JP2002052074A - Sterilizing and washing spray product and method of manufacturing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sterilizing and washing spray product usable in any places at any times and storable for a long period of time, without its sterilizing properties being reduced even if electrolyzed sterilizing water generated by a sterilizing water generating device is stored for a long period of time. SOLUTION: An aqueous solution, with sodium bromide and sodium chloride dissolved therein so that the solution contains bromine ion and chlorine ion in a certain ratio in the form of halogen ions, is electrolyzed so that electrolyzed water generated by a membrane-less electrolyzer has a pH of 6 to 8. The electrolyzed water is packed in a sealed container, as an inert gas such as helium or nitrogen is pressurized and the container is shielded from light, to provide the spray product. A method of manufacturing the product is also described.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spray product for electrolytic disinfection and washing water, wherein the disinfecting power does not decrease even during long-term storage, and a method for producing the spray product. Further, the present invention also provides a process for producing water containing hypohalous acid obtained by electrolyzing water containing bromide ions as halogen ions, in a closed container under pressure of an inert gas while shielding light and air. The present invention relates to a germicidal cleaning spray product which is filled into a product. More specifically, the present invention relates to a method for preparing a pH 6 containing hypohalous acid obtained by electrolyzing water containing a halogen ion.
The present invention relates to a method for producing a sterilized cleaning spray product by filling an electrolytically produced water of No. 8 with light into air and filling it in a closed container under pressurization of an inert gas.

[0002]

2. Description of the Related Art Conventionally, medical solutions such as an aqueous solution of ethyl alcohol, benzalkonium chloride, chlorhexidine hydrochloride, chlorhexidine gluconate, and the like have been used for disinfection and sterilization of treatment, nursing, kitchen, cooking utensils, and the like. Various adverse effects such as water pollution and hospital infection have occurred. In order to prevent this adverse effect, attention has recently been paid to a technique using electrolytic acidic water as a method for removing bacteria using functional water that does not use the chemical solution. That is, it is well known that when water is electrolyzed, oxygen is generated from the anode and hydrogen is generated from the cathode.However, when a small amount of electrolyte such as salt is added using an ion exchange membrane to perform electrolysis, Highly active oxygen and chlorine are generated from the anode compartment during the development period to produce electrolytic acid water with a high hydrogen ion concentration (low pH), while hydrogen is generated from the cathode compartment and a low hydrogen ion concentration (high p
It is also known to produce H) electrolytically reduced water. At this time, the electrolyzed acidic water obtained from the anode side has a pH of 2.7 or less, an oxidation-reduction potential of 1,100 mV or more, available chlorine of 30 to 40 ppm, and dissolved oxygen of 20 ppm or more, and has an effect of eliminating bacteria in a short time. It is said to be safe for people and the environment. However, unlike the conventional disinfecting and disinfecting agents using a chemical such as ethyl alcohol and benzalkonium chloride, such electrolytically generated water has no advantage in having a persistent chemical or the like, and has the advantage of returning to ordinary water upon contact with organic substances. However, since the water generated from the anode chamber of the electrolytic device using the diaphragm is highly acidic, having a pH of 2.7 or less, there is a problem that the skin is roughened and the equipment is corroded.

[0003] In view of the above situation, the present inventors have developed bromine ions obtained by using an electrolysis apparatus without using an ion exchange membrane, other halogen ions,
For example, it has been found that an aqueous solution containing chlorine ions is electrolyzed to produce sterile water having a weak acidity or neutrality and a high sterilizing effect, and a method and an apparatus have already been applied for a patent (Japanese Patent Application Laid-Open No. 11-226092). Gazette, JP-A-11-347557). The electrolyzed water obtained in these prior arts of the present inventors has excellent bactericidal activity even at pH 6 to 8, shows a high bactericidal effect in a short contact treatment time, and is characterized by no rough skin and corrosion of instruments. Is what you do. That is, the electrolytically produced water in which bromine ions and other halogen ions obtained by the above prior art are adjusted to a fixed ratio is pH
When it is 6 or more, it has excellent germicidal power, exhibits excellent germicidal power even in a short time, and exhibits an excellent germicidal effect of preventing rough skin and corrosion of instruments. However, the electrolytically produced water produced by the apparatus has a problem that the concentration of hypohalous acid gradually decreases in accordance with the elapsed time after the production and the sterilizing power is reduced.

[0004]

The germicidal washing water obtained by the above-mentioned electrolysis apparatus of the present inventors cannot exert the expected germicidal effect at all after use for a long period of storage, so that the germicidal washing water is unavoidably sterilized near the water tap. A water generator had to be provided. Therefore, in order to sufficiently exhibit the sterilizing effect, it was necessary to use the generated electrolytic sterilizing water immediately. Therefore,
In the germicidal washing water obtained by the prior art, the installation place of the apparatus for producing the germicidal water is limited, and it cannot be easily moved anytime and anywhere, and there is a big problem that it lacks convenience. . It is an object of the present invention to improve the storage means of electrolyzed water obtained by the apparatus, and to maintain the sterilizing and cleaning effect of the electrolyzed water without providing the electrolyzing apparatus in a water tap. Things. In the present invention, the electrolytically produced water for sterilization and washing obtained by the above-described apparatus, after a lapse of time after production, the sterilization power is reduced,
By filling the container with an improved storage method, the electrolyzed water having excellent sterilizing power can be used whenever necessary.

[0005]

SUMMARY OF THE INVENTION According to the present invention, an effective storage means for electrolytically produced water for sterilization and cleaning can be used at any time, regardless of the setting place, and at any time, and the sterilizing power can be maintained for a long time. Sterilizing cleaning water to be exerted can always be supplied. The effective storage means of the electrolyzed water of the present invention is to be filled and stored in a storage container shielding air and light,
Since the sterilizing power of the electrolyzed water does not decrease the long-term preservability, the convenience of use is high only by moving the storage container, and it is possible to provide sterilizing water that exhibits the expected sterilizing and cleaning effect anytime and anywhere. Has advantages. That is, in the present invention, electrolytically generated water having a pH of 6 to 8 containing hypohalous acid obtained by electrolyzing water to which a halide salt composed of a bromine compound and another halogen compound has been added is converted into light and A sterilizer that shields air and stores it in a closed container using an inert gas.It completely shields light and air to reduce the decomposition of hypohalous acid, thereby achieving a long-term sterilization effect. Wash water can be provided.

The present invention is based on the following configuration. (1) Electrolyzed water containing a hypohalous acid obtained by electrolysis of water containing a halogen ion and electrolyzed water having a pH of 6 to 8 is supplied to a spray container while shielding light and air and pressurizing an inert gas. A sterilized cleaning spray product that is filled. (2) The above (1) using bromine ions alone or water containing bromine ions and chlorine ions as halogen ions.
Sterilization cleaning spray products. (3) Electrolysis of an aqueous solution of sodium bromide alone or sodium bromide and sodium chloride in a fixed ratio using an electrolytic device using a ferrite electrode for the anode and a titanium or stainless steel electrode for the cathode without using a diaphragm. The sterilized cleaning spray product according to the above (1) or (2), wherein the generated water is adjusted to a pH of 6 to 8 and the electrolyzed water obtained is used. (4) pH6 containing hypohalous acid obtained by electrolysis of water containing at least odorous ions in an electrolytic apparatus using a ferrite electrode for the anode and a titanium or stainless steel electrode for the cathode without using a diaphragm. A method for producing a sterilizing cleaning spray product by filling a spray container with the electrogenerated water of No. 8 under light shielding and pressurizing with an inert gas.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, it is a basic condition that light and air are shielded when storing electrolyzed water. That is, the electrolyzed water is stored in a closed container, shielding light and air, and sprayed to the outside at any time, so that the time-dependent change of the original sterilizing active ingredient of the electrolyzed water is suppressed and the sterilizing power is reduced. For a long time. In the present invention, the closed container used for shielding light is effectively an aerosol container using an inert gas, for example, a double spray container such as a bag-in-can. As such a container, an aluminum can, an inner plastic coat can, or a synthetic resin bottle whose light shielding property is enhanced by vapor deposition or coloring can be used. Also, to shield air,
Inert gas such as nitrogen or helium is injected to replace air, but helium is suitable as the inert gas, and the pressure of the gas is 0.6 to 1.0 MPa, preferably about 0.8 MPa.

The electrolytically produced water used for the sterilization and washing in the present invention is the one obtained by the apparatus described in the above-mentioned JP-A-11-188364. This electrolytically produced water is prepared by dissolving sodium bromide and sodium chloride in a fixed ratio of bromide ion and chloride ion as halogen ions, without using a diaphragm, using a ferrite electrode for the anode and a titanium electrode for the cathode. Alternatively, it is produced by electrolysis in an electrolysis apparatus using a stainless steel electrode, and then adjusting the generated electrolysis water to have a pH of 6 to 8. The electrolyzed water used in the present invention has almost no chlorine at a pH of 6 to 8 and contains about 90 to 40% of hypochlorous acid. It has no chlorine odor. Compared to generated water,
Although the reduction of residual chlorine concentration and the reduction of sterilizing power are slow,
When water containing bromine ions is electrolyzed, it has higher oxidizing and sterilizing power than chlorine and the like. In the present invention, it is appropriate to fill a closed container with electrolytically produced water obtained by electrolyzing a mixed aqueous solution of chlorine ions and bromine ions under a pressure of an inert gas such as nitrogen or helium.

The present invention will be described in detail with reference to the drawings. FIG. 1 shows an outline of an apparatus for producing electrolytic sterilization water for carrying out the present invention, and FIG. 2 shows an example of a bag-in-can double container suitable for storing and using the electrolytically produced water of the present invention. In the process diagram of the present invention shown in FIG.
, A mixed solution of sodium bromide and sodium chloride in a weight ratio of 1: 9 is put in advance, and this is supplied to the electrolysis apparatus 1 via a metering pump. A fixed amount of this aqueous electrolyte solution is added by the metering pump P2, electrolysis is performed in the electrolysis apparatus 1, and the generated electrolyzed water is once stored in the electrolysis sterilized water storage tank 13. The residual chlorine concentration of the stored liquid is about 20 ppm, pH
Is confirmed to be about 7, and is sent to the sterilizing / cleaning spray product filling device via the liquid sending pipe 11 by the pump P1. In FIG. 1, the electrolytic sterilizing water sent from the electrolytic apparatus 1 to the electrolytic sterilizing water storage tank 13 and stored therein is automatically valved.
Until the residual chlorine concentration reaches the set value by the action of V1 and the pump P1, circulation is performed between the electrolytic device 1 and the electrolytic sterilizing water storage tank 13, during which the supply of clean water is stopped to continue the electrolytic treatment. The electrolytically produced water produced by the production apparatus shown in FIG.
It is sent to the sterilization washing spray product filling device by the liquid sending pipe,
Fill a 200cc aerosol container equipped with an aerosol valve under a pressurized inert gas such as nitrogen or helium. At this time, about 0.8 helium was used as an inert gas.
It was used at a pressure of MPa (25 ° C.).

FIG. 2 shows a double aerosol type spray container which contains the electrolytic purified water of the present invention and is suitable for its use. An expandable bag 22 is accommodated in a pressure-resistant container 21. . The housing of the valve 24 mounted on the top of the pressure vessel 21 and the outlet of the bag 22 are heat-sealed, so that the bag 22 hangs inside the pressure-resistant container 21 from the valve 24 on the top. It is suspended. Pressure vessel 2
The upper part of 1 has a cylindrical shape so as to be a passage when the sterilizing and cleaning liquid 23 of the present invention filled in the bag body 22 is ejected to the outside. As the electrolysis solution, a solution having a pH of 6 to 8, which has a higher oxidizing and bactericidal activity than chlorine or the like, and has a high ratio of hypohalous acid, which is difficult to volatilize like chlorine, is used. Inert gas such as nitrogen and helium is 0.8
Fill to a pressure of about MPa (25 ° C). In using the spray container, the bag 22 is compressed and deformed by the pressure of the inert pressurized gas 25 when the valve 24 is opened, so that the sterilizing cleaning liquid 23 in the bag 22 passes through the top of the container. It is injected from the valve 24 to the outside.

[0011]

Example 1 The maintainability of the sterilizing power of the electrolyzed purified water of the present invention was tested. The purification equipment used is a PET or aluminum can that is sterilized water that has no bactericidal effect after standing for 10 minutes after purification using a flow-through disinfecting water purifier (Omega Co., BK-HT Ver.4). Was filled in an aerosol container, and a test for maintaining the sterilizing power was conducted. As a test sample for filling the container,
The following (1) to (5) were used. (1) Physiological saline (2) Sterilized water 1 (PET container) (3) Sterilized water 2 (PET container) (4) Sterilized water 3 (Epoxyphenol-based inner coated aluminum container) (5) Sterilized water 4 (Epoxyphenol) In the test method, E. coli IFO 3301 (
(Escherichia coli) subcultured once a month on a normal agar medium was used. In addition, as a preparation of a bacterial solution for inoculation, one loop of E. coli was inoculated into 7 ml of a normal medium, and cultured with shaking at 37 ° C. for 18 hours. After shaking, the suspension was diluted 1/1000 with physiological saline. It was used as a bacterial solution for inoculation. The effects of the test drug solution on the bacteria during the culture were examined as follows. 5 ml of physiological saline was inoculated with 0.05 ml of the inoculum for inoculation, and the 1/100 dilution of the inoculated bacterial liquid was separated into 0.5 ml aliquots, and 5 ml of the test drug solution was further diluted 1/100 with 0.5 ml. Two plates each prepared in a petri dish were prepared. To that petri dish
25 ml of SCDLP agar medium was poured, mixed, and cultured at 37 ° C. for 24 hours. This value was defined as the viable count after 0 seconds. Further, the time-dependent change after inoculation of the bacterial solution into the test solution was examined as follows. 0.05 ml of the bacterial solution for inoculation was inoculated into 5 ml (two each) of the test drug solution and shaken. 0.05 after 5, 10, 30 seconds
The resulting mixture was diluted with 4.95 ml of physiological saline, placed in two Petri dishes of 0.5 ml each, mixed with 25 ml of SCDLP agar medium, and cultured at 37 ° C. for 24 hours. Table 1 shows the time-dependent changes after inoculation into the test solution of E. coli.

[0012]

[Table 1] (Unit: pcs / ml) ────────────────────────────────── Sample No. 0 After 5 seconds After 10 seconds After 30 seconds ────────────────────────────────── (1) Physiological saline Water 4.46 × 10 ⁴ 4.59 × 10 ⁴ 4.67 × 10 ⁴ 4.40 × 10 ⁴ ───────────────────────────────── ─ (2) Sterilized water 1 3.61 × 10 ⁴ 4.49 × 10 ⁴ 4.01 × 10 ⁴ 4.15 × 10 ⁴ ─────────────────────────── ─────── (3) Sterilized water 2 4.66 × 10 ⁴ 3.78 × 10 ⁴ 4.80 × 10 ⁴ 4.68 × 10 ⁴ ───────────────────── ───────────── (4) Sterilized water 3 4.25 × 10 ^{4 *} <200 <200 <200 殺菌────────────── (5) Sterilized water 4 4.06 × 10 ^{4 *} <200 <200 <200 ────────────────────────────────── * 200 / ml or less colony count Indicates impossible.

From the test results in the above Table 1, it was found that the samples 3 and 4 in the light-shielded state by the aluminum can maintained the antibacterial effect.

[0014]

Embodiment 2 As the aerosol type container of the storage container, a transparent PET bottle for shutting off air and an aluminum can for shutting off both light and air were used. Transparent PET
A bottle and an opaque aluminum can are filled with 120 cc of electrolytically sterilized water immediately after production produced by the method described in JP-A-11-347557 developed by the present inventors, and helium is filled in these containers with about 0.8 MPa (25 ° C.). Then, two types of sterilizing cleaning sprays were prepared for each of 20 sprays and stored in a room for a long period of time, and changes over time such as a decrease in residual chlorine concentration and a decrease in sterilizing power were examined. The measurement of the residual chlorine concentration is carried out by the usual method of measuring the color development generated by adding N, N-diethylparaphenylenediamine using a photoelectric colorimeter. The number was adjusted to 2 × 10 7 CFU / ml, and 0.5 ml of the filter paper was placed on a filter paper having a diameter of 6 cm, sprayed with electrolytic sterilizing water, and the weight of the filter paper with the bacteria was measured and sprayed until the weight increased by 0.5 g.

The sterilized filter paper is immersed in 5 ml of a sterile physiological saline solution, squeezed well with a glass jar, and the water is transferred to a platinum loop, Tryptic soy broth (TBS, Difco).
After static culture at 48 ° C for 48 hours, the presence or absence of bacterial growth was visually determined by the turbidity of the medium.

[0016]

[Table 2] ────────────────────────────────────Storage days 0 1 3 5 10 20 40 ─透明 Transparent PET residual salt concentration 21.3 16.5 8.3 3.1 0 (ppm) ── ───────────────────────────── Bactericidal effect Yes Yes Yes Very low No ────────────── ────────────────────── Spray cans Residual salt concentration 21.1 19.8 18.8 17.5 16.1 14.5 12.3 (ppm) ────────────殺菌 Sterilization effect Yes Yes Yes Yes Yes Yes Yes ────────────────────── ──────────────

According to the sterilizing effect shown in Table 2 above, in the transparent PET bottle satisfying only the condition of the inert gas atmosphere, the sterilizing effect decreases with time, while the inert gas atmosphere and the light shielding In the spray cans satisfying both conditions, the bactericidal effect was sufficiently maintained even after 40 days.

[0018]

According to the present invention, the use of the sterilizing cleaning spray container allows the sterilizing cleaning water generated by the existing sterilizing cleaning water generator using the electrolytic device to be filled into the aerosol-type container, thereby providing the electrolytic sterilizing water. The sterilizing power does not decrease even if the product is stored for a long time, and it can be used anywhere and anytime, and a sterilizing cleaning spray product that can be stored for a long time can be provided. Further, by using bromine ions alone or as a mixture with chlorine ions as halogen ions, the
But it has high purifying and bactericidal properties, contains a lot of hypohalous acid,
It is possible to provide a germicidal cleaning spray that does not reduce germicidal power even when stored for a long time.

[Brief description of the drawings]

FIG. 1 is a process diagram showing a process for producing electrolytic sterilized water according to the present invention.

FIG. 2 is a bag-in-can double spray container suitable for storing and using the electrolyzed water of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrolyzer 2 Case 3 Electrolysis passage 4 Titanium cathode 5 Ferrite anode 6 Packing 7 Lid 8 Water inlet 9 Electrolyzed water outlet 10 Electrolyte aqueous solution tank 11 Liquid feed pipe to sterilization washing spray product filling device 12 Water inlet 13 Electrolysis Sterilized water storage tank 21 Outer can 22 Inner flexible bag 23 Electrolyzed water of the present invention 24 Valve 25 Pressurized inert gas

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C02F 1/46 B65D 83/14 A (72) Inventor Kunihiko Fukuzuka 7 Habinogaoka, Habino, Osaka 2-3-2 (72) Inventor Kenji Nakamura 6-3-41 Nishiawaji, Higashiyodogawa-ku, Osaka-shi, Osaka F-term (reference) 3E014 PA01 PB01 PC02 PC03 PC07 PC11 PD01 PD22 4C058 AA06 AA12 AA28 AA29 BB07 JJ06 JJ08 JJ24 4D061 DA01 DB10 EA03 EA04 EB14 EB28 EB30 EB39 ED12 ED13 GA02 GC18

Claims (4)

[Claims] 1. A pH containing hypohalous acid obtained by electrolyzing water containing a halogen ion.
A sterilized cleaning spray product characterized in that 6 to 8 electrolytically produced water is filled in a spray container while shielding light and air and under an inert gas pressure. 2. The sterilizing and cleaning spray product according to claim 1, wherein bromine ions are used alone or water containing bromine ions and chlorine ions is used as the halogen ions. 3. An electrolytic apparatus using sodium bromide alone or an aqueous solution in which sodium bromide and sodium chloride are dissolved in a fixed ratio, using a ferrite electrode as an anode and a titanium or stainless steel electrode as a cathode without using a diaphragm. The sterilized cleaning spray product according to claim 1 or 2, wherein electrolyzed water obtained by electrolysis and adjusting the generated water to pH 6 to 8 is used. 4. Use of a ferrite electrode as an anode and a titanium or stainless steel electrode as a cathode, and containing hypohalous acid obtained by electrolysis of water containing at least bromine ions in an electrolytic apparatus without using a diaphragm. PH6
A method for producing a sterilizing and cleaning spray product, comprising filling a spray container with the electrolytically produced water of (1) to (8) under light shielding and pressurization of an inert gas.