JPH09201585A - Electrolyzed water, method for increasing its sterilizing power, and bactericide - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide electrolyzed water having excellent bactericidal power and capable of sustaining the bactericidal power for a long time, a method for increasing the bactericidal power, and a bactericide containing the electrolyzed water as a main component. To do. SOLUTION: In electrolyzed water obtained by electrolysis of an aqueous solution of a chlorine compound such as NaCl, by containing or adding iodine or its compound and / or fluorine or its compound in at least one stage before and during the electrolysis. An electrolyzed water characterized by being obtained, a method for increasing the sterilizing power of the electrolyzed water, and a bactericide containing the electrolyzed water as a main component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to electrolyzed water (particularly, functional water for sterilization useful as a sterilizing / disinfecting agent), a method for increasing its sterilizing power, and a sterilizing agent.

[0002]

2. Description of the Related Art Conventionally, functional water for sterilization containing hypochlorous acid (HClO) ions obtained by electrolyzing a saline solution has been used, for example, in hygiene management in hospitals (hospital rooms, operating rooms, examination rooms, washrooms). , Environmental disinfection of kitchens, disinfection of equipment and fingers), hygiene management in restaurants and restaurants, powdery mildew,
It is considered to be useful as a sterilizing and disinfecting agent against fungal disease-causing bacteria such as downy mildew and is already on the market.

[0003] Such functional water for sterilization also has 1) lower cost than conventional disinfectants, 2) less rough hands than conventional disinfectants, and 3) persistence compared to conventional disinfectants. However, in the future, it may be used not only as an external disinfectant but also as an internal drug because it is effective against Helicobacter pylori causing gastric ulcer.

Referring to FIG. 1, a method of producing functional water for sterilization by electrolysis of saline, for example, will be described. The inside of the electrolytic cell 1 is divided by a diaphragm 2 into regions on the anode side and the cathode side.
By introducing saline solution (water / NaCl) 3a, 3b into each region and applying a voltage V, an electrolytic reaction is caused in the vicinity of the anode 4 and the cathode 5. As a result, by electrolysis of saline solution, chlorine obtained at the anode is dissolved in water to produce hypochlorous acid (HClO), and strong acidic electrolyzed acidic water 6 mainly composed of this is produced as functional water for sterilization. To do. On the other hand, alkaline water 7 is produced from the cathode side.

Since the HClO generated on the anode side has a sterilizing power larger than that of sodium hypochlorite (NaClO), it is used in a wide range of applications as the above-mentioned various sterilizing agents. However, this electrolyzed acidic water containing HClO has an excellent bactericidal action against sterilization, viruses and fungi, and is safe.

As described above, when the electrolyzed acidic water is produced by electrolysis, when chlorine obtained by electrolyzing the saline solution is dissolved in water, a part of the chlorine is dissolved as shown in the following formula (1). It is hydrolyzed to HOCl, and the equilibrium as in the formula (1) is maintained. HOCl is a weak acid and dissociates as shown in the following formula (2).

[0007]

Embedded image

These equilibrium relationships are determined by the pH and temperature of water, and chlorine in water takes three forms: molecular chlorine Cl ₂ , hypochlorite HOCl, and hypochlorite ion OCl ⁻ . All of these are called free chlorine. These equilibrium relationships are as shown in FIG. FIG. 2 shows pH value-chlorine concentration characteristics by the colorimetric method of electrolyzed acidic water.

Recently, soft-oxidized water obtained by adjusting the pH of electrolyzed acidic water to 5.0 to 5.5 has been announced, and it is known that the sterilizing power is enhanced, but the range of enhancement is at most 2.
~ 3 times. Also, if electrolytic acidic water is left at room temperature,
Its free chlorine concentration drops rapidly. Even under storage in a cool and dark place, the concentration of free chlorine gradually decreases and the bactericidal power is lost.

Furthermore, "Pharmacological and Clinical" Vol. 3, No. 9,
Page 72, item 4 and page 75, right column, lines 3 to 6 describe that the addition of potassium iodide to electrolytic acidic water as described above has little effect on bactericidal activity.

[0011]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide electrolyzed water having excellent sterilizing power and capable of sustaining the sterilizing power for a long period of time, a method for increasing the sterilizing power, and the main component of the electrolyzed water. The purpose is to provide the respective bactericides.

[0012]

[Means for Solving the Problems] That is, according to the present invention, by containing or adding at least one of iodine or its compound and fluorine or its compound at least one stage before and during the electrolysis of a chlorine compound. The present invention relates to the electrolyzed water obtained and a bactericide containing the electrolyzed water as a main component.

The present invention also uses electrolyzed water obtained by containing or adding at least one of iodine or a compound thereof and fluorine or a compound thereof at least one stage before and during electrolysis of a chlorine compound. It also provides a method of increasing the sterilizing power.

In the present invention, "electrolyzed water" includes not only the strongly acidic electrolyzed water described above but also weakly alkaline water, and usually has a pH in the range of 2 to 10 (hereinafter the same). .

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Before or during the electrolytic production of the electrolyzed water and bactericide of the present invention, the above iodine or its compound, fluorine or its compound is iodine and / or fluorine such as Na, K or the like. It may be contained or added in the form of a compound with an alkali metal or an alkaline earth metal such as Ca or Mg, or a simple substance such as I ₂ .

Further, the content or addition amount of the above iodine or its compound or fluorine or its compound is 0.
01 to 1 mol / l, further 0.05 to 0.5 mol / l (when iodine or its compound and fluorine or its compound are used in combination, 0.01 to 1 mol / l in total, more preferably 0.05 to 0.5 mol / l
l) is desirable. If this content or addition amount is too small, the bactericidal activity of the electrolyzed water as a bactericide becomes weak.

Also, at least one of the above iodine or its compound and fluorine or its compound is added at least at one stage before or during the electrolysis of the chlorine compound.

In the method for enhancing the sterilizing power of the electrolyzed water of the present invention, the iodine or the compound thereof, the fluorine or the compound thereof is the alkali metal such as iodine and / or fluorine such as Na or K or the alkali such as Ca or Mg. It is preferable to contain or add it in the form of a compound with an earth metal or a simple substance such as I ₂ .

For the same reason as above, the content or addition amount of iodine or its compound, fluorine or its compound is 0.01 to 1 mol / l, more preferably 0.05 to 0.5 mol / l (iodine or its compound). When fluorine and its compound are used in combination, the total amount is 0.01 to 1 mol / l, and further 0.
It is desirable to set it to 05 to 0.5 mol / l).

At least one of the above iodine or its compound and fluorine or its compound is contained or added in at least one stage before and during the electrolysis of the chlorine compound.

In the electrolyzed water of the present invention, the method for increasing its sterilizing power and the sterilizing agent, for example, salt water is electrolyzed to obtain electrolyzed water as functional water for sterilization on the anode side. Using the electrolytic cell as shown, at least one of iodine or its compound and fluorine or its compound may be added to the salt solution on the anode side for electrolysis. Also, NaC
It is desirable to obtain electrolyzed water containing chlorine, for example, hypochlorous acid or hypochlorite ion, by electrolyzing a chlorine compound such as l.

[0022]

The present invention will be described in more detail with reference to the following examples.

Example 1 Based on the present invention, saline was contained in the electrolytic cell shown in FIG. 1 and electrolysis was carried out at a current density of 1.58 A / dm ² using a constant current circuit of 2.4 A.

By adding an iodine compound or a fluorine compound before or during the electrolysis, the bactericidal activity is enhanced. To show this, for example, 6.4 × 10 ⁷ Staphylococcus aureus (100 μl) was added to 1.5 ml of electrolyzed water obtained by adding potassium iodide and electrolyzing for 10 minutes before electrolysis and from the start of electrolysis. Add after addition of 1.5 ml of electrolyzed water obtained by adding potassium iodide after 5 minutes and in addition to 1.5 ml of electrolyzed water with addition of potassium iodide after 10 minutes of electrolysis When the number of viable bacteria after 5 minutes has passed (hereinafter, the same),
The results are shown in Tables 1A, 1B and 1C below. The number of viable bacteria was 35 on Brain Heart Infusion Agar
The culture was performed at 24 ° C. for 24 hours, and the number of colonies was counted to obtain the same (hereinafter, the same).

According to this, when the potassium iodide according to the present invention is added before electrolysis, the bactericidal activity is 5 to 10 times stronger than when it is added after electrolysis, and it is added during electrolysis. In this case, it can be seen that the bactericidal power is two times or more stronger than that in the case of adding after electrolysis.

Table 1A ─────────────────────────────────── KI addition conditions NaCl Electrolyzed water Dilution ratio CFU / ml pH of maximum effective concentration (viable cell count) Dilution ratio ─────────────────────────────────── Before electrolysis Addition 0.05% 9.78 10-fold dilution <100 (20-fold dilution after addition <100 20-fold dilution 10 minutes electrolysis) 40-fold dilution 4.00 × 10 ⁴ ──────────────────── ────────── 0.10% 9.53 10-fold diluted <100 20-fold diluted <100 20-fold diluted 40-fold diluted 4.10 × 10 ⁴ ────────────────── ──────────── 0.20% 9.92 10-fold dilution <100 20-fold dilution <100 20-fold dilution 40-fold dilution 7.60 × 10 ⁴ ──────────────── ────────────────────

Table 1B ─────────────────────────────────── KI addition conditions NaCl Electrolyzed water Dilution ratio CFU / ml Maximum effective concentration pH (viable cell count) Dilution factor ─────────────────────────────────── Electrolysis Add 0.05% 3.32 10-fold dilution <100 (Start electrolysis or dilute 20-fold 7.90 x 10 ³ 5 minutes after 10-fold dilution Add 40-fold dilution 6.60 x 10 ⁵ and combine ──────────── ─────────────────── Total 10 minutes electrolysis) 0.10% 2.66 10-fold dilution <100 20-fold dilution 2.40 × 10 ³ 10-fold dilution 40-fold dilution 5.40 × 10 ⁵ ─ ──────────────────────────── 0.20% 2.68 10-fold dilution <100 20-fold dilution 2.00 × 10 ² 10-fold dilution 40-fold dilution 3.25 × 10 ⁵ ───────────────────────────────────

Table 1C ─────────────────────────────────── KI addition conditions NaCl Electrolyzed water Dilution ratio CFU / ml Maximum effective concentration pH (viable cell count) Dilution factor ─────────────────────────────────── After electrolysis Addition 0.05% 2.89 1-fold dilution <100 (10-minute electrolysis is 2-fold diluted <100 Add after 2 times dilution) 4-fold dilution 2.47 × 10 ⁴ ────────────────── ──────────── 0.10% 2.28 2-fold dilution <100 4-fold dilution <100 4-fold dilution 8-fold dilution 2.15 × 10 ⁴ ─────────────── ────────────── 0.20% 2.28 2-fold dilution <100 4-fold dilution <100 4-fold dilution 8-fold dilution 6.00 × 10 ² ───────────── ──────────────────────

As is clear from this result, the sterilizing power of electrolyzed water can be remarkably enhanced by adding KI which is an iodine compound before or during electrolysis according to the present invention.

Example 2 Since the concentration of free chlorine in electrolyzed water gradually decreases with time, the sterilizing power gradually decreases accordingly. Even in such a case, it was found that the electrolyzed water according to the present invention can maintain the bactericidal activity by adding an iodine compound or a fluorine compound before or during electrolysis. That is, electrolyzed acidic water obtained by electrolyzing 0.1% saline solution in the same manner as in Example 1 without adding an iodine compound or a fluorine compound was 4-fold diluted, and stored for 3 days after electrolysis to obtain bactericidal activity. Of 2.1 × 10 ⁸ Staphylococcus aureus, and a solution electrolyzed in the same manner as in Example 1 after adding potassium iodide or sodium fluoride was diluted 20 times, and 3
The viable cell counts were determined for the case of allowing it to act on S. aureus after being stored for a day.
It was as follows.

Table 2 ─────────────────────────────────── Sample viable cell count ────── ───────────────────────────── Control 2.1 × 10 ⁸ pieces ─────────────── ──────────────────── KI or NaF-free (electrolytic acid water) 5.2 × 10 ⁷ pieces ─────────────── ──────────────────── 0 electrolyzed water obtained by adding KI (0.1 mol / l) before electrolysis ────────── ────────────────────────── 0 electrolyzed water obtained by adding NaF (0.1 mol / l) before electrolysis ─── ──────────────────────────────── KI (0.1 mol / l) solution 1.8 × 10 ⁸ pieces ───── ───────────────────────────── NaF (0.1 mol / l) solution 1.9 × 10 ⁸ pieces ──────── ────────────────────────────

As described above, it is apparent that the electrolyzed water according to the present invention can be completely sterilized even when the electrolyzed acidic water alone or the KI solution or the NaF solution alone can hardly be sterilized.

Further, it has been found that the electrolytic water according to the present invention, when stored, retains the bactericidal activity for a much longer period as described below as compared with the case where KI or NaF is not added.

Table 3 below shows that for each elapsed time, electrolyzed acidic water as above and electrolyzed water obtained by adding KI (O.1 mol / l) before electrolysis acted on Staphylococcus aureus, It is the result of testing for the presence of subsequent bacteria.

Table 3 ──────────────────────────────────── Elapsed time Electrolyzed acidic water KI before electrolysis Electrolyzed water obtained by adding (0.1 mol / l) ──────────────────────────────────── ─ 0.5 hours − − 1 hour − − 2 hours ± − 8 hours +++ − 1 week +++ − ────────────────────────────── ─────── (-) Bacteria are not found (±) Bacteria are found a little (+++) Many bacteria are found

From these results, it can be seen that the electrolyzed acidic water loses its sterilizing power after 2 hours.
It can be seen that the electrolyzed water obtained by adding (0.1 mol / l) maintains the bactericidal activity even after 1 week.

Example 3 9.9 × 10 ⁷ Staphylococcus aureus (100 μl) was added to 1.5 ml of electrolyzed acidic water having the same bactericidal power as in Example 2, and 0.1 mol / l of sodium iodide was added. Table 4 below shows the respective viable cell counts obtained in the same manner as in Example 2 with and without addition of electrolyzed water obtained by electrolysis after being stored in the same manner as in Example 2. .

Table 4 ─────────────────────────────────── Sample viable cell count ────── ───────────────────────────── Control 9.9 × 10 ⁷ pieces ─────────────── ──────────────────── NaI-free (electrolytic acid water) 1.4 × 10 ⁷ pieces ───────────────── ────────────────── 0 electrolyzed water obtained by adding NaI (0.1 mol / l) before electrolysis ──────────── ──────────────────────── NaI (0.1mol / l) solution 1.0 × 10 ⁸ pieces ───────────── ──────────────────────

As described above, almost no sterilization was performed with only the electrolyzed acidic water or the NaI solution, but the electrolyzed water according to the present invention could be completely sterilized.

Example 4 1.0 × 10 ⁸ Staphylococcus aureus (100 μl) was added to the same electrolyzed acidic water with reduced bactericidal activity as in Example 2, and 0.1
Regarding the case where electrolyzed water obtained by electrolyzing after adding mol / l of potassium fluoride was added to the one stored in the same manner as in Example 2, the viable cell counts obtained in the same manner as in Example 2 are The results are shown in Table 5 below.

Table 5 ─────────────────────────────────── Sample viable count ────── ───────────────────────────── Control 1.0 × 10 ⁸ pieces ─────────────── ──────────────────── KF-free (electrolytic acid water) 1.3 × 10 ⁷ ───────────────── ────────────────── 0 electrolyzed water obtained by adding KF (0.1 mol / l) before electrolysis ──────────── ──────────────────────── KF (0.1mol / l) solution 1.6 × 10 ⁷ ───────────── ──────────────────────

As described above, almost no sterilization was possible with only the electrolyzed acidic water or the KF solution, but the electrolyzed water according to the present invention could be completely sterilized.

Example 5 1.2 × 10 ⁸ Staphylococcus aureus (100 μl) was added to 1.5 ml of electrolyzed acidic water whose sterilizing power was the same as in Example 2, and 0.1 mol / l of calcium iodide was added. After that, electrolysis water obtained by electrolysis was added to the one stored in the same manner as in Example 2, and the viable cell counts obtained in the same manner as in Example 2 were as shown in Table 6 below. .

Table 6 ─────────────────────────────────── Sample viable cell count ────── ───────────────────────────── Control 1.2 × 10 ⁸ pieces ─────────────── ──────────────────── CaI ₂ no addition (electrolytic acid water) 1.5 × 10 ⁷ pieces ──────────────── ─────────────────── 0 electrolyzed water obtained by adding CaI ₂ (0.1 mol / l) before electrolysis ───────── ────────────────────────── CaI ₂ (0.1 mol / l) liquid 2.1 × 10 ⁸ pieces ─────────── ─────────────────────────

As described above, almost no sterilization was possible with only the electrolyzed acidic water or the CaI ₂ solution, but the electrolyzed water according to the present invention could be completely sterilized.

Example 6 A staphylococcus aureus obtained by electrolyzing after adding KI to a commercially available iodine-containing bactericide (iodine tincture, iodoglycerin) or according to the present invention according to the production method of Example 1
When a sample obtained by diluting the electrolyzed water described in 1 above with each concentration was made to act and a comparative test of sterilization performance was performed, the results shown in Table 6 below were obtained. The effective iodine concentration was quantified as follows. Quantitative method: Accurately measure 5 ml of the sample solution, and add potassium iodide 0.5.
g, 20 ml of water and 1 ml of dilute hydrochloric acid, and titrate with 0.1N sodium thiosulfate solution (indicator: starch test solution 2 ml).

Table 7 ─────────────────────────────────── Sample effective iodine concentration Viable cell count ─── ──────────────────────────────── Control 0 1.80 × 10 ⁸ pieces ──────────── ──────────────────────── Electrolyzed water after KI addition 1.5 μg / ml 1.52 × 10 ⁸ pieces ───────────── ─────────────────────── Electrolyzed water after addition of KI 2.5 μg / ml 1.30 × 10 ⁸ pieces ────────────── ────────────────────── Electrolyzed water after KI addition 5.0 μg / ml 4.70 × 10 ⁷ ────────────── ───────────────────── after KI added electrolyzed water 7.0μg / ml 1.30 × 10 ⁷ cells ────────────── ──────────────────── KI addition electrolyzed water 10.0 μg / ml 0 piece ──────────────────── ──────────────── Iodine tincture 10.0 μg / ml 4.72 × 10 ⁷ ──────────────────────── ─────────── Iodoglycerin 10.0 μg / ml 4.80 × 10 ⁷ ───────────────────────────── ───────

From these results, electrolyzed water obtained by electrolyzing after adding KI according to the present invention is about 2 per unit of effective iodine concentration than iodine tincture or iodoglycerin.
It had a bactericidal power more than double. Therefore, the electrolyzed water after the addition of KI is effective even if the effective iodine concentration is used at a concentration lower than that of the commercially available product.

Although the present invention has been described with reference to the embodiments, the above-described embodiments can be variously modified based on the technical idea of the present invention.

For example, in addition to the above-mentioned iodine compound and fluorine compound individually added to the above-mentioned electrolyzed water, both can be added (combined) at the same time. Also, iodine or fluorine may be added in the form of a compound or simple substance with an alkali metal or alkaline earth metal other than those mentioned above.

The chlorine compound may be added before or during the electrolysis of the chlorine compound, or at least one of these stages. Addition before or during electrolysis is
It may be carried out in the electrolytic cell shown in FIG.

The electrolyzed water according to the present invention can be produced by electrolysis of water-soluble chlorides such as potassium chloride aqueous solution and ammonium chloride aqueous solution, in addition to the above-mentioned saline solution.

[0053]

The function of the electrolyzed water of the present invention is as follows.
Since it is obtained by electrolysis of an aqueous solution of a chlorine compound containing or added at least one of iodine or its compound and fluorine or its compound before and / or during electrolysis, the sterilizing power of electrolyzed water can be enhanced. At the same time, the effective period of the sterilizing power can be extended.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an electrolyzed water producing apparatus.

FIG. 2 is a pH value-chlorine concentration characteristic diagram by the colorimetric method of the same electrolyzed water.

[Explanation of symbols]

 1 ... Electrolyte tank 2 ... Diaphragm 3a, 3b ... Saline solution 4 ... Anode 5 ... Cathode 6 ... Electrolyzed water (functional water for sterilization)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A61K 33/16 ADZ A61K 33/16 ADZ 33/18 33/18 33/20 ADB 33/20 ADB A61L 2/02 A61L 2/02 Z C02F 1/50 531 C02F 1/50 531L 531K 550 550D 560 560F 1/76 1/76 A

Claims (8)

[Claims] 1. Electrolyzed water obtained by containing or adding at least one of iodine or its compound and fluorine or its compound in at least one stage before and during electrolysis of a chlorine compound. 2. The electrolyzed water according to claim 1, wherein at least one of iodine or a compound thereof and fluorine or a compound thereof is contained or added in the form of a compound with an alkali metal or an alkaline earth metal or as a simple substance. . 3. The content or addition amount of iodine or its compound or fluorine or its compound is 0.01 to 1 mol / l (when iodine or its compound and fluorine or its compound are used in combination, the total is 0.01 to 1 mol / l). 1 mol / l),
The electrolyzed water according to claim 1 or 2. 4. The method according to claim 1, which is used as a bactericide.
The electrolyzed water described in any one of 1. 5. The sterilizing power of electrolyzed water obtained by containing or adding at least one of iodine or its compound and fluorine or its compound at least one stage before and during electrolysis of a chlorine compound. Method. 6. The method according to claim 5, wherein at least one of iodine or a compound thereof and fluorine or a compound thereof is contained or added in the form of a compound with an alkali metal or an alkaline earth metal or a simple substance. 7. A bactericide comprising electrolyzed water obtained by containing or adding at least one of iodine or its compound and fluorine or its compound in at least one stage before and during electrolysis of a chlorine compound. 8. The bactericide according to claim 7, wherein at least one of iodine or a compound thereof and fluorine or a compound thereof is contained or added in the form of a compound with an alkali metal or an alkaline earth metal or as a simple substance. .