon dioxide is discharged, the valve 38 is closed and the high pressure carbon dioxide 7 is introduced into the plating tank 1 for a predetermined time. By doing so, the inside of the plating tank 1 is pressurized and heated, a critical state of carbon dioxide is formed, and this supercritical carbon dioxide comes into contact with the object 4 to be processed, and the object 4 and the anode 3 are processed. Quickly and efficiently clean the adhering moisture and dry it. At this time, if the stirrer 6 is operated to stir the supercritical carbon dioxide, the diffusion is enhanced and the cleaning efficiency is improved.

After washing and drying the object to be treated 4 in this way, the compression pump 24 is stopped and the valve 25 is closed to stop the introduction of carbon dioxide, and instead the valve 38 is opened, after the use in the plating tank 1 is finished. Of carbon dioxide is introduced into the conduit 37 and moved to the gas storage tank 15 for storage. At that time, a flow is generated in the system during the movement of the carbon dioxide, and the anode 3 and the object to be treated 4 are washed. This situation is as shown in FIG. Therefore,
An object to be processed 4 that has been dried after the above various pretreatments is placed in the plating tank 1.

Under such circumstances, the valve 30 or 3
1. In this example, the valve 30 is opened and the electrolyte solution tank 11 is opened.
The electrolyte solution 9 therein is sent out to the solution sending pump 33, and at the same time, a predetermined surfactant 34 is added to the solution 9 and sent into the plating tank 1.

The electrolyte solution 9 and the surfactant 34 form two layers in the plating tank 1 as shown in FIG. Under this circumstance, the compression pump 24 is driven, the heating means 26 is operated to open the gas container 8, guide the internal carbon dioxide 7 to the compression pump 24, and pressurize the carbon dioxide 7 to a pressure higher than the critical pressure,
Further, the carbon dioxide is heated to a critical temperature or higher by the heating means 26 to generate supercritical carbon dioxide, which is then supplied to the valve 25.
It is introduced into the plating tank 1 through the opening valve.

Thus, the supercritical carbon dioxide is added to the plating tank 1
When it is introduced into the plating tank 1, it diffuses into the plating tank 1 at high speed, rapidly mixes with the electrolyte solution 9 and the surfactant 34 and becomes an emulsion, and the fine particles of the electrolyte solution 9 diffuse into the plating tank 1 at high density. , Contact the surface of the object 4 to be processed.

Under this condition, the switch 5 is closed and the anode 3
When the cathode 4 and the cathode 4 are energized, pure nickel as the anode piece is electrolyzed and deposited in the emulsified electrolyte solution 9, which adheres to the surface of the object to be treated 4. At that time, the stirrer 6 is activated,
The emulsion substance is agitated to evenly distribute the electrolytic nickel ions so that they are densely adhered to the surface of the object to be treated 4. This situation is as shown in FIG.

Moreover, the electrolysis of the electrolytic nickel ions,
Since the deposition and the deposition are performed in the supercritical state, the electrolytic nickel ions diffuse quickly in the plating tank 1 and are evenly distributed at a high density to be deposited on the front surface and the back surface of the object to be treated 4. Therefore, compared with the conventional plating method in which an anode material is electrolyzed and deposited in an electrolyte solution, the so-called plating contact is very good, and a uniform and dense plating state is obtained on the front and back surfaces of the object to be treated 4. And a good finished surface can be obtained.

Therefore, unlike the conventional plating method, there is no need to separately plate the front surface and the back surface of the object to be processed 4, the productivity can be improved accordingly, and the object 4 to be processed has a complicated shape. Even in such a case, it is possible to easily cope with it without requiring an auxiliary electrode.

After the plating process is completed, the switch 5 is turned off.
F, when the stirrer 6 is stopped and the valve 45 is opened, the carbon dioxide is decompressed and moves to a state below the critical point,
The electrolytic solution 10 and the surfactant 34 are restored to the two-layer state while being vaporized or liquefied rapidly. This situation is as shown in FIG.

After that, the valve 45 is opened, the used electrolyte solution 18 is pushed out together with the surfactant 34 from the plating tank 1, and this is introduced from the conduit 42 to the liquid storage tank 21 to be accommodated therein. After discharging 18, the valve 45 is closed and the valve 38 is opened instead to push out the used carbon dioxide from the plating tank 1 and guide it through the conduit 37 to the gas reservoir 16 for storage. At that time, a flow is generated in the system during the movement of the carbon dioxide, and the anode 3 and the object to be treated 4 are washed.

After discharging the carbon dioxide after use, the valve 38
Is closed and the valve 25 is opened during that time to introduce high-pressure carbon dioxide 7 into the plating tank 1. This way,
The inside of the plating tank 1 is pressurized and heated to form a supercritical state of carbon dioxide.
To remove the moisture adhering to the object to be treated 4 and the anode 3 at high speed and efficiently and to dry it. At this time, if the stirrer 6 is operated to stir the supercritical carbon dioxide, the diffusion is enhanced and the cleaning efficiency is improved.

After the object 4 is washed and dried in this way, the compression pump 24 is stopped, the valve 25 is closed, the introduction of carbon dioxide is stopped, the lid (not shown) of the plating tank 1 is opened, and the plating process is performed. When the object 4 to be processed is taken out, a series of plating work is completed.

It should be noted that the carbon dioxide after use is the gas storage tank 16
When a predetermined amount is stored in the column, the external valve is opened, the used carbon dioxide is introduced to the column 40 through the return pipe 39, and the column 40 removes the water and the oil / fat content in the carbon dioxide. It is absorbed, regenerated to the initial state, and when appropriate, returned to the compression pump 24 and reused. Therefore, it is possible to eliminate the waste of releasing the carbon dioxide after use into the atmosphere and prevent the deterioration of the working environment due to the release.

When the acid solution 17 and the electrolyte solutions 18 and 19 after use are stored in the liquid storage tanks 20 to 22 in a predetermined amount, they are separated from the mixed surfactant, or they are not separated and have a slightly high concentration. After preparation and regeneration, each solution tank 11,1
Reflux to 2,14. Therefore, there is no trouble of complicated pumping back of the plating solution or the like and concentration adjustment after the object 4 is collected as in the conventional case.

When a plurality of plating layers are formed on the object 4 to be processed, that is, when so-called layered plating is performed, after the first layer is plated, the object 4 to be processed is not taken out of the plating tank 1 and the above-mentioned pretreatment is performed. It suffices to carry out and perform the plating process.
Therefore, like the conventional overplating, after plating,
The object 4 to be treated is taken out of the plating tank one by one, and it is moved to each tank to perform pretreatment, which improves productivity.

FIG. 8 shows another embodiment of the present invention, and the same reference numerals are used for the components corresponding to those of the above-mentioned embodiment. Note that FIG. 8 illustrates only a main part of the embodiment, and supplies and discharges of supercritical or subcritical carbon dioxide to and from the reaction baths 1 and 1a, a configuration of a storage portion, supply and discharge of various solutions, and The structure of the storage portion is not shown, and the portion is substantially the same as that in FIG.

In this embodiment, a plurality of reaction baths 1 and 1a which are substantially the same, two in the embodiment, are arranged in parallel, and these are connected by conduits 52 and 53, and the valves 5 and 5 are connected to the conduits 52 and 53.
Insert 4,55. These reaction baths 1 and 1a can alternately execute the same treatment process, and a part of a series of plating treatment processes in one reaction bath 1, for example, pretreatment, a series of plating treatment processes in the other reaction bath 1a. The remaining part, for example, the plating process and the post-process are executed to realize a series of plating processes.

That is, the object to be treated 4 is placed in one of the reaction baths 1.
Pretreatment such as degreasing cleaning, pickling, etc. is performed in part of the plating treatment step, and various gases and solutions after use are stored in the storage tank (not shown). In the other reaction bath 1a, the pretreatment process has already been completed, the plating process is performed, and the object 4 to be treated after the plating process is collected, washed and dried, and various gases and solutions after use are stored in the storage tank (shown in the figure). (Omitted).
This situation is like step 1. In this case, carbon dioxide for the reaction bath 1a is introduced into the conduit 52 on the downstream side of the valve 54.

Next, in step 2, the reaction bath 1 has already completed the pretreatment process and has carried out the plating treatment, and the object 4 to be treated after the plating treatment is recovered, washed and dried, and various gases and solutions after use are used. Is stored in the storage tank (not shown). on the other hand,
In the reaction bath 1a, after the plating treatment is completed, a new object 4 is attached, pretreatment such as degreasing cleaning and pickling of the object 4 is performed, and various gases and solutions after use are stored in the storage tank ( (Not shown).

As described above, in this embodiment, the series of plating operations are rationalized by alternately performing the pre-processing and post-processing of the plating process, that is, a part of the whole process and the rest of the process in the plurality of reaction baths 1 and 1a. I try to do it quickly and objectively.

The method of depositing and depositing the electrolyzed electrode substance on the other electrode substance as in the above-described embodiment can be applied to the same electroforming and anodic oxide film forming methods in principle. Similar effects can be obtained. The present invention can also be applied to an electrolysis method in which an electrolytic substance and an electrode substance are accommodated in a reaction bath, one electrode substance is electrolyzed, and this is collected on the other electrode substance side. With this, it can be applied to, for example, electrolytic refining of metals, electrolytic extraction, electrolytic polishing, etc., and the same effects as described above can be obtained.

Further, an object to be treated is contained in a reaction bath capable of accommodating an electrolytic substance, and the electrolytic substance contained in the electrolyte solution is deposited and adhered on the object to be treated, and electroless plating or chemical conversion treatment method without applying an external electric field. The present invention can also be applied to this, and by doing so, the same effect as described above can be obtained.

[0071]

As described above, the invention of claim 1 forms a reaction bath containing an electrolytic substance and an electrolyte solution in a supercritical state or a subcritical state, and electrolyzes the electrode substance under the state. Alternatively, the electrolyzed electrode material and / or the electrolyte material contained in the electrolyte solution is deposited and adhered to the other electrode material, so that it is suitable for electrochemical treatment such as electroplating, and is supercritical or subcritical carbon dioxide. , You can perform each processing step safely, reasonably and promptly,
Reasonably and quickly treats carbon dioxide and treatment solutions after use, suppresses the amount of pickling solution and plating solution used, and further reduces the amount of waste liquid generated from plating work to prevent environmental pollution. However, it is possible to improve the working environment to improve productivity and reuse them.
In addition, the distribution of plating can be dramatically improved, and a beautiful finish can be achieved, and precise and uniform plating can be easily achieved on the back surface and concave portions of the object to be processed, and the productivity can be improved. You can do this, electroforming method or anodic oxide film forming method,
It is applicable to the electrolytic polishing method, and has the effect of improving its productivity and obtaining a good finished state.

According to the second aspect of the present invention, the reaction bath containing the electrolytic substance is formed in a supercritical state or a subcritical state, the electrolytic substance is electrolyzed under the state, and this is collected on the other electrode substance side. By doing so, it can be applied to the electrolytic extraction and refining methods of metals, and the productivity can be improved and a good finished state can be obtained. According to the invention of claim 3, the reaction bath containing the electrolytic substance is formed in a supercritical state or a subcritical state, and the electrolytic substance is deposited and adhered to the object to be treated under the state, so that an external electric field is required. It can be applied to electroless plating and chemical conversion treatment methods, and its productivity can be improved and a good finished state can be obtained. In the invention of claim 4, the electrode material is electrolyzed, or after the electrolyzed electrode material and / or the electrolytic material contained in the electrolyte solution is deposited and adhered to the other electrode material, or the electrolytic material is electrolyzed, and the other is electrolyzed. After collecting on the electrode material side, since the reaction bath transitioned from the supercritical state or subcritical state to the state below the critical point, the electrolyte solution and the supercritical or subcritical substance were returned to the two-layer state, and their discharge was performed. At the same time, it is possible to realize a rapid flow in the system such as a reaction bath at the time of the above-mentioned transition to promote cleaning and drying of the object to be treated.

According to a fifth aspect of the present invention, after electrolysis of the electrode substance or electrolytic substance, a substance in a supercritical state or a substance in a subcritical state is introduced into the reaction bath to wash the electrode substance or to form an oxide film. Since they are removed, they can be treated reasonably and quickly to promote their drying. In the invention of claim 6, after electrolysis of the electrode substance or the electrolytic substance, a substance in a supercritical state or a substance in a subcritical state is introduced into the reaction bath, and the electrode substance or the electrolyte substance collecting side is washed or dried. By doing so, it is possible to perform such treatment reasonably and quickly and promote the drying thereof. The invention of claim 7 introduces a substance in a supercritical state or a substance in a subcritical state, an electrolytic substance and a surfactant into the reaction bath at the time of electrolysis of the electrode substance, so that the inside of the reaction bath is in a supercritical state or a subcritical state. Since it is emulsified at a critical level, electrode substances or electrolytic substances can be deposited and adhered uniformly and quickly and with high density. For example, the plating coverage can be dramatically improved and a beautiful finish can be obtained, and the back surface of the object to be treated can be obtained. It is possible to easily realize precise and uniform plating on the concave portion and the concave portion and improve the productivity.

According to the eighth aspect of the present invention, before the electrolysis of the electrode substance or the electrolytic substance, the substance in the supercritical state or the substance in the subcritical state, the oxide film removing solution, and the surfactant are introduced into the reaction bath. Since the inside of the reaction bath is emulsified in a supercritical state or a subcritical state, these treatments can be performed reasonably, quickly and with high density. According to the invention of claim 9, a storage tank is provided outside the reaction bath which can communicate with the reaction bath, and the used supercritical substance or subcritical substance, electrolytic substance or cleaning or oxide film removing substance is stored in the storage bath. By doing so, it is possible to suppress the discharge of them, and to recycle them and promote rational and effective use. The invention according to claim 10 regenerates the used supercritical substance or subcritical substance stored in the storage tank and recirculates it to the reaction bath, or the used electrolytic substance or cleaning or oxide film removal stored in the storage tank. Since the substance is regenerated and refluxed in each solution tank, it is possible to effectively use the supercritical substance or subcritical substance after use, the electrolytic substance after use, or the cleaning or oxide film removing substance.

In the eleventh aspect of the present invention, since the deposition and deposition of the electrode material and the pretreatment step thereof, or the electrolysis and collection of the electrolytic material and the pretreatment step thereof are performed in a single reaction bath, each of the treatment steps is performed. It is possible to eliminate the bathtub, reduce the facility cost and make the installation space compact, eliminate the complexity of moving the object to be treated for each bath, and improve the work efficiency. According to the invention of claim 12, at least two reaction baths capable of carrying out the deposition and deposition of the electrode substance and the treatment process before and after it or the electrolysis and collection of the electrolytic substance and the treatment process before and after it are provided. Since a part of the treatment process is executed, the rest of the treatment process is executed in the other reaction bath, and these treatments are alternately executed between the reaction baths, a series of reaction baths is used. It is possible to perform a series of processing operations reasonably and quickly by dividing the processing steps into two and alternately performing these. According to a thirteenth aspect of the present invention, the electrode material is electrolyzed, or after the electrolyzed electrode material is deposited and adhered to the other electrode material, the reaction bath is used to deposit and adhere a plurality of layers of electrode material to the other electrode material. By doing so, it is possible to continue the pretreatment and deposition adhesion of the electrode material of the next layer without carrying out the object to be treated from the reaction bath, and it is possible to improve workability and productivity.

According to a fourteenth aspect of the present invention, a reaction bath containing an electrolytic substance is formed in a supercritical state or a subcritical state, and the electrode substance is electrolyzed under the state, or the electrolyzed electrode substance and / or electrolyte. Since the electrolytic substance contained in the solution is deposited and adhered to the other electrode substance, it is so suitable for electrochemical treatment such as electroplating, using supercritical or subcritical carbon dioxide, Each treatment process can be performed safely, rationally and promptly, carbon dioxide and treatment solution after use can be treated rationally and promptly, and the amount of pickling solution and plating solution used can be reduced, It is possible to reduce the amount of waste liquid generated, prevent environmental pollution, improve the working environment to improve productivity, and reuse them. In addition, the distribution of plating can be dramatically improved, and a beautiful finish can be achieved, and precise and uniform plating can be easily achieved on the back surface and concave portions of the object to be processed, and the productivity can be improved. This can be applied to the electroforming method, the anodic oxide film forming method, and the electrolytic polishing method, and there is an effect that the productivity can be improved and a good finished state can be obtained.

According to a fifteenth aspect of the present invention, a reaction bath containing an electrolytic substance is formed in a supercritical state or a subcritical state, the electrolytic substance is electrolyzed under the state, and this is collected on the other electrode substance side. Therefore, the method can be applied to the electrolytic extraction and refining methods of metals, and the productivity can be improved and a good finished state can be obtained. According to the sixteenth aspect of the invention, the reaction bath containing the electrolytic substance is formed in a supercritical state or a subcritical state, and the electrolytic substance is deposited and adhered to the object to be treated under the state. It is applicable to electroless plating and chemical conversion treatment methods that do not require it, and has the effect of improving its productivity and obtaining a good finished state. In the invention of claim 17, the electrode material is electrolyzed, or after the electrolyzed electrode material and / or the electrolytic material contained in the electrolyte solution is deposited on the other electrode material, or the electrolytic material is electrolyzed,
After collecting this on the other electrode material side, since it was possible to transfer the reaction bath from the supercritical state or subcritical state to the low pressure side, the electrolyte solution and the supercritical or subcritical substance were returned to the two-layer state, and those At the same time as the discharge, it is possible to form a rapid flow in the system such as the reaction bath at the time of the above-mentioned transition to promote cleaning and drying of the object to be treated.

According to the eighteenth aspect of the present invention, a storage tank, which can communicate with the reaction bath, is provided outside the reaction bath, and the supercritical state substance or subcritical state substance or electrolytic substance after use or cleaning is used in the storage bath. Alternatively, since the oxide film-removing substance is stored, it is possible to prevent the discharge of the substance and to regenerate it or to use it reasonably and effectively. Claim 1
The invention of 9 is to regenerate a used supercritical substance or subcritical substance stored in a storage tank and recirculate it to a reaction bath, or to use an electrolytic substance or a cleaning or oxide film removal substance stored in the storage tank after use. Since it is regenerated and refluxed in the reaction bath, it is possible to effectively use the supercritical substance or subcritical substance after use, the electrolytic substance after use, or the cleaning or oxide film removing substance. The invention of claim 20 is
Since the deposition and adhesion of electrode material and its pretreatment step or the electrolysis and collection of the electrolytic material and its pretreatment step can be treated in a single reaction bath, the bath for each treatment step is eliminated and the equipment cost is reduced. Thus, the installation space can be made compact, the complexity of moving the object to be treated for each bath can be eliminated, and the work efficiency thereof can be improved.

According to a twenty-first aspect of the present invention, at least two reaction baths capable of carrying out the deposition and deposition of electrode material and the treatment steps before and after it or the electrolysis and collection of the electrolytic material and the treatment steps before and after it are provided. Since a part of the treatment process is performed in the reaction bath, the rest of the treatment process is performed in the other reaction bath, and these treatments can be performed alternately between the reaction baths, a plurality of reaction baths can be used. A series of processing steps can be divided into two and performed alternately, and a series of processing operations can be performed reasonably and quickly. In the invention of claim 22, the electrode material is electrolyzed, or the electrolyzed electrode material is deposited and adhered to the other electrode material, and then the reaction bath is used to deposit a plurality of layers of electrode material on the other electrode material. Since the adhesion is performed, the pretreatment of the electrode material of the next layer and the deposition adhesion can be continued without carrying out the object to be treated from the reaction bath, and the workability and the productivity can be improved.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an embodiment of the present invention, in which a single reaction bath is used to carry out multiple steps of plating treatment.

FIG. 2 is an explanatory diagram showing a degreasing and cleaning treatment step of the plating treatment.

FIG. 3 is an explanatory diagram sequentially showing an oxide film removal process and an object activation process of the plating process.

FIG. 4 is an explanatory diagram showing an acid solution discharging and cleaning step of the plating process.

FIG. 5 is an explanatory view sequentially showing a plating process of the plating process.

FIG. 6 is an explanatory diagram showing an electrolyte solution discharging and cleaning step of the plating treatment.

FIG. 7 is an explanatory diagram showing a drying and cleaning step of the plating process.

FIG. 8 is an explanatory diagram showing a main part of a second embodiment of the present invention, in which two reaction baths are used to perform pre-processing and post-processing steps of a plating process.

[Explanation of symbols]

1,1a Reaction bath 3 Electrode material (anode) 4 Electrode material (cathode) 9,11 Electrolyte solution 13 Acid solution (oxide film removal solution) 20-22 Storage tanks 34-36 Surfactant

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hideo Yoshida             5-33-6 Kumegawa-cho, Higashimurayama-shi, Tokyo (72) Inventor Seizo Miyata             3-18-18 Shimohoya, Hoya-shi, Tokyo (72) Inventor Masato Sone             3-11-8 Honmachi, Koganei-shi, Tokyo (72) Inventor Fumiko Iwao             4-3-5-4 Kasumi, Narashino City, Chiba Prefecture (72) Inventor Yoshihiro Asai             2-11-4 Higashimachi, Koganei-shi, Tokyo (72) Inventor Daie Asai             2-11-4 Higashimachi, Koganei-shi, Tokyo

Claims (22)

[Claims] 1. A reaction bath capable of accommodating an electrolytic substance accommodates electrode materials of a cathode and an anode, electrolyzes one electrode substance, or electrolyzes the electrode substance and / or the electrolytic substance contained in an electrolyte solution. In the electrochemical treatment method such as electroplating so as to deposit and adhere to the electrode substance, the reaction bath containing the electrolytic substance and the electrolyte solution is formed in a supercritical state or a subcritical state, and under the state, An electrochemical treatment method such as electroplating, characterized in that an electrode material is electrolyzed, or the electrolyzed electrode material and / or an electrolyte material contained in an electrolyte solution is deposited and attached to the other electrode material. 2. A reaction bath capable of accommodating an electrolytic substance, accommodating cathode and anode electrode substances, and electrolyzing the electrolytic substance,
In an electrochemical treatment method such as electroplating in which this is collected on the other electrode material side, a reaction bath containing an electrolyte is formed in a supercritical state or a subcritical state, and the electrolysis is performed under the state. A method for electrochemical treatment such as electroplating, characterized in that a substance is electrolyzed and collected on the side of the other electrode substance. 3. An electrochemical treatment method such as electroplating in which an object to be treated is contained in a reaction bath capable of containing an electrolytic substance, and the electrolytic substance contained in an electrolyte solution is deposited and adhered to the object to be treated. An electrochemistry such as electroplating, characterized in that a reaction bath containing an electrolytic substance is formed in a supercritical state or a subcritical state, and under the state, the electrolytic substance is deposited and adhered to an object to be treated. Processing method. 4. The electrode material is electrolyzed, or the electrolyzed electrode material and / or the electrolyte material contained in an electrolyte solution is deposited and adhered to the other electrode material, or the electrolyte material is electrolyzed, and the other electrode is electrolyzed. The method for electrochemical treatment such as electroplating according to claim 1, 2 or 3, wherein the reaction bath is transferred from a supercritical state or a subcritical state to a state below the critical point after collection on the material side. 5. Prior to electrolysis of the electrode substance or electrolytic substance, a substance in a supercritical state or a substance in a subcritical state is introduced into the reaction bath to wash the electrode substance or remove an oxide film. An electrochemical treatment method such as electroplating according to 1 or 2 or 3. 6. After electrolysis of the electrode substance or electrolytic substance, a substance in a supercritical state or a substance in a subcritical state is introduced into the reaction bath, and the electrode substance or electrolytic substance collecting side is washed or dried. Item 1 or 2 or 3
An electrochemical treatment method such as the electroplating described. 7. When the electrode material is electrolyzed, a supercritical substance or a subcritical substance, an electrolytic substance and a surfactant are introduced into the reaction bath so that the inside of the reaction bath is in the supercritical state or the subcritical state. The method for electrochemical treatment such as electroplating according to claim 1, wherein the method is emulsified. 8. Prior to electrolysis of the electrode substance or electrolytic substance, a substance in a supercritical state or a substance in a subcritical state, an oxide film removing solution, and a surfactant are introduced into the reaction bath, The electrochemical treatment method such as electroplating according to claim 5, wherein the emulsion is emulsified in a supercritical state or a subcritical state. 9. A storage tank, which is capable of communicating with the reaction bath, is provided outside the reaction bath, and the used supercritical substance or subcritical substance, electrolytic substance or cleaning or oxide film removing substance is stored in the storage bath. An electrochemical treatment method such as electroplating according to claim 1, 2 or 3 or 5. 10. The used supercritical substance or subcritical substance stored in the storage tank is regenerated and refluxed in a reaction bath, or the used electrolytic substance or cleaning or oxide film removal substance stored in the storage tank is used. 10. The electrochemical treatment method such as electroplating according to claim 9, wherein the solution is regenerated and refluxed in each solution tank. 11. The electroplating according to claim 1, 2 or 3, wherein the deposition and deposition of the electrode material and the pretreatment step thereof or the electrolysis and collection of the electrolytic material and the pretreatment step are performed in a single reaction bath. Etc. Electrochemical treatment method. 12. At least two reaction baths capable of carrying out the deposition and attachment of the electrode substance and the treatment process before and after it or the electrolysis and collection of the electrolytic substance and the treatment process before and after it are provided, and one of the reaction baths is used for the reaction. The electricity according to claim 1 or 2 or 3, wherein a part of the treatment steps is executed, the rest of the treatment steps is executed in the other reaction bath, and these treatments are alternately executed between the reaction baths. Electrochemical treatment method such as plating. 13. The electrode material is electrolyzed, or after the electrolyzed electrode material is deposited and adhered to the other electrode material, the reaction bath is used to deposit and adhere a plurality of layers of electrode material to the other electrode material. An electrochemical treatment method such as electroplating according to claim 1. 14. A reaction bath capable of containing an electrolytic substance contains electrode materials for a cathode and an anode, and one of the electrode substances is electrolyzed, or the electrolyzed electrode substance and / or an electrolytic substance contained in an electrolyte solution is added to the other. In an electrochemical reaction device such as electroplating that deposits and adheres to the electrode substance, the reaction bath containing the electrolytic substance is formed in a supercritical state or a subcritical state, and the electrode substance is electrolyzed under the state. Or an electrolytic reaction device such as electroplating, characterized in that the electrolyzed electrode substance and / or the electrolytic substance contained in the electrolyte solution is deposited and adhered to the other electrode substance. 15. Electrochemistry such as electroplating in which a cathode and an anode electrode materials are contained in a reaction bath capable of containing an electrolyte material, and the electrolyte material is electrolyzed and collected on the side of the other electrode material. In a dynamic reaction apparatus, a reaction bath containing an electrolytic substance is formed in a supercritical state or a subcritical state, the electrolytic substance is electrolyzed under the state, and the electrolytic substance is collected on the other electrode substance side. An electrochemical reaction device for electroplating, etc. 16. An electrochemical reaction device such as electroplating, wherein an object to be treated is contained in a reaction bath capable of containing an electrolytic substance, and the electrolytic substance contained in an electrolyte solution is deposited and adhered to the object to be treated. An electrochemistry such as electroplating, characterized in that a reaction bath containing an electrolytic substance is formed in a supercritical state or a subcritical state, and under the state, the electrolytic substance is deposited and adhered to an object to be treated. Reaction device. 17. The electrode material is electrolyzed, or after the electrolyzed electrode material and / or the electrolytic material contained in the electrolyte solution is deposited and adhered to the other electrode material, or the electrolytic material is electrolyzed, and the other electrode is electrolyzed. The electrochemical reaction apparatus for electroplating or the like according to claim 14, 15 or 16, wherein the reaction bath is allowed to shift from a supercritical state or a subcritical state to a low pressure side after collection on the substance side. 18. A storage tank, which is capable of communicating with the reaction bath, is provided outside the reaction bath, and a supercritical substance, a subcritical substance, an electrolytic substance, cleaning, or oxide film removal after use in the storage bath. Claim 1 which stores a substance
An electrochemical reaction device such as electroplating according to 4 or 15 or 16. 19. The used supercritical substance or subcritical substance stored in the storage tank is regenerated and refluxed to the reaction bath, or the used electrolytic substance or cleaning or oxide film removal substance stored in the storage tank is used. The electrochemical reaction device for electroplating or the like according to claim 16, which recycles and reuses. 20. The process according to claim 14 or 15 or 16, wherein the deposition and deposition of the electrode material and the pretreatment step thereof or the electrolysis and collection of the electrolytic material and the pretreatment step thereof can be processed in a single reaction bath. Electrochemical reaction device such as electroplating. 21. At least two reaction baths capable of carrying out the deposition and deposition of the electrode material and the treatment steps before and after it, or the electrolysis and collection of the electrolytic material and the treatment steps before and after it are provided, and one of the reaction baths is used for the reaction. The electroplating according to claim 14 or 15 or 16, wherein a part of the treatment steps is carried out, the rest of the treatment steps are carried out in the other reaction bath, and these treatments can be performed alternately between the reaction baths. Electrochemical reaction device such as. 22. Electrolyzing the electrode material, or depositing and depositing the electrolyzed electrode material onto the other electrode material, and then depositing and depositing a plurality of layers of electrode material onto the other electrode material using the reaction bath. An electrochemical reaction device such as electroplating according to claim 14 or 15.