JP2001079549A - Production of electrolytic water, electrolyzed water on cathode side, electrolytic auxiliary and water electrolytic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide electrolyzed water superior in elimination performance of super-oxide anions. SOLUTION: In a production method of the electrolytic water, an electrolytic solution containing gallic acid or its salt is fed to an electrolytic bath 1 provided with a cathode 2 and an anode 3 partitioned with a membrane 4, and also the total concentration of gallic acid ions or the gallic acid in the electrolytic solution is made in a range of 1×10-4 to 1×10-2M, and a direct current of 2×10-3 to 1×10-1 A/cm2 electric current density per unit area of the electrode for 1 liter electrolytic solution is applied with a flow flux of 500-4000 ml/min. By this method, hydroxy ions produced at the cathode 2 side by the electrolysis and the gallic acid ions are allowed to react to produce hydrogen ions. Obtained electrolyzed water on the cathode 2 side is superior in eliminating performance of super-oxide anions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing electrolyzed water for electrolytically decomposing an electrolytic solution containing gallic acid under specific conditions, a cathode-side electrolyzed water, an electrolysis auxiliary and an electrolysis apparatus for water.

[0002]

2. Description of the Related Art The principle of electrolysis was announced by Michael Faraday in 1834, and applied technology using electrolysis has been developed in the industrial field. In particular, the remarkable progress of the manufacturing technology of a membrane used as a diaphragm has produced many applied technologies including an electrodialysis method. When pure water containing no ions is electrolyzed, oxygen gas and hydrogen ions are generated on the anode side, and hydrogen gas and hydroxyl ions are generated on the cathode side, but a high voltage is required. Therefore, electrolysis of electrolyzed water to which an electrolyte is added is generally performed.

For example, in an electrolytic solution containing sodium chloride or the like as an electrolytic auxiliary, chlorine ions move to the anode and sodium ions diffuse to the cathode by application of a direct current. Therefore, the following reactions take place at both poles.

[0004] First, at the anode, chlorine ions emit electrons to convert chlorine ions into chlorine molecules. Water molecules emit electrons at the anode to generate hydrogen ions and oxygen molecules, and react with chlorine ions diffused and moved from the cathode to become hydrochloric acid.
When hydrochloric acid is formed, the hydrogen ion concentration increases, and chlorine gas partially becomes hypochlorous acid. Therefore, on the anode side, an acidic solution is formed by hydrochloric acid and hypochlorous acid. Due to such a composition, the anode-side electrolyzed water is widely used as a bactericide.

On the other hand, when a DC voltage is applied to the cathode, water is reduced to generate hydrogen molecules and hydroxide ions, and sodium ions, which are cations in the electrolyte ionized in the electrolyte, are applied to the cathode. The chlorine ion, which is the counter ion, moves to the anode side, and on the cathode side, the hydroxide ion and the sodium ion are paired to form sodium hydroxide, indicating alkalinity. As a result, the cathodic electrolysis water is frequently used in drinking water because it suppresses abnormal fermentation in the gastrointestinal tract and has an antacid effect in the gastrointestinal tract.

[0006] When sodium chloride is not used as an electrolytic aid, hydrochloric acid and hypochlorous acid are not generated on the anode side.
In this case, since the pH of the anode-side electrolyzed water is close to that of the skin and hair and has no irritation, it is also used for drinking and cooking.
Currently, due to the diversity of electrolyzed water, a device that produces electrolyzed water on the cathode side by directly electrolyzing tap water has been distributed on the market.
The flowing water type and the batch type are becoming popular for general household use.
In addition, inventions have been made in which calcium and other compounds are added to the electrolyte for nutritional supplementation to electrolyze water, and furthermore, studies have been made to elucidate the excellent characteristics of electrolyzed water.

[0007] For example, Shirahata et al. Report that water produced by electrolysis on the cathode side eliminates active oxygen (Biochemical).
And Biophysical Research Communications 234, 269-274, (1997)). According to the report, reduced water generated on the cathode side shows SOD-like activity like ascorbic acid. In addition, the activity of the reduced water is attributed to atomic hydrogen (referred to as active hydrogen in the report). On the cathode side, H ⁺ and OH ⁻ are generated by electrolysis of water molecules, and the active hydrogen is a hydrogen atom (H) obtained by changing the H ⁺ , and a stable H
₂ (hydrogen gas).

On the other hand, Japanese Patent Application Laid-Open No. 11-92388 discloses a neutralization reaction between an electrolytic solution obtained by electrolyzing an electrolyte solution using an inert electrode to generate free hydroxyl ions on the cathode side and ascorbic acid. There is disclosed a free hydrogen ion-containing product liquid containing the generated free hydrogen ions. In the examples of this publication, an anion exchange membrane is used, a sodium chloride solution is put on each of the cathode side and the anode side, and a direct current is applied for 9 minutes to obtain an electrolytic solution. The pH was adjusted to 7.0 by adding L-ascorbic acid to obtain a product solution containing free hydrogen ions. In this publication, it is assumed that free hydrogen ions generated by a neutralization reaction between free hydroxyl ions and L-ascorbic acid act as scavengers of free radicals. The use of the solution is intended to restore canine renal function.

[0009]

Since the electrolyzed water has various effects, the electrolyzed water is drunk or used externally for the purpose of maintaining health or promoting health. However, the mechanism of action of the electrolyzed water on living organisms is still unknown. Unknown. Among them, Japanese Patent Application Laid-Open No.
In JP-A-92388, electrolytically produced water is used, and L-ascorbic acid is added to generate hydrogen ions for the purpose of a free radical scavenger action. However, in the method described in this publication, L-ascorbic acid must be separately added to the obtained cathode-side electrolysis water, and preparation and addition treatment of L-ascorbic acid are required. In particular, L-ascorbic acid is liable to be oxidized due to its own properties, and thus requires disadvantageous preparation, which is disadvantageous.

In addition to the above-mentioned scavenger action, there is an interest in the contribution of cathodic electrolysis water to health. However, if the concentration of hydroxide ions is increased by strong electrolysis, the cathodic electrolysis water will inevitably occur. pH rises. However, drinking the cathodic electrolysis water exceeding pH 11 or
It is extremely difficult to use it externally or as an injection, considering that the pH of body fluid is around neutral.

Further, in the electrolysis of water, the properties of electrolyzed water generated between the electrodes differ depending on the current, the electrolysis time, the type of electrode used, and the type of separator separating the electrodes. For example, when L-ascorbic acid is added as an electrolyte, L-ascorbic acid is ionized by enediol groups at the 2nd and 3rd positions in an aqueous solution, and moves to the anode side when an anion exchange membrane is used as a diaphragm. Therefore, it cannot react with hydroxyl ions in the cathode-side electrolytically generated water. In particular, when L-ascorbic acid is used as a component of the electrolytic aid, there is a disadvantage that ascorbic acid is automatically oxidized as described above, the reducing property is reduced in a short time, and the stability is lacking.

[0012] In addition, it is difficult to use for drinking etc. if high alkalinity is exhibited by strong electrolysis, but it is meaningless if the components contributing to health are reduced as a result of suppressing the degree of electrolysis. In particular, the mechanism of action of electrolyzed water on living organisms is still unknown, and together with elucidation thereof, a simple method of producing electrolyzed water having a specific effect is desired.

[0013]

The present inventors have studied in detail the composition of the electrolytic solution, the components in the electrolytically produced water on the cathode side, and the electrolysis conditions. When electrolysis is performed, the pH of the cathode-side electrolyzed water can be suppressed to 10 or less, and it has been found that the obtained cathode-side electrolyzed water has an extremely high superoxide anion scavenging ability, and the present invention has been completed. .

That is, the above-mentioned problems are as described in (1) to (13) below.
Achieved by

(1) An electrolytic solution containing gallic acid or a salt thereof is supplied to an electrolytic cell having a cathode and an anode separated by a diaphragm, and the total concentration of gallic acid ions or gallic acid in the electrolytic solution is supplied. Is in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M, and a current density of 2 × 10 ⁻³ to 1 × 10 ⁻¹ A / cm ² per unit area of the electrode per liter of the electrolytic solution. A method for producing electrolytic water, wherein a direct current is applied at a flux of 500 to 4000 ml / min.

(2) The electrolyte further comprises inositol
Or 1 × 10 ^-Four~ 1 × 10^-2M's
The electrolysis according to the above (1), which is contained in a range.
Water production method.

(3) The electrolyte further comprises L-ascor
1 × 10 total of boric acid or its salt ^-Four~ 1 × 10^-2M's
(1) or characterized in that it is contained in a range.
(2) The method for producing electrolyzed water according to (2).

(4) An electrolytic solution containing gallic acid or a salt thereof is supplied to an electrolytic cell having a cathode and an anode separated by a diaphragm, and the total concentration of gallic ion or gallic acid in the electrolytic solution is supplied. Is in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M, and a current density of 2 × 10 ⁻³ to 1 × 10 ⁻¹ A / cm ² per unit area of the electrode per liter of the electrolytic solution. Cathode-side electrolyzed water obtained by applying a direct current at a flux of 500 to 4000 ml / min.

(5) The electrolyte further comprises inositol
Or 1 × 10 ^-Four~ 1 × 10^-2M's
The cathode according to the above (4), which is contained in a range.
Side electrolyzed water.

(6) The electrolyte further comprises L-ascor
1 × 10 total of boric acid or its salt ^-Four~ 1 × 10^-2M's
(4) or characterized in that it is contained in a range.
(5) The cathode-side electrolyzed water according to (5).

(7) The superoxide anion scavenging ability is such that in ESR measurement, the relative signal intensity with the manganese marker is 50 to 100% of the difference from pure water.
The cathode-side electrolyzed water according to any one of (1) to (6).

(8) The dissolved oxygen content is 6.5 to 0.11 m
The cathode-side electrolyzed water according to any one of the above (4) to (7), which is g / liter.

(9) The hydrogen ion concentration is 4.0 to 1
The cathode-side electrolyzed water according to any one of the above (4) to (8), which is 0.0.

(10) The gallic acid or a salt thereof is added with 1 ×
One or more compounds selected from the group consisting of sodium chloride, potassium chloride, calcium chloride, and magnesium chloride with respect to 10 ^-4 M are 1 × 10 ^-4 to 1 × 10 ^-2 M; .

(11) The composition further contains inositol or a phosphate compound thereof, and the gallic acid or a salt thereof 1 × 1
The electrolytic aid according to the above (10), wherein the inositol or its phosphate compound is from 1 × 10 ⁻⁴ to 1 × 10 ⁻² M with respect to 0 ⁻⁴ M.

(12) Further, L-ascorbic acid or
Contains its salt, said gallic acid or its salt 1 × 10^-Four
The L-ascorbic acid or a salt thereof is 1 ×
10 ^-Four~ 1 × 10^-2M (1)
0) or the electrolytic aid according to (11).

(13) A means for supplying gallic acid or a salt thereof to an electrolytic cell having a cathode and an anode separated by a diaphragm, and the total concentration of gallic acid ions or gallic acid in the electrolytic solution on the cathode side is set to 1 × Means to be in the range of 10 ⁻⁴ to 1 × 10 ⁻² M, and a current density of 2 × 10 ⁻³ to 1 × 10 ⁻¹ A / cm ² per unit area of the electrode per 1 liter of the electrolytic solution Means for applying a direct current at a flux of 500 to 4000 ml / min.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION (1) Method for Producing Electrolyzed Water First, an electrolytic solution containing gallic acid or a salt thereof is supplied to an electrolytic cell having a cathode and an anode separated by a diaphragm, And the total concentration of gallic acid ions or gallic acid in the electrolyte is in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M;
For 1 liter of the electrolyte, 2 per unit area of the electrode
A method for producing electrolyzed water, characterized in that a direct current having a current density of × 10 ^-3 to 1 × 10 ^-1 A / cm ² is applied at a flux of 500 to 4000 ml / min. In the present invention, hydroxyl ions are generated on the cathode side by electrolysis of water, and this reacts with gallic acid to generate hydrogen ions, and such cathode-side electrolyzed water has excellent superoxide anion scavenging ability. It was completed after finding that it had. In the present invention, hydroxyl ions generated on the cathode side by the electrolysis of water are referred to as “free hydroxyl ions”, and hydrogen ions generated by reacting the free hydroxyl ions with gallic acid ions or gallic acid are referred to as “free hydroxyl ions”. It is referred to as “hydrogen ion”. Hereinafter, a preferred embodiment of the present invention will be described with reference to FIG.

In FIG. 1, an electrically neutral neutral film, which is an uncharged film, is used as a diaphragm, and a platinum-iridium alloy electrode is used as an electrode. First, an electrolytic solution 9 in which gallic acid or a salt thereof is dissolved is put in a storage tank 8, and the electrolytic solution 9 is supplied to the electrolytic cell 1 through a filter 7. The electrolytic solution 9 having the same composition is supplied to both the cathode 2 side and the anode 3 side separated by the diaphragm 4. Next, a direct current having a current density is applied to the electrodes, and the cathodic electrolysis water 5 and the anodic electrolysis water 6 are applied.
Get.

Gallic acid is a compound which has a property of strongly dissociating protons of a carboxyl group bonded to a benzene nucleus in an aqueous solution, but having a strong reducing power in an alkaline aqueous solution and rapidly absorbing oxygen from the air. . When the gallic acid is contained in the electrolytic solution 9, it is dissociated into gallic acid ions and hydrogen ions in the electrolytic solution. Therefore, the negatively charged gallate ions by the application of the current move to the anode side. However, not all of the gallic acid ions are transferred to the anode side, and the remaining gallic acid ions and unreacted gallic acid are present on the cathode side. Accordingly, on the cathode side, the water molecules are electrolyzed to generate hydrogen molecules (H ₂ ) and free hydroxyl ions (OH ⁻ ), and the free hydroxyl ions move to the diffusion layer via the electric double layer, Then, it reacts with gallic acid or gallic ion present on the cathode side. Specifically, the hydrogen ion (H) of the hydroxyl group of gallic acid or gallic ion and the free hydroxyl group (O
H ^-) and form a -OOH substituted, -OO by releasing at the same time free hydrogen ions ^- forming a. The reaction between gallic acid and free hydroxyl ions is represented by the following equation.

[0031]

Embedded image

As shown in the above formula, 2M free hydroxide ion reacts with 1M gallic acid, and finally 4M free hydrogen ion is generated. Although 3M hydroxyl groups are bonded to gallic acid, only hydroxyl groups having a conjugated double bond are bonded to free hydroxyl ions generated by electrolysis of water molecules on the cathode side. Only hydroxyl groups react with free hydroxyl ions. Then, the cathode-side electrolyzed water thus obtained is excellent in superoxide erasing ability as shown in Examples described later.

Conventionally, there has been a finding that cathode-side electrolyzed water contributes to health, but the reason has not been clarified. However, the present inventor paid attention to free hydroxyl ions generated on the cathode side by electrolysis, and considered that the free hydroxyl ions acted on a substance in a living body to produce some kind of biological contributing substance.
Although the identification of such a substance in the living body is not yet clear, it has been found that the electrolytically produced water obtained by actually reacting free hydroxide ions with gallic acid has excellent superoxide anion scavenging ability. is there. This superoxide anion scavenging ability is considered to be due to free hydrogen ions generated by the above reaction. The free hydrogen ions obtained in this way are stable in water molecules unless free cations are present.

Here, the electrolysis water has different components and free hydroxyl ion concentrations depending on the raw water used and the type of electrolyte to be added. Therefore, simply adding gallic acid after obtaining the cathodic electrolysis water would result in insufficient free hydroxyl ion concentration required for the reaction or gallic acid reacting with other components to cause free hydrogen ion represented by the above formula. And gallic acid suitable for the amount of free hydroxyl ions contained in the cathodic electrolysis water cannot be added, and as a result, it is extremely difficult to obtain electrolysis water having a greater superoxide anion scavenging ability. It will be difficult. The present invention is to clarify the characteristics of such electrolyzed water and the effects obtained by specific additives, and to provide a method for easily producing the same.
On the anode side, water molecules are electrolyzed to generate hydrogen ions (H ⁺ ) and oxygen molecules (O ₂ ), and gallic acid is formed by the hydrogen ions and the gallic acid ions transferred to the anode side. Is done.

The present invention is characterized in that gallic acid is used. However, a salt of gallic acid can be used in combination with gallic acid or in place of gallic acid. Here, as a salt of gallic acid contained in the electrolytic solution, an alkali metal such as sodium or potassium, an alkaline earth metal such as calcium or magnesium, or the like can be used. In the present invention, gallic acid or a sodium salt, potassium salt or calcium salt of gallic acid is preferred. These may be used alone or in combination of two or more.

The total concentration of gallic acid and gallic acid ions in the cathode-side electrolyte at the time of current application is 1 × 10 ^-4.
To 1 × 10 ⁻² M, more preferably 5 × 10 ^{−4 to} 5 × 10 ⁻³ M, and particularly preferably 1 × 10 ⁻³ M.
３3 × 10 ⁻³ M. As described above, gallic acid ions migrate to the anode side in the electrolytic solution, but a gallic acid ion or gallic acid concentration sufficient to react with free hydroxide ions generated on the cathode side in the above range can be ensured. . In addition, the cathodic electrolysis water shows alkalinity by electrolysis, but by adding gallic acid in the above range, it reacts with the carboxyl group of gallic acid in the catholyte electrolytic solution to neutralize it, and it is actually used. The pH can be adjusted to a range suitable for

In the present invention, a direct current is applied to one liter of the electrolytic solution to perform electrolysis. The direct current applied to the electrode installed in the electrolytic cell has a current density per unit area of the electrode of 2 × 10 ⁻³ to 1 × 10 ⁻¹ A / cm ² , more preferably 1 × 10 ^{−2 to} 7 ×. 10 ⁻² A / cm ² , especially 1.
It is 5 × 10 ^{-2 to} 3 × 10 ^-2 A / cm ² . 2 × 10 ^-3
If it is less than A / cm ² , sufficient free hydrogen ions will not be generated to react with gallic acid set in the above range, while if it exceeds 1 × 10 ^-1 A / cm ² , the concentration of free hydroxyl ions will increase. Because it is too much.

The current having a current density in the above range is 500 to 4000 ml / min, more preferably 1000 to 3000 ml / min, particularly 1500
Applied to ~ 2500 ml / min electrolyte. The amount of water electrolysis varies depending on the amount of the electrolytic substance contained in the electrolytic solution, the current density per unit electrode, the required unit area, and the application time, but the concentration of gallic ion and gallic acid in the electrolytic solution and the applied current By adjusting the amount within the above range, it is possible to easily obtain a cathode-side electrolyzed water having a superior superoxide anion scavenging ability and a pH which can be easily administered to a living body.

In order to carry out the method of the present invention, there are known means for adjusting the current supply amount in accordance with the supply amount of the electrolyte, the electrolyte concentration, the pH of the electrolyte, etc., and the electrolytic solution in accordance with the current supply amount. Using known means for adjusting the supply amount, electrolyte concentration, electrolyte pH, and the like, the water on the cathode side containing free hydrogen ions can be easily obtained. For example, in the case of performing the batch method, the current density and the application time of the direct current of the flux may be adjusted so as to maintain the above-mentioned range with respect to 1 liter of the electrolytic solution having the gallic acid ion concentration. Also, in the case of the flowing water method, electrolysis is performed so as to be in the above range from the concentration of gallic acid ions and gallic acid in the electrolytic solution, the total amount of applied current, and the flux of the electrolytic solution.

In the present invention, the reaction between the free hydroxide ion generated on the cathode side and the gallic acid or gallic acid ion may be ensured, and the electrolytic solution containing gallic acid is not necessarily used as shown in FIG. It is not necessary to supply both to and the anode. Therefore, a pipe for supplying different electrolytes may be provided on the cathode side and the anode side, and the electrolyte containing gallic acid may be supplied only to the cathode side. That is, the concentration of “gallic acid ion or gallic acid in the electrolytic solution” of the present invention may be maintained at least in the cathode-side electrolytic solution.

In the present invention, the raw water to which gallic acid is added is:
There is no particular limitation. However, deionized water by ion exchange resin, deionized water by combination of ion exchange resin and distillation, distilled water by distillation, pure water by reverse osmosis membrane or reverse osmosis membrane and combination of distillation or ion exchange resin, tap water, Any of natural groundwater and the like can be used.

As the diaphragm provided in the electrolytic cell, either a charged film or an uncharged film can be used. Therefore, any of an anion exchange membrane, a cation exchange membrane, and an amphoteric membrane, which are charged membranes, can be employed. Further, a neutral film which is an uncharged film can also be employed. The charged membrane is more preferably a charged membrane than a neutral membrane because it can further enhance the ion selectivity, but may be appropriately selected depending on the purpose of use of the electrolyte or the electrolyzed water.
The charged membrane is preferable in that when a large concentration gradient occurs between the anode side and the cathode side, reverse transport of ions can be prevented from occurring.

The electrode may be any electrode as long as it is a platinum-based electrode, but it is an absolute condition that it is an irreversible electrode.
With a reversible electrode, the electrode itself directly participates in the chemical reaction,
This is because it is impossible to perform only the transfer of electrons.
Therefore, the composition of the obtained electrolysis water also changes. Therefore, in addition to the platinum electrode, titanium, stainless steel, or the like can be preferably used. Of these, platinum electrodes are most preferred. This is because the platinum electrode has an extremely low ionization tendency and is extremely stable as an electrode.

Further, sodium chloride,
One or more compounds selected from the group consisting of potassium chloride, calcium chloride and magnesium chloride may be added. This is because the applied voltage can be reduced by adding the electrolyte. In the case where a chloride such as sodium chloride is contained in the electrolytic solution, the electrolytic solution supplied to the cathode side and the anode side requires sodium chloride with respect to a total of 1 × 10 ⁻⁴ M of gallic acid or a salt thereof. , Potassium chloride, calcium chloride and magnesium chloride, the sum of at least one compound selected from the group consisting of 1 × 10 ⁻⁴ to 1 ×
10 ⁻² M, more preferably 5 × 10 ⁻⁴ to 1 × 10 ⁻² M,
In particular, it is 1 × 10 ^{−3 to} 5 × 10 ⁻³ M. When the amount of chloride such as the above sodium chloride exceeds 1 × 10 ^-2 M, the pH becomes 1
On the other hand, when the concentration is less than 1 × 10 ⁻⁴ M, the ionization of gallic acid proceeds, and the concentration of gallic acid ion migrating to the anode side is improved. Because you do. The cations such as sodium and potassium contained in chloride are
It shifts to the cathode side and forms sodium hydroxide on the cathode side, causing an increase in alkalinity. On the other hand, it is known that potassium replaces sodium in a living body to exert a blood pressure lowering effect, calcium contributes to bone formation, and magnesium contributes to intestinal regulation. Therefore, a secondary effect can be obtained by selecting the composition of the electrolytic solution according to the purpose of use of the cathodic electrolysis water. In addition, pH of electrolyzed water
Varies depending on the content of the chloride, and can be appropriately adjusted depending on the purpose of use.

In the present invention, inositol or a phosphate compound thereof is added to gallic acid or a salt thereof, or in addition to the above-mentioned chloride, in a concentration of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M.
The electrolyte solution may be contained within the range described above. This will be described with reference to FIG.

First, FIG. 2 uses gallic acid, sodium chloride and inositol as electrolytes. Tap water 1
9 is supplied as raw water, and an electrolyte is supplied to tap water 19 via an injection device 18 to obtain an electrolyte. This is supplied to both the cathode 12 side and the anode 13 side through the filter 17 through the diaphragm 14 of the electrolytic cell 11. Next, a direct current is applied to the electrodes to obtain cathode-side electrolysis water 15 and anode-side electrolysis water 16.

Even if inositol is contained in the electrolytic solution, inositol itself is hardly ionized and does not directly participate in electrolysis. However, this addition provides an antioxidant effect and helps nutrition.

The content of inositol phosphate is 1 × 10 ⁻⁴ M for gallic acid or a salt thereof, and 1 × 10 ⁻⁴ to 1 × 1 for the total of inositol or a phosphate compound thereof.
It is 0 ^-2 M, more preferably 5 × 10 ^{−4 to} 5 × 10 ⁻³ M, particularly 1 × 10 ^{−3 to} 5 × 10 ⁻³ M. If the inositol or its phosphate exceeds 1 × 10 ⁻² M, it is difficult to dissolve. On the other hand, if it is less than 1 × 10 ⁻⁴ M, the inositol or its phosphate becomes a trace and becomes insufficient as a nutrient. Inositol phosphates include inositol monophosphate, inositol diphosphate, inositol triphosphate, and inositol hexaphosphate, all of which are preferred.

In the present invention, the electrolyte further comprises L-ascor
1 × 10 total of boric acid or its salt ^-Four~ 1 × 10^-2M,
More preferably, 5 × 10^-Four~ 5 × 10^-3M, especially 1
× 10^-3~ 3 × 10^-3M may be contained in the range.
10^-2If it exceeds, the acidity of the electrolyzed water is too strong to drink
1 × 10^-FourIf less than 4mg / lit.
Because it is difficult to make it fall below L-
The addition of ascorbic acid dissolves the resulting electrolytically produced water.
The amount of oxygen can be reduced, the pH can be adjusted,
Free hydrogen can be generated by ascorbic acid
it can. Sodium as a salt of L-ascorbic acid,
Alkali metals such as potassium, calcium, magnesium
Alkaline earth metals such as metals can be used.
In the present invention, L-ascorbic acid or L-ascorbic acid
Acid sodium, potassium or calcium salts
Preferably, there is. In addition, besides using one kind,
Two or more kinds may be used in combination.

(2) Cathode-side electrolysis water The second aspect of the present invention is to supply an electrolytic solution containing gallic acid or a salt thereof to an electrolytic cell having a cathode and an anode separated by a diaphragm, The total concentration of gallic acid ions or gallic acid in the mixture is in the range of 1 × 10 ^-4 to 1 × 10 ^-2 M,
For 1 liter of the electrolyte, 2 per unit area of the electrode
Cathode-side electrolyzed water obtained by applying a DC current having a current density of × 10 ^-3 to 1 × 10 ^-1 A / cm ^{2 at} a flux of 500 to 4000 ml / min.

The cathodic electrolysis water of the present invention contains unreacted gallic acid and gallic acid ions, and free hydrogen ions generated by gallic acid and free hydroxyl ions. The amount of ions is very small. This is because the free hydroxide ion reacts with gallic ion contained in the electrolytic solution or reacts with sodium transferred from the anode to form a pair.

The electrolytically produced water on the cathode side according to the present invention may be further added to gallic acid or a salt thereof in the same range as described in the above-mentioned method for producing electrolyzed water.
One or more compounds selected from the group consisting of potassium chloride, calcium chloride and magnesium chloride may be added. Similarly, the electrolytic solution may contain inositol or a phosphate compound thereof. In addition, similarly, the electrolytic solution may further contain L-ascorbic acid or a salt thereof.

Accordingly, the electrolytically generated water on the cathode side contains an electrolytic solution.
Inositol phosphate, L-
It depends on the content of ascorbic acid, etc.
At least unreacted gallic acid, gallate ion and gallic
The acid was 0.95 × 10^-Four~ 0.95 × 10^-2M is good
More preferably 4.75 × 10^-Four~ 4.75x
10^-3M, particularly preferably 0.95 × 10^-3~ 2.85
× 10^-3M included. Also, potassium, magnesium, cal
When containing sodium, sodium, etc., the total is 0.9
5 × 10^-Four０0M is preferred, and more preferably 4.75.
× 10^-Four~ 4.75 × 10^-3M, particularly preferably 0.9
5 × 10^-3~ 2.85 × 10^-3M. Also, wild boar
Toll or its phosphate is 1 × 10^-2~ 0M
And more preferably 5 × 10^-3~ 5 × 10
^-3M, especially 1 × 10^-3~ 3 × 10^-3M. Furthermore,
L-ascorbic acid or a salt thereof is 0.95 × 10^-3
０0M, more preferably 4.75
× 10^-Four~ 4.75 × 10 ^-3M, especially 0.95 × 10
^-3~ 2.85 × 10^-3M.

In particular, even when inositol is contained in the electrolytic solution, inositol itself does not directly participate in electrolysis because it is hardly ionized. However, this addition provides an antioxidant effect and helps nutrition. For this reason, the SOD enzyme-like activity is enhanced in the living body, and the antioxidant action against free radicals is higher than that of conventional electrolytically produced water on the cathode side, thereby contributing to prevention of various diseases.

Also, L-ascorbic acid or a salt thereof can reduce the dissolved oxygen in the cathode-side electrolyzed water due to their reducing property, and can prevent the generated water from being oxidized and stabilized. Therefore, the SOD enzyme-like activity is increased in vivo,
The antioxidant action against free radicals can be increased as compared with the conventional cathode-side electrolyzed water.

The electrolytically produced water on the cathode side of the present invention has a superoxide anion scavenging ability and a relative signal intensity with a manganese marker in ESR measurement of 50 to 10 which is a difference from pure water.
0%, more preferably 60-100%, especially 80-1
00%.

Here, the elimination ability of the superoxide anion was determined by the ES of the control solution using pure water prepared as follows.
It shall be calculated from the R signal intensity and the ESR signal intensity of the test solution.

The test solution was prepared by adding 35 μl of 5.5 mM diethylenetriaminepentaacetic acid (DETAPAC) to 50 μl of 2 mM hypoxanthine-phosphate buffer, and then adding 50 μl of pure water and 5,5-dimethyl-1-pyrroline-phosphate.
Add 17 μl of oxide (DMPO) and finally add 0.4
Unit / ml xanthine oxidase-phosphate buffer 5
Add 0 μl to obtain a target solution for generating superoxide anion. On the other hand, instead of the pure water, 5
Add 0 μl to prepare a test solution.

In the ESR spectrum of the target solution,
As ESR measurement conditions, measurement temperature: room temperature, microwave output: 3.7 mW, sweep magnetic field: 339.1 mT ± 5.5 m
The signal intensity is measured at T, magnetic field modulation: 100 KHz, modulation width: 0.1 mT, time constant: 0.12 seconds, and sweep time: 60 seconds.

For the ESR spectra of the test solution and the control solution, the signal intensity of manganese and the earliest signal intensity of superoxide anion are measured, respectively. The signal intensity of manganese in the control solution is C ₀ , the earliest signal intensity of the superoxide anion is C ₁ , the signal intensity of manganese in the test solution is S ₀ , and the earliest signal intensity of the superoxide anion is S ₁ , The following equation, (C ₁ / C ₀ −S ₁ / S ₀ ) × 100
/ (C ₁ / C ₀ ) according to the superoxide anion scavenging ability.

Therefore, when C ₀ is 50 and C ₁ is 30, the superoxide anion scavenging ability of the sample solution when S ₀ is 100 and S ₁ is 10 is (30-1).
0 × 50/100) × 100/30 = 83%.

An object of the present invention is to react free hydroxyl ions generated on the cathode side with gallic acid and the like to obtain electrolytically generated water on the cathode side which is excellent in superoxide anion scavenging ability. As shown in the examples, the cathodic electrolysis water of the present invention has excellent superoxide anion scavenging ability as compared with gallic acid itself, the cathodic electrolysis water obtained by performing electrolysis without containing gallic acid. .

The cathode-side electrolysis water of the present invention has a dissolved oxygen content of 6.5 to 0.11 mg / liter, more preferably 5 to 0.11 mg / liter.
To 0.11 mg / liter, particularly preferably 3 to 0.1 mg / l.
1 mg / liter. The raw water contains oxygen, and even if the obtained cathode-side electrolyzed water is allowed to stand, it contains oxygen and oxidizes the solution itself. Therefore, by reducing the amount of dissolved oxygen, it is possible to prevent oxidation of the cathodic electrolysis water, and also to prevent the oxidative action of the living body when it is administered to the living body.

In addition, the hydrogen ion concentration of the cathode-side electrolyzed water of the present invention is preferably 4.0 to 10.0 regardless of whether chloride, inositol and the like are contained in the electrolyte and electrolyzed. More preferably, it is 6 to 9.5, especially 7 to 8. As described above, if it is less than 4.0, the acidity is strong, while if it is more than 10.0, it is bitter and not suitable for drinking.
However, it can be used outside the above range depending on the purpose of use.

Although not limited, the oxidation-reduction potential of the cathode-side electrolyzed water of the present invention is -60 to -300 mV, more preferably -100, according to the electrolyte concentration and the applied current in the above ranges. ~ -300mV, especially -200 ~
The range is -300 mV. The oxidation-reduction potential is a value measured at a liquid temperature of 25 ° C. using a glass electrode as a reference electrode. This oxidation-reduction potential is determined by the concentration of dissolved hydrogen and dissolved oxygen contained. The electric conductivity is 1
3 to 60 mS / m, more preferably 13 to 50 mS / m
m, especially 13 to 40 mS / m.

(3) Electrolytic Aid The third aspect of the present invention is that gallic acid or a salt thereof is added to 1 × 10 ^-4.
An electrolytic assistant characterized in that at least one compound selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride is 1 × 10 ⁻⁴ to 1 × 10 ⁻² M with respect to M.

Electrolysis of an electrolytic solution containing gallic acid or a salt thereof as galvanic acid makes it possible to obtain cathodic electrolysis water having excellent superoxide anion scavenging ability. However, if gallic acid is simply added, sufficient hydrogen can be obtained. Ions cannot be generated, and it is difficult to adjust the pH. However, according to the present invention, it is possible to provide an excellent electrolysis assistant having a reduced applied current by previously mixing a chloride such as sodium chloride and gallic acid or a salt thereof with the electrolysis assistant.

[0068] for 1 × 10 ^-4 M to the gallic acid or its salt, sodium chloride, potassium chloride, one or more compounds selected from the group consisting of calcium chloride and magnesium chloride, 1 × 10 ^-4 ~1 × 10 ^-2 M, more preferably 3 × 10 ⁻⁴ to 1 × 10 ⁻² M,
In particular, it is 3 × 10 ⁻³ to 1 × 10 ⁻² M. Within the above range,
This is because a sufficient amount of gallic acid or gallic acid ion for obtaining superoxide anion scavenging ability can be easily obtained in the cathodic electrolysis water.

Further, the electrolysis auxiliary of the present invention may further contain inositol or a phosphate compound thereof. 1 × 10 ⁻⁴ M of the gallic acid or a salt thereof, wherein the inositol or the phosphate compound thereof is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁴ M
⁻² M, more preferably 5 × 10 ^{−4 to} 5 × 10 ⁻³ M, particularly 1 × 10 ^{−3 to} 5 × 10 ⁻³ M. By the incorporation of the inositol, the oxidation of the electrolytic solution itself can be prevented, and the oxidation of the resulting electrolyzed water can be prevented.

The electrolytic assistant of the present invention may contain L-ascorbic acid or a salt thereof. In this case, the ratio of the L-ascorbic acid or a salt thereof to 1 × 10 ⁻⁴ M of the gallic acid or a salt thereof is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² M, more preferably 5 × 10 ⁻² M. ^{-4 to} 5 × 10
⁻³ M, particularly preferably 1 × 10 ^{−3 to} 3 × 10 ⁻³ M.

(4) Electrolysis apparatus for water The fourth aspect of the present invention is a means for supplying gallic acid or a salt thereof to an electrolytic cell having a cathode and an anode separated by a diaphragm, and a gallic in the cathode-side electrolyte. Means for making the total concentration of acid ions or gallic acid in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M, and 2 × 10 ⁻³ to 1 × 1 to 1 × 1 liter of the electrolytic solution per unit area of the electrode Means for applying a direct current having a current density of × 10 ^-1 A / cm ^{2 at} a flux of 500 to 4000 ml / min.

According to the present invention, the superoxide anion scavenging ability can easily produce the cathodic electrolyzed water.

As the "means for supplying gallic acid or a salt thereof to the electrolytic cell provided with a cathode and an anode separated by a diaphragm", a known electrolytic cell for supplying electricity while supplying sodium chloride as an electrolyte is used in the present invention. Can be added gallic acid or a salt thereof as an electrolyte. Since gallic acid is easily oxidized by air, inositol and L-ascorbic acid may be added to the electrolyte together with gallic acid or a salt thereof, but in this case, pipes for supplying these components to the electrolytic cell are separately provided. You may.

However, in this apparatus, the total concentration of gallic acid ions or gallic acid in the catholyte-side electrolyte is set to 1 × 10 ^-4 to 1 × 10 ^-4.
It is necessary to have means for setting the range of × 10 ^-2 M. Such concentration can be adjusted by adjusting the concentration of gallic acid or a salt thereof added as an electrolysis assistant and the mixing ratio with raw water.

The electrolytic device is capable of handling one liter of the electrolytic solution.
And 2 × 10 2 per unit area of the electrode ^-3~ 1 × 10^-1A
/ Cm^TwoDC current of 500 to 4000 m
means for applying at a flux of 1 / min. For example, known
Gallic acid ions or gallic acid in the electrolyte by means
Of the electrode surface to be used in accordance with this concentration
The amount of current is controlled according to the product, and the application time is adjusted.

In the electrolysis apparatus of the present invention, any of a charged membrane and an uncharged membrane can be used as the diaphragm provided in the electrolytic cell.
What is necessary is just to select suitably according to the purpose of use of an electrolyte and electrolysis water. In addition, when the cathode-side electrolysis water is mainly used, it is preferable to have an anion exchange membrane. This is because unnecessary anions can be removed from the cathode side.

The electrode may be any electrode as long as it is a platinum-based electrode, but as described above, it is an absolute condition that the electrode is an irreversible electrode. This is because if the electrode is a reversible electrode, the electrode itself directly participates in a chemical reaction, and cannot only transfer electrons. Therefore, in addition to the platinum electrode, titanium,
Stainless steel or the like can be preferably used. Of these, platinum electrodes are most preferred.

According to the present invention, electrolytically produced water excellent in superoxide anion elimination ability can be easily obtained. By using a compound containing a chloride such as sodium chloride as an electrolytic aid, electrolytically produced water containing hydrochloric acid or hypochlorous acid can be obtained on the anode side, and can be used for purposes such as sterilization. . Further, the cathodic electrolysis water contains free hydrogen ions generated by the reaction of gallic acid ions and free hydroxyl ions, and the cathodic electrolysis water has an excellent superoxide anion scavenging ability, so that it can be used for drinking. Can be used for other external purposes.

[0079]

The present invention will now be described more specifically with reference to examples.

(Example 1) Using the apparatus shown in FIG.
M gallic acid and 1 mM NaCl
A solution having an electric conductivity of 18.51 mS / m (25 ° C.) was prepared and placed in a storage tank. Then, using an electrode formed by coating a platinum iridium alloy on titanium metal and an uncharged membrane as a diaphragm, a DC current having a current density of 1.25 × 10 ⁻² A / cm ² per electrode area was used. Was applied at a flow rate of 2200 ml / min, and the electrolysis water on the cathode side was collected by a flowing water method.

With respect to the obtained cathode-side electrolysis water, p
H, redox potential (ORP), dissolved oxygen concentration (DO),
The electric conductivity (EC) was measured, and the erasing ability of the superoxide anion was examined by electron spin resonance (ESR).

The elimination ability of the superoxide anion was as follows.

First, 50 μl of pure water was added to a mixture of 50 μl of 2 mM hypoxanthine-phosphate buffer and 35 μl of 5.5 mM DETAPAC-phosphate buffer, and 5,5-dimethyl-1-phosphate was used as a spin trapping agent. Pyrroline-oxide (DMP for ESR, manufactured by Labotech Inc.)
O) 17 μl was added, and 50 μl of a 0.4 unit / ml xanthine oxidase-phosphate buffer was added, and after 1 minute by ESR, a sweep was started to obtain an ESR spectrum. This is defined as the superoxide anion scavenging ability of the target solution. The water used for the preparation was all pure water.

Next, a test solution was prepared in the same manner as above except that 50 μl of the cathodic electrolysis water obtained in Example 1 was used instead of 50 μl of pure water, and the ESR was measured in the same manner as the target solution. FIG. 3 shows the ESR of the target solution, and FIG. 4 shows the ESR of the test solution.

The elimination ability of the superoxide anion by the ESR method is shown by the relative signal intensity ratio with manganese.
The smaller the value of the relative signal intensity ratio, the higher the erasing ability. Other results are as follows.

Gallic acid concentration: 0.74 mM pH: 4.62, ORP: -135 mV, DO: 6.45 mg / l, EC: 14.2 mS / m Superoxide anion scavenging ability: 100%.

(Example 2) In addition to the electrolyte solution of Example 1,
Except for the addition of mM inositol, the same procedure as in Example 1 was carried out to collect the cathodic electrolysis water.

With respect to the obtained cathode-side electrolysis water, p
H, redox potential (ORP), dissolved oxygen concentration (DO),
The electric conductivity (EC) was measured, and the erasing ability of the superoxide anion was examined by electron spin resonance (ESR). FIG. 5 shows the results of ESR. The ES of the target solution
The attachment of the R diagram is omitted. Other results are as follows.

Gallic acid concentration: 0.76 mM pH: 4.51, ORP: -141 mV, DO: 6.31 mg / l, EC: 13.09 mS / m Superoxide anion scavenging ability: 100%.

(Example 3) Using an apparatus shown in FIG. 1, a concentration of 1 m was added to 20 liters of water purified by an ion exchange resin.
M gallic acid, 1 mM inositol and 2 mM NaC
1 and a solution having an electric conductivity of 28 mS / m was prepared and placed in a storage tank. Next, using an electrolytic cell composed of an electrode coated with a platinum iridium alloy on titanium metal and an uncharged film, 2.08
DC current of a current density of × 10 ^-2 A / cm ² is 2200 m
The applied water was applied at a flow rate of 1 / min, and the electrolysis water on the cathode side was collected by a flowing water method.

The pH, oxidation-reduction potential, dissolved oxygen concentration, and electric conductivity of the obtained electrolyzed water were measured, and the elimination ability of superoxide anion was examined by the ESR method. FIG. 6 shows the results of ESR. As can be seen from FIG. 6, in Example 3, the superoxide anion was completely eliminated. The ES of the target solution measured at the same time
The R diagram is not shown. Other results are as follows.

Gallic acid concentration: 0.75 mM pH: 7.99 ORP: -218 mV DO: 4.56 mg / l EC: 24.6 mS / m Superoxide anion scavenging ability: 100%.

Example 4 Using the apparatus shown in FIG. 2, a solution was dissolved in 20 liters of tap water to a concentration of 1 mM gallic acid, 1 mM inositol and 1 mM NaCl, and the solution was adjusted to an electric conductivity of 60 mS / m. Was prepared and placed in a storage tank. Then, a direct current having a current density of 2.08 × 10 ⁻² A / cm ² was applied at a flow rate of 2200 ml / min using an electrolytic cell composed of an electrode in which a platinum iridium alloy was coated on titanium metal and an uncharged film. And electrolyzed water on the cathode side was collected by a flowing water method.

The pH, oxidation-reduction potential, dissolved oxygen concentration and electric conductivity of the obtained electrolyzed water were measured, and the superoxide anion scavenging ability was examined by ESR.
FIG. 7 shows the results of ESR. The attachment of the ESR diagram of the target solution was omitted. As can be seen from FIG. 7, in Example 4, the superoxide anion was completely eliminated. Other results are as follows.

Gallic acid concentration: 0.74 mM pH: 9.69 ORP: -251 mV DO: 1.34 EC: 60 mS / m Superoxide anion scavenging ability: 100%.

(Example 5) Using the apparatus shown in FIG. 2, 20 ml of tap water was dissolved to a concentration of 1 mM gallic acid, 1 mM inositol and 1 mM CaCl ₂ ,
Prepare a solution so that the electric conductivity is 53 mS / m,
Put in storage tank. Next, using an electrolytic cell composed of an electrode coated with a platinum iridium alloy on titanium metal and an uncharged film, 1.46 × 10 ⁻² A / cm.
A direct current having a current density of ² was applied at a flow rate of 2200 ml / min, and the electrolysis water on the cathode side was collected by a flowing water method.

The pH, oxidation-reduction potential, dissolved oxygen concentration and electric conductivity of the obtained electrolyzed water were measured, and the elimination ability of superoxide anion was examined by ESR.
FIG. 8 shows the result of ESR. The attachment of the ESR diagram of the target solution was omitted. As can be understood from FIG. 8, in Example 5, the superoxide anion was completely eliminated. Other results are as follows.

Gallic acid concentration: 0.98 mM pH: 5.41 ORP: -144 mV DO: 3.94 mg / l EC: 44.5 mS / m Superoxide anion scavenging ability: 100%.

Example 6 A solution having an electric conductivity of 30.5 mS / m was prepared by dissolving in 20 liters of water purified by an ion exchange resin so as to have a concentration of 1 mM gallic acid, 1 mM inositol and 2 mM KCl. And placed in a storage tank. Next, a direct current having a current density of 1.67 × 10 ⁻² A / cm ² was applied at a flow rate of 2200 ml / min using an electrolytic cell composed of an electrode having a platinum iridium alloy coated on titanium metal and an uncharged film. And apply
Cathode-side electrolysis water was collected by flowing water.

The pH, oxidation-reduction potential, dissolved oxygen concentration and electric conductivity of the obtained electrolyzed water were measured, and the elimination ability of superoxide anion was examined by the ESR method. FIG. 9 shows the results of ESR. The ES of the target solution
The attachment of the R diagram is omitted. As can be understood from FIG. 9, in Example 6, the superoxide anion was completely eliminated. Other results are as follows.

Gallic acid concentration: 0.97 mM pH: 5.2 ORP: -152 mV DO: 5.5 mg / l EC: 23.6 mS / m Superoxide anion scavenging ability: 100%.

(Example 7) As an electrolytic solution of Example 1,
Further, the same operation as in Example 1 was carried out except that 1 mM L-ascorbic acid was added, to obtain cathode-side electrolyzed water.

The pH, oxidation-reduction potential, dissolved oxygen concentration and electric conductivity of the obtained electrolyzed water were measured, and the elimination ability of superoxide anion was examined by the ESR method. FIG. 10 shows the results of ESR. In addition, E of the target solution
The attachment of the SR diagram is omitted. As can be understood from FIG. 10, in Example 7, the superoxide anion was completely eliminated. Other results are as follows.

Gallic acid concentration: 0.78 mM pH: 8.2 ORP: -170 mV DO: 0.08 mg / l EC: 42 mS / m Superoxide anion scavenging ability: 100%.

(Comparative Example 1) Superoxoxide anion scavenging ability was measured in the same manner as in Example 1 except that a pure aqueous solution of 2 mM calcium lactate was used in place of the cathodic electrolysis water of Example 1. . The results are shown in FIG. In addition,
The superoxide anion scavenging ability was 0%. It was confirmed that the pure aqueous solution of calcium lactate hardly eliminated superoxide anion.

(Comparative Example 2) An electrolytic solution dissolved in pure water to give 2 mM calcium glycerophosphate was flowed at 2.2 L / min, and a current density of 2.3 × 10 ^-2 A / cm ² was passed through the electrolytic solution. DC current is applied at a flow rate of 2200 ml / min,
Cathode-side electrolysis water was collected by flowing water.

The superoxoxide anion scavenging ability was measured in the same manner as in Example 1 using the obtained cathode-side electrolyzed water. FIG. 12 shows the result. The superoxide anion scavenging ability was 0%. In calcium glycerophosphate, it was confirmed that the superoxoxide anion was hardly eliminated.

(Comparative Example 3) A pure aqueous solution of gallic acid having a concentration of 1 mM was used in the same manner as in Example 1, and the superoxide anion scavenging ability was measured by ESR. The result is shown in FIG. Superoxide anion scavenging ability
43.8%.

Comparative Example 4 Cathode-side electrolyzed water was obtained in the same manner as in Example 1, except that 1 mM of gallic acid was not used. Superoxide anion scavenging ability was measured by ESR in the same manner as in Example 1 using the cathode-side electrolyzed water. The result is shown in FIG. The superoxide anion scavenging ability was 2.2%.

(ESR Measurement Conditions) The ESR measurement conditions were as follows.

Sample solution: 50 μl Trapping agent: 5,5-dimethyl-1-pyrroline-oxide (17 μl) Measurement temperature: room temperature Microwave output: 3.7 mW Sweep magnetic field: 339.1 mT ± 5.5 mT Magnetic field modulation: 100 KHz modulation Width: 0.1 mT Time constant: 0.12 seconds Sweep time: 60 seconds (Results) The cathodic electrolysis water of the present invention is composed of 1M gallic acid and 2M free hydroxyl ion as shown in the above formula. React to produce 4M free hydroxyl ions. When the elimination ability of various test solutions for superoxide anion was measured by ESR, the elimination ability of the cathodic electrolysis water obtained without adding gallic acid of Comparative Example 4 was 2.2%. For example, as shown in Example 1, the cathode-side electrolysis water of the present invention had an extremely high value of 100%. Further, in Comparative Example 3, since the elimination ability of gallic acid alone was 43.8%, the cathodic electrolysis water of the present invention exhibited excellent superoxide anion elimination ability more than twice that of the gallic acid solution. It is clear to have.

It is not clear why the cathode-side electrolyzed water of the present invention has excellent superoxide anion scavenging ability. However, when gallic acid is contained in the electrolyte and when it is not contained, only the amounts of free hydroxyl ions, free hydrogen ions, and gallic acid contained are different. As is apparent from Comparative Example 3, since gallic acid has a small elimination ability of superoxide anion, the elimination ability of the superoxide anion of the electrolytically produced water on the cathode side of the present invention is based on the above formula. It is thought to be due to free hydrogen ions generated by the reaction with the acid ions.

That is, although a hydroxyl ion is generated also on the anode side, it is characterized in that a free hydrogen ion is generated twice as much as a 2M free hydroxyl ion on the cathode side. The cathode-side electrolysis water of the present invention is excellent in superoxide anion scavenging ability as shown in Examples 1 to 7.

Further, as shown in Example 7, L-
In the case where ascorbic acid is added, the amount of dissolved oxygen is reduced. Therefore, it is possible to prevent oxidation of the obtained electrolysis water.

[0115]

The present invention is characterized in that hydroxyl ions generated on the cathode side by electrolysis react with gallate ions to generate hydrogen ions. The cathodic electrolysis water obtained by the present invention is excellent in superoxide anion scavenging ability. Further, according to the present invention, it is possible to adjust the cathode-side electrolyzed water having excellent superoxide anion eliminating ability by a simple method.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a preferred apparatus for producing electrolyzed water of the present invention.

FIG. 2 is a schematic diagram showing a preferred apparatus for producing electrolyzed water according to the present invention.

FIG. 3 shows an ESR using the target solution used in Example 1.
It is a figure which shows the result of.

FIG. 4 is a diagram showing the results of a test solution ESR using the cathode-side electrolyzed water generated in Example 1.

FIG. 5 is a diagram showing the results of a test solution ESR using the cathode-side electrolyzed water generated in Example 2.

FIG. 6 is a view showing a result of a test solution ESR using the cathode-side electrolyzed water generated in Example 3.

FIG. 7 is a view showing a result of a test solution ESR using the cathode-side electrolyzed water generated in Example 4.

FIG. 8 is a diagram showing the results of a test solution ESR using the cathode-side electrolyzed water generated in Example 5.

FIG. 9 is a view showing a result of a test solution ESR using the cathode-side electrolyzed water generated in Example 6.

FIG. 10 is a diagram showing the results of a test solution ESR using the cathode-side electrolyzed water generated in Example 7.

FIG. 11 is a view showing the result of ESR of the test solution of Comparative Example 1.

FIG. 12 is a graph showing the results of ESR of the test solution of Comparative Example 2.

FIG. 13 is a diagram showing the result of ESR of the solution of Comparative Example 3.

FIG. 14 is a diagram showing the result of ESR of the solution of Comparative Example 4.

[Explanation of symbols]

 1, 11: electrolytic cell, 2, 12: cathode, 3, 13: anode, 4, 14: diaphragm, 5, 15: cathode-side electrolyzed water, 6, 16: anode-side electrolyzed water, 7, 17: filter , 8, 18: storage tank, 9, 19: electrolyte, 10: pump, 18: injection device, 19: tap water

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Takayoshi Hanaoka 1041-2 Ueda, Ueda-shi, Nagano F-term (reference) 4D061 DA03 DB18 DC08 DC13 EA02 EB01 EB04 EB12 EB30 EB39 ED12 ED13 ED20 FA13 GC05 GC06 GC11 GC12 GC18

Claims (13)

[Claims] An electrolytic solution containing gallic acid or a salt thereof is supplied to an electrolytic cell having a cathode and an anode separated by a diaphragm, and the total concentration of gallic acid ions or gallic acid in the electrolytic solution is measured. The range is 1 × 10 ⁻⁴ to 1 × 10 ⁻² M, and 2 × per unit area of the electrode per 1 liter of the electrolyte.
A method for producing electrolyzed water, comprising applying a direct current having a current density of 10 ^-3 to 1 × 10 ^-1 A / cm ^{2 at} a flux of 500 to 4000 ml / min. 2. The production of electrolyzed water according to claim 1, wherein said electrolytic solution further contains inositol or a phosphate compound thereof in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M. Method. 3. The electrolytic solution according to claim 1, wherein the electrolytic solution further contains L-ascorbic acid or a salt thereof in a total range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M. Method for producing electrolyzed water. 4. An electrolytic solution containing gallic acid or a salt thereof is supplied to an electrolytic cell having a cathode and an anode separated by a diaphragm, and the total concentration of gallic acid ions or gallic acid in the electrolytic solution is measured. The range is 1 × 10 ⁻⁴ to 1 × 10 ⁻² M, and 2 × per unit area of the electrode per 1 liter of the electrolyte.
Cathode-side electrolyzed water obtained by applying a direct current having a current density of 10 ⁻³ to 1 × 10 ⁻¹ A / cm ^{2 at} a flux of 500 to 4000 ml / min. 5. The cathode-side electrolytic production according to claim 4, wherein the electrolytic solution further contains inositol or a phosphate compound thereof in a range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M. water. 6. The electrolytic solution according to claim 4, wherein the electrolytic solution further contains L-ascorbic acid or a salt thereof in a total range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² M. Cathode side electrolysis water. 7. The superoxide anion scavenging ability of E
The cathode-side electrolyzed water according to any one of claims 4 to 6, wherein in the SR measurement, a relative signal intensity with respect to a manganese marker is 50 to 100% of a difference from pure water. 8. The cathode-side electrolyzed water according to claim 4, wherein the amount of dissolved oxygen is 6.5 to 0.11 mg / liter. 9. The cathode-side electrolyzed water according to claim 4, wherein the hydrogen ion concentration is 4.0 to 10.0. 10. The gallic acid or a salt thereof is added to 1 × 10 ^−4.
An electrolytic assistant characterized in that at least one compound selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride is 1 × 10 ⁻⁴ to 1 × 10 ⁻² M with respect to M. 11. The gallic acid or a salt thereof containing 1 × 10 ⁻⁴ M of inositol or a phosphate compound thereof.
The inositol or phosphate compound thereof is 1
Electrolysis aid according to claim 10, wherein it is a ^{× 10 -4 ~1 × 10 -2 M} . 12. The composition further comprises L-ascorbic acid or a salt thereof, wherein the L-ascorbic acid or a salt thereof is 1 × 10 ⁻⁴ M relative to the gallic acid or a salt thereof 1 × 10 ⁻⁴ M.
Electrolysis aid according to claim 10 or 11, wherein the a to 1 × 10 ^-2 M. 13. A means for supplying gallic acid or a salt thereof to an electrolytic cell having a cathode and an anode separated by a diaphragm, and the total concentration of gallic acid ions or gallic acid in the electrolytic solution on the cathode side being 1 × 10 ^-4 to 1 × 10 ^-2 means a range of M, and with respect to the electrolyte solution one liter DC ^{2 × 10 -3 ~1 × 10 -1} a / cm 2 current density per unit area of the electrode Means for applying an electric current at a flux of 500 to 4000 ml / min.