JP2003073868A - Method for activating surface of base material and apparatus therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for activating the surface of a base material, which is suitable for pretreatment in electrochemical treatment, for instance, electrodeposition, can remove an oxide film on the surface of the base metal while simultaneously degreasing the surface, effectively and rationally, with a safe and inexpensive solution, increases productivity, reduces cost of equipment, and rationalizes waste liquid treatment to recycle it and prevent environmental pollution, and to provide an apparatus therefor. SOLUTION: The method for activating the surface of the base material comprises degreasing the surface of a material to be treated 3 or removing the oxide film. The method is characterized by dissolving compressed carbon dioxide into a predetermined amount of water 5, and preparing a solution for oxide film removal having a predetermined acidic concentration.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for pretreatment in an electrochemical treatment such as electroplating, and uses a safe and inexpensive solution to simultaneously perform degreasing treatment on the surface of a base material such as metal and removal of an oxide film. A method of activating the surface of the base material and its treatment that enables efficient and rationalization, improves productivity and reduces equipment costs, rationalizes waste liquid treatment, reuses it, and prevents environmental pollution. Regarding the device.

[0002]

2. Description of the Related Art For example, in an electrochemical treatment such as electroplating, degreasing washing or acid washing in the pretreatment process removes oils and fats and an oxide film on the metal surface to be treated, and activates the metal surface. By applying chemical treatment, a good metal film can be coated.

The degreasing cleaning is carried out by immersing the object to be treated in an alkaline aqueous solution, and the pickling is carried out by immersing the object to be treated in an acidic aqueous solution diluted with sulfuric acid or hydrochloric acid, and then washing them with water, The effluent was charged with an acidic or alkaline chemical to neutralize it and then discharged from the factory.

Therefore, the conventional pretreatment process requires a dedicated bathtub and a washing bath, which requires a large scale of equipment and
Various chemicals and a large amount of water are required to increase the treatment cost, and moreover, it is time-consuming due to the presence of water washing between the degreasing treatment and the pickling, and not only the productivity is poor, but also lead and Since heavy metals such as zinc and tin could not be removed and a wastewater treatment facility for that purpose was required, facility costs increased.

Further, in the conventional pretreatment process, the working environment is bad because the work is forced under the condition that the treatment liquid is scattered and harmful gas is generated. There is a risk that the treated product may be vulnerable to hydrogen, and a separate means is required to remove this hydrogen fragility.

In order to solve such a problem, in Japanese Patent Laid-Open No. 2000-73191, a solution containing phosphine as an organic solvent is used, and an object to be treated is dipped in the solution or is brushed. And spray it,
It does not require dangerous chemicals such as strong acid or cyanide or toxic chemicals, and removes fats and oils and oxide film without substantially invading the base material.

However, the above-mentioned phosphine is expensive and promotes an increase in production cost, and at the same time, there is a problem that oil and fat and oxide film cannot be removed sufficiently.

A cleaning method using a supercritical fluid or a subcritical high-density fluid as a cleaning solvent is known as a cleaning method for semiconductors, precision machine parts, etc., for example, Japanese Patent Laid-Open No. 2000-3088.
It is proposed in Japanese Patent No. 62-62. However, the method
It can be used to remove oil and fat from machine parts,
It is not possible to remove the oxide film of mechanical parts, etc. In that case, a separate oxide film removal process is required, which leads to poor productivity and an increase in equipment costs.

As another method, carbon dioxide, which is a cleaning medium, is pressurized, particulate dry ice is ejected from a cleaning gun, and this is sprayed on the surface of the member to be cleaned to remove oil and fat on the surface of the member. A method of blowing it off is known. However, this method is also similar to the above, and although it can deal with the removal of oil and fat, it has a problem that it cannot deal with the removal of the oxide film.

[0010]

The present invention solves such a problem, and is suitable for pretreatment in electrochemical treatment such as electroplating, and degreasing the surface of a base material such as metal with a safe and inexpensive solution. A base material that enables efficient and rational simultaneous treatment and removal of oxide film to improve productivity and reduce equipment costs, streamline waste liquid treatment, and reuse it and prevent environmental pollution. An object of the present invention is to provide a surface activation treatment method and a treatment apparatus therefor.

[0011]

According to a first aspect of the present invention, there is provided a method for activating a surface of a base material, which comprises degreasing or removing an oxide film on a surface of a member to be treated, wherein pressurized carbon dioxide is dissolved in a predetermined amount of water. Then, create an oxide film removal solution consisting of carbonated water with a predetermined acidic concentration, and easily and inexpensively create a safe oxide film removal solution with an inexpensive material. The oxide film removal solution with a high concentration can be easily prepared.

According to a second aspect of the present invention, the oxide film removing solution is brought into contact with the member to be treated to remove the oxide film of the member to be treated, so that the oxide film can be easily and surely removed. There is. The invention of claim 3 atomizes the carbon dioxide, contacts the particulate carbon dioxide with the member to be treated, and separates or peels off oil and fat on the surface of the member,
The precision of the degreasing treatment is improved as compared with the conventional degreasing treatment by the dipping method. According to the invention of claim 4, as compared with the conventional processing method in which the oxide film removal treatment and the degreasing treatment are simultaneously performed and these treatments are performed separately, these treatments can be efficiently and inexpensively and rationally performed, and the productivity is improved. We are trying to reduce equipment costs.

According to a fifth aspect of the present invention, the member to be treated is housed in a closed space or an open space, and the oxide film removing treatment and the degreasing treatment are performed at the same time so that various working conditions can be dealt with. ing. According to the sixth aspect of the present invention, the water and carbon dioxide are stirred to efficiently perform the degreasing treatment and oxide film removal. According to the invention of claim 7, the water is sprayed, and the carbon dioxide is supplied into the spray to increase the contact area between the water and the carbon dioxide and improve the solubility of the carbon dioxide. . According to the invention of claim 8, after the degreasing treatment or the oxide film removal treatment, the treatment liquid is depressurized and drained to reduce the solubility of carbon dioxide and reduce the acidity of the oxide film removal solution, The treated liquid after use is rationally processed and its safety is ensured to realize drainage to sewage and prevent environmental pollution.

According to the invention of claim 9, the treatment liquid after use is decompressed and heated, the treatment liquid is decomposed into water and carbon dioxide, and these are discharged or reused, so that the safety of the drainage water. In addition to ensuring the property, we are trying to make effective use of water and carbon dioxide after decomposition. According to a tenth aspect of the invention, after the degreasing treatment or the oxide film removal treatment, the used treatment liquid is transferred to another container, a new member to be treated is accommodated in the container, and the oxide film of the member to be treated is disposed. By performing the removal treatment and the degreasing treatment at the same time, the productivity of the oxide film removal treatment and the degreasing treatment of the member to be treated is improved and the mass production thereof is attempted.

According to an eleventh aspect of the present invention, in the activation treatment device for the base material surface for degreasing or removing an oxide film on the surface of a member to be treated, pressurized carbon dioxide is supplied to a closable bath containing a predetermined amount of water. Then, the carbon dioxide is dissolved in the water to make it possible to prepare an oxide film removal solution having a predetermined acidic concentration,
Create an oxide film removal solution consisting of carbonated water with a predetermined acid concentration, and easily and inexpensively create a safe oxide film removal solution with an inexpensive material, and adjust the pressure state to obtain a desired acid concentration The solution for removing the oxide film is made easy.

According to a twelfth aspect of the present invention, the oxide film can be removed by immersing the member to be processed in the oxide film removing solution or spraying the oxide film removing solution onto the member to be processed. It is adapted to work conditions. According to a thirteenth aspect of the present invention, the carbon dioxide is supplied into the water to be atomized, the particulate carbon dioxide is brought into contact with the member to be treated, and oils and fats on the surface of the member can be separated or peeled off. The precision of the degreasing treatment is improved as compared with the degreasing treatment by the dipping method.

According to a fourteenth aspect of the present invention, the oxide film removing treatment and the degreasing treatment can be simultaneously performed, and these treatments can be efficiently and inexpensively and rationally performed as compared with a conventional treatment method in which these treatments are performed separately. We are trying to improve productivity and reduce equipment costs. According to a fifteenth aspect of the present invention, the member to be treated is housed in a closed space or an open space, and the oxide film removal treatment and the degreasing treatment can be performed at the same time, and various work conditions can be dealt with. According to a sixteenth aspect of the present invention, the carbon dioxide is introduced from the lower part of the bath, the water is introduced from the upper part of the bath to bubble the carbon dioxide to promote dissolution of the carbon dioxide, and the water and the carbon dioxide. I try to improve the stirring with.

According to a seventeenth aspect of the present invention, water is sprayed onto the bath, the carbon dioxide is supplied into the spray to enhance the dissolution of carbon dioxide and improve the agitation of water and carbon dioxide. I have to. According to the invention of claim 18, after the degreasing treatment or the oxide film removal treatment, the treatment liquid is depressurized to allow drainage, the solubility of carbon dioxide is lowered, and the acidity of the oxide film removal solution is lowered to be used. The subsequent treatment liquid is reasonably treated and its safety is ensured to realize drainage to sewage and prevent environmental pollution.

According to a nineteenth aspect of the present invention, the treatment liquid after use is decompressed and heated to decompose the treatment liquid into water and carbon dioxide, which can be discharged or reused to ensure the safety of the drainage. In addition to ensuring the above, we are trying to make effective use of water and carbon dioxide after decomposition. In the invention of claim 20, after the degreasing treatment or the oxide film removal treatment, the used treatment liquid is transferred to another container, a new member to be treated is accommodated in the container, and the oxide film of the member to be treated is placed. The removal treatment and the degreasing treatment can be performed at the same time, the productivity of the oxide film removal treatment and the degreasing treatment of the member to be treated is improved, and the mass production can be achieved.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the illustrated embodiment in which the present invention is applied to the steps of degreasing and oxide film removal (hereinafter referred to as pickling) which are pretreatments for electroplating (nickel plating) will be described. In FIG. 2, reference numeral 1 is a stainless steel bottomed cylindrical pressure-resistant degreasing tank or pickling tank (hereinafter referred to as a bath), the inner surface of which is lined with vinyl chloride or hard rubber. The lid 2 is airtightly and detachably attached to the upper opening.

A member 3 to be treated, which is an object of degreasing and oxide film removal, is housed in the bath 1 so that it can be taken in and out.
A stirrer 4 such as a stirrer is housed in the bottom portion thereof. Further, water 5 such as tap water and pure water is stored in the bathtub 1,
A water supply pipe 6 is connected to the upper peripheral surface thereof, and the pipe 6 supplies a water supply source 7
Is in communication with.

In the figure, 8 is an open / close valve inserted in the water supply pipe 6, 9 is a heater mounted on the peripheral surface of the bath 1, and the water 5 is heated to a predetermined temperature, in the embodiment, 50 to 150 ° C. In this case, the warm water heated to the above temperature may be supplied to the bathtub 1.

A gas container 10 containing carbon dioxide, which is a safe and stable pressurized liquid or pressurized gas, is installed outside the bath 1. The gas conduit 11 has a compression pump 12 and an on-off valve 13. It is connected to the lower peripheral surface of the bathtub 1 via the.

The compression pump 12 applies as high a pressure as possible to the carbon dioxide at a predetermined pressure, in the embodiment, carbon dioxide at atmospheric pressure or higher, preferably 2 atmospheric pressure or higher to subcritical or supercritical pressure or higher. It is pressurized and supplied into the bath 1 to be dissolved in the water 5 to generate carbonic acid (H ₂ CO ₃ ) water. Since the pressure value in this case is related to the acidity of the oxide film removal solution, it is appropriately and optimally adjusted depending on the condition of the oxide film.

A communication pipe 14 is connected to the lower portion of the bath 1, an opening / closing valve 15 is inserted in the pipe 14, and its downstream end is connected to a storage tank 16. The storage tank 16
Is configured to have substantially the same and substantially the same volume as the bathtub 1, and a heater 17 is attached to the peripheral surface thereof so that the stored liquid 18 contained in the tank 17 can be heated to a predetermined temperature. There is. In the embodiment, the stored liquid 18 is heated to about 50 ° C.,
Carbonated water, which is the main component of the stored liquid 18, can be decomposed into water and carbon dioxide.

The return pipe 1 is attached to the storage tank 16.
9, 20 are connected, and the other ends thereof are connected to the bath 1 and the compression pump 12 so that the decomposed water and carbon dioxide can be refluxed. In the figure, 21 and 22 are opening / closing valves inserted in the return pipes 19 and 20, and 23 is a filter or ion exchange resin inserted in the return pipe 19.

A discharge pipe 24 is connected to the lower part of the storage tank 16 and its downstream end communicates with the sewer.
An on-off valve 5 is inserted in the discharge pipe 24.

The apparatus for activating the surface of the base material thus constructed has a pressure-tight bath 1 that can be sealed, and water 5 in the bath 1.
And a gas container 10 capable of supplying liquid carbon dioxide to the bathtub 1, which is liquid carbon dioxide having a high density in the embodiment, and a treatment liquid after degreasing and oxide film removal treatment of the bathtub 1. Storage tank 1 that can temporarily store
6 and.

Therefore, unlike the conventional case, a dedicated degreasing tank, pickling tank, water washing tank and neutralization tank are not required, so that the equipment is simple and the equipment cost can be reduced and the installation space can be made compact. Since the structure is simple, it can be manufactured easily and inexpensively. Moreover, since the treatment liquid after the treatment is decomposed into water and carbon dioxide by the storage tank 16 and impurities such as an oxide film precipitated in the treatment liquid are removed as described later, the treatment liquid can be reused. , Effective use and reduction of consumption can be achieved.

Next, when performing degreasing and oxide film removal processing by the processing apparatus, the member 3 to be processed is housed in the bath 1, the lid 2 is attached and the inside is sealed, and then the water source 7 is used.
The water 5 is supplied to the bathtub 1 from above, and the member 3 to be treated is immersed in the water 5.

After a fixed amount of the water 5 is supplied, carbon dioxide is supplied from the gas container 10 to the bath 1, which is pressurized by the compression pump 12, and the water 5 is heated via the heater 9. Around this, the stirring bar 4 is operated to stir the water 5. Therefore, the carbon dioxide in the water 5 is atomized and moves at high speed, and a large amount of the particulate carbon dioxide collides with the member 3 to be treated, and the oil and fat adhering to the surface of the member 3 is separated and degreased.

In this case, the carbon dioxide is supplied from the bottom of the bath 1 and rises in the water 5 in a bubbling state, so that the carbon dioxide is rapidly dissolved and saturated in the water 5 to promote the increase in solubility. Together with the stirrer 4, a uniform and precise stirring effect is obtained and the degreasing action is enhanced.

If, instead of the above method, the water 5 is atomized into the bath 1 and the carbon dioxide is supplied at the same time to mix them, the contact area between them is further increased, In addition to promoting the increase in solubility, a precise stirring effect is obtained, and the degreasing action is further enhanced.

Simultaneously with the stirring, the carbon dioxide is dissolved in the water 5 to form carbonic acid (H ₂ CO ₃ ) and the water 5 becomes acidic. In this case, since the carbon dioxide is pressurized to a high pressure, dissolution in the water 5 is promoted and the amount of dissolution is proportional to the pressure. Therefore, the above-mentioned acidity rises, acidity sufficient for pickling (PH3 to 4) is rapidly formed, and it comes into contact with the oxide film on the surface of the processed member 3 after degreasing, and decomposes and removes the oxide film. To do. Moreover,
Since the water 5 is heated, the dissolution of carbon dioxide is promoted, the increase of the acidity is promoted, and the decomposition action of the oxide film is promoted.

In this way, the degreasing of the member 3 to be processed and the removal of the oxide film are carried out simultaneously, and the oil and fat and the oxide film are removed.
Settles on the bottom of the. Then, the above process is executed for a predetermined time, and when sufficient degreasing and oxide film removal effects are obtained, the supply of carbon dioxide is stopped, the drive of the stirring bar 4 is stopped, and the on-off valve 15 is opened.

In this way, the pressure inside the bath 1 is reduced,
When the solubility of the carbon dioxide decreases, the treatment liquid is guided to the communication pipe 14 and pushed out to the storage tank 5, and when the whole amount moves to the storage tank 5, the open / close valve 15 is closed. This situation is as shown in FIG.

Since the stored liquid 18 in the storage tank 5 is depressurized and the solubility of carbon dioxide is lowered, its acidic concentration is rapidly lowered and becomes weakly acidic, so that there is no fear of actual damage. Therefore, the on-off valve 25 can be opened and the stored liquid 18 can be directly discharged to the sewage through the discharge pipe 24.

At this time, when heavy metal is present in the stored liquid 18, carbon dioxide disappears from the liquid 18,
Separated from the carbonated water and settled in the tank 5. Therefore, it becomes possible to collect together with other foreign matter and an oxide film through a filter (not shown) provided in the discharge pipe 24, ensuring the safety of the drainage and preventing environmental pollution.
After its recovery, it can be treated as ordinary waste.

On the other hand, according to the present invention, the stored liquid 18 can be reused. In that case, the heater 17 is heated and the stored liquid 18 in the storage tank 5 is heated to about 50.degree. By doing so, the carbonated water of the stored liquid 18 is decomposed into carbon dioxide and water, and these are separated into a gas-liquid two layer. In other words, gaseous carbon dioxide is located at the upper level and water is located at the lower level.

Therefore, if the on-off valves 21 and 22 are opened,
The decomposed carbon dioxide and water are returned to the return pipe 19,
Guided by 20, it travels to the bath 1 and compression pump 12 where they can be reused. At this time, the carbon dioxide and the water are removed of heavy metals, oxide films, and foreign substances by the filter 23 inserted in the return pipes 19 and 20, respectively. In this case, carbon dioxide is completely released from the stored liquid 18 by the decomposition, so that the heavy metals, the oxide film, and the like are completely precipitated, and these can be accurately collected.

Since the storage tank 16 is configured substantially the same as the bath 1, the storage tank 16 is, for example,
Another member to be processed 3 is housed in the inside, and thereafter, the stored liquid 1
8 to the storage tank 16 and the gas container 1
Replenish high-pressure carbon dioxide from 0 and supply water 5 to water source 7
If the inside of the storage tank 16 is set to the above-mentioned pressure and temperature conditions by replenishing it from above, degreasing of the member 3 to be processed and removal of the participating film can be performed in the tank 16 as well, and the productivity thereof increases.

After the above treatment of the storage tank 16, the degree of fouling of the stored liquid 18 is checked, and if it is fouled, the pressure is reduced to weak acidity and drained to sewage. On the other hand, the stored liquid 18
If the fouling is slight, the tank 16 can be decompressed and the stored liquid 18 can be decomposed into water and carbon dioxide for reuse.

Further, the bathtub 1 or the storage tank 16
If the pressure of carbon dioxide and the heating temperature by the heaters 9 and 17 are set to high pressure and high temperature as much as possible, the degreasing and oxide film removal treatments can be performed with high accuracy and high efficiency. Therefore, if the carbon dioxide is brought into a supercritical state, the degreasing and oxide film removal treatments can be performed with higher accuracy and efficiency.

As described above, the present invention is an inexpensive material of water and carbon dioxide, and simultaneously performs degreasing cleaning of the member to be treated 3 and removal of the oxide film, and does not require complicated water washing between them. Can be easily and quickly processed to improve productivity. In addition, since it does not require the use of conventional harmful alkali or acidic chemicals as a degreasing cleaning or oxide film removal medium, it improves the working environment under harmful gas generation,
This can be done safely, quickly and easily.

Moreover, the treatment liquid after degreasing and removal of the oxide film is treated safely and promptly to ensure the rationalization and safety of the treatment liquid, and the conventional complicated neutralization work is abolished, so that the treatment liquid can be treated by a simple method. It is designed for safe wastewater treatment and reuse.

3 to 5 show another embodiment of the present invention, and the same reference numerals are used for the portions corresponding to the configurations of the above-described embodiments. In this embodiment, a carbonated water production tank 26 similar to the bath 1 is provided, and water and high-pressure carbon dioxide are supplied to the tank 26 in the same manner as in the above-described embodiment to generate carbonated water 27 having a predetermined acidic concentration. Is generating.

Then, the carbonated water 27 is guided to the spray gun 29 through the conduit 28, and the conduit 3 is introduced into the spray gun 29.
High-pressure carbon dioxide is led from the gas container 10 via 0. In the figure, 31 and 32 are open / close valves inserted in the conduits 28 and 29, and 33 is a heater provided on the downstream side of the conduit 30 as much as possible (also inside the spray gun 29). Carbon is heated so that it can be formed into a supercritical state.

As shown in FIG. 4, the nozzle 34 of the spray gun 29 is formed with the injection ports 35, 36 communicating with the conduits 28, 30 separated from each other, and communicated with a compressed air source (not shown) outside the injection port 36. An annular hole 37 is formed. FIG. 5 shows another arrangement form of the injection ports 35 and 36, which are arranged concentrically inside and outside, and an annular hole 37 communicating with a compressed air source (not shown) is formed outside the injection port 36 for carbon dioxide. ing. In the figure, 38 is a degreasing and pickling work space.

That is, this embodiment, as described above,
Instead of accommodating the member to be treated 3 in the closed bath 1 and treating degreasing and oxide film removal with the closed space,
The member 3 to be processed is housed in an open work space 38, and carbonated water 27 and carbon dioxide in a supercritical state are sprayed onto the member 3 to be processed through a spray gun 29. By doing so, carbon dioxide in the supercritical state is ejected from the ejection port 36, the carbonated water 27 is ejected from the ejection port 35, and these are treated.
Sprayed on.

At this time, the carbon dioxide adiabatically expands when it is jetted, and is generated in dry ice by the heat of vaporization. When the dry ice is jetted vigorously, it is atomized and collides with the member 3 to be treated. 3 Remove the oil and fat on the surface,
Blow off and degrease.

On the other hand, the carbonated water 27 collides with the member 3 to be treated after degreasing, decomposes and removes the oxide film of the portion, and blows it off. At that time, the carbonated water 27 is cooled in the course of the movement of the conduit 28, the solubility of carbon dioxide is lowered, the acid concentration is lowered, and the action of removing the oxide film may be lowered. Therefore, the carbonated water 27 is heated to a high temperature, and the periphery of the nozzle 34 of the spray gun 29 is appropriately heated to prevent a decrease in the solubility of the carbon dioxide or a decrease in the oxide film removing action.

In this way, after the carbonated water 27 and the supercritical carbon dioxide are sprayed on the member 3 to be treated, the dry ice sublimes on the sprayed surface and the carbonated water scatters vigorously,
Drys instantly.

The operation of the spray gun 29 is performed by, for example, moving the nozzle 34 in the direction of the arrow in FIG. 4, first spraying supercritical carbon dioxide on the processing surface of the member 3 to be processed, and after degreasing the carbon dioxide. The oxide film is removed by spraying water 27. In this case, in the example of FIG. 5, the nozzle 36 is located outside the nozzle 35,
Since the spraying of supercritical carbon dioxide precedes the spraying of the carbonated water 27 onto the processed surface of the member to be processed 3, the spray gun 29 is used.
There is an advantage that the desired procedure, that is, the degreasing-oxide film removal can be naturally obtained regardless of the operation direction.

Further, an annular air flow is ejected coaxially from the annular opening 37 around the supercritical carbon dioxide ejection port 36,
Since the disturbance of the jet of dry ice is prevented and the shaping thereof is promoted, the reliability of the processing position when the nozzle 34 is separated from the member 3 to be processed can be obtained.

As described above, in this embodiment, the member 3 to be processed is
Degreasing and oxide film removal are performed simultaneously. Moreover, since the working space 38 is an open space, the space can be easily obtained. On the other hand, if the work space 38 is cut off from the surroundings, that is, the oxygen supply is cut off and the work is performed in a carbon dioxide atmosphere, the member 3 to be processed after degreasing and oxide film removal is performed.
Can be prevented, and a favorable metal film can be obtained by performing the next plating treatment in such an atmosphere.

[0056]

As described above, according to the first aspect of the present invention, pressurized carbon dioxide is dissolved in a predetermined amount of water to prepare an oxide film removing solution of carbonated water having a predetermined acidic concentration, which is inexpensive. A safe oxide film removing solution can be easily prepared at a low cost with a material, and an oxide film removing solution having a desired acidic concentration can be easily prepared by adjusting the pressure state. According to the invention of claim 2, the oxide film removing solution is brought into contact with the member to be treated to remove the oxide film of the member to be treated. Therefore, the oxide film can be easily and surely removed.

According to the invention of claim 3, the carbon dioxide is atomized, and the carbon dioxide in the particulate form is brought into contact with the member to be treated to separate or peel off the oil and fat on the surface of the member. The degreasing treatment accuracy can be improved as compared with the treatment. According to the invention of claim 4, since the oxide film removal treatment and the degreasing treatment are simultaneously performed, these treatments can be efficiently and reasonably and inexpensively performed as compared with a conventional treatment method in which these treatments are performed separately, and productivity is improved. It is possible to improve and reduce the equipment cost. According to the invention of claim 5, the member to be treated is housed in a closed space or an open space, and the oxide film removing treatment and the degreasing treatment are performed at the same time. Therefore, various working conditions can be dealt with. .

According to the sixth aspect of the present invention, since the water and carbon dioxide are stirred, the degreasing treatment and the oxide film removal can be efficiently performed. According to the invention of claim 7, since the water is sprayed and the carbon dioxide is supplied into the spray, the contact area between the water and the carbon dioxide can be expanded and the solubility of the carbon dioxide can be improved. In the invention of claim 8, after the degreasing treatment or the oxide film removal treatment, the treatment liquid is depressurized and drained, so that the solubility of carbon dioxide is reduced and the acidity of the oxide film removal solution is reduced. , It is possible to rationally treat the treated liquid after use and ensure its safety to realize drainage to sewage and prevent environmental pollution.

According to the invention of claim 9, the treatment liquid after use is decompressed and heated, the treatment liquid is decomposed into water and carbon dioxide, and these are discharged or reused. It is possible to ensure safety and to effectively use water and carbon dioxide after decomposition. According to a tenth aspect of the invention, after the degreasing treatment or the oxide film removal treatment, the used treatment liquid is transferred to another container, a new member to be treated is accommodated in the container, and the oxide film of the member to be treated is disposed. Since the removal treatment and the degreasing treatment are performed at the same time, the productivity of the oxide film removal treatment and the degreasing treatment of the member to be treated can be improved and the mass production thereof can be achieved.

According to the eleventh aspect of the present invention, pressurized carbon dioxide is supplied to a sealable bath containing a predetermined amount of water, and the carbon dioxide is dissolved in the water to prepare an oxide film removing solution having a predetermined acidic concentration. By enabling an oxide film removal solution of carbonated water with a predetermined acidic concentration, it is possible to easily and inexpensively create a safe oxide film removal solution with an inexpensive material, and by adjusting the pressure state, An oxide film removing solution having a desired acidic concentration can be easily prepared.

According to the twelfth aspect of the present invention, the oxide film can be removed by immersing the member to be processed in the oxide film removing solution or spraying the oxide film removing solution onto the member to be processed. Various working conditions can be dealt with. According to the invention of claim 13, the carbon dioxide is supplied into the water to atomize the carbon dioxide, the carbon dioxide in the particulate form is brought into contact with the member to be treated, and the oil or fat on the surface of the member can be separated or peeled off. Compared with the conventional degreasing process by the immersion method,
The processing accuracy can be improved.

According to the fourteenth aspect of the present invention, since the oxide film removing treatment and the degreasing treatment can be simultaneously performed, these treatments are efficient, inexpensive and rational as compared with the conventional treatment method in which these treatments are performed separately. It is possible to improve productivity and reduce equipment cost. According to the fifteenth aspect of the invention, since the member to be treated is housed in the closed space or the open space and the oxide film removing process and the degreasing process can be simultaneously performed, it is possible to meet various working conditions. Claim 1
In the invention of 6, the carbon dioxide is introduced from the lower part of the bathtub, and the water is introduced from the upper part of the bathtub, so that the carbon dioxide is bubbled to promote dissolution of carbon dioxide and Stirring can be improved.

According to the seventeenth aspect of the invention, since water is sprayed into the bath and the carbon dioxide is supplied into the spray, the solubility of carbon dioxide and the agitation of water and carbon dioxide can be improved. . In the invention of claim 18, after the degreasing treatment or the oxide film removal treatment, the treatment liquid is depressurized to allow drainage, so that the solubility of carbon dioxide is lowered and the acidity of the oxide film removal solution is lowered, It is possible to reasonably treat the treated liquid after use and ensure its safety to realize drainage to sewage and prevent environmental pollution.

According to a nineteenth aspect of the present invention, since the treatment liquid after use is decompressed and heated, the treatment liquid is decomposed into water and carbon dioxide, and these can be discharged or reused. It is possible to secure the property and to effectively utilize the water and carbon dioxide after decomposition. In the invention of claim 20, after the degreasing treatment or the oxide film removal treatment, the used treatment liquid is transferred to another container, a new member to be treated is accommodated in the container, and the oxide film of the member to be treated is placed. Since the removal treatment and the degreasing treatment can be performed at the same time, the productivity of the oxide film removal treatment and the degreasing treatment of the member to be treated can be improved and the mass production can be achieved.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an embodiment of the present invention, in which an oxide film removal treatment solution is prepared in a closed bath, a member to be treated is immersed in the solution, and the degreasing treatment and the oxide film removal treatment are simultaneously performed. It shows the situation.

FIG. 2 shows a state in which the used treatment liquid is transferred to another container (storage tank) after the degreasing treatment and the oxide film removal treatment, and is drained or decomposed or regenerated.

FIG. 3 shows another embodiment of the present invention, in which an oxide film removal treatment solution is prepared in a closed bath, the solution and supercritical carbon are supplied to a spray gun, and the treatment target member is stored in an open space. The degreasing process and the oxide film removing process are simultaneously performed.

FIG. 4 is a front view showing a state of a nozzle of the spray gun.

FIG. 5 is a front view showing another form of the nozzle of the spray gun.

[Explanation of symbols]

1 bathtub 3 Processed member 5 water 16 containers (storage tanks)

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C02F 1/68 520 C02F 1/68 520C 530 530A 540 540C 540Z F term (reference) 4D011 AA12 AA16 AD03 4D037 AA08 AB11 BA23 BB06 BB07 CA02 CA15 4K053 PA03 PA12 QA01 RA14 RA28 SA07 SA19 XA11 XA22 YA02 YA04

Claims (20)

[Claims] 1. A method for activating the surface of a base material for degreasing or removing an oxide film on a surface of a member to be treated, wherein pressurized carbon dioxide is dissolved in a predetermined amount of water to obtain an oxide film removing solution having a predetermined acidic concentration. A method for activating a surface of a base material, the method comprising: 2. The method for activating the surface of a base material according to claim 1, wherein the oxide film removal solution is brought into contact with the member to be processed to remove the oxide film of the member to be processed. 3. The method for activating the surface of a base material according to claim 1, wherein the carbon dioxide is atomized, the carbon dioxide in the particulate form is brought into contact with the member to be treated, and the fat and oil on the surface of the member is separated or peeled off. . 4. The method for activating the surface of a base material according to claim 1, wherein the oxide film removal treatment and the degreasing treatment are performed simultaneously. 5. The method for activating the surface of a base material according to claim 4, wherein the member to be treated is housed in a closed space or an open space, and the oxide film removing treatment and the degreasing treatment are simultaneously performed. 6. The method for activating the surface of a base material according to claim 1, wherein the water and carbon dioxide are stirred. 7. The method for activating the surface of a base material according to claim 6, wherein the water is sprayed and the carbon dioxide is supplied into the spray. 8. The method for activating the surface of a base material according to claim 1, wherein the treatment liquid is depressurized and drained after the degreasing treatment or the oxide film removal treatment. 9. The treatment liquid after use is depressurized and heated,
The method for activating the surface of a base material according to claim 8, wherein the treatment liquid is decomposed into water and carbon dioxide, and these are discharged or reused. 10. After the degreasing treatment or the oxide film removal treatment, the used treatment liquid is transferred to another container, a new member to be treated is accommodated in the container, and the oxide film removal treatment of the member to be treated is carried out. The method for activating the surface of a base material according to claim 1 or 3, wherein the degreasing treatment and the degreasing treatment are simultaneously performed. 11. An activation treatment apparatus for a base material surface for degreasing or removing an oxide film on a surface of a member to be treated, wherein pressurized carbon dioxide is supplied to a closable bath containing a predetermined amount of water, An apparatus for activating the surface of a base material, which is capable of producing an oxide film removal solution having a predetermined acidic concentration by dissolving the above in water. 12. The oxide film can be removed by immersing the member to be processed in the solution for removing an oxide film or spraying the solution for removing an oxide film onto the member to be processed.
The activation treatment device for the surface of the base material according to 1. 13. The method according to claim 11, wherein the carbon dioxide is supplied into the water to atomize the carbon dioxide, and the carbon dioxide in the particulate form is brought into contact with the member to be treated so that the oil and fat on the surface of the member can be separated or separated. Base material surface activation treatment device. 14. The apparatus for activating the surface of a base material according to claim 11 or 13, wherein the oxide film removal treatment and the degreasing treatment can be performed simultaneously. 15. The activation treatment apparatus for the surface of a base material according to claim 14, wherein the member to be treated is housed in a closed space or an open space, and the oxide film removing treatment and the degreasing treatment can be performed simultaneously. 16. The carbon dioxide is introduced from the lower part of the bath and the water is introduced from the upper part of the bath.
The activation treatment device for the surface of the base material according to 1. 17. The apparatus for activating the surface of a base material according to claim 16, wherein water is sprayed on the bath and the carbon dioxide is supplied during the spraying. 18. The apparatus for activating the surface of a base material according to claim 11 or 13, wherein after the degreasing treatment or the oxide film removal treatment, the treatment liquid is depressurized to allow drainage. 19. The activation of the surface of the base material according to claim 18, wherein the treatment liquid after use is decompressed and heated to decompose the treatment liquid into water and carbon dioxide, which can be discharged or reused. Processing equipment. 20. After the degreasing treatment or the oxide film removal treatment, the used treatment liquid is transferred to another container, a new member to be treated is accommodated in the container, and the oxide film removal treatment of the member to be treated is carried out. 12. The degreasing process and the degreasing process can be simultaneously performed.
Alternatively, the activation treatment device for the surface of the base material according to claim 13.