KR100658409B1 - Electrolyzed water of anode side and process for production thereof - Google Patents

Abstract

The present invention contains less than 0.1 mM of water-soluble inorganic salts, 1 to 50 mM of ascorbic acid, a redox potential of 85 to 50 mA, dissolved oxygen of 8 to 15 mg / L, pH of 3.70 to 2.80, and superoxide. Non-uniformization of superoxide radicals, wherein the positive electrode electrolyzed water is taken out by electrolysis of an aqueous electrolyte solution containing less than 0.1 mM of aqueous electrolyte and a water-soluble inorganic salt and 1 to 50 mM of ascorbic acid having a radical non-uniformity. It is a manufacturing method of positive electrode electrolytic water which has a function.

Description

Anode electrolytic water and its manufacturing method {ELECTROLYZED WATER OF ANODE SIDE AND PROCESS FOR PRODUCTION THEREOF}

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram which shows an example of the manufacturing apparatus of the positive electrode electrolytic water of this invention.

FIG. 2 is an example of the ESR spectrum showing the heterogeneity of the superoxide radicals in the anode electrolyzed water of Example 1. FIG.

3 is an example of the ESR spectrum of the superoxide radical of the cathode electrolyzed water of Example 1. FIG.

4 is another example of an ESR spectrum showing the heterogeneity of superoxide radicals in the positive electrode electrolyzed water of Example 2. FIG.

5 is another example of the ESR spectrum of the superoxide radical of the cathode electrolyzed water of Example 2. FIG.

6 is another example of an ESR spectrum showing heterogeneity of superoxide radicals in the anode electrolyzed water of Example 3;

7 is another example of the ESR spectrum of the superoxide radical of the cathode electrolyzed water of Example 3. FIG.

8 is an example of the ESR spectrum of the superoxide radical of the positive electrode electrolyzed water of Comparative Example 1. FIG.

9 is an example of the ESR spectrum of the superoxide radical of the cathode electrolyzed water of Comparative Example 1. FIG.

10 is an example of an ESR spectrum showing a superoxide radical of distilled water of Comparative Example 2. FIG.

FIG. 11 is a graph showing the relationship between the electrolytic current density and the dissolved enzyme amount when the electrolytic solution of the electrolyte solution shown in Example 1 is electrolyzed. FIG.

(Description of Major Symbols in Drawings)

2: electrolyte solution tank

4: electrolyte solution

6: pump

8: electrolyte solution supply pipe

10: electrolytic cell

12: anode

14: cathode

16: diaphragm

18: anode chamber

20: cathode chamber

22 electrolytic power supply

24: anode electrolytic water extraction tube

26: cathode electrolytic water extraction tube

The present invention relates to an anode electrolyzed water having a function of disproportionating superoxide radicals and a method for producing the same. More specifically, the present invention relates to a method for producing cathode electrolytic water which electrolyzes an aqueous electrolyte solution containing only ascorbic acid as an electrolytic aid, and extracts the cathode electrolytic water generated on the anode side, and a cathode electrolytic water having the above-mentioned disproportionation action. .

An electrolytic cell in which an inert electrode made of platinum, platinum alloy, etc. is disposed therein through a diaphragm is used to electrolyze an aqueous solution in which an electrolyte such as an alkali metal chloride is sparse and to produce a low pH electrolytic electrolytic water (acidic water). The technique of extracting a) and using this anode electrolytic water for sterilization or disinfection is well known. As the diaphragm, a charged membrane having an ion exchange resin in the form of a membrane or an uncharged membrane having a microporous structure is used.

The said positive electrode electrolytic water contains hypochlorous acid in it. The use of the sterilization or disinfection utilizes the strong oxidation and chlorination of hypochlorous acid. Such a usage method is being spread in medical institutions and the like. In addition, ozone and dissolved oxygen contained in a small amount in the electrolyzed electrolytic water have a granulation production-promoting action, and therefore, their use as an adjuvant for surgical treatment has also been studied.

On the other hand, the negative electrode electrolytic water (alkaline water) produced on the negative electrode side is also obtained by electrolyzing this using tap water instead of the electrolyte lean solution. This is conventionally used for beverages and the like. A method of producing electrolytic water by adding an organic acid such as ascorbic acid or gallic acid to the aqueous electrolyte solution or tap water as an additive, not as an electrolytic aid (US Pat. No. 5,736,027) is also known.

In these methods, ascorbic acid is used in the presence of an electrolytic aid. The purpose of adding ascorbic acid is to control the pH of the cathode electrolyzed water and to remove free chlorine in the anode electrolyzed water.

In addition, although not directly related to the above method, a well-known Kolbe reaction is a reaction in which an organic acid such as carboxylic acid is electrolyzed to release carbon dioxide from the anode side and to produce a compound in which two organic acid residues are bonded. For example, a method of producing citric acid from acetic acid using Kolbe reaction has been known for a long time.

Ascorbic acid has OH groups at positions 2 and 3 in the molecule. The ascorbic acid is an acidic region, a third of -OH -O ^- dissociates into H ⁺ and indicates the acid. In the basic region, -OH at position 2 is dissociated into -O ^- and H ⁺ . However, since this dissociation degree is low, it has not been used as an electrolytic aid. In addition, the electrolytic process when electrolyzing aqueous ascorbic acid solution is complicated, and intermediate products are not specified, but are basically recognized as redox reactions.

Ascorbic acid is a powerful reducing agent in itself. It is also well known in the aqueous solution that automatic oxidation occurs in itself and the reducing power is lowered. In general, ascorbic acid is automatically oxidized by the following process.

AsA, MDA, DHA, and DKG represent ascorbic acid, monodihydroascorbic acid, dihydroascorbic acid, and 2,3-diketoguronic acid, respectively.

Recently, it has been found that ascorbic acid dissociates and dissipates superoxide radicals, which are widely known as active oxygen. Ascorbic acid was therefore attracting attention as an antioxidant.

The heterogeneous reaction of a superoxide radical here is represented by following Reaction Formula 2. In other words, the superoxide radicals disappear to produce hydrogen peroxide.

Ascorbic acid is useful for dissipating the superoxide radicals as described above, but anolyte electrolytic water has not yet been reported to increase the disproportionation of superoxide radicals by electrolysis of ascorbic acid aqueous solution.

MEANS TO SOLVE THE PROBLEM This inventor focused on the ability to non-uniformize the superoxide radical which the said ascorbic acid has, and examined variously in order to obtain the positive electrode electrolytic water which maintains this capability. As a result, it was found that when electrolytic solutions of relatively low concentrations of ascorbic acid were electrolyzed without using an inorganic electrolyte such as a water-soluble metal salt as an electrolytic aid, anodized electrolytic water with increased ability to disproportionate superoxide radicals was found.

The present invention has been completed based on the above findings, and an object thereof is to provide an anode electrolyzed water having an improved ability to disproportionate superoxide radicals.

The object of the present invention is achieved by the following.

[1] A water-soluble inorganic salt containing less than 0.1 mM, ascorbic acid 1 to 50 mM, the redox potential is 85 to 50 kPa, the dissolved oxygen is 8 to 15 mg / L, the pH is 3.70 to 2.80, and superoxide Anode electrolytic water with a heterogeneous action of radicals.

[2] Heterogeneous action of superoxide radicals characterized by electrolytically dissolving an aqueous electrolyte solution containing less than 0.1 mM of water-soluble inorganic salt and 1-50 mM of ascorbic acid to extract the positive electrode electrolytic water according to the above [1]. Method for producing an anode electrolytic water having.

[3] A method for producing positive electrolytic water having a heterogeneous action of the superoxide radical according to the above [2], which is electrolyzed using an electrolytic cell having a diaphragm.

[4] A method for producing positive electrolytic water having a disproportionation action of the superoxide radical according to the above [2], wherein the current density during electrolysis is 0.003 to 0.03 A / cm 2.

[5] Electrolytic current density of 0.003-0.03 A / cm2 by supplying an aqueous electrolyte solution containing less than 0.1 mM of water-soluble inorganic salt and 1-50 mM of ascorbic acid to a continuous flow electrolyzer having a diaphragm at a flow rate of 500-3000 ml / min. A method for producing positive electrolytic water having a disproportionation action of the superoxide radical according to the above [2], which is electrolyzed continuously.

[6] An electrolytic solution containing less than 0.1 mM of water-soluble inorganic salt and 1 to 50 mM of ascorbic acid was supplied to a continuous flow electrolyzer without a diaphragm at a flow rate of 4 to 50 ml / min to provide an electrolytic current density of 0.003 to 0.03 A /. A method for producing positive electrolytic water having a heterogeneous action of the superoxide radical according to the above [2], which is electrolyzed continuously in cm 2.

When electrolytic water obtained by electrolyzing an aqueous electrolyte solution is used for beverages, sterilization, and disinfection, an aqueous solution of an electrolyte is added to a tap water or tap water with a water-soluble inorganic salt such as sodium chloride or potassium chloride. Since tap water originally contains a certain amount of inorganic salts, it acts as an electrolyte.

On the other hand, a technique for producing electrolytic water by electrolyzing an aqueous electrolyte solution in which an electrolyte and ascorbic acid is added has been reported. In this case, ascorbic acid is used as an additive for removing alkalinity (for example, Japanese Patent Laid-Open No. 11-33552). In addition, a method of suppressing the production of free chlorine in electrolytic water by electrolyzing an aqueous electrolyte solution containing ascorbic acid as an additive and reducing hypochlorous acid in electrolytic water produced on the anode side to ascorbic acid ( Japanese Patent Laid-Open No. 8-229563).

In both of these cases, an electrolyte composed of a water-soluble inorganic salt is contained as an electrolytic aid in an aqueous electrolyte solution, and ascorbic acid is further coexisted. Ascorbic acid is used as an additive which is not directly related to electrolysis to the last.

Generally, when electrolyzing electrolyte (electrolyte adjuvant), such as sodium chloride, and the aqueous electrolyte solution which melt | dissolved ascorbic acid (additive), the following reaction occurs.

1. Cathode side

In addition, AsANa represents sodium ascorbate. Cathode ascorbic acid of the third H ⁺ is replaced by sodium ions in the electrolytic water is being the sodium salt. As a result, the second H ^+, only be used as a non-uniform screen for superoxide. Therefore, the nonuniformity is halved.

2, anode side

The side of the positive electrode, and the hypochlorite chlorination operation and 2 above, and the third H ⁺ of by oxidation, ascorbic acid by the disappearance, as shown in the Scheme 9, and thus non-uniform screen of superoxide is not at all occur.

The above is the electrolytic reaction of both poles in the case of using an electrolyte as an electrolytic aid and using an aqueous electrolyte solution in which ascorbic acid is added as an additive. In this case, disproportionation of the superoxide occurs only at the cathode side, but the amount of this disproportionation reaction is reduced by the amount of sodium ascorbate produced.

On the anode side, as described above, the chlorination and oxidation of ascorbic acid by hypochlorous acid cause H ⁺ in the 2nd and 3rd positions of ascorbic acid to disappear, so that the heterogeneous reaction of superoxide does not occur at all. Do not.

On the other hand, the electrolytic reactions of both poles in the case of electrolyzing an aqueous electrolyte solution in which only ascorbic acid is dissolved as an electrolyte are shown below.

1, cathode side

Scheme 3

By electrolysis as shown in Scheme 10, hydrogen in the second and third positions in ascorbic acid causes an electrophilic reaction on the surface of the cathode, and hydrogen gas is generated on the cathode side. Since DHA generated by electrolysis cannot release H ⁺ , no heterogeneity of superoxide radicals occurs. In addition, ascorbic acid anions are transported to the anode side. Therefore, no disproportionation of the superoxide radical by the ascorbic acid anion occurs.

2. Anode side

Scheme 6

As shown in Scheme 11, the ascorbic acid anion becomes ascorbic acid by reacting with H ⁺ generated by oxidation of water at the anode. On the other hand, as shown in Scheme 12, the oxygen gas generated at the anode is consumed by oxidizing ascorbic acid to 2,3-diketoguronic acid, and serves to reduce the amount of dissolved oxygen in the anode electrolyzed water. But this ratio is not large.

In addition, in the positive electrode, some hydrogen ions are excessively present due to the difference in diffusion rates of ascorbic anion and hydrogen ions, in addition to the reaction shown in Scheme 11 above. Therefore, compared with the case where only ascorbic acid exists, hydrogen ion is increasing. As a result, the amount of disproportionation of superoxide radicals increases at the anode side.

In summary,

1) When an aqueous solution of an electrolyte such as sodium chloride or potassium chloride is used as an electrolytic aid and an electrolyte solution containing ascorbic acid as an additive is used, the cathode electrolytic water shows a disproportionation effect, but sodium ascorbate or The heterogeneous action is reduced by the amount consumed as potassium corbate. The positive electrode electrolyzed water contains hypochlorous acid, and most of the ascorbic acid is consumed by the hypochlorous acid. Therefore, the anode electrolyzed water does not exhibit disproportionation.

2) In the case of electrolyzing an aqueous electrolyte solution in which only ascorbic acid is used as an electrolytic aid, hydrogen in the second and third positions of ascorbic acid is dehydroascorbic acid at the negative electrode due to electrophilic reaction. Therefore, the disproportionation reaction can hardly be confirmed on the cathode side.

On the anode side, ascorbic acid anion transported from the cathode reacts with hydrogen ions generated in the electrode reaction of water to return to ascorbic acid and exhibit non-uniformity. In addition, the disproportionation of the electrolytic water of the positive electrode increases due to the slightly excessive hydrogen ions generated. The amount of ascorbic acid consumed by dissolved oxygen is very small.

In the present invention, an aqueous electrolyte solution containing only ascorbic acid as an electrolytic aid is electrolyzed so that the redox potential (ORP) is 85 to 50 kPa and the pH is 3.70 to 2.80. The anolyte electrolytic water thus obtained has a particularly high disproportionation ability of the superoxide radical, compared with the anolyte electrolyzed water outside the range of the redox potential and pH. For this reason, this positive electrode electrolytic water can be used for various uses, such as sterilization, granulation production, health maintenance, beauty, etc. In addition, since ascorbic acid is a vitamin whose safety has been confirmed to the human body, the positive electrode electrolyzed water produced by using this as an electrolytic aid is very safe.

Embodiment of the invention

Hereinafter, the present invention will be described in detail with reference to the drawings.

There is no particular limitation on the electrolytic apparatus used when producing the positive electrode electrolytic water of the present invention having the disproportionation action of the superoxide radical, and any of the electrolytic water producing apparatuses conventionally used can be used. That is, any type of electrolytic device can be used regardless of the size of the electrolytic device, the presence or absence of a diaphragm in the electrolytic cell, and the like.

1 is a schematic view showing an example of an electrolytic apparatus used for producing the positive electrode electrolyzed water of the present invention having a disproportionation action of a superoxide radical.

In FIG. 1, 2 is an electrolyte solution tank, The electrolyte aqueous solution 4 is stored in the inside.

The electrolyte aqueous solution 4 contains 1 to 50 mM, preferably 2 to 20 mM of ascorbic acid. The pH of this aqueous electrolyte solution is about 3.70 to 2.80. When the concentration of ascorbic acid is less than 1 mM, the conductivity is low, making electrolysis difficult. Moreover, when it exceeds 50 mM, there exists a sense which will stick when applying the obtained electrolytic electrolyzed water to skin etc., and it may be unsuitable depending on a usage method.

It is preferable that the said electrolyte aqueous solution 4 does not contain substantially electrolytes, such as water-soluble inorganic salts other than ascorbic acid. The content of the water-soluble inorganic electrolyte is preferably 0.1 mM or less, more preferably 0.02 mM or less, in total of each of the water-soluble inorganic electrolytes.

As a manufacturing method of such aqueous electrolyte solution 4, the method of dissolving ascorbic acid in distilled water and purified water (pure water), such as deionized water in the said concentration range, is illustrated.

(6) is a pump attached to the electrolyte aqueous solution supply pipe 8, and by operating the pump 6, the electrolyte aqueous solution 4 is transferred to the electrolytic cell 10 through the supply pipe 8.

The electrolytic cell 10 has a positive electrode 12 and a negative electrode 14 which are spaced apart from each other at predetermined intervals to face each other, and a diaphragm 16 provided to be spaced apart from both poles between the two poles. In the electrolytic cell 10, an anode chamber 18 is formed between the anode 12 and the diaphragm 16, and a cathode chamber 20 is formed between the cathode 14 and the diaphragm 16. The positive electrode 12 and the negative electrode 14 are made of an electrochemically inert metal material. Platinum, a platinum alloy, etc. are preferable as an electrode material. The diaphragm 16 prevents mixing of the positive electrode electrolytic water in the positive electrode chamber 18 and the negative electrode electrolytic water in the negative electrode chamber 14, and is made of a material to which an electrolytic current is transmitted. As a diaphragm, what is conventionally used for electrolysis is used suitably as an electrolytic diaphragm, such as an ion exchange membrane and an electroless membrane.

The supply pipe 8 is branched from the upstream side of the electrolytic cell 10 to the branch pipes 8a and 8b, and each of the branch pipes 8a and 8b is connected to the anode chamber 18 and the cathode chamber 20. It is.

22 is an electrolytic power source, the positive terminal of which is connected to the positive electrode 12 and the negative terminal of the negative electrode 14.

The aqueous electrolyte solution transferred to the anode chamber 18 and the cathode chamber 20 through the branch pipes 8a and 8b is electrolyzed here. 0.003-0.03 A / cm <2> is preferable and, as for electrolytic current density, 0.01-0.02 A / cm <2> is more preferable. When the electrolytic current density is less than 0.003 A / cm 2, the amount of dissolved oxygen in the positive electrode electrolytic water flowing out of the positive electrode chamber cannot be made higher than that of the aqueous electrolyte solution. When the electrolytic current density exceeds 0.03 A / cm 2, the amount of production of the positive electrode electrolytic water does not increase in accordance with the current value, which is uneconomical.

Therefore, by controlling the electrolytic current density within the above range, the amount of dissolved oxygen in the positive electrode electrolyzed water flowing out of the positive electrode chamber can be at least an electrolyte solution, preferably 8-15 mg / l, more preferably 9-14 mg / l. .

In this invention, pH of positive electrode electrolytic water obtained is adjusted to 3.70-2.80, and the redox potential (ORP) is 85-50 Pa by adjusting electrolytic current density suitably within the said range.

The cathode electrolytic water produced by electrolysis as described above is taken out through the anode electrolytic water extraction tube 24. At the same time, the cathode electrolyzed water is taken out through the cathode electrolyzed water outlet tube 26.

The electrolytic cell 10 has a structure in which a diaphragm is provided therein, but the electrolytic cell 10 is not limited thereto, and an electrolytic cell of a non-diaphragm structure in which the diaphragm is not provided can be suitably used.

In such a non-diaphragm electrolytic cell, the positive electrode plate is placed close to each other without providing a diaphragm between the positive electrode plate and the negative electrode plate, and the electrolyte is continuously supplied between the negative and positive electrode plates while being electrolytically supplied to the downstream side of the positive electrode. An example of the structure is a structure in which anode electrolytic water in the vicinity of the anode surface is continuously taken out. Specifically, the electrolytic cell etc. shown by Unexamined-Japanese-Patent No. 6-246272 can be illustrated.

In addition, the presence or non-uniformity of the superoxide radical of electrolytic water is judged by the presence or absence of the signal of superoxide radical by the electron spin resonance apparatus (ESR) mentioned later.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

The aqueous electrolyte solution containing ascorbic acid was electrolyzed using the electrolytic apparatus shown in FIG. However, in the electrolytic cell, five platinum plates (7.5 cm x 11.5 cm) were arranged in parallel at intervals of 2.5 mm each, and an electroless septum was provided therebetween. And the said platinum plate was made into the positive electrode and the negative electrode alternately, and it was set as the structure which provided the four electrolytic cell in total integrally side by side. The electrolytic cell volume was 86.4 mL, and the electrolyte solution was supplied to this electrolytic cell at a flow rate of 2000 mL / min, to obtain positive and negative electrolytic water. The electrolytic current density was adjusted to 0.02 A / cm 2.

PH of the positive electrode electrolytic water obtained was 3.68, and ORP was 82 kPa.

The aqueous electrolyte solution was prepared by adding ascorbic acid to 2 mM concentration in deionized water. In addition, since deionized water was used, the content of the water-soluble inorganic salt in the aqueous electrolyte solution was extremely small (less than 0.01 mM).

Using the prepared electrolyzed water as a sample, the presence or absence of extinction by the heterogeneous reaction of the superoxide radical was examined using ESR as described below.

1) Generation of Superoxide Radicals

Superoxide radicals were generated using 2 mM hypoxanthine and 0.4 mM unit / ml xanthine oxidase.

2) Spin trap by DMPO

50 μl of 2 mM hypoxanthine monophosphate buffer

5.5 mM DETAPAC (diethylenetriaminepentaacetic acid)-35 μl phosphate buffer

16 μl DMPO (5,5-dimethy-1-pyrroline-N-oxide)

0.4 unit / ml xanthine oxidase-50 μl of phosphate buffer

Was placed in a flat cell, set in an ESR apparatus, sweep was started after 1 minute, and the presence or absence of a signal based on the superoxide radical was confirmed.

3) ESR measurement condition

Measurement temperature: room temperature

Microwave Output: 3.7㎽

Small magnetic field: 339.1 mT ± 5.5 mT

Magnetic field modulation: 100 ㎑ (external modulation)

Modulation Width: 0.1 mT

Time constant: 0.12 seconds

Draft time: 1 minute

It was.

4) Measurement result

The obtained ESR spectrum was shown to FIG. 2 and FIG. 2 shows a case where positive electrode electrolyzed water was used as a sample. From the point that the signal of the superoxide radical can be confirmed, it is clear that the superoxide radical is disproportionate and almost disappears.

In addition, the dissolved oxygen amount was 14.99 mg / L.

3 is a spectrum when cathode electrolytic water is used as a sample. It is clear that the signal of the superoxide radical (signal indicated by arrow a in the figure) can be confirmed, and that the superoxide radical is not eliminated and is not disproportionated.

Example 2

Electrolyzed water was prepared in the same manner as in Example 1 except that the concentration of ascorbic acid in the aqueous electrolyte solution was set to 50 mM and the current density was set to 0.01 A / cm 2.

About each of the obtained positive electrode and negative electrode electrolytic water, the signal of superoxide radical was confirmed like Example 1 using ESR.

The obtained ESR spectrum was shown to FIG. 4 and FIG. 4 is a spectrum of anode electrolytic water. Since the signal of the superoxide radical cannot be confirmed, it is clear that the superoxide radical is disproportionate and almost disappears.

In addition, the dissolved oxygen amount was 12.3 mg / L. Moreover, pH was 2.87 and ORP was 55 kPa.

5 is a spectrum when cathode electrolytic water is used. The signal of the superoxide radical (signal indicated by arrow a in the figure) can be confirmed. In other words, it is clear that the superoxide radicals are not eliminated and are not homogenized.

(Performance Evaluation Test of Anode Electrolyzed Water)

The sensory test of skin care was done using the positive electrode electrolytic water manufactured by the said Example 2. For comparison, a sensory test was conducted using positive electrode electrolyzed water (strongly acidic water) obtained by electrolysis of a NaCl aqueous solution having a concentration of 0.25% by mass under the same conditions using the same apparatus.

The test method is as described below.

1) Test subjects: 14 healthy people who are susceptible to rough skin

2) Test Method: Seven out of 14 persons were treated with positive electrode electrolyzed water obtained by electrolyzing aqueous solution of ascorbic acid containing electrolyte (inventive product), and another person twice a day with positive electrode electrolyzed water obtained by electrolytic solution containing NaCl containing electrolyte (comparative product). Apply to hand and face over 21 days in proportions.

The test results obtained are shown in Table 1.

Sensory test results for rough skin Ascorbic acid anode electrolytic water group% NaCl anode electrolytic water group% Irritant. Moisturizing. Cool. Bad smell. Whitening effect. Skin roughness is improved. 0 86 100 0 43 86 43 29 86 86 29 57

The positively electrolytic water obtained by electrolyzing NaCl-containing electrolyte aqueous solution is generally used so-called electrolyzed water, having a pH of 2.5 and a redox potential (ORP) of 1250 Pa. The positive electrode electrolyzed water of Example 2 of the present invention had no irritation and bad smell, and was superior to the positive electrode electrolyzed water obtained by electrolyzing NaCl-containing electrolyte aqueous solution also with respect to the moisture retention. The reason why the positive electrode electrolyzed water of the present invention exhibits such desirable properties is strongly suggested to be the result of the increased antioxidant activity of the positive electrode electrolyzed water by electrolysis. PH of the positive electrode electrolytic water obtained was 2.85, and ORP was 52 kPa.

Example 3

Anode electrolytic water was prepared in the same manner as in Example 1 except that the concentration of ascorbic acid in the electrolyte aqueous solution was 20 mM and the current density was 0.02 A / cm 2.

About each of the obtained positive electrode and negative electrode electrolytic water, the signal of superoxide radical was confirmed like Example 1 using ESR.

The obtained ESR spectrum was shown to FIG. 6 and FIG. 6 is a case where positive electrode electrolytic water is used. Since the signal of the superoxide radical cannot be confirmed, it is clear that the superoxide radical is disproportionate and almost disappears.

7 is a case where cathode electrolytic water is used. The signal of the superoxide radical (signal indicated by arrow a in the figure) can be confirmed, and it is clear that the superoxide radical is not eliminated and is not uniform.

Comparative Example 1

Electrolysis was carried out in the same manner as in Example 1 using 2 mM NaCl as the aqueous electrolyte solution. ESR spectrum was obtained like Example 1 using obtained positive electrode electrolytic water and negative electrode electrolytic water.

8 and 9 show ESR spectra of anode electrolytic water and cathode electrolytic water. In the case of Comparative Example 1 using NaCl as the electrolytic aid, it was found that the signal of the superoxide radical was confirmed in any electrolyzed water, and these electrolyzed waters did not have the scavenging ability of the superoxide radical.

Comparative Example 2

Using the distilled water without electrolysis, the heterogeneous capacity of the superoxide was investigated by the same measuring method as in Example 1. The ESR spectrum measured in FIG. 10 was shown. In the case of pure water, the scavenging of the superoxide radicals cannot be confirmed at all, so that there is no disproportionation capability.

In addition, the dissolved oxygen amount is 9.65 mg / l.

Reference Example 1

When ascorbic acid is normally dissolved in purified water, dissolved oxygen in purified water is consumed, and the dissolved oxygen amount shows a value of 8 mg / L or less. On the other hand, when an ascorbic acid aqueous solution is electrolyzed, oxygen is generated by electrolysis of water at the anode. For this reason, when electrolytic solution of ascorbic acid solution is used, oxygen generated by electrolysis is added to the dissolved oxygen dissolved in the ascorbic acid aqueous solution before the electrolysis, and the dissolved oxygen concentration is higher than that of the raw water before electrolysis.

Therefore, ascorbic acid aqueous solution before electrolysis and electrolyzed water after electrolysis can be easily distinguished by comparing the amount of dissolved oxygen, when time has not passed since electrolysis.

FIG. 11 is a graph showing the relationship between the electrolytic current density and the dissolved oxygen amount when the ascorbic acid aqueous solution shown in Example 1 is electrolyzed using the same electrolytic apparatus as in Example 1. FIG. When electrolysis is performed, the amount of dissolved oxygen in the positive electrode electrolytic water inevitably increases.

In addition, dissolved oxygen is the same as dissolved oxygen generated when NaCl is used as an electrolytic aid, and this has the effect of contributing to skin regeneration and skin repair.

The positive electrode electrolytic water of the present invention has a particularly high disproportionation ability of superoxide radicals, compared with the positive electrode electrolytic water outside the redox potential and pH range. Therefore, the positive electrode electrolytic water can be used for various applications such as sterilization, granulation production, health maintenance, beauty, and the like. In addition, since ascorbic acid is a vitamin whose safety has been confirmed to the human body, the positive electrode electrolyzed water produced by using this as an electrolytic aid is very safe.

Claims (6)

delete 0.1 mM of water-soluble inorganic salt which electrolytically extracts electrolytic electrolyzed water by controlling an electrolyte solution containing less than 0.1 mM of water-soluble inorganic salt and 1-50 mM of ascorbic acid while controlling the current density within the range of 0.003 to 0.03 A / cm 2. Less than 1 to 50 mM of ascorbic acid, a redox potential of 85 to 50 mV, dissolved oxygen of 8 to 15 mg / l, pH of 3.70 to 2.80, and anodic electrolytic water having a disproportionation action of superoxide radicals. Manufacturing method. The method for producing anolyte electrolyzed water according to claim 2, which has a heterogeneous action of superoxide radicals electrolyzed using an electrolytic cell having a diaphragm. delete 3. An electrolyte solution containing less than 0.1 mM of water-soluble inorganic salt and 1 to 50 mM of ascorbic acid is supplied to a continuous flow electrolyzer having a diaphragm at a flow rate of 500 to 3000 ml / min to provide an electrolytic current density of 0.003 to 0.03. A method for producing cathode electrolytic water having a heterogeneous action of superoxide radicals which are continuously electrolyzed at A / cm 2. The electrolyte solution according to claim 2, wherein an aqueous electrolyte solution containing less than 0.1 mM of water-soluble inorganic salts and 1 mM to 50 mM of ascorbic acid is supplied to a continuous flow electrolyzer without a diaphragm at a flow rate of 4 to 50 ml / min to provide an electrolytic current density of 0.003. A method for producing cathode electrolytic water having a heterogeneous action of superoxide radicals which are continuously electrolyzed at ˜0.03 A / cm 2.

Images