JP2003147591A - Surface treatment method for object to be treated and treatment equipment for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment method for an object to be treated which is adequate for an electrochemical treatment of, for example, the object to be treated, averts the contact of the object to be treated and the atmosphere air, homogenously activates the surface of the object to be treated with high accuracy, makes it possible to obtain the good deposition of metal ions, rationally feeds and discharges surface treating fluid and treating liquid, performs the effective utilization thereof, obstructs the discharge of the fluid outside the system, makes the realization of a rational system, the improvement in productivity and mass production possible, permits the rational and safe conduction of the electrochemical treatment work permits downsizing and cost lowering of the equipment and permits convenient maintenance and a treatment equipment for the same. SOLUTION: The surface treating fluid is introduced into a reaction chamber 4 in which the object to be treated can be housed. After the surface treatment of the object to be treated, the surface treating fluid is introduced into a separating vessel 4. The surface treating fluid separated of contaminants is circulated to the above reaction chamber 4. The circulating route of the surface treating fluid including the reaction chamber 4 is communicatively connected during the surface treatment of the object to be treated. The surface treating fluid is always circulated in the circulating route.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for, for example, electrochemical treatment of an object to be treated, avoids contact between the object to be treated and the atmosphere, activates the surface of the object to be treated with high accuracy and uniformly, and Good ion deposition can be achieved, and the surface treatment fluid and treatment solution can be rationally supplied and discharged to prevent their effective use and discharge to the outside of the system, realizing a rational system and improving productivity. In addition, the present invention relates to a surface treatment method of an object to be treated and a treatment apparatus thereof, which can be mass-produced, can perform electrochemical treatment work reasonably and safely, and can downsize equipment and cost, and is convenient for maintenance.

[0002]

2. Description of the Related Art For example, a conventional electroplating process is 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 space are required, and the equipment cost becomes high, and the work environment is deteriorated because the work is forced to be performed in a situation where the processing liquid is scattered and harmful gas is generated.
Moreover, there is a problem that the immersion requires a long time and productivity is poor.

In order to solve such a problem, the applicant has introduced a supercritical substance, an electrolyte solution and a surfactant into a reaction bath and electroplating them under these emulsion conditions. However, after plating, the supercritical substance is vaporized and discharged to the outside of the bath to develop an electrochemical treatment method that makes it possible to wash the reaction bath, electrodes, etc. without requiring a washing liquid. It has already been proposed as the Japanese Patent Application No. 2000-253572.

[0004]

DISCLOSURE OF THE INVENTION The present invention further improves and embodies the electrochemical processing method and the processing apparatus thereof which have already been developed, and is suitable for electrochemical processing of an object to be processed, for example. Avoiding contact with the atmosphere and activating the surface of the object to be treated with high precision and homogeneity, and obtaining good deposition of metal ions, and rationalizing the supply and discharge of the surface treatment fluid and treatment liquid. Prevents effective use and discharge to the outside of the system, realizes a rational system, improves productivity and mass production, and can perform electrochemical treatment work reasonably and safely, and also downsizing equipment and low cost. It is an object of the present invention to provide a method of treating a surface of an object to be treated, which is convenient for maintenance, and an apparatus for treating the surface.

[0005]

Therefore, according to the invention of claim 1, the surface treatment fluid is introduced into a reaction tank capable of accommodating the object to be treated, and after the surface treatment of the object to be treated, the surface treatment fluid is removed. In the surface treatment method of the object to be treated, which is introduced into the separation tank and circulates the surface treatment fluid from which contaminants are separated into the reaction tank, in the surface treatment of the object to be treated, a circulation path of the surface treatment fluid including the reaction tank. In comparison with a method in which the surface treatment fluid is continuously circulated in the circulation path and the surface treatment fluid is retained in the reaction tank for surface treatment, surface treatment of the object to be treated with the surface treatment fluid, for example, degreasing cleaning or Along with being able to perform drying with high accuracy and speed, avoiding contact between the object to be processed and the atmosphere, for example, active treatment of the surface of the object to be processed can be performed with high accuracy and reliability, and good deposition of metal ions, for example, can be obtained. Electroplating and stacking multiple layers It is preferably in Tsu key.

According to a second aspect of the present invention, when degreasing or cleaning the object to be treated or drying the object, the surface treatment fluid is circulated all the time so that surface activation treatment such as degreasing or cleaning the object to be treated or drying the object can be performed with high accuracy. And I try to do it surely and quickly. According to the invention of claim 3, after the surface treatment of the object to be treated, the gas generated by the electrochemical reaction in the surface treatment fluid is separated or removed to prevent the gas from being mixed into the system, A good electrochemical reaction with respect to the object to be treated can be obtained, and the surface treatment fluid can be regenerated accurately. According to the invention of claim 4, after the surface treatment of the object to be treated, oxygen and hydrogen in the surface treatment fluid are separated or removed to prevent mixing of oxygen and hydrogen generated by an electrochemical reaction into the system. In addition, a good electrochemical reaction with respect to the object to be treated can be obtained, and the surface treatment fluid can be regenerated accurately.

According to a fifth aspect of the present invention, after the surface treatment, oxygen and hydrogen in a surface treatment fluid generated by an electrochemical reaction are burned to generate water, and the water is separated or removed. A fluid is circulated in the circulation path to safely and easily remove the oxygen and hydrogen, prevent the harmful effects caused by the mixing of oxygen, hydrogen and water, and to perform the drying by the surface treatment fluid smoothly and efficiently. ing. According to a sixth aspect of the present invention, after introducing the surface treatment fluid and a pickling solution or an electrolytic solution into the reaction tank, the supply / discharge path of the reaction tank is blocked, and the object to be treated is pickled or electrochemically reacted. The movement of the pickling solution or electrolyte and its inflow into the circulation route are prevented, so that the pickling and electrochemical reaction can be performed stably, and the corrosion of the circulation route and system troubles are prevented. .

According to a seventh aspect of the present invention, after the object to be treated is pickled or electrochemically reacted, the surface treatment fluid in the reaction tank is circulated to the circulation path, and the pickling solution or the electrolytic solution is added. 9. The surface treatment fluid is separated from the circulation path, the surface treatment fluid and the pickling solution, the electrolytic solution, etc. are separately treated, and these are treated reasonably and safely to regenerate them. In the invention, after pickling or electrochemical reaction of the object to be treated, the surface treatment fluid in the pickling solution or the electrolytic solution is separated, and this is refluxed to the circulation path of the surface treatment fluid, Alternatively, during the electrochemical reaction, the surface treatment fluid mixed in the pickling solution or the electrolytic solution is effectively used.

According to a ninth aspect of the present invention, the surface treatment fluid comprises:
For pressurized fluids above atmospheric pressure or supercritical or subcritical fluids, in the case of pressurized fluids above atmospheric pressure, surface treatment fluids are easily available, and the system can be manufactured and operated inexpensively and safely. In the case of a critical or subcritical fluid, a high surface diffusivity allows a good surface treatment state to be obtained.

According to a tenth aspect of the present invention, there is provided a sealable reaction tank for accommodating an object to be treated and introducing a surface treatment fluid, and a surface treatment fluid after the surface treatment of the object to be treated from the reaction vessel. A surface treatment apparatus for a processing object, comprising: a separation tank that is transferred and is capable of separating contaminants in the surface treatment fluid, wherein the surface treatment fluid from which the contaminants have been separated can be circulated to the reaction tank. During the surface treatment of the object to be treated, a circulation path of the surface treatment fluid including the reaction tank is communicated, the surface treatment fluid can be circulated throughout the circulation path, and the surface treatment fluid is retained in the reaction tank for surface treatment. Compared with the method, the surface treatment of the object to be treated with the surface treatment fluid, such as degreasing, cleaning, and drying, can be performed with high accuracy and speed, and the contact between the object and the atmosphere is avoided, and the surface treatment of the object is activated. With high accuracy and certainty For example obtained good deposition of the metal ions, and preferably in the electroplating or multilayer lap plating. In addition, the storage tank for storing the surface treatment fluid and the treatment liquid after use is substantially abolished, the equipment can be made compact and the cost can be reduced, and the surface treatment fluid can be quickly regenerated.

In the eleventh aspect of the present invention, when the object to be treated is degreased or washed or dried, the surface treatment fluid can be circulated all the time, and surface activation treatment such as degreasing or washing or drying the object to be treated can be performed with high accuracy. And it can be done quickly. The invention of claim 12 makes it possible to separate or remove the gas generated by the electrochemical reaction in the surface treatment fluid, prevent the gas from entering the system, and obtain a good electrochemical reaction with respect to the object to be treated. At the same time, the surface treatment fluid can be regenerated accurately. The invention of claim 13 is
A reactor that can separate or remove oxygen and hydrogen in the surface treatment fluid is inserted in the circulation path to prevent oxygen and hydrogen from entering the system and their adverse effects, and to accurately reproduce the surface treatment fluid. I try to do well.

According to a fourteenth aspect of the present invention, a dehydrator capable of separating water is inserted downstream of the reactor in the circulation path to safely and easily remove oxygen and hydrogen, and to mix oxygen, hydrogen and water. This prevents harmful effects and allows the surface treatment fluid to dry smoothly and efficiently. According to a fifteenth aspect of the present invention, the surface treatment fluid and a pickling solution or an electrolytic solution are provided in the reaction tank so that the supply and discharge paths of the reaction tank can be shut off after they are introduced into the reaction tank. The movement of the pickling solution or electrolyte and its inflow into the circulation route are prevented, so that the pickling and electrochemical reaction can be performed stably, and the corrosion of the circulation route and system troubles are prevented. .

According to a sixteenth aspect of the present invention, after the object to be treated is pickled or electrochemically reacted, the surface treatment fluid in the reaction tank is circulated to the circulation path, and the pickling solution or electrolytic solution is provided. Is separated from the circulation path of the surface treatment fluid, the surface treatment fluid, the pickling solution, and the electrolytic solution are separately treated, and they are treated reasonably and safely so that they can be regenerated. There is. In the invention of claim 17, a treatment liquid recovery tank capable of separating the surface treatment fluid in the pickling solution or the electrolytic solution is inserted in the discharge passage of the reaction tank, and the collection tank is provided in the circulation passage of the surface treatment fluid. It is designed to make effective use of the surface treatment fluid mixed with the pickling solution or the electrolytic solution during communication, pickling or electrochemical reaction.

According to the eighteenth aspect of the present invention, the surface treatment fluid is a pressurized fluid at atmospheric pressure or higher or a supercritical or subcritical fluid. When the pressurized fluid at atmospheric pressure or higher, the surface treatment fluid is not available. It is easy, the system can be manufactured and operated inexpensively and safely, and in the case of supercritical or subcritical fluids, high diffusivity enables good surface treatment conditions to be obtained. In the invention of claim 19, a plurality of the reaction tanks are provided, the reaction tanks are connected to the circulation path, and a pressurized fluid or a supercritical or subcritical fluid at an atmospheric pressure or higher, and a pickling solution or Introducing the electrolytic solution and
In each reaction tank, degreasing and washing of the object to be treated, pickling, and drying,
While making it possible to sequentially perform electroplating and drying, the adjacent reaction tanks are communicated with each other so that the fluid used can be supplied and discharged, and in the reaction tank that processes the successive steps, after processing the preceding reaction tank, By making it possible to supply the used fluid to the subsequent reaction tank and using the used surface treatment fluid and the used acid solution etc. in each reaction tank one by one, it is possible to make effective use of it and also to treat the surface of the object to be treated and each treatment. The process is rationalized and the mass production is attempted.

According to a twentieth aspect of the present invention, there is provided a tank main body, which accommodates therein a jig capable of mounting an object to be processed and a stirring means and which can supply and discharge the surface treatment fluid of the object to be processed, and the tank main body. In a surface treatment apparatus for an object to be processed having a reaction tank having a lid capable of sealing a lid, a single or a plurality of the jigs are detachably attached to the lid, and the lid and the jig are integrated. In addition to facilitating the handling of them, the jig, lid, and tank body can be easily maintained. In the twenty-first aspect of the invention, the lid and the jig are configured to be able to move up and down integrally, so that they can be easily put in and taken out from the tank body.

According to a twenty-second aspect of the present invention, the cross-sectional shape of the chamber of the tank main body and the cross-sectional shape of the jig are formed in similar shapes to each other, and these are arranged concentrically to form a tank main body. In addition to streamlining and downsizing the jig manufacturing, it is possible to efficiently accommodate and process a large number of objects.
We are trying to mass-produce it. According to a twenty-third aspect of the present invention, the cross-sectional shape of the chamber of the tank body and the cross-sectional shape of the jig are formed in a circular shape, and these are arranged concentrically so that a large number of workpieces can be efficiently processed. It can be stored and processed, and its mass production is achieved, and the surface treatment fluid and the used solution can be stirred accurately. According to a twenty-fourth aspect of the present invention, the jig is divided into a plurality of pieces, and the jigs are rotatably connected to each other so that the jig can be easily opened and closed, and an object to be processed can be easily attached to and detached from the jig. ing.

According to a twenty-fifth aspect of the present invention, an electrode capable of energizing the jig is attached to the lid body to promote integration of the lid body, the jig and the electrode, thereby facilitating the convenience of handling them and facilitating maintenance. I am trying. According to a twenty-sixth aspect of the present invention, the same electric potential is applied between the jigs arranged adjacent to each other, and the electrochemical reaction such as electroplating is made uniform with respect to the processing object mounted on each jig. A uniform electrochemical reaction such as electroplating can be obtained on the object to be processed.

According to a twenty-seventh aspect of the present invention, an electrode is arranged at the center of the chamber, the electric field strength of each jig is set uniformly, and uniform electroplating or the like is applied to an object to be processed mounted on the jig. The electrochemical reaction of can be obtained. According to a twenty-eighth aspect of the present invention, a stirring shaft capable of rotating the stirring means is attached to the center of the lid body, the electrode is coaxially arranged outside the stirring shaft, and the lid body, the jig, the electrode, and the stirring means. Promote the integration of
We are trying to make them easier to handle and easier to handle.

In a twenty-ninth aspect of the present invention, a pressurized fluid having a pressure equal to or higher than atmospheric pressure or a supercritical or subcritical fluid, an acid pickling solution, and an electrolytic solution are sequentially introduced into the reaction tank to degrease and wash the object to be treated. , Pickling, drying, and electroplating can be sequentially performed, adjacent reaction tanks can be connected to each other to supply and discharge a fluid to be used, and a preceding reaction tank for processing successive steps After the treatment, the fluid to be used can be supplied to the subsequent reaction tanks, and the surface treatment fluid to be used and the acid solution to be used are sequentially used in each reaction tank to effectively utilize the surface treatment object surface. The treatment and each treatment process can be performed rationally, and the mass production is attempted. According to a thirtieth aspect of the present invention, the electrode is composed of an insoluble member, and a supercritical or subcritical fluid and an electrolytic solution are introduced into the reaction tank to allow an electrochemical reaction of an object to be processed, thereby having high diffusivity. In the presence of a supercritical or subcritical fluid having the above, the deposition of metal ions on the object to be processed can be performed satisfactorily and uniformly, wear of the electrode is eliminated, and there is no interruption due to replacement of the electrode, and the electrochemical reaction Is trying to improve productivity.

[0020]

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 using a supercritical or subcritical fluid will be described with reference to FIGS. In FIG. 9, reference numeral 1 denotes a box-shaped processing apparatus installed in a working chamber, in which a door 2 is provided at a middle height position on the front surface thereof so as to be openable and closable, and a pressure resistant reaction tank 4 is provided at a lower part of the processing chamber 3 facing the door 2. It is provided.

The reaction tank 4 is opened upward, and an object to be plated or the like can be removably mounted in a chamber inside thereof.
An object storage container 5 which is a so-called plating jig,
After accommodating the electrodes and the like, sealing this with a lid 6, and further locking the lid 6 via a clamp ring described later, after the work is completed,
It is possible to take them out together.

Immediately below the reaction tank 4, first and second processing liquid tanks 7 and 8 capable of accommodating different kinds of plating liquids are arranged in parallel, and these solutions are supplied via liquid transfer pumps 9 and 10. It can be selectively supplied to the reaction tank 4. A pressure resistant processing liquid recovery tank 11 which is a separation tank is provided immediately below the reaction tank 4 and the processing liquid recovery tank 11 has substantially the same volume and pressure resistance as the reaction tank 4. The treatment liquid after the treatment inside is flowed down by the action of gravity, and this is heated so that the carbon dioxide and the treatment liquid can be separated.

The reaction tank 4 and the processing liquid recovery tank 11 are connected by a processing liquid discharge pipe 12, and a processing liquid discharge valve 13 is inserted in the pipe 12. The discharge valve 13 can be opened when supercritical water or subcritical fluid is introduced into the reaction tank 4 and during degreasing cleaning and drying in the reaction tank 4, while it can be closed during pickling and plating treatment in the reaction tank 4. Has been A pressure-resistant separation tank 14 is provided on the downstream side of the reaction tank 4, and the separation tank 14 has the same shape and the same configuration as the processing liquid recovery tank 11. The oil and fat inside can be separated and removed.

In addition, reference numeral 15 in the drawing denotes a pickling solution storage tank capable of containing a pickling solution for removing an oxide film, which can supply the pickling solution to the reaction tank 4, and 16 is the liquid feed pump. A pressure pump installed in parallel with 9, 10 pressurizes carbon dioxide, which is a supercritical or subcritical generation fluid, as a surface treatment fluid to a density of 0.4 or more, and liquid carbon dioxide is liquid or gaseous or supercritical or subcritical It is possible to pressurize to the state.

In the figure, 17 is a condensing and collecting tank provided in the rear part of the processing apparatus 1, which is a supercritical or subcritical product fluid which is connected to the refrigerator 18 immediately below through a refrigerant conduit and is introduced into the tank 17. A certain carbon dioxide is cooled so that it can be liquefied. In addition, 19 is a control panel incorporating various electric devices, 20 is a rectifier, 21 is a relay box, 22 is a transformer, 23 is an oil tank, and 24 is a dehydration column which is a dehydrator.

As shown in FIGS. 6 to 8, the reaction tank 4 has a bottomed cylindrical tank body 25, a lid 6 for closing the opening of the body 26, and a closed state of the lid 6. And a clamp ring 27 which is made of thick-walled stainless steel, and its peripheral surface is lined with vinyl chloride or hard rubber for insulation. A reduced diameter clamp seal portion 28 is provided on the outer peripheral surface of the upper portion of the tank body 25, and a plurality of tongue-shaped clamp claws 29 are formed on the peripheral surface of the middle portion of the seal portion 28.

The clamp ring 27 is rotatably attached to the clamp seal portion 28, and a ring-shaped engaging portion 30 engageable with the engaging claw 29 is formed in the middle height portion of the inner peripheral surface thereof. Then, the annular grooves 31, 32 are provided above and below the locking portion 30.
Is formed. Of these, the clamp claw 29 is engaged with the annular groove 31, and a plurality of tongue-shaped clamp claws 33 are formed immediately below the groove 31, so that the clamp claw 33 can be engaged with the clamp claw 29. ing.

A clamp claw of the lid 6 described later engages with the annular groove 32, and a plurality of tongue-shaped clamp claws 34 are formed immediately above the annular groove 32.
It can be engaged with the clamp claw. The lid body 6 is formed in a disc shape of large and small stages, and a plurality of clamp claws 35 are formed on the circumferential surface of the maximum diameter part thereof, and the clamp claws 35 are detachable from the clamp claws 34. The lid 6 is removable.

A substantially disk-shaped boss portion 37 that can be fitted into the chamber 36 of the reaction tank 4 is provided on the lower portion of the lid 6 in a protruding manner.
A plurality of screw holes 38 are formed on the peripheral surface of the boss portion 37, and bolts 39 or screws are screwed into the screw holes 38 to detachably mount the object storage container 5.

Through holes 40 and 41 of different sizes are provided in the central portion of the lid 6 and on both sides thereof, and a stirring shaft 42 is inserted into the through hole 40 in the central portion, and a fan is provided at the lower end portion of the shaft 42. 43 is attached, and a motor 44 is attached to the upper end of the shaft 42.
Is provided with a belt pulley. Further, similar electrode rods 45, 46 are inserted into the through holes 41, 41 on the large diameter side, and a positive potential and a negative potential are applied to them.

Of these, one end of a conductive member 47 such as carbon is attached to the lower end of the electrode rod 45 for applying a positive potential, and the other end is an electrode tube 48 mounted on the peripheral surface of the stirring shaft 42.
Is connected so that it can be energized. The electrode tube 48 is
It is composed of an insoluble electrode member such as bon or ferrite, is exposed to an electrolytic solution, and cannot be eluted even when placed in an electric field. Further, one end of a conductive member (not shown) such as a carbon is attached to the lower end of the electrode rod 46 to which a negative potential is applied, and the other end is connected to the upper end of the object-to-be-processed container 5 so as to be energized. Has been done.

In the figure, reference numeral 49 denotes a conductive frame which constitutes the object-to-be-processed container 5, and allows the object to be processed to be hooked or clipped. Numerals 50 to 53 are ports open to the outer surface of the tank body 25, which communicate with the chamber 36 and are connected to predetermined conduits.

FIG. 5 shows an outline of the device of the present invention, which is denoted by 54 in the figure.
Is a gas cylinder containing liquefied and stored carbon dioxide which is a supercritical or subcritical forming fluid.
5 and the conduit 56, and can be introduced into the heater 57 via the condensation recovery tank 17 and a cooler described later. The heater 57 includes a heater and a stirrer, and heats the carbon dioxide to a temperature capable of forming a supercritical or subcritical state,
This can be supplied to the reaction tank 4 via the conduit 58 and the introduction valve 59.

Liquid supply conduits 60, 61 communicating with the first and second processing tanks 7, 8 are connected to the reaction tank 4, and liquid supply valves 62, 63 are inserted into these liquid supply conduits 60, 61. The first and second processing tanks 7 and 8 are equipped with a heater and a stirrer.

A gas recovery pipe 64 communicating with the separation tank 14 is connected to the upper portion of the reaction tank 4, and a gas recovery valve 65 and a pressure regulating valve 66 are inserted in the pipe 64. The gas recovery valve 6
The valve 5 is opened during the degreasing cleaning step and the drying step, and can be closed during the pickling step and the plating step.
Further, the pressure regulating valve 66 is a pipe line on the downstream side of the valve 66,
That is, the pressure of the processing gas conduit 64 is set to a low pressure, that is, 6 in the embodiment.
It can be set to MPa.

On the other hand, a discharge pipe 67 communicating with the outside is connected to the bottom of the treatment liquid recovery tank 11, and the discharge valve 6 is connected to the pipe 67.
8 is inserted, and a treatment liquid recovery pipe 69 is connected to the upstream side of the discharge pipe 67. The processing liquid recovery pipe 69 is
A pressure regulating valve 70 and a shutoff valve 71 are inserted in the pipe 69 so as to communicate with the first and second treatment liquid tanks 7 and 8 through a refining unit, and the pressure of the treatment liquid is made substantially atmospheric by the pressure regulating valve 70. The pressure can be adjusted.

One end of a bypass pipe 72 is connected to the upper portion of the processing liquid recovery tank 11, and the other end of the bypass pipe 72 is connected to the gas recovery pipe 64 upstream of the gas recovery valve 65. A shutoff valve 73 that also serves as a check valve is inserted. The shut-off valve 73 guides the separated carbon dioxide and the bypass pipe 72 to the gas recovery pipe 64 in the process of treating the pickling solution and the plating liquid discharged into the treatment liquid recovery tank 11. In the figure, reference numerals 74, 75 and 76 denote heaters provided in the reaction tank 4, the treatment liquid recovery tank 11 and the separation tank 14.

The separation tank 14 and the reactor 78 are inserted in the gas recovery pipe 64, of which the reactor 78 is the separation tank 14
It is located on the downstream side of. The reactor 78 contains a catalyst having a base composition of metals of iron, chromium and aluminum in a substantially cylindrical container, and passes a treatment gas through the catalyst to bring it into contact with the catalyst to perform pickling or plating in the reaction tank 4. Hydrogen and oxygen generated in the treatment process are burned to generate water, and hydrogen and oxygen are removed, and the generated water is removed from the dehydration columns 24 and 2.
It is possible to absorb in 4.

One end of the return pipe 79 is connected to the downstream side of the dehydration columns 24, 24, and the other end thereof is connected to the condensation recovery tank 17 via the condensation recovery tank inlet valve 80 to collect unused and regenerated carbon dioxide. Can be cooled and liquefied. One end of the injection pipe 81 is connected to the outlet of the condensing and collecting tank 17, and the other end is connected to the midstream portion of the conduit 56. A cooler 82 and a pressurizing pump 16 are inserted in the injection pipe 81 to surely liquefy the carbon dioxide in the gas-liquid mixture flowing out from the condensing and collecting tank 17 and pressurize the carbon dioxide.
It is possible to supply to 7.

In the drawing, 83 is a condensation recovery tank outlet valve inserted upstream of the injection pipe 81, and 84 is a refrigerant conduit piped to the cooler 82, which is in communication with the refrigerator 18. Reference numeral 85 is a pressure regulating valve inserted between the reactor 78 and the dehydration column 24, and can set a low pressure in a pipe line downstream of the valve 77.

The surface treatment apparatus thus constructed has a pre-plating treatment, that is, degreasing, pickling, washing, and drying treatments, a plating treatment, and a post-plating treatment, that is, recovery and drying of the object 4 as described later. Since the multi-step process is performed in a single reaction tank 4, the structure is simple and the installation space is compact compared to the conventional plating method and equipment that requires a dedicated bath for each processing. The cost can be reduced. Moreover, since the storage tank that temporarily stores the used carbon dioxide and the treatment liquid is virtually abolished, the equipment can be made compact and the cost can be reduced accordingly, and the regeneration and circulation of the treatment liquid can be performed quickly. It

In addition, the device of the present invention, the degreasing, pickling,
Various discharges from the cleaning, drying, and plating operations, that is, a plating solution containing carbon dioxide, a pickling solution, and a surfactant are divided into a gas and a liquid, and are divided into a processing solution recovery tank 11 and a separation tank 14. Since they are discharged and regenerated, and they are not discharged to the outside of the system, there is no need for expensive and large-sized waste water and exhaust treatment facilities as in the conventional case. Moreover, since the pickling solution and the plating solution after use are recycled without being discharged to the outside of the system, consumption of these can be suppressed to the minimum and the plating cost can be reduced.

Further, since each of the above treatments is carried out using supercritical or subcritical carbon dioxide having good diffusibility, compared with the conventional plating method in which the object to be treated is immersed in the plating solution, the acid solution is used. A very small amount of the electrolyte solution and the electrolyte solution is sufficient. Therefore, it is possible to save the amount of the electrolyte solution and to reduce the size and weight of the emission treatment facility, and to improve the productivity in combination with the above.

On the other hand, in the apparatus of the present invention, the introduction pipe 58, the gas pipe 64, the communication pipe 77, the return pipe 79, and the injection pipe are used during the degreasing and washing process of the object to be plated, the drying process, and the regenerating process (including ion supply). Since a closed circuit of 81 etc. is formed and the unused and regenerated carbon dioxide is circulated through these, the degreasing washing or drying step and the regenerating step can be performed reasonably and quickly at a time, and the productivity is improved. .

Further, as described later, the reaction tank 4 is hermetically sealed until each step of the degreasing and washing step, the pickling step, the drying step and the plating treatment step, especially each step before the plating treatment is completed,
In addition, the supercritical or subcritical fluid is circulated to avoid contact between the object to be plated and the atmosphere, especially oxygen, so that the surface of the object to be plated can be activated reliably and accurately.
The metal ions can be reliably deposited on the surface.
Therefore, it is possible to surely realize the multi-layer plating on the object to be plated.

Further, in the apparatus of the present invention, a closed circuit is formed by the gas conduit 64, the communication pipe 77, the return pipe 79, the injection pipe 81, etc., and the unused and regenerated carbon dioxide is circulated in these circuits, The degreasing washing or drying process and the regenerating process can be performed reasonably and quickly at a time, and the productivity is improved.

Further, the apparatus of the present invention is such that the first and second processing liquid tanks 7,
8, a closed circuit is formed by the conduits 60, 61, the processing liquid discharge pipe 12, etc., and unused and regenerated pickling liquid or plating liquid can be supplied to these, so that the above-mentioned pickling process or plating process, The regeneration process can be performed reasonably and quickly, the productivity is improved, and the solution can be effectively used.

On the other hand, the apparatus of the present invention requires three pressure-resistant processing tanks 4, 11 and 14. Of these, the processing liquid recovery tank 11
The separation tank 14 has substantially the same shape and size, is openable and airtight, and is equipped with an appropriate heating device. Further, the reaction tank 4 is
As shown in FIG. 6, it has a tank main body 25, a lid body 6 and a clan ring 27, and the clan ring 27 can be rotated through an appropriate actuator (not shown).

The lid 6 is movable up and down through a suitable actuator (not shown), and the motor 44 is attached thereto.
Agitation shaft 42 that is connected to the positive and negative electrode rods 45, 46
Then, the object storage container 5 is attached, one end of the conductive member 47 is connected to the one electrode rod 45 on the anode side, and the other end is connected to the electrode tube 48 mounted on the outer peripheral surface of the stirring shaft 42. There is. Therefore, these and the lid 6 are integrally assembled, and as described later, they can be easily and promptly taken in and out of the chamber 36, and they can be taken out from the reaction tank 4, so that these and the reaction tank 4 can be maintained. Easy to do.

When electroplating is carried out using such a surface treatment apparatus, the object to be plated, which is the object to be processed, is placed inside the frame 49 of the object-to-be-processed container 5 directly or through an appropriate clip. Attach an object. Next, the storage container 5
The peripheral edge of the upper end of the is attached to the peripheral surface of the boss 37 of the lid body 6 which has been removed from the tank body 25 in advance, through the bolt 39. At that time, the stirring shaft 4 is provided at the center of the object storage container 5.
2, the electrode tube 48 is positioned on the peripheral surface thereof, one end of the conductive member 47 is attached to the lower end of one electrode rod 45, and the other end is electrically connected to the electrode tube 48.

In this way, after the objects to be plated are attached to the object-to-be-processed container 5, these are hoisted by an actuator and moved to directly above the tank main body 25, and the object is to be hung down, and the object-to-be-processed container 5 etc. Is housed in the chamber 36,
The lid 6 is placed on the open end of the tank body 25. A clamp ring 27 is preliminarily attached to the outer periphery of the opening of the tank body 25, and the lid 6 is provided between the plurality of clamp claws 34 of the ring 27.
The plurality of clamp claws 35 are fitted.

Then, the clamp ring 27 is pushed and rotated in the closing direction via an actuator (not shown), and when the clamp claws 34 and 35 are vertically positioned and engaged, the positioning pin is attached to the clamp ring 27 and the lid. Insert into 6 and lock them.

When degreasing and cleaning the object to be plated stored in the reaction tank 4 under such a condition, the condensation recovery tank inlet / outlet valves 80 and 81, the introduction valve 59, the gas recovery valve 65, the processing liquid discharge valve 13 , The shutoff valve 73 is opened, and the pressure regulating valves 66, 8 are opened.
5 is gradually set to a low pressure, and the opening / closing valve 55 is opened. By doing so, the liquefied carbon dioxide filled in the gas cylinder 54 is jetted and vaporized, and the vaporized carbon dioxide is supplied to the conduit 5
6 is moved to the condensing and collecting tank 17 and is cooled and liquefied in the collecting tank 17 to be in a gas-liquid mixed state.

The carbon dioxide is guided from the condensation recovery tank 17 to the cooler 82 through the injection pipe 79, and the cooler 82 is supplied.
Is further cooled and liquefied, and the whole amount is liquefied. The liquefied carbon dioxide is guided to the pressurizing pump 16 to have a pressure of about 10 MPa,
Pressurized to a density of 0.4 or higher, and then heated by the heating device 57 to approximately 50
It is heated to 0 ° C., reaches a supercritical state or a subcritical state, and in this state flows into the reaction tank 4 from the conduit 58.

The carbon dioxide is slightly decompressed after flowing into the reaction tank 4, and a part of the carbon dioxide flows from the reaction tank 4 into the separation tank 14 through the gas recovery pipe 64 to pressurize the tank 14 and at the same time from the tank 14. It moves to the return pipe 79 through the reactor 78 and the dehydration column 24 and pressurizes these pipes. Also,
A part of the carbon dioxide is discharged from the reaction tank 4 into the processing liquid discharge pipe 1
After flowing into the processing liquid recovery tank 11 via 2, the pressure of the tank 11 is increased, and at the same time, it is guided to the bypass pipe 72 and merges with the gas recovery pipe 64 to pressurize these pipe lines.

Thereafter, the pressurized and heated carbon dioxide is further supplied from the introduction pipe 58 to the reaction tank 4, and the reaction tank 4 and the pipes around the reaction tank 4 reach the supercritical state. That is, the reaction tank 4, the upstream end of the gas recovery pipe 64, the treatment liquid discharge pipe 1
2. The treatment liquid recovery tank 11 and the bypass pipe 72 are placed in a supercritical state at the highest pressure and temperature in the system (about 10 MPa, 50 ° C.).

Further, the gas recovery pipe 6 between the pressure regulating valves 66 and 85
4, the separation tank 14 and the reactor 78 are placed in a subcritical state under the next high pressure and high temperature state (about 6 MPa, 22 ° C.) in the system, and the dehydration column 24 and the return pipe downstream of the pressure regulating valve 85. 79 is placed in the lowest pressure and lowest temperature sub-critical state in the system.

Under such a condition, the motor 44 is driven, the stirring shaft 42 linked to the belt and the belt pulley is rotated to rotate the fan 43, and the supercritical carbon dioxide in the reaction tank 4 is stirred. In addition, the reaction tank 4 and the processing liquid recovery tank 1
1 and each of the heaters 74 to 76 in the separation tank 14 are heated.

In this way, the supercritical carbon dioxide diffuses while circulating in the reaction tank 4, contacts the object to be plated in the tank 4, and the object to be plated and the electrode rod 45 on the anode side.
Of oil and fat adhering to the lower end portion of the conductive member 47, the electrode tube 48, the lower end portion of the electrode rod 46 on the cathode side, and the like,
Cleans foreign substances at high speed and efficiently. Moreover, since the use of water and solution as in conventional emulsion cleaning is abolished, the later-described drying of the object to be plated is promoted accordingly.

As described above, according to the present invention, since the object 4 to be processed is degreased and washed with supercritical carbon dioxide, the use of a harmful degreasing agent can be avoided as compared with the conventional method of immersing the object 4 in the degreasing liquid. It eliminates the need to improve the working environment, and this can be done safely, quickly and easily, and because degreasing cleaning is performed in the reaction tank 4, there is no need for a dedicated degreasing tank as in the past, and the equipment cost is reduced accordingly. Can be reduced.

The oil and fat removed by the degreasing and cleaning is conveyed to the processing gas moving in the gas recovery pipe 64, that is, supercritical or subcritical carbon dioxide, and the separation tank 14
And is decompressed and heated in the tank 14 to be recovered.
After the recovery, the processing gas is guided to the reactor 78, contacts the metal catalyst contained in the reactor 78, burns oxygen and hydrogen in the processing gas, removes them, and produces water. To be done. Thereafter, the processing gas is further decompressed by the pressure regulating valve 85 and moved to the dehydration column 24, and the column 24
Then, the generated water is absorbed and regenerated, and the regenerated gas moves to the downstream side in the return pipe 79.

After moving to the downstream end of the return pipe 79, the processing gas is guided to the condensation recovery tank 17, cooled and liquefied in the recovery tank 17, and further cooled and liquefied in the cooler 82. After the whole amount is liquefied, it is pressurized by the pressure pump 16 and heated by the heater 57 to be stored in the reaction tank 4,
Restore the supercritical state.

As described above, since the degreasing cleaning is performed by circulating carbon dioxide in the system, compared to the case where supercritical carbon dioxide is contained in the reaction tank 4, degreasing with clean carbon dioxide is performed. Cleaning can be performed, and degreasing cleaning can be performed with high accuracy. Further, the carbon dioxide is regenerated after being degreased and washed and separated from contaminants while circulating in the system, so that the carbon dioxide is effectively utilized. And in the meantime,
Since carbon dioxide is not exhausted to the outside of the system at all, consumption or consumption of carbon dioxide is extremely small, and the consumed amount is replenished from the gas cylinder 54. After forming the supercritical state in the reaction tank 4, the treatment liquid discharge valve 13 may be closed to perform degreasing cleaning.

After degreasing and cleaning for a predetermined time, the work is finished and the next pickling is performed. During this pickling, the sealed state of the reaction tank 4, the stored state of the object storage container 5, and the stored state of the object to be plated are maintained as they are. Under this condition, for example, the pressure pump 16 and the motor 44 are used. Is temporarily stopped, and the condensation recovery tank inlet / outlet valves 80, 81, the introduction valve 59, the processing liquid discharge valve 13, the gas recovery valve 65, etc. are closed. That is, the reaction tank 4 was shut off from the peripheral pipe line, and instead, the opening / closing valve (not shown) of the pickling solution storage tank 15 was opened, and the liquid feeding pump (not shown) was driven to warm it. The pickling solution is supplied to the reaction tank 4.

In this case, the reaction tank 4 is maintained at a high pressure, but since the pickling solution has a higher density than the internal carbon dioxide, the pickling solution can be easily sent to the reaction tank 4. The reaction tank 4 is hermetically sealed and maintains a high pressure state as in the degreasing cleaning, and the heater 74 is heated to maintain a supercritical state.

When the motor 44 is driven and the acid solution is stirred under such a condition, the supercritical carbon dioxide diffuses at high speed and comes into contact with the surface of the object to be plated, and the oxide film on the surface of the object to be plated. Are removed and the surface is activated. In this case, if an appropriate surfactant is added to the acid solution to make it emulsion, the oxide film is uniformly and efficiently removed, and the pickling efficiency is improved.

As described above, the pickling is rational and efficient by maintaining the airtight state in the reaction tank 4 and utilizing the supercritical state at the time of degreasing cleaning without newly supplying carbon dioxide. You can do well. Then, after pickling for a predetermined time, the processing liquid discharge valve 13 and the gas recovery valve 65 are opened.

In this way, the pressure in the reaction tank 4 is reduced, the supercritical carbon dioxide inside is vaporized, and a two-layer state of carbon dioxide and the pickling solution is formed in the reaction tank 4. Of these, carbon dioxide having a low density flows out to the gas recovery pipe 64 side, and the pickling solution after use having a high density is guided to the process liquid discharge pipe 12 together with the oxide film and flows down to the process liquid recovery tank 11. To do.

In this case, the treatment liquid recovery tank 11 is located immediately below the reaction tank 4, and the pickling solution drops due to gravity, so that the treatment liquid recovery tank 11 moves quickly to the treatment liquid recovery tank 11 in combination with the ejection speed. , To prevent the reaction tank 4 from remaining. Further, since the treatment liquid recovery tank 11 communicates with the gas recovery pipe 64 via the bypass pipe 72, it absorbs and buffers the inflow pressure of the pickling liquid.

On the other hand, in the treatment solution recovery tank 11, the heater 75 is heated before and after the discharge of the pickling solution, and the heating separates the pickling solution from the carbon dioxide mixed in the solution. The separated carbon dioxide is pushed out to the bypass pipe 72 and moved to the gas recovery pipe 64.

The removed oxide film is discharged to the outside by opening the discharge valve 68, and the pickling solution after removing the oxide film is
The pressure inside the pipe is lowered to approximately atmospheric pressure via the pressure regulating valve 70, and the shutoff valve 71
Is opened and sent to a refining section (not shown), and the purified pickling solution flows down to the pickling solution storage tank 15 or its recovery tank.

As described above, according to the present invention, since the oxide film on the object to be plated is removed under the supercritical condition, the object to be plated is pickled as compared with the conventional pickling method in which the object to be plated is immersed in the pickling solution. The amount of liquid used can be reduced, and this can be done quickly and easily, and because acid pickling is performed in the reaction tank 4, there is no need for a dedicated pickling tank as in the past, and the equipment cost can be reduced accordingly. Can be achieved.

In this case, the reaction tank 4, the processing liquid discharge pipe 12,
When it is desired to prevent the pickling solution from adhering to the treatment liquid recovery tank 11 and the liquid supply pipes 60 and 61, a water tank portion is provided in the tank 15, and this water is supplied through the pumps 9 and 10 and the liquid supply pipes 60 and 61. Then, the intended purpose is achieved by supplying the reaction solution to the reaction tank 4, flowing it down to the treatment liquid recovery tank 11 and washing it with water. Further, at the time of pickling, the reaction tank 4 is shut off from the peripheral pipeline, so that the pickling solution is prevented from flowing out to the inside of the system, especially to the gas recovery pipe 64 and the return pipe 79 side. Corrosion due to pickling solution can be prevented.

Thus, the object to be plated is dried before and after the pickling solution is purified and returned to the storage tank 15.
In this case, the condensation recovery tank inlet / outlet valves 80, 81, the gas introduction valve 59, and the gas recovery valve 65 which are closed after the degreasing cleaning are opened, and the pressurizing pump 16 is driven to react the pressurizing carbon dioxide. It is supplied or replenished into the tank 4 to maintain and form the supercritical state in the reaction tank 4, and the carbon dioxide is circulated and moved into the system.

By doing so, the supercritical carbon dioxide comes into contact with the object to be plated, the electrode tube 48, the object to be plated container 5, the water adhered to the conductive member 47, etc., and diffuses this rapidly and precisely. To dry. In this case, the water is transported to carbon dioxide and removed by the dehydration column 24 to maintain the carbon dioxide drying efficiency.

As described above, in the drying, the supercritical carbon dioxide is introduced into the reaction tank 4, and is rapidly diffused and discharged, and is circulated in the system. Therefore, the reaction tank 4 is shut off from the system. Compared with the case of drying by drying, moisture is efficiently and promptly transported and dried quickly.

After the material to be plated is dried in this way, the driving of the pressure pump 16 and the motor 44 is temporarily stopped, and the condensation recovery tank inlet / outlet valves 80 and 81, the processing liquid discharge valve 13, the gas recovery valve 65, etc. are closed. Then, instead, the liquid supply pumps 9 and 10 of the first and second processing tanks 7 and 8 are driven to apply a predetermined plating liquid to the reaction tank 4.
Supply to. In this case, a suitable surfactant is added to the plating solution and placed.

Under these circumstances, the condensation recovery tank inlet / outlet valves 80 and 81 and the introduction valve 59 are opened, and the pressurizing pump 1
6 is driven to pressurize and heat the carbon dioxide in the system to supply it into the reaction tank 4, and when the inside of the reaction tank 4 is maintained in a supercritical state, the introduction valve 59 is closed, and the reaction tank is closed. Shut off 4 from the system. Around this, the motor 44 is driven and the stirring shaft 42 is rotated to stir the supercritical carbon dioxide and the plating solution.

By doing so, the supercritical carbon dioxide diffuses into the reaction tank 4 at high speed, the plating solution and the surfactant are rapidly mixed and emulsified, and the fine particles of the plating solution are converted into the reaction tank 4.
It diffuses in high density inside and contacts the surface of the object to be plated.

Under this condition, when a power switch (not shown) connected to the electrode rods 45 and 46 is turned on to energize the electrode tube 48 on the anode side and the object storage container 5 on the cathode side, the plating solution Pure nickel ions are deposited on the surface of the object to be plated. At that time, the emulsion substance is agitated by the rotation of the fan 43 to uniformly distribute the electrolytic nickel ions, and the ions are densely adhered to the surface of the object to be plated.

In this case, the electrode tube 48 is provided in the center of the reaction tank 4.
Since the anode is located in the reaction vessel 4, and the object-to-be-processed container 5 serving as the cathode and the object to be plated are located in the outer peripheral portion of the reaction tank 4, the same potential is applied to the positive and negative electrodes. Linear electric lines of force are formed radially toward the object storage container 5 or the object to be plated. This situation is as shown in FIG.

In this case, the object storage container 5 is the electrode tube 4
Since the objects to be plated are located on the concentric circles 8 and the objects to be plated are attached to the storage container 5, all the objects to be plated are placed at the same potential. Therefore, when the object to be plated is the same, substantially the same current density can be obtained for the object to be plated, and a uniform plated state can be obtained. Therefore, as compared with the conventional plating method in which the pair of electrodes are separated from each other in the plating tank, a more uniform plating state can be obtained.

Moreover, since the reaction tank 4 and the object storage container 5 have a circular cross section and are arranged concentrically,
A large number of objects to be plated can be efficiently arranged at equidistant positions, the mass productivity or productivity of plating can be improved, and a good stirring effect of the plating solution and supercritical carbon dioxide by the fan 43 can be obtained, and uniform plating can be achieved. Ion distribution can be obtained and uniform and high quality plating can be obtained.

Further, since the electrolysis, precipitation and adhesion of the electrolytic nickel ions are carried out in a supercritical state, the electrolytic nickel ions are rapidly diffused in the reaction tank 4 and are uniformly distributed at a high density. It adheres to the front and back of the plated object. 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 can be obtained on the front and back surfaces of the object to be plated. A good finished surface can be obtained.

Therefore, unlike the conventional plating method, there is no trouble of separately plating the front surface and the back surface of the object to be plated, the productivity can be improved accordingly, and even when the object to be plated has a complicated shape. , Can be easily dealt with without requiring an auxiliary electrode. Further, since the electrode tube 48 is made of an insoluble member and does not elute even when placed in an electrolytic solution and an electric field, there is no trouble of replacing the electrode as in the conventional case.

Further, during the plating, the reaction tank 4 is shut off from the peripheral pipelines, so that the plating solution is prevented from flowing out to the inside of the system, particularly to the gas recovery pipe 64 and the return pipe 79 side. It is possible to prevent corrosion due to the plating solution.

Thus, after the plating process is completed, the electrode application switch is turned off, the fan 43 is stopped, and the treatment liquid discharge valve 13, the gas recovery valve 65, the introduction valve 59, and the condensation recovery tank inlet / outlet valves 80 and 83 are opened. Speak. In this way, the inside of the reaction tank 4 is depressurized and the supercritical carbon dioxide is depressurized and rapidly vaporized or liquefied, which forms a two-layer state with the plating solution or the surfactant. Is extruded into the gas recovery pipe 64, the plating solution or the surfactant having a high density is extruded into the treatment liquid discharge pipe 12, and flows down into the treatment liquid recovery tank 11.

In the treatment liquid recovery tank 11, the heater 75 is heated before and after the discharge of the plating liquid, and by this heating, the plating liquid and the carbon dioxide mixed in the liquid are separated and separated. Carbon dioxide is pushed out to the bypass pipe 72 and moves to the gas recovery pipe 64. In addition, the plating solution or the surfactant is reduced to a substantially atmospheric pressure via the pressure regulating valve 70, moves to a refining section (not shown), and is flowed down to the first or second processing tank 7, 8 after refining. As described above, in this embodiment, the used plating solution and the surfactant are returned to the original first or second processing tanks 7 and 8 for reuse.

After plating the object to be plated in this manner, it is dried. In this case, the operation of the pressurizing pump 16 is continued, and supercritical carbon dioxide is supplied or replenished into the reaction tank 4 so that the object to be plated, the electrode tube 48, the object to be plated container 5, the conductive member 47, etc. It comes into contact with the adhered plating liquid or the like, diffuses this at high speed, and pushes it out to the gas recovery pipe 64.

As described above, in the above-mentioned drying, supercritical carbon dioxide is introduced into the reaction tank 4, and this is rapidly diffused and discharged, and the system is circulated, so that water is efficiently transported and dried quickly. To do. In this case, the water carried to the carbon dioxide is removed by the dehydration column 24 to maintain the drying efficiency.

After drying the object to be plated in this manner, the object to be plated is taken out from the reaction tank 4. In this case, pressurizing pump 16
And the motor 44 are stopped, and the introduction valve 59, the gas recovery valve 65,
The processing liquid discharge valve 13 is closed. Then, the positioning pin (not shown) is pulled out, the clamp ring 27 is opened and rotated through the actuator, and the clamp claw 3 of the ring 27 is rotated.
4 and the clamp claw 35 of the lid 6 are disengaged. This situation is as shown in FIG.

After that, the lid 6 is lifted up via the actuator to store the object-to-be-processed container 5, the object to be plated, and the electrode rod 4.
5, 46, the stirring shaft 42, the electrode tube 48, the conductive member 47, etc. are taken out from the reaction tank 4 as a unit. This situation is as shown in FIG. After that, the bolt 39 is removed, the object storage container 5 is removed from the lid body 6, and the object to be plated inside is removed to complete a series of plating operations.

In the above-mentioned embodiment, the supercritical or subcritical fluid is used as the cleaning and degreasing, the electrochemical reaction, and the drying medium, but the present invention is not limited to this, and the pressurized fluid above atmospheric pressure, for example, dioxide. It is also possible to use carbon, and by doing so, the pressure-resistant processing tanks 4, 11, 14 required for forming a supercritical or subcritical state, pressure-resistant pipelines, heating and pressurizing means, etc. are unnecessary. Therefore, there is an advantage that it can be manufactured at low cost and the work can be performed easily and safely.

Further, in the above-described embodiment, the single reaction tank 4 is used.
, A plurality of such reaction tanks 4 are provided, each of these reaction tanks 4 is sequentially and independently carried out, and the reaction tanks 4 for performing successive processing steps are provided. Between the four, the supercritical carbon dioxide, the acid solution, the plating solution, the surfactant, etc. used in the reaction tank 4 on the preceding side are supplied to the reaction tank 4 on the following side after the completion of the process, and the effective utilization thereof is achieved. The mass production of the electrochemical treatment may be attempted.

Further, in the case of performing multi-layer plating, that is, so-called layer plating, on the object to be plated, the above-mentioned respective steps may be repeatedly and continuously processed. Therefore, unlike the conventional overplating, each time the plating is finished, the object to be plated is taken out of the reaction tank one by one, and it is moved to each tank for pretreatment, which improves productivity and reduces carbon dioxide. It is possible to prevent consumption due to release of the like. Moreover, since it eliminates the concern about contact with the outside air when taking out the object to be plated from the reaction tank as in the past, the active surface of the object to be processed can be reliably and safely maintained, which is effective for the above-mentioned overplating. There are many advantages.

10 to 12 show another embodiment of the present invention, and the same reference numerals are used for the components corresponding to the above-mentioned configurations. Among them, FIG. 10 shows a second embodiment of the present invention, and this embodiment realizes the polarities of the electrode rods 45 and 46 by a simple switching operation of the rectifier 20.

Even if the polarities of the electrode rods 45 and 46 are changed in this way, metal ions are not released from the electrode tube 48 and only function to form an electric field with the object storage container 5. , Their electrochemical reaction is not hindered, the selection and modification of the electrodes are allowed, and their rational use and work can be obtained. Moreover, the lines of electric force at that time are the objects to be processed container 5
From the inside toward the inner electrode tube 48,
The same effect as the above can be obtained.

FIG. 11 shows a third embodiment of the present invention,
In this embodiment, a plurality of object storage containers 5, 5a, 5b having similar shapes to each other are provided, and these are arranged concentrically and equidistantly about the electrode tube 48, and the adjacent electrode tubes 48 and The same potential is applied between the processed material storage containers 5 and 5a and the pair of processed material storage containers 5 and 5b, and the chamber 3
A plurality of processing object storage containers 5, 5a, 5b arranged in 6
By doing so, the mass production of plating and the simplification of the structure are attempted. In this case, the object storage containers 5, 5a, 5b
Although they are arranged concentrically, they can also be applied to a conventional plating method in which they are arranged in parallel to each other and a reaction tank having a substantially rectangular cross section.

FIG. 12 shows a fourth embodiment of the present invention,
In this embodiment, the to-be-processed object storage container 5 is formed so that it can be divided into two in the vertical direction, and the base end portions thereof are rotatably connected via a hinge 87, and the other end portions are connected by an appropriate clip. In this way, the object to be plated can be easily taken in and out of the container 5.

The method of depositing and depositing the electrolyzed electrode material on the other electrode material as in the above-described embodiment can be applied to the same electroforming and anodic oxide film forming method in principle. Similar effects can be obtained. Further, 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 tank, one electrode substance is electrolyzed, and the other electrode substance is collected. 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 housed in a reaction tank capable of containing an electrolytic substance, and the electrolytic substance contained in the electrolyte solution is deposited and adhered to the object to be treated, and electroless plating or chemical conversion treatment method without applying an external electric field. The present invention can be applied to
By doing so, the same effect as described above can be obtained.

[0102]

As described above, according to the invention of claim 1, during the surface treatment of the object to be treated, the circulation path of the surface treatment fluid including the reaction tank is communicated with the surface treatment fluid throughout the circulation path. Since it circulates, surface treatment of the object to be treated with the surface treatment fluid, such as degreasing cleaning and drying, can be performed with high accuracy and speed, as compared with the method in which the surface treatment fluid is retained in the reaction tank to perform the surface treatment. Avoiding contact between the object to be treated and the atmosphere, for example, activation treatment of the surface of the object to be treated can be performed with high accuracy and reliability, for example, good deposition of metal ions can be obtained, and it is suitable for electroplating and multi-layer overlay plating. There is.

According to the second aspect of the present invention, when the object to be treated is degreased or washed or dried, the surface treatment fluid is circulated throughout, so that the surface activation treatment such as degreasing or washing or the drying of the object to be treated is enhanced. It can be done accurately and quickly. According to the invention of claim 3, after the surface treatment of the object to be treated, the gas generated by the electrochemical reaction in the surface treatment fluid is separated or removed, so that the gas is prevented from entering the system. A good electrochemical reaction with respect to the object to be treated can be obtained, and the surface treatment fluid can be regenerated accurately.

According to the fourth aspect of the invention, after the surface treatment of the object to be treated, the oxygen and hydrogen in the surface treatment fluid are separated or removed, so that the oxygen and hydrogen produced by the electrochemical reaction are introduced into the system. It is possible to prevent contamination, obtain a good electrochemical reaction with respect to the object to be treated, and accurately regenerate the surface treatment fluid. According to the invention of claim 5, oxygen and hydrogen in the surface-treated fluid after the surface treatment are burned to generate water, and the surface-treated fluid obtained by separating the water is circulated in the circulation path. It is possible to safely and easily remove hydrogen, prevent oxygen, hydrogen, and water from being mixed into the system and the adverse effects thereof, and to perform the drying by the surface treatment fluid smoothly and efficiently.

According to a sixth aspect of the present invention, after introducing the surface treatment fluid and the pickling solution or the electrolytic solution into the reaction tank, the supply and discharge passages of the reaction tank are shut off, and the object to be treated is pickled or electrochemically reacted. As a result, it is possible to prevent the pickling solution or electrolyte from moving and flowing into the circulation path, to ensure stable pickling and electrochemical reaction, and to prevent corrosion of the circulation path and system troubles in advance. You can In the invention of claim 7, after the pickling or the electrochemical reaction of the object to be treated, the surface treatment fluid in the reaction tank is circulated to the circulation path, and the pickling solution or the electrolytic solution is added to the surface treatment fluid. Since it is separated from the circulation path of, the surface treatment fluid and the pickling solution, the electrolytic solution, etc. can be treated separately, and they can be treated reasonably and safely to regenerate them.

According to an eighth aspect of the present invention, after the pickling or electrochemical reaction of the object to be treated, the surface treatment fluid in the pickling solution or the electrolytic solution is separated, and this is refluxed to the circulation route of the surface treatment fluid. Therefore, during the pickling or the electrochemical reaction, the surface treatment fluid mixed in the pickling solution or the electrolytic solution can be effectively used. In the invention of claim 9, since the surface treatment fluid is a pressurized fluid at atmospheric pressure or higher or a supercritical or subcritical fluid, in the case of a pressurized fluid at atmospheric pressure or higher, the surface treatment fluid is easily available, The system can be manufactured and operated inexpensively and safely, and in the case of a supercritical or subcritical fluid, there is an effect that a good surface treatment state can be obtained due to high diffusivity.

According to the tenth aspect of the present invention, during the surface treatment of the object to be treated, the circulation route of the surface treatment fluid including the reaction tank is communicated with the circulation route, and the surface treatment fluid can be circulated throughout the reaction. Compared with the method of surface treatment by allowing the surface treatment fluid to stay in the tank, the surface treatment of the object to be treated with the surface treatment fluid, such as degreasing, cleaning, and drying, can be performed with high accuracy and speed, and the object to be treated and the atmosphere It is possible to avoid contact and perform the activation treatment on the surface of the object to be treated with high accuracy and reliability, and obtain good deposition of metal ions, for example, which is suitable for electroplating and multi-layer overplating. Moreover, since the storage tank for storing the surface treatment fluid and the treatment liquid after use is substantially abolished, the equipment can be made compact and inexpensive, and the surface treatment fluid can be quickly regenerated.

According to the eleventh aspect of the present invention, when the object to be treated is degreased or washed or dried, the surface treatment fluid can be circulated all the time. It can be performed with high accuracy and speed. According to the twelfth aspect of the invention, the gas generated by the electrochemical reaction in the surface treatment fluid can be separated or removed, so that the gas, for example, oxygen and hydrogen is prevented from being mixed into the system, which is good for the object to be treated. It is possible to obtain various electrochemical reactions and to accurately regenerate the surface treatment fluid.

According to the thirteenth aspect of the present invention, since a reactor capable of separating or removing oxygen and hydrogen in the surface treatment fluid is inserted in the circulation path, the mixture of oxygen and hydrogen into the system and its adverse effects are obviated. Therefore, the surface treatment fluid can be regenerated accurately. In the invention of claim 14, since a dehydrator capable of separating water is inserted in the downstream side of the reactor of the circulation path, oxygen and hydrogen can be safely and easily removed, and an adverse effect due to mixing of oxygen, hydrogen and water can be obtained. It is possible to prevent this from occurring and to dry the surface treatment fluid smoothly and efficiently.

According to a fifteenth aspect of the present invention, the surface treatment fluid and the pickling solution or the electrolytic solution can be introduced into the reaction tank, and after introducing these into the reaction tank, the supply / discharge passage of the reaction tank can be cut off. Since it is installed in the equipment, it prevents the pickling solution or electrolytic solution from moving and flowing into the circulation path, which enables stable pickling and electrochemical reaction, and prevents corrosion of the circulation path and system troubles. be able to. Claim 16
In the invention, after the pickling or the electrochemical reaction of the object to be treated, the surface treatment fluid in the reaction tank is circulated to the circulation path, and the pickling solution or the electrolytic solution is added to the surface treatment fluid. Since it can be separated from the circulation path, the surface treatment fluid, the pickling solution, and the electrolytic solution are treated separately,
It is possible to process them reasonably and safely and to regenerate them.

According to a seventeenth aspect of the present invention, a treatment liquid recovery tank capable of separating the surface treatment fluid in the pickling solution or the electrolytic solution is inserted into the discharge passage of the reaction tank, and the recovery tank is connected to the surface treatment fluid. Since the fluid is connected to the circulation path, it is possible to effectively utilize the surface treatment fluid mixed in the pickling solution or the electrolytic solution during pickling or electrochemical reaction. In the invention of claim 18, the surface treatment fluid is a pressurized fluid at atmospheric pressure or higher, or a supercritical or subcritical fluid. Therefore, in the case of a pressurized fluid at atmospheric pressure or higher, the surface treatment fluid is easily available. The system can be manufactured and operated inexpensively and safely, and in the case of a supercritical or subcritical fluid, there is an effect that a good surface treatment state can be obtained due to high diffusivity.

According to a nineteenth aspect of the present invention, a plurality of the reaction tanks are provided, the reaction tanks are connected to the circulation path, and a pressurized fluid or a supercritical or subcritical fluid at an atmospheric pressure or higher is added to the reaction tank and an acid. A cleaning solution or an electrolytic solution is sequentially introduced to enable degreasing cleaning, pickling, drying, electroplating, and drying of the object to be processed in each reaction tank, while connecting adjacent reaction tanks. In addition to being able to supply and discharge the fluid used,
In the reaction tank that processes the successive steps, after the processing of the preceding reaction tank, the used fluid can be supplied to the subsequent reaction tank, so the used surface treatment fluid, the used acid solution, etc. are used sequentially in each reaction tank By doing so, while making effective use of it,
The surface treatment of the object to be treated and each treatment step can be reasonably performed, and the mass production can be achieved.

According to the twentieth aspect of the present invention, a single or a plurality of jigs are detachably attached to the lid body to promote the integration of the lid body and the jigs, and to facilitate the handling of them and to make the jigs and the lids. The body and the tank body can be easily maintained. According to the twenty-first aspect of the invention, the lid and the jig can be integrally lifted and lowered, so that they can be easily and quickly taken in and out of the tank body. According to a twenty-second aspect of the invention, a cross-sectional shape of the chamber of the tank body is
Since the cross-sectional shape of the jig is formed to be similar to each other and they are arranged concentrically, the manufacturing of the tank body and the jig can be rationalized and made compact, and a large number of objects can be efficiently processed. It can be housed and processed, and its mass production can be achieved. In the invention of claim 23, since the cross-sectional shape of the chamber of the tank body and the cross-sectional shape of the jig are formed in a circular shape and these are arranged concentrically, a large number of objects to be processed can be efficiently processed. It can be housed and treated, mass production thereof can be achieved, and the surface treatment fluid, the used solution, and the like can be agitated accurately.

According to the twenty-fourth aspect of the present invention, since the jig is divided into a plurality of parts and they are rotatably connected to each other, the jig can be easily opened and closed, and the object to be processed can be easily attached to and detached from the jig. be able to. According to the twenty-fifth aspect of the present invention, since the lid is provided with an electrode capable of energizing the jig, integration of the lid, the jig and the electrode is promoted, and the convenience of handling them and the ease of maintenance can be achieved. it can. According to the twenty-sixth aspect of the present invention, since the same electric potential is applied between the jigs arranged adjacent to each other, the electrochemical reaction such as electroplating can be made uniform with respect to the object to be processed attached to each jig, There is an effect that a uniform electrochemical reaction such as electroplating can be obtained for each object to be treated.

According to the twenty-seventh aspect of the present invention, since the electrode is arranged at the center of the chamber, the electric field strength of each jig is set to be uniform, and the object to be processed mounted on the jig is uniformly electroplated. There is an effect that an electrochemical reaction such as can be obtained. Claim 28
In the invention, since the stirring shaft capable of rotating the stirring means is attached to the center of the lid, and the electrode is coaxially arranged outside the stirring shaft, the lid, the jig, the electrode and the stirring means are integrated. The convenience of handling them and the ease of maintenance can be promoted.

In a twenty-ninth aspect of the present invention, a pressurized fluid having a pressure equal to or higher than atmospheric pressure or a supercritical or subcritical fluid, an acid pickling solution, and an electrolytic solution are sequentially introduced into the reaction tank to degrease and wash the object to be treated. , Pickling, drying, and electroplating can be sequentially performed, adjacent reaction tanks can be connected to each other to supply and discharge the fluid to be used, and the preceding reaction tanks can be used to process successive steps. After the treatment, the use fluid can be supplied to the subsequent reaction tanks.By using the surface treatment fluid and the acid solution, etc., used in each reaction tank one after another, the effective use of the surface treatment fluid and the object to be treated can be achieved. It is possible to rationally perform the surface treatment and each treatment step, and to mass-produce the same.

According to the thirtieth aspect of the present invention, the electrode is made of an insoluble member, and a supercritical or subcritical fluid and an electrolytic solution are introduced into the reaction tank to enable an electrochemical reaction of the object to be treated. In a supercritical or subcritical fluid having a high diffusivity, metal ions can be deposited satisfactorily and uniformly on the object to be processed, the wear of the electrode is eliminated, and there is no interruption due to replacement of the electrode, etc. The productivity of the electrochemical reaction can be improved.

[Brief description of drawings]

FIG. 1 is a front view of a device of the present invention.

FIG. 2 is a front view showing an internal state of the device of the present invention.

FIG. 3 is a left side view of FIG. 1, showing an internal state of the device of the present invention.

FIG. 4 is a plan view of FIG. 1, showing an internal state of the device of the present invention.

FIG. 5 is a schematic view showing a flow of the device of the present invention.

FIG. 6 is an enlarged cross-sectional view showing a reaction tank applied to the device of the present invention, in which a lid body having a jig attached thereto is mounted on the reaction tank, and these are locked by a clamp ring, and the electrochemical reaction of the object to be treated is performed. It shows the situation in preparation for the reaction.

FIG. 7 is a cross-sectional view taken along the line AA of FIG. 6, showing the state of energization between the jig and the electrodes in the reaction tank slightly reduced.

FIG. 8 is a plan view of a reaction tank applied to the apparatus of the present invention, showing an open state immediately before locking of the lid and the clamp ring with the electrodes and the motor omitted.

FIG. 9 is a bottom view of a lid body applied to the device of the present invention.

FIG. 10 is a cross-sectional view showing the main parts of the second embodiment of the present invention, showing an energized state in which the polarities of the jig and the electrodes in the reaction tank are changed.

FIG. 11 is a cross-sectional view showing a main part of a third embodiment of the present invention, in which a plurality of jigs are arranged concentrically around an electrode in a reaction tank, and the current supply state is shown.

FIG. 12 is a plan view showing an essential part of a fourth embodiment of the present invention, showing a situation of a jig configured in two.

[Explanation of symbols] 4 reaction tanks 5 jigs (processing object storage container) 6 lid 11 Separation tank (treatment liquid recovery tank) 14 Separation tank 24 Dehydrator (dehydration column) 25 tank body 36 chambers 42 stirring shaft 43 Stirring means (fan) 45,46 electrode (electrode rod) 48 electrodes (electrode tube) 78 reactor

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masato Sone             3-11-8 Honmachi, Koganei-shi, Tokyo (72) Inventor Nobuyoshi Sato             1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture             Asahi Engineering Co., Ltd.

Claims (30)

[Claims] 1. A surface treatment fluid in which a surface treatment fluid is introduced into a reaction tank capable of accommodating an object to be treated, and after the surface treatment of the object to be treated, the surface treatment fluid is introduced into a separation tank to separate contaminants. In the method of surface-treating an object to be treated, which circulates into the reaction tank, during the surface treatment of the object to be treated, a circulation path of the surface-treatment fluid including the reaction tank is communicated with the surface-treatment fluid throughout the circulation path. A method for treating the surface of an object to be treated, which comprises circulating the object. 2. The surface treatment method for the object to be treated according to claim 1, wherein the surface treatment fluid is constantly circulated during degreasing or cleaning of the object to be treated or drying thereof. 3. The surface treatment method for an object to be treated according to claim 1, wherein after the surface treatment of the object, the gas generated by the electrochemical reaction in the surface treatment fluid is separated or removed. 4. The surface treatment method for an object to be treated according to claim 3, wherein oxygen and hydrogen in the surface treatment fluid are separated or removed after the surface treatment of the object to be treated. 5. The object according to claim 4, wherein oxygen and hydrogen in the surface-treated fluid after the surface treatment are burned to generate water, and the surface-treated fluid separated from the water is circulated in the circulation path. Surface treatment method for treated objects. 6. The surface treatment fluid and the pickling solution or the electrolytic solution are introduced into the reaction tank, and then the supply / discharge passage of the reaction tank is shut off to carry out pickling or electrochemical reaction of the object to be treated.
A method for surface treatment of an object to be treated as described above. 7. After pickling or electrochemical reaction of the object to be treated, the surface treatment fluid in the reaction tank is circulated to the circulation path, and the pickling solution or electrolytic solution is circulated in the surface treatment fluid. The method for surface treatment of an object to be treated according to claim 6, wherein the surface treatment method is separated from the path. 8. The method according to claim 7, wherein after the pickling or electrochemical reaction of the object to be treated, the surface treatment fluid in the pickling solution or the electrolytic solution is separated and refluxed to the circulation path of the surface treatment fluid. Surface treatment method of the object to be treated. 9. The surface treatment method for an object to be treated according to claim 1, wherein the surface treatment fluid is a pressurized fluid at atmospheric pressure or higher, or a supercritical or subcritical fluid. 10. A reaction vessel capable of accommodating an object to be treated and introducing a surface treatment fluid therein, and a surface treatment fluid after the surface treatment of the object to be treated is transferred from the reaction vessel, and In a surface treatment apparatus for an object to be treated, comprising a separation tank capable of separating contaminants in the surface treatment fluid, and allowing the surface treatment fluid from which the contaminant has been separated to be circulated to the reaction tank, the surface of the object to be treated A surface treatment apparatus for an object to be treated, characterized in that a circulation path of a surface treatment fluid including the reaction tank is communicated during processing, and the surface treatment fluid can be circulated throughout the circulation path. 11. The surface treatment apparatus for the object to be treated according to claim 10, wherein the surface treatment fluid can be circulated throughout the time of degreasing or cleaning the object to be treated or drying the same. 12. The gas produced by an electrochemical reaction in the surface treatment fluid can be separated or removed.
A surface treatment apparatus for an object to be treated as described above. 13. The surface treatment apparatus for an object to be treated according to claim 12, wherein a reactor capable of separating or removing oxygen and hydrogen in the surface treatment fluid is inserted in the circulation path. 14. The surface treatment apparatus for an object to be treated according to claim 13, wherein a dehydrator capable of separating water is inserted downstream of the reactor in the circulation path. 15. The reaction tank is provided with the surface treatment fluid and a pickling solution or an electrolytic solution so as to be introduced, and after introducing these into the reaction tank, a supply / discharge path of the reaction tank can be blocked. 10. The surface treatment apparatus for the article to be treated according to 10. 16. After pickling or electrochemical reaction of the object to be treated, the surface treatment fluid in the reaction tank is circulated to the circulation path, and the pickling solution or electrolytic solution is added to the surface treatment fluid. 16. The surface treatment apparatus for an object to be treated according to claim 15, wherein the surface treatment apparatus can be separated from the circulation path. 17. A treatment liquid recovery tank capable of separating the surface treatment fluid in the pickling solution or the electrolytic solution is inserted into the discharge passage of the reaction tank, and the collection tank is connected to the circulation passage of the surface treatment fluid. The surface treatment apparatus for an object to be treated according to claim 10. 18. The surface treatment fluid is a pressurized fluid at atmospheric pressure or higher, or a supercritical or subcritical fluid.
0. The surface treatment apparatus for the object to be treated according to 0. 19. A plurality of said reaction tanks are provided, these reaction tanks are connected to said circulation path, and pressurized fluid or supercritical or subcritical fluid at atmospheric pressure or more, and pickling solution or electrolyte solution are provided in said reaction tank. Are sequentially introduced, and degreasing and cleaning of the object to be treated in each reaction tank, pickling, drying, electroplating, and drying can be sequentially performed, while connecting adjacent reaction tanks,
16. The object to be treated according to claim 15, wherein a fluid to be used can be supplied and discharged, and in a reaction tank for treating successive steps, the fluid to be used can be supplied to a subsequent reaction tank after the treatment of the preceding reaction tank. Surface treatment equipment. 20. A tank main body, which accommodates a jig capable of mounting an object to be processed and a stirring means, and which can supply and discharge the surface treatment fluid of the object, and a lid capable of sealing the tank main body. In a surface treatment apparatus for an object to be treated having a reaction tank equipped with a body,
A surface treatment apparatus for an object to be treated, wherein one or a plurality of the jigs are detachably attached to the lid. 21. The surface treatment apparatus for an object to be treated according to claim 20, wherein the lid and the jig can be integrally raised and lowered. 22. The surface of the object to be treated according to claim 20, wherein the cross-sectional shape of the chamber of the tank main body and the cross-sectional shape of the jig are formed in a similar shape, and these are arranged concentrically. Processing equipment. 23. The surface treating apparatus for an object to be treated according to claim 22, wherein the cross-sectional shape of the chamber of the tank body and the cross-sectional shape of the jig are formed in a circular shape, and these are arranged concentrically. . 24. The surface treating apparatus for the object to be treated according to claim 22, wherein the jig is divided into a plurality of pieces, and the jigs are rotatably connected to each other. 25. The surface treatment apparatus for an object to be treated according to claim 20, wherein an electrode capable of energizing the jig is attached to the lid body. 26. The surface treatment apparatus for an object to be treated according to claim 20 or 23, wherein the same potential is applied between jigs arranged adjacent to each other. 27. The surface treatment apparatus for an object to be treated according to claim 20, wherein an electrode is arranged at the center of the chamber. 28. The object to be treated according to claim 20 or 23, wherein a stirring shaft capable of rotating the stirring means is attached to the center of the lid, and the electrode is coaxially arranged outside the stirring shaft. Surface treatment equipment. 29. A pressurized fluid at atmospheric pressure or higher or a supercritical or subcritical fluid, a pickling solution, and an electrolytic solution are sequentially introduced into the reaction tank to perform degreasing cleaning and pickling of an object to be treated. The surface treatment apparatus for an object to be treated according to claim 20, wherein the drying, the electroplating, and the electroplating can be sequentially performed. 30. The object to be processed according to claim 20, wherein the electrode is made of an insoluble member, and a supercritical or subcritical fluid and an electrolytic solution are introduced into the reaction tank to enable electroplating of the object to be processed. Surface treatment equipment for objects.