JP2002038195A - Cleaning agent, method for producing the cleaning agent, apparatus for producing the cleaning agent and cleaning method using the cleaning agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial cleaning agent having high safety and excellent in cleaning performance. SOLUTION: The cleaning agent contains an electrolytic water obtained by applying voltage on pure water after adding citric acid using an electrolytic auxiliary adding device 15. Thus, troubles regarding the safety to human body are completely removed, and especially in the cleaning of a polishing apparatus for semiconductor or the like in which mixing of metallic ion (alkali metal) is extremely disadvantageous, an influence of such pollutant is completely removed, and further, high cleaning performance is acquired.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent, a method for manufacturing the cleaning agent, an apparatus for manufacturing the cleaning agent, and a cleaning method using the cleaning agent.

[0002]

2. Description of the Related Art Conventionally, for example, a copper nozzle portion of a thermal spraying apparatus for injecting a molten metal at a high temperature is always in contact with circulating cooling water, and a carbon-like black film always adheres to this portion along with the operation time. Come. This coating reduces the cooling capacity of the nozzle and, in turn, shortens the life of the nozzle. This carbon-like film does not fall off with normal cleaning,
The removal was labor and time consuming. Further, when cleaning a semiconductor polishing apparatus or the like, removal of the slurry adhered to the polishing apparatus is not easily performed, and conventionally, much labor has been required. In particular, devices handling such semiconductors are reluctant to mix metal ions such as sodium and potassium (especially alkali metals), and the cleaning agents that can be used for cleaning are also limited.

[0003] On the other hand, washing may be carried out using a strong acid as a washing solution, but the use of a powerful drug is difficult.
It requires great effort and cost in terms of environmental conservation, such as ensuring the safety of workers and treating waste liquid generated after washing.

[0004]

In view of the above situation, the present invention has been made to provide a cleaning agent suitable for each of the above cleanings,
To solve the above problems.

[0005]

Means for Solving the Problems A cleaning agent according to the first invention of the present application is obtained by adding water to an electrolytic auxiliary containing at least one of citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid and glycolic acid. And electrolyzed water obtained by applying a voltage. The term "cleaning agent" as used herein means not only a detergent, but also includes a cleaning aid, that is, a cleaning accelerator used together with the detergent to promote its cleaning effect. This is the same in the following.

[0006] By adopting such a configuration, the cleaning agent according to the first invention of the present application is capable of removing citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid, and glycolic acid which have little effect on the human body with respect to water. The cleaning ability was enhanced by adding an electrolysis auxiliary including at least one and applying a voltage. That is, while using a highly safe acid and applying a voltage to water to which such an acid was added, a high cleaning ability was obtained.

[0007] The cleaning agent according to the second invention of the present application is characterized in that it has electrolytic water obtained by adding a citric acid to pure water and then applying a voltage.

The cleaning agent according to the second invention of the present application is obtained by adding citric acid, which is contained in foods such as natural fruits and the like and does not cause harm even when it enters the human body, to pure water, As a result, safety issues to the human body have been completely eliminated. In particular, in the cleaning of a semiconductor polishing apparatus or the like, which extremely dislikes the incorporation of metal ions (especially alkali metals), such an effect is completely eliminated, and further, an extremely high cleaning power is exhibited. It is.

[0009] The method for producing a cleaning agent according to the third invention of the present application is characterized in that an electrolytic auxiliary agent containing at least one of citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid, and glycolic acid is added to water, and the voltage is reduced. This is characterized in that electrolyzed water is obtained by the application and at least this electrolyzed water is contained as a component.

[0010] The method for producing a cleaning agent according to the third invention of the present application having the above-mentioned structure makes it possible to obtain the cleaning agent according to the first invention of the present application.

[0011] The cleaning agent manufacturing apparatus according to the fourth invention of the present application is characterized in that an electrolytic auxiliary agent containing at least one of citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid and glycolic acid is added to water. It is characterized by comprising a device 15 and a power supply device capable of applying an electrolysis voltage to water after the addition of the electrolysis auxiliary.

The apparatus for manufacturing a cleaning agent according to the fourth aspect of the present invention having the above-described configuration provides specific means for carrying out the third aspect of the present invention, and the cleaning agent according to the first aspect of the present invention. Are provided as specific means for obtaining

The cleaning method using the cleaning agent according to the fifth invention of the present application is to apply a physical force after or while bringing the cleaning agent into contact with the object to be cleaned. The cleaning agent is characterized in that it contains electrolytic water obtained by adding an electrolytic auxiliary agent containing at least one of citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid, and glycolic acid to water and applying a voltage to the water. I do.

The cleaning method using the cleaning agent according to the fifth aspect of the present invention having the above-described structure is a method in which the effect of the cleaning agent according to the first aspect of the present invention is adapted to cleaning by a more preferable method. Yes, it is possible to obtain a high cleaning effect.
That is, it is possible to effectively perform cleaning by applying a physical force after reducing the adhesion ability of the object to be removed and used with the cleaning agent.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. In this method for producing a detergent, an electrolysis auxiliary containing at least one of citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid, and glycolic acid is added to water, and a voltage is applied to obtain electrolyzed water. It contains electrolyzed water as a component. Here, a method for producing a cleaning agent will be described, typically using citric acid as an electrolysis auxiliary.

First, in the first step, pretreated water is prepared. This pretreatment water is generated by adding citric acid to pure water. In this addition, the concentration of citric acid is preferably 0.3 to 0.8% by weight, particularly preferably 0.5 to 5% by weight (water 2
10-100 g of citric acid per liter). Then, in the second step, two electrodes, a cathode and an anode, are inserted into the pretreated water obtained by adding the citric acid in the first step, and a voltage is applied to the pretreated water to perform electrolysis. Do. Each of the electrolyzed water generated at both the cathode and the anode can obtain an effect as a cleaning agent even when used alone as it is, but by mixing the electrolyzed water generated at both the cathode and the anode, a higher cleaning ability is obtained. A cleaning agent can be obtained. As a cleaning agent obtained by mixing the same amount of electrolyzed water generated at the cathode and the anode, the pH value is 1.5 to 3.0, and OR
Those having a characteristic of P (redox potential) of -100 mV to 50 mV are suitable. In particular, a pH value of 1.9 to
2.7 are preferred as cleaning agents.

When manufacturing a cleaning agent suitable for a semiconductor polishing apparatus, citric acid needs to be added to pure water as described above.
From the viewpoint of cost, distilled water or ordinary tap water can be used instead of pure water. It is also possible to use groundwater in addition to general tap water such as tap water.

In the above, as the electrolysis auxiliary,
Although citric acid is used, it is also possible to use ascorbic acid, oxalic acid, acetic acid, formic acid, or glycolic acid. However, citric acid is the most effective as an electrolysis auxiliary in terms of the cleaning performance and safety of the obtained cleaning agent. Further, it is also possible to use an aqueous solution containing at least one of ascorbic acid, oxalic acid, acetic acid, formic acid and glycolic acid together with citric acid as an electrolysis auxiliary. Further, an aqueous solution obtained by mixing at least two kinds of ascorbic acid, oxalic acid, acetic acid, and formic acid can be used as the electrolysis auxiliary.

The above electrolytic treatment is suitably performed using an electrolytic device. The electrolyzer includes a diaphragm electrolyzer and a non-diaphragm electrolyzer. Diaphragm electrolysis is one in which a diaphragm is placed between an anode and a cathode, and non-diaphragm electrolysis is one in which no such diaphragm is placed between both electrodes. In addition, any of the above-mentioned devices includes two types of devices, a storage type (batch type) and a continuous type. In the storage type, the water to be electrolyzed is stored in a tank to produce a cleaning agent, and the pretreatment water is replaced each time the cleaning agent is generated. In the continuous type, an electrolytic treatment is performed on running water, and a desired cleaning agent can be continuously generated.

Hereinafter, using a batch type diaphragm electrolysis apparatus,
The case of performing the electrolytic treatment will be described. As shown in FIG. 1, this apparatus comprises a tank 1 for storing pretreatment water, two electrode plates, an anode 2 and a cathode 3 arranged in the tank 1, and two electrodes 2, 3
And a power supply device 4 connected to the power supply and supplying a direct current.
As shown in FIG. 1, the tank 1 is divided into two by a diaphragm 6. One of the compartments of the tank 1 is an anode chamber 1
An electrode plate serving as the anode 2 is provided as a, and the other section is provided with an electrode plate serving as the cathode 3 as the cathode chamber 1b. Discharge ports 7a and 7b are provided in the anode chamber 1a and the cathode chamber 1b of the tank 1, respectively. The upper part of the tank 1 is open, and a predetermined amount of pretreatment water can be introduced into the tank 1 from above the tank 1. The electrolyzed water obtained by electrolysis is
From these discharge ports 7a and 7b, it is possible to discharge to the outside of the tank 1. Reference numerals 8a and 8b in FIG. 1 denote valves for opening and closing the discharge ports 7a and 7b, respectively. Reference numeral 5 in FIG. 1 indicates a timer for setting the electrolysis time.

As described above, the diaphragm is placed between the two electrodes (the anode 2 and the cathode 3) in the electrolytic cell 1, the electrolytic auxiliary is added to the above-mentioned water, and the water is electrolyzed under predetermined conditions. Acidic electrolyzed water is generated on the anode side, and acidic electrolyzed water is also generated on the cathode side. The electrolysis time is preferably 3 to 15 minutes, and the current is 0.5 to 3 A (preferably 0.8 to 1.5) per 2 liters of treated water (1 liter for each pole room).
It is appropriate to carry out electrolysis at about A) and at a voltage of about 9 to 20 V. After the electrolytic treatment, the valves 8a and 8b are opened, and the electrolytic water may be taken out from the discharge ports 7a and 7b.

For the electrodes 2 and 3, it is appropriate to use a platinum film, ferrite, carbon, stainless steel, titanium or the like. In particular, platinum-coated electrodes are preferred, and carbon and stainless steel electrodes are advantageous in terms of cost. This platinum-coated electrode is obtained by plating or baking a platinum group such as platinum, iridium, palladium, and rhodium on a titanium plate to form a coating. If necessary, a small amount of a metal oxide is added. The diaphragm 6 can be implemented by using a ceramic, resin, or glass fiber film. In particular, polyester on the substrate, non-woven fabric of glass fiber, resin coating treatment of 0.2 ~ 200μm pore size,
Further, the present invention can be carried out with a general material used for a battery or a membrane filter to which hydrophilicity is added.

Conventionally, a common electrolyte is NaC
In this invention, citric acid is used in place of such an electrolyte. In the case of general electrolysis using, for example, salt (NaCl) as an electrolysis auxiliary, strongly acidic electrolyzed water is generated at the above-described anode, and strongly alkaline electrolyzed water is generated at the cathode. On the other hand, in the present invention in which citric acid is used as an electrolysis auxiliary, acidic electrolyzed water is generated in both the anode and the cathode (in both the anode chamber 1a and the cathode chamber 1b, the acidic electrolyzed water is generated). Generated). For this reason, in the present invention, it is possible to use the electrolyzed water generated in the positive and negative electrodes as a cleaning agent, and there is no waste such as discarding one electrolyzed water as in the electrolysis using the above-mentioned general salt.
The cleaning agent can be efficiently generated.

As an electrolysis apparatus other than the batch type (reservoir type), a continuous electrolysis apparatus can be used. This is different from the above-mentioned batch type apparatus in that electrolysis is performed on flowing water. When using this device,
It is unnecessary to generate pretreatment water in advance as described above.

Referring to FIG. 2, another embodiment in which an electrolytic treatment is performed using a continuous diaphragm type apparatus will be described. This apparatus uses general tap water or water such as ground water or pure water or distilled water stored in a tank as a water source, and is connected to such a water source to obtain raw water to be electrolyzed (water before treatment). Things. A constant amount of raw water is automatically supplied from a water source by a pressure pump or the like. Therefore, according to this apparatus, a constant amount of electrolyzed water can be generated every hour.

More specifically, this electrolysis apparatus supplies a tank 1 provided with an anode 2 and a cathode 3, a water conduit 10 connected to the tank 1 and guiding water from a water source to the tank 1, and supplying an electrolysis voltage to both electrodes. The apparatus includes a power supply device 4, a pump 14 for pumping water from the water conduit 10 to the tank 1, a water flow adjusting device 11 such as a pressure regulating valve, an electrolysis auxiliary agent adding device 15, a control device 16, and various sensors. In the tank 1, an anode 2 side on which the anode 2 is arranged and a cathode 3 side on which the cathode 3 is arranged are separated by a diaphragm 6. Water mouth 9a,
9b and discharge ports 7a and 7b. The water inlets 9a and 9b are connected to the water passage 10 for guiding water to be electrolyzed to the tank 1. One end of the water conduit 10 is branched into two, and each of the branched water inlets 9
a, 9b. And headrace channel 1
0 is connected to a water source such as a tap. The above water flow adjusting device 11 is a strainer provided in the water conduit 10. Headrace 1
0 is provided with the pump 14 described above. An electrolysis auxiliary agent adding device 15 is connected to the water conduit 10 via the pump 14. This electrolysis auxiliary agent adding device 15
Is a tank for supplying an electrolysis auxiliary (when citric acid is supplied, it is a citric acid aqueous solution supply tank, hereinafter simply referred to as tank 15). A water level sensor 18 is provided in the tank 15. The water level sensor 18 is controlled by the control unit 1
6 and sends the detection result to the control unit 16. The headrace 10 is provided with a detection sensor 17 such as an electric conductivity sensor or a pH sensor. This detection sensor 17
Sends data to the control unit 16.

In the above apparatus, the pump 14
Raw water obtained from a water source such as tap water is guided into the water conduit 10 from the connection end 13, and the raw water is moved toward the tank 1. The amount of water to be introduced can be adjusted by opening and closing the water flow adjusting device 11 in the middle of the water conduit 10, ie, the valve of the strainer. Further, the control unit 16 includes a water level sensor 18.
And the information from the detection sensor 17 described above,
By controlling the opening and closing of a valve (not shown) of No. 5, the amount of the electrolytic auxiliary agent (citric acid) to be introduced into the water from the water source can be adjusted. The water pumped through the water conduit 10 is continuously introduced to the anode 2 side and the cathode 3 side in the tank 1 at the above-mentioned water inlets 9a and 9b. Then, in the tank 1, the electrolyzed water generated on each of the anode 2 side and the cathode 3 side is discharged to the other from the discharge ports 7a and 7b. The treated water volume is 1 liter to 30 liters per minute (each electrode water is 0.1 liter).
5 to 15 liters), and in this case, the electrolytic power is 5 to 20 A (preferably 10 to 20 A) per 2 liters of treated water (1 liter of each bipolar water).
It is appropriate to perform the electrolysis at a voltage of about 12 to 35 V.

In the apparatus shown in FIG. 2, the method of supplying the water to be electrolyzed and the structure other than the structure in which the pre-generation of the pretreatment water is not necessary are the same as those in the embodiment shown in FIG. It is. However, as for the tank 1, in the batch type of FIG. 1, there is no particular restriction on the shape as long as it has a predetermined capacity because it is necessary to store stepped water. On the other hand, as shown in FIG. In order to facilitate the movement of water, a shape such as a cylindrical shape is preferable.

Each of the above electrolyzers is provided with a diaphragm. In addition, the electrolysis is performed by using a non-diaphragm electrolyzer which performs electrolysis without placing a partition 6 between the two electrodes 2 and 3. It is also possible (not shown). In this method, the diaphragm of the continuous diaphragm-free production apparatus is eliminated, and the solution produced by the cathode and the anode is mixed to be produced. In this case, it is not necessary to provide two inlets (water inlets) and two outlets (discharge outlets) of water into the tank 1, and both may be implemented as one. As for the non-diaphragm electrolysis device, there are a batch type non-diaphragm electrolysis device and a continuous type non-diaphragm electrolysis device, and any of them can be implemented.

FIG. 3A shows an example of the above-mentioned batch type diaphragmless electrolysis apparatus. In the embodiment shown in FIG. 1, the diaphragm 6 is eliminated and the tank 1 is not partitioned, and the generated electrolytic water (cleaning agent) is discharged from one discharge port 7 provided with a valve 8. Things. Other configurations are the same as those of the embodiment shown in FIG.

FIG. 3 (B) shows an example of the above continuous type diaphragmless electrolysis apparatus. In the embodiment shown in FIG. 2, the tank 6 is excluded without partitioning the tank 6, and the number of water inlets 9 is one and the number of outlets 7 is also one. In FIG. 3B, only the tank 1 is shown, but the other configuration than the tank 1 is the same as the embodiment shown in FIG.

The continuous type apparatus continuously performs not only the electrolytic treatment as the second step but also all the steps of cleaning agent generation including the first step in both cases of the diaphragm and the non-diaphragm. It is an apparatus for manufacturing a cleaning agent. That is, the apparatus shown in FIG. 2 and FIG. 3 (B) is an additive for adding an electrolysis auxiliary containing at least one of citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid, and glycolic acid to water of a water source. This is a manufacturing apparatus provided with a device (electrolysis auxiliary agent adding device 15) and a power supply device (negative and positive electrodes 2, 3 and a power supply device 4) capable of applying an electrolysis voltage to water after the addition of the electrolysis auxiliary. .

Regardless of the type of separator (batch type or continuous type) shown in FIGS. 1 and 2, the same cleaning water is produced by mixing the generated cathode and anode electrolytic water in the same amount. A high cleaning liquid can be generated. The electrolyzed water of each of the cathode and anode generated by the diaphragm type electrolysis apparatus can be mixed immediately before the washing to form a cleaning agent. In addition, the diaphragmless device shown in FIG. 3 (batch type, continuous type)
In the case of using a solution, the solution produced by the cathode and the anode is mixed and produced. Therefore, there is no need to perform mixing, and a desired cleaning liquid can be directly generated.

As described above, conventional general electrolyzed water using salt is generally divided into alkaline and acidic, and + and-. When citric acid is used, it is divided into + and-, but both are acidic water. Can be. Therefore, even if the water on the positive side and the water on the negative side are mixed, it can be used as acidic water. In particular, by mixing the electrolyzed water generated on the + side and the − side, it is possible to obtain electrolyzed water having a higher cleaning ability than the single electrolyzed water on each of the + side and the − side. This is because such a mixed solution becomes a very unstable solution due to radicals in which + ions and-ions are mixed. At this time, the power to be electrically stable increases the cleaning ability. It is considered something. If the above mixture is left as it is, the balance of ions becomes stable and the effect becomes weak over time. However, according to experiments, even after three months of production,
A sufficient effect can be obtained. Therefore, by mixing water on the + side and the-side at the time of production, even if a detergent is produced, a sufficient effective period as a product can be ensured. In addition, when the liquids on the + side and the-side are stored independently and made into a mixed liquid after three months, the effect is almost the same as that of the liquid immediately after production. Therefore, in order to obtain an initial effect, it is effective to store the + side liquid and the − side liquid independently and to make a mixed liquid immediately before use. Specifically, if the above-mentioned + side and − side waters are separately stored and commercialized as a set (sold as a two-part cleaning agent), and the user mixes them at the time of use, The highest cleaning performance can be obtained.

If the cleaning agent obtained by the above-described method is used to remove the adhered matter (scale) adhered to the inside of the pipe, the adhered matter can be effectively removed. In particular, for cooling water piping that has deteriorated due to adhered matter (scale), it is necessary to remove the matter (scale) in the piping generated by cooling water circulation and restore the inner surface performance to its original state. It is effective. In addition, if the cleaning agent is caused to flow periodically, it is possible to prevent the generation of the adhered matter (scale) of the pipe and to prevent the pipe from being clogged or deteriorated.

In the case of the above-mentioned piping, the main fixing substances are calcium oxide, silica, iron oxide and the like. By using the cleaning agent according to the present invention, as described above,
The connection between the fixed objects and the connection between the fixed object and the inner surface of the pipe can be separated.

Further, the use of the above-described cleaning agent according to the present invention can also effectively remove the slurry and the like scattered and fixed during polishing around the polishing apparatus. , CMP (Chemical M
echanical Polishing) It is suitable for removing slurry and the like stuck around the equipment. In the case of glass polishing, it is necessary to remove slurry and the like generated by friction between cerium oxide and glass powder solidified by air and polishing, and the cleaning agent according to the present invention is also optimal for such removal. In particular, in the removal of slurry and the like generated during the manufacturing process of semiconductor wafers, the incorporation of metal ions (particularly alkali metals) is disliked, but the cleaning agent according to the present invention does not have such a problem and provides a high cleaning effect. Can be.

An embodiment suitable for performing the cleaning using the above-described cleaning water in various cleaning will be described below.

As a cleaning method suitable for removing the scale and the like in the pipe, the cleaning agent is brought into contact with an object to be cleaned such as a pipe, or after the cleaning agent is brought into contact with the object to be cleaned. Preferably, a force is applied. In particular,
The cleaning agent according to the present invention is injected into the pipe, and the pipe is filled with the cleaning agent for a predetermined time or more. After that, drainage is performed, and a jet jet or the like of a jet water washing device is injected, and a physical force is applied to separate and flow out the attached matter. In addition, a cleaning agent is injected into a pipe, a tank, or the like, circulated for a certain period of time by a circulation pump, and then discharged. Also in this case, a physical force can be applied by pumping. When the injection of the jet jet or the like or the use of a circulation pump or the like is not possible, a foaming agent can be added and the physical force of the foam can be applied to detach the deposits and the like. However, depending on the situation, if any of the above physical forces cannot be applied,
A cleaning agent may be injected into the pipe (in comparison with a case where physical force is applied), and after filling the pipe with the cleaning agent for a long time, draining and cleaning may be performed.

When removing slurry or the like scattered and fixed during polishing around the polishing apparatus such as CMP, a well-known general cleaning agent and the cleaning agent according to the present invention are used together (mixed). Cleaning is also effective. As described above, even when the general cleaning agent and the cleaning agent according to the present invention are used in combination, even when the cleaning agent according to the present invention is used alone, the cleaning agent is poured into an apparatus and physically rubbed with a spatula or the like. It is effective to clean the apparatus by applying strong force.
In particular, when the copper nozzle portion of the thermal spraying device comes into contact with the circulating cooling water, the adhered film is reduced by about 1 to this cleaning agent.
After soaking for a while, it can be easily removed with a toothbrush. In this case, the longer the immersion time, the easier the film can be removed. When the target object is small, the target object may be immersed in a container or a tank containing a cleaning agent, and may be cleaned by applying a physical force as needed.

[0041]

Hereinafter, preferred examples of the cleaning agent will be described in comparison with comparative examples. However, this embodiment is provided for better understanding of the effect (cleaning ability) of the cleaning agent according to the present invention, and the embodiment is not limited to such an embodiment. Table 1 shows the experimental results of Examples 1-4 and Comparative Example 1 with respect to the cleaning ability. In each of Examples 1 to 4 and Comparative Example, the processing time was set to 10 minutes by the timer 5 using the batch type diaphragm electrolysis apparatus shown in FIG. 1, and was obtained at an electrolysis voltage of 100 V and a current of 0.7 A. It is a thing. Example 1 is a cleaning agent obtained by applying an electrolytic voltage to a 1% aqueous citric acid solution and mixing electrolytic water on the anode side and electrolytic water on the cathode side. In Example 2, an electrolytic water was applied to a 1% aqueous solution of citric acid, and electrolytic water on the anode side was used as a cleaning agent. Example 3 is citric acid 1%
The electrolytic water on the cathode side obtained by applying an electrolytic voltage to the aqueous solution was used as a cleaning agent. Example 4 is ascorbic acid 1%
This is a cleaning agent obtained by mixing electrolytic water on the anode side and electrolytic water on the cathode side, obtained by applying an electrolytic voltage to an aqueous solution. Comparative Example 1 above
Is electrolysis water on the anode side obtained by applying an electrolysis voltage to a 1% aqueous solution of common salt. As a test piece, a copper plate placed in the air and completely covered with a brown oxide film was used. This test piece was immersed in each of the above Examples 1 to 4 and Comparative Example, and changes with time on the surface of the test piece were visually observed.

[0042]

[Table 1] Elapsed time 5 minutes 10 minutes 1 hour 1 day Example 1 Slightly brown gloss Full metallic luster Full metallic gloss Example 4 Brown Brown Slightly brown Slightly brown Comparative Example 1 Brown Brown Slightly brown Glossy

As a result, as shown in Table 1 above, in Example 1, the effect of removing the oxide film from the test piece was the most remarkable, and complete metallic luster was restored by immersion for 1 hour. Following Example 1, Example 2 showed high removal ability.
It is. Then, following Example 2, Example 3 showed a high removal ability. In Examples 1 to 3, an extremely high removal ability is recognized as compared with Comparative Example 1. In Example 4, a certain removal ability was also observed. From these results, it was found that the electrolytic water of the citric acid aqueous solution obtained by mixing the anode and the anode had the highest cleaning effect, the electrolytic water on the anode side of the citric acid aqueous solution had the highest cleaning effect, and then the citric acid aqueous solution It can be seen that the electrolyzed water on the cathode side has a high cleaning effect, and the electrolyzed water of the ascorbic acid aqueous solution obtained by mixing the positive and negative electrodes also has the cleaning effect. In particular, in the case of electrolyzed water of citric acid aqueous solution, all of the electrolyzed water alone on the anode side, the electrolyzed water on the cathode side alone, and the electrolyzed water mixed with both electrodes have higher cleaning ability than that obtained by electrolyzing a saline solution. It can be seen that it has. On the other hand, the electrolytic water on the anode side of the saline solution also has a cleaning ability, but cannot be used in applications that dislike metal ions (particularly alkali metals). In this respect, the electrolyzed water using ascorbic acid aqueous solution, which has the same cleaning ability as the electrolyzed water using saline solution, has no such problem together with the electrolyzed water using citric acid aqueous solution. Is advantageous.

In Example 1 shown in Table 1 above, immediately after the electrolysis, the cathode side and the electrolyzed water on both sides were mixed, and the experiment was started immediately. Next, Table 2 shows Example 1 used immediately after the production, Example 5 three months after the production (after mixing), and electrolyzed water on the anode / cathode side alone after electrolysis. The results obtained by immersing the test piece in Example 6 in which both electrolytic waters were mixed immediately after the test after storage for 3 months and immediately before the test, and visually observing the change over time on the test piece surface are shown.
Each of Examples 5 and 6 was obtained by applying an electrolytic voltage to a 1% aqueous citric acid solution using the apparatus of FIG. 1 under the same conditions as in the experiment of Table 1. The same copper plate as in the experiment was used.

[0045]

[Table 2] Elapsed time 5 minutes 10 minutes 1 hour 1 day Example 1 Slightly brown gloss Complete metallic gloss Complete metallic gloss Metallic luster

As a result, although Example 5 was inferior to Example 1, a high removal ability was recognized. In addition, it was found that Example 6 had substantially the same effect as Example 1. From this, it can be seen that a sufficient cleaning ability can be obtained even if a mixture of electrolyzed water on both the cathode side and the positive side immediately after electrolysis is used after 3 months, and after 3 months from the electrolysis, For those using a mixture of electrolyzed water on both the cathode side and the positive side,
It can be seen that the same cleaning effect as that used immediately after electrolysis and mixing was obtained.

[0047]

According to the first aspect of the present invention, it is possible to provide a cleaning agent which is highly safe for a human body and has extremely high cleaning ability. Therefore, by using the cleaning agent according to the present invention, in the cleaning of industrial products,
It is possible to perform extremely effective cleaning without having to worry about securing the safety of the cleaning operator.

By implementing the second invention of the present application, it is possible to provide a highly safe cleaning agent even when it enters the body. In addition, metal ions (particularly alkali metal The present invention can provide a cleaning agent exhibiting extremely high cleaning performance without such an effect even in the cleaning of industrial products, which extremely dislikes the contamination of (1).

By implementing the third invention of the present application, the first invention of the present application
A preferable production method for obtaining the cleaning agent according to the present invention can be provided.

By implementing the fourth invention of the present application, the third application of the present invention
It is possible to provide specific means for carrying out the invention of the present invention,
This makes it possible to provide a manufacturing apparatus suitable for providing the first cleaning agent of the present application.

By implementing the fifth invention of the present application, the first invention of the present application is realized.
Thus, an effective method of using the cleaning agent according to the present invention can be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a manufacturing apparatus according to an embodiment of the present invention.

FIG. 2 is an explanatory diagram of a manufacturing apparatus according to another embodiment.

FIG. 3A is an explanatory view of a manufacturing apparatus according to another embodiment, and FIG. 3B is an explanatory view of a manufacturing apparatus according to yet another embodiment.

[Explanation of symbols]

 1 tank 2 anode 3 cathode 4 power supply device 5 timer 6 diaphragm

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C02F 5/00 620 C02F 5/00 620C 620D C11D 7/60 C11D 7/60 11/00 11/00 17 / 08 17/08 C23G 1/02 C23G 1/02 C25B 1/04 C25B 1/04 H01L 21/304 622 H01L 21/304 622Q (72) Inventor Akira Narita 2-5-1 Honjo-cho, Higashinada-ku, Kobe-shi No. F-term in Star-Tack Co., Ltd. (reference) 3B201 AA03 AA13 AB51 BB05 BB21 BB88 BB89 BB90 BB92 BB93 BB96 CC21 4D061 DA03 DB07 EA02 EB01 EB04 EB12 EB14 EB37 EB39 EC01 EC02 ED12 GA22 GA04 DC02 DA08 FA03 4K021 AA01 AB25 BA02 BA19 DA09 DB05 DB12 DB18 DB28 DC15 4K053 PA06 QA01 RA07 RA45 RA46 RA47 RA48 SA05 TA15 YA11

Claims (5)

[Claims] 1. Citric acid, ascorbic acid, oxalic acid,
A cleaning agent comprising electrolytic water obtained by applying a voltage to water to which an electrolytic auxiliary agent containing at least one of acetic acid, formic acid, and glycolic acid has been added. 2. A cleaning agent comprising electrolytic water obtained by adding citric acid to pure water and applying a voltage. 3. An electrolysis aid containing at least one of citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid, and glycolic acid is added to water, and a voltage is applied to obtain electrolyzed water. A method for producing a cleaning agent, characterized in that it is contained as a component. 4. An adding apparatus for adding an electrolysis auxiliary containing at least one of citric acid, ascorbic acid, oxalic acid, acetic acid, formic acid, and glycolic acid to water, and electrolyzing water after the addition of the electrolysis auxiliary. An apparatus for producing a cleaning agent, comprising: a power supply device capable of applying a voltage. 5. The method according to claim 5, wherein the cleaning agent is brought into contact with the object to be cleaned or after the cleaning agent is brought into contact with the object, and at the same time, a physical force is applied. A cleaning method using a cleaning agent, characterized by containing an electrolysis water obtained by adding an electrolysis aid containing at least one of oxalic acid, acetic acid, formic acid, and glycolic acid and applying a voltage.