JP6214855B2 - Slightly acidic hypochlorous acid water containing fine bubbles, method for producing and using the same - Google Patents

Description

The present invention relates to a method for producing and using a slightly acidic hypochlorous acid water containing fine bubbles in which carbon dioxide gas is dissolved.

Hypochlorous acid water is so-called electrolytic water based on hypochlorous acid (HOCl) as a sterilization base, and is an aqueous solution of electrolytic hypochlorous acid. Electrolytic hypochlorite is an aqueous sodium hypochlorite solution produced by electrolyzing saline in a non-diaphragm electrolytic cell, and the sterilizing component of electrolytic hypochlorite is hypochlorite ions (ClO ⁻ ). Sodium hypochlorite (NaOCl) is designated as a food additive, sterilizing various foods such as fruits and vegetables, equipment for manufacturing and processing various foods, equipment or environmental hygiene management, drinking water, pool water It is widely used for sterilization of bath water and sewage. The chlorine component of the aqueous sodium hypochlorite solution varies depending on the pH of the aqueous solution, and exists as hypochlorous acid in the acidic water region at pH 3.0 or higher and as hypochlorite ion on the alkali side. In particular, it is known that in the slightly acidic region around pH 5.0, there is little or no volatile chlorine gas, and only hypochlorous acid having stronger bactericidal power than hypochlorite ions (Kunimoto Hotta). Harmful microorganism management technology, Volume 1, p751-757, Fuji Techno System 2000).

  Therefore, in order to use a sodium hypochlorite aqueous solution as sterilizing water, it is important to adjust the pH to a slightly acidic region around pH 5.0. It shall be called “water”. For this purpose, organic acids, inorganic acids or carbon dioxide are used. Among these, when an inorganic acid such as hydrochloric acid is mixed with an aqueous sodium hypochlorite solution, there is a risk of generating toxic chlorine gas. When adjusting pH with acetic acid or lactic acid for food addition, safety can be ensured by using an infusion pump in a sealed system, and this technology has been put to practical use (Health) Manufactured by Aqualizer T-30). As a method of adjusting pH with carbon dioxide gas, a method of bubbling carbon dioxide gas into an aqueous sodium hypochlorite solution (JP-A-10-24294) and a method of adjusting pH with a carbon dioxide gas dissolver comprising a membrane module are also disclosed ( JP 2004-307405). Carbon dioxide gas is a tasteless and odorless inert gas that dissolves quickly in water and has excellent handling properties, such as no sudden pH drop even if accidentally over-injected.

  However, although slightly acidic hypochlorous acid water has excellent properties as sterilizing water, it is unstable to heat, and even when stored in a sealed container in a cool and dark place, it is difficult to maintain an effective chlorine concentration for a long time. Since it has, the present condition is to install a hypochlorous acid water generator and prepare it when necessary. Electrolyzed water prepared by electrolyzing dilute saline and dilute hydrochloric acid is roughly divided into electrolytic hypochlorous acid based on hypochlorite ion and hypochlorous acid based on hypochlorous acid. The Of these, the stability of hypochlorous acid water is greatly affected by pH and storage temperature, and it has been reported that refrigerated storage at pH 3 or higher may extend the usage period (right Nishimoto). Child, Kei Inoue, Effect of pH and temperature on the stability of electrolyzed water, Functional Water Study 2: 71-74, 2000).

  The stability of hypochlorous acid water is also available as a catalog download (PDF) on the website of Morinaga Engineering Co., Ltd. (http://www.morieng.co.jp/fwgroup/purester.html). Among them, if pure star water (effective chlorine concentration 17 ppm, pH 6.52) and strongly acidic electrolyzed water (effective chlorine concentration 15 ppm, pH 3.95) are left in an open system at room temperature (25 ° C.), 24 hours later The residual rate is 58% for pure star water and 0.3% for strongly acidic electrolyzed water. Under light-shielding / sealed system / room temperature, the remaining rate after 40 days is 78% for pure star water and 58% for strongly acidic electrolyzed water. It is shown that. On the other hand, hypochlorous acid water based on hypochlorous acid is based on sterilization and lacks storage stability. Therefore, it is currently prepared and used by electrolysis or the like when necessary. As a solution to this problem, a method for filling a sealed container into a sealed container to improve storage stability is disclosed (Japanese Patent Laid-Open Nos. 5-78776 and 9-28761), but still has sufficient stability over a long period of time. It has not reached.

  Although slightly acidic hypochlorous acid water is known to have excellent properties as sterilizing water, the problem of thermal instability has not been solved. Inconvenienced. Under such circumstances, the present inventors have conducted research on long-term storage of hypochlorous acid water, and as a result, have come to obtain the knowledge that long-term storage can be realized under certain conditions. The mechanism has not been clarified yet. However, slightly acidic hypochlorous acid water containing fine bubbles having a particle size of 50 μm or less can withstand long-term storage as described in detail below.

JP 10-24294 A JP2004-307405 JP-A-5-7876 JP-A-9-28761 Kunimoto Hotta, Harmful Microorganism Management Technology, Volume 1, p751-757, Fuji Techno System 2000 Nishimoto Yoko, Inoue Kei, Effect of pH and temperature on the stability of electrolyzed water, Functional Water Research 2: 71-74, 2000

This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method and usage method of the said slightly acidic hypochlorous acid water.

  The microbubble-containing slightly acidic hypochlorous acid water of the present invention that solves the above problems is an aqueous solution containing hypochlorous acid in which carbon dioxide gas is dissolved, and the hypochlorous acid in which the carbon dioxide gas is dissolved An aqueous solution containing a fine bubble having a particle size of 50 μm or less by a microbubble generator is included. The carbon dioxide gas dissolved in the aqueous solution containing hypochlorous acid used in the present invention acts to adjust the pH of the aqueous sodium hypochlorite solution to a slightly acidic region near pH 5.0 as described above. It is in a state suitable for use as sterilizing water. In addition, when the particle size of the fine bubbles is 50 μm or less, the bubbles having a particle size of less than or equal to the particle size are referred to as microbubbles, or further, those having a particle size of 1 μm or less and the minute nanobubbles. The slightly acidic hypochlorous acid water of the present invention is made into fine bubbles under the production conditions by the microbubble generator, and has a storage period exceeding several tens of days.

  Fine bubbles with a particle size of 50 μm or less are a series of phenomena in which the ascending speed in the liquid is slow, sometimes drops, shrinks due to the self-pressurizing effect due to the interfacial tension, and eventually dissolves and disappears in the liquid. Follow the process of. In the meantime, the self-crushing action involves the decomposition of water molecules and the like, and the generation of free radicals, or the amount of bubbles that come into contact with food, etc. due to the large specific surface area becomes extremely large, and sterilization with mixed hypochlorous acid. It exhibits characteristics such as making the effect remarkably strong. In the present invention, an aqueous solution containing hypochlorous acid in which carbon dioxide gas is dissolved is made into fine bubbles to obtain slightly acidic hypochlorous acid water composed of fine bubbles having a particle size of 50 μm or less. Examples of other gas applicable to the present invention include an inert gas such as nitrogen gas (or argon gas). Nitrogen gas does not shift the pH of the fine bubble mixture to the acidic region. However, it is considered that there is an advantage that microbubbles generated by the fine bubble generating nozzle dissolve in water when transferred to nanobubbles, thereby preventing oxidation and contributing to maintaining freshness.

  The microbubble-containing slightly acidic hypochlorous acid water in which the above carbon dioxide gas is dissolved is mixed with electrolytic hypochlorous acid or commercial sodium hypochlorite aqueous solution diluted to a desired effective chlorine concentration using a pump. And a step of preparing hypochlorous acid water having a pH of 5 to 6 and a step of conducting the obtained slightly acidic hypochlorous acid water to a microbubble generator to generate fine bubbles having a particle size of 50 μm or less. It can be manufactured by an applied method. The electrolytic hypochlorous acid diluted to the desired chlorine concentration or a commercially available sodium hypochlorite aqueous solution is an aqueous solution containing hypochlorous acid described in claim 1.

  In the production method of the present invention, a pump for mixing carbon dioxide gas and a microbubble generator for conducting the slightly acidic hypochlorous acid water obtained thereby are used. The type of the pump is not particularly limited, but a pump having a high gas-liquid mixing capability, such as a spiral pump, is preferable. On the other hand, for the microbubble generator, a pressure reduction method, a gas-liquid shearing method, and the like are known. The present invention is required to be composed of fine bubbles having a particle size of 50 μm or less, and any means may be used as long as this requirement is satisfied. However, for example, the use of the fine bubble generating nozzle disclosed in Japanese Patent Application Laid-Open No. 2010-125427 leads to favorable results. In particular, when the apparatus in which the above-described invention was carried out was used, the finely acid-containing slightly acidic hypochlorous acid water containing the finest results that were most effective in long-term storage could be easily and reliably produced.

  In the production method of the present invention, a mixing tank is disposed between the pump and the microbubble generator, and a mixed fluid of air and carbon dioxide gas mixture and hypochlorous acid water is temporarily stored in the mixing tank. Steps can be added. By temporarily storing the mixed fluid in the mixing tank, an aqueous solution containing hypochlorous acid in which the carbon dioxide gas is dissolved and saturated water of mixed water containing an inert carbon dioxide gas are generated, which leads to a more preferable result. .

  There are various methods of using finely acid-containing hypoacidic hypochlorous acid water in which carbon dioxide gas is dissolved according to the present invention. For example, cleaning, spraying, coating, and other methods applied to liquids can be applied. . However, the slightly acidic hypochlorous acid water of the present invention is composed of a hypochlorous acid aqueous solution in which carbon dioxide gas containing fine bubbles having a particle diameter of 50 μm or less is dissolved. The usage is effective. For example, as a method of using finely acidic water containing fine bubbles containing dissolved carbon dioxide gas, the slightly acidic hypochlorous acid water is composed of a hypochlorous acid aqueous solution in which carbon dioxide gas is dissolved. The aqueous chloric acid solution contains fine bubbles with a particle size of 50 μm or less. The above slightly acidic hypochlorous acid aqueous solution is prepared to have an effective chlorine concentration of 5 to 20 ppm and pH of 5.0 to 6.7, poured into a bucket, and cut flowers. There is a method of landing by inserting into the slightly acidic hypochlorous acid water containing the fine bubbles. Furthermore, spraying this fine bubble-containing slightly acidic hypochlorous acid water on a target region using a spraying means can be cited as an example. That is, it comprises a hypochlorous acid aqueous solution in which carbon dioxide gas is dissolved, and the above hypochlorous acid aqueous solution contains fine bubbles containing fine bubbles having a particle size of 50 μm or less. By spraying the target object or the sealed space where it exists, an environment having an effective chlorine concentration of 10 to 30 ppm and a pH of 5.0 to 6.9 is formed, and the sealed space is sterilized. According to this method of use, it becomes possible to fill the sprayed area with the slightly acidic hypochlorous acid water containing fine bubbles. can do.

  As described above, since the present invention contains microbubbles composed of microbubbles or nanobubbles B having a particle size of 50 μm or less in a hypochlorous acid aqueous solution in which carbon dioxide gas is dissolved, microbubbles having excellent thermal stability. A slightly acidic hypochlorous acid aqueous solution is provided. According to the present invention, the desired slightly acidic hypochlorous acid water can be easily produced by passing the slightly acidic hypochlorous acid water in which the carbon dioxide gas is dissolved to the microbubble generator. Can do. In addition, according to the present invention, it exhibits an excellent bactericidal effect on the sterilization of microorganisms that survive as biofilms on the surface of plants such as vegetables, and even when sprayed with a humidifier or the like, effective chlorine is contained in fine mist. The effect of maintaining the concentration is obtained, and in addition, by using the plastic bucket for cut flowers as fried water, the inner wall surface of the plastic bucket that comes into contact with the fried water is sterilized. It is possible to provide a slightly acidic hypochlorous acid water containing fine bubbles that brings about an effect.

  Hereinafter, the present invention will be described in more detail with reference to embodiments. FIG. 1 shows an example of an apparatus 10 used for carrying out a method for producing a slightly acidic hypochlorous acid water containing fine bubbles according to the present invention. In the figure, reference numeral 11 denotes a pump composed of a vortex pump, which takes in gas such as carbon dioxide gas and air through a gas intake passage 12, takes in liquid through a liquid intake passage 13, and mixes the introduced fluid to give a predetermined value. It functions to send out by pressure.

  The gas intake path 12 includes an air inflow path having an air flow rate regulator 14, a carbon dioxide gas cylinder 15 with a flow rate regulator for supplying carbon dioxide gas, and a nitrogen gas cylinder 16 with a flow rate regulator for supplying nitrogen gas. The gas inflow path consisting of is connected. Reference numeral 17 denotes a mixing branch valve, which is provided for selecting the supply of an inert gas typified by the carbon dioxide gas and the nitrogen gas, and for adjusting each supply amount. In addition, the liquid intake passage 13 is provided with an electrolytic sub-sulfur generation unit 18 that generates electrolytic sub-sulfur.

  The electrolytic hyponitrous generator 18 is equipped with an electrolytic hyposulfur generator in order to use electrolytic hyposulfur generated by electrolyzing dilute saline in the present invention. Drinkable water is used as water, and salt or potassium chloride is dissolved. Further, in addition to the hypochlorite ion water generated by the electrolytic hypochlorite generator, it is possible to provide the liquid intake path 13 with a device for adding other desired disinfectant if necessary.

  The pump 11 is connected to the fine bubble generating nozzle 22 by piping 19 and 21 via the mixing tank 20. The fine bubble generating nozzle 22 injects a mixed fluid of the air-fuel mixture such as air and carbon dioxide, electrolytic hyponitrous acid, and other sterilizing agents, and generates fine bubbles with a diameter preferably smaller than 20 micrometers. The obtained finely acid-containing slightly acidic hypochlorous acid water is stored in the fine bubble mixture tank 23. Further, the mixing tank 20 acts to temporarily hold a mixed fluid of a mixture of air and gas, hypochlorous acid water, and other sterilizing agent to be added if necessary, and generate a saturated state.

  As the fine bubble generating nozzle 22, as shown in detail in FIG. 2, the fine bubble generating nozzle of Japanese Patent No. 4804527 is used. The nozzle 22 according to the above-mentioned patent invention has one end opened as an inlet 24 for the fine bubble mixture, the inside becomes a flow path, the other end is closed as a wall surface 25 on which the liquid flow collides, and the peripheral surface near the other end A cylindrical nozzle case 27 having a nozzle hole 26 that passes through the inside and outside of the case, a plate surface 28 that is disposed inside the nozzle case and collides with the fine bubble mixture, and blocks the flow path, and In order to allow the fine bubble mixed liquid flow to pass through the plate surface 28 in a compressed state and to cause expansion in the downstream space, a compression / expansion member 30 having pores 29 is provided, and the nozzle hole 26, the compression / expansion member 30, In this configuration, the agitation members 31 are provided so as to be spaced apart from each other.

  The stirring member 31 is formed of a cylindrical structure, and a gap 32 is provided between the outer peripheral surface of the cylinder and the inner peripheral surface of the nozzle case 27. A slit 33 leading to the gap 32 is provided around the circumference of the cylindrical structure. The stirring means 34 and 35 are provided upstream and downstream of the slit 33. The illustrated stirring means 34 and 35 are made of a mesh material. The agitating member 31 is in contact with a step 26a formed inside the nozzle case at the downstream end, and is in contact with the inner peripheral surface of the nozzle case at the upstream flange 31a, thereby forming the gap 31. Yes.

  The fine bubble generating nozzle 22 shown in FIG. 3 has a nozzle hood 22a that covers the tip, and is provided with a connecting cylinder 22b in the axial direction so that a cleaning hose 22c can be connected to the connecting cylinder 22b. The nozzle 22 is fitted into the tip of a cylindrical adapter 22d, and a nozzle hood 22a is airtightly attached to the tip of the nozzle 22 via a sealing means 22e. The pipe 21 is connected to the rear connection port 22f. Although the fine bubble generating nozzle 22 used in the apparatus 10 can be expected to have a suitable effect, the present invention cannot be achieved without this nozzle. For example, there is a partial difference as a nozzle, and even if the result of the above-mentioned apparatus 10 cannot be reached, it is possible to produce a slightly acidic hypochlorous acid water containing fine bubbles that is still practical. In this case, the subject of the present invention could be achieved although it was not perfect, and thus the produced microbubble-containing slightly acidic hypochlorous acid water is within the scope of the present invention.

When the apparatus 10 is started, air, carbon dioxide gas, or nitrogen gas or both of them flow into the pump 11 through the gas intake path 12, and hypochlorous acid generated in the electrolytic hypoxia generation unit 18. Electrolytic hyponitrous acid containing acid ions (ClO ⁻ ) and other sterilizing agents flow into the pump 11 through the liquid intake path 13. The fluid composed of the gas and the liquid is sent from the pump 11 to the mixing tank 20 at a required pressure, stored in the tank for a predetermined time, and then ejected from the fine bubble generating nozzle 22 and smaller than 20 micrometers. Microbubbles or microbubbles having a diameter are stored in the microbubble mixture tank 23 as microbubbles. Since it is already the microbubble-containing slightly acidic hypochlorous acid water of the present invention when sprayed from the microbubble generating nozzle 22, it can be directly acted on the object or the like without storing it. The method is the same as the conventional method, which is the same as preparing the required amount for each use. On the other hand, the microbubble-containing slightly acidic hypochlorous acid water composed of the microbubbles or nanobubbles B of the present invention retains the same effect as that of production for a long period of several tens of days if stored in a sealed system. Therefore, this point will be clarified by experiments below.

  Using the apparatus 10 shown in FIG. 1, carbon dioxide gas (2 NL / min) and nitrogen gas (1 NL / min) supplied from the carbon dioxide gas cylinder 15 and the nitrogen gas cylinder 16 are swirled into the electrolytic hyposulfur diluted to an effective chlorine concentration of 50 ppm. Mixing in the pump 11, hypochlorous acid water having a pH of around 5.5 was prepared in the mixing tank 20. The obtained slightly acidic hypochlorous acid water was conducted to the fine bubble generating nozzle 22 to produce the fine bubble-containing slightly acidic hypochlorous acid water of the present invention. After diluting electrolytic hyponitrous water with tap water, the pH was adjusted to slightly acidic with lactic acid (referred to as slightly acidic hypochlorous acid), and used as a control group for stability experiments.

ＮＴ： 未測定
なお、本発明の各実験において、有効塩素濃度の測定には柴田科学社製有効塩素濃度測定器ＡＱ−１０２Ｐを使用し、ｐＨの測定には佐藤計量器製ｐＨメーターＳＫ‐６２０ＰＨを使用した。
表１から明らかなように、乳酸でｐＨ調製した対照区の微酸性次亜水は、従来と同様に有効塩素濃度が５０℃５日で消失したが、実施例１の微細気泡含有微酸性次亜塩素酸水は、８０％以上の有効塩素濃度を４０日経過後も保持していた。 <Example 1>
The fine bubble-containing slightly acidic hypochlorous acid water of the present invention and the slightly acidic hypochlorite water of the control group are each dispensed and sealed in a 2 L-volume PET bottle, and 10 ° C., 20 ° C., 30 ° C., 40 ° C., 50 The results of Tables 1 and 2 were obtained by storing in a thermostat at 60 ° C. and 60 ° C. and measuring changes in effective chlorine concentration and pH over time.

NT: Not measured In each experiment of the present invention, an effective chlorine concentration measuring device AQ-102P manufactured by Shibata Kagakusha is used for measuring effective chlorine concentration, and a pH meter SK-620PH manufactured by Sato Keiki Co., Ltd. is used for measuring pH. It was used.
As can be seen from Table 1, the slightly acidic hypochlorous acid in the control group prepared by adjusting the pH with lactic acid disappeared in 5 days at 50 ° C. as in the conventional case. The chlorous acid water maintained an effective chlorine concentration of 80% or more after 40 days.

表２によれば、本発明による実施例１の微細気泡を含む微酸性の次亜塩素酸水は、６０℃４０日という条件で保存した場合でも、これを殺菌水として使用することによって、被検菌を全て死滅させることができた。 <Example 2>
The microbubble-containing slightly acidic hypochlorous acid water stored at 60 ° C. for 40 days was applied to Escherichia coli and the like by the following method to examine its bactericidal effect. Each microorganism was cultured overnight at 37 ° C. in a soybean / casein / digest medium (Digo, manufactured by Nippon Shinyaku Co., Ltd.), and then thoroughly washed with physiological saline. Next, fine bubble-containing slightly acidic hypochlorous acid water (effective chlorine concentration: 12.8 ppm, pH 5.9) stored at 10 ° C. for 40 days and fine bubble-containing slightly acidic hypochlorous acid water stored at 60 ° C. for 40 days ( Dilute the number of bacteria to 10 ⁵ to 10 ⁶ with an effective chlorine concentration of 13 ppm, pH 6.1) (within 1% of the amount of added bacterial solution), leave it for 1 minute, add soybean / casein / digest medium (1 ml), Centrifugation at 000 rpm, resuspension in physiological saline (1 ml), and the number of viable bacteria is measured with a soybean / casein / digest agar medium (Digo, manufactured by Nippon Shinyaku Co., Ltd.) by a serial dilution method to confirm the bactericidal effect did. The results are shown in Table 2.

According to Table 2, the slightly acidic hypochlorous acid water containing the fine bubbles of Example 1 according to the present invention was used as sterilizing water even when stored under the condition of 60 ° C. for 40 days. All the bacteria were killed.

<Example 3>
Finely acid-containing slightly acidic hypochlorous acid water (28 ppm, pH 5.1) was sprayed using a commercially available humidifier, the generated mist mist was collected, the effective chlorine concentration was measured, and about 20 ppm was confirmed. As described above, according to the present invention, a desired effective chlorine concentration can be maintained by spraying the slightly acidic hypochlorous acid water containing fine bubbles onto the object or the region where the object exists using the spraying means. I can see that

表３に示される如く、１ｇのカット野菜には１０^３〜１０^５の一般細菌が検出されるが、微細気泡を含む微酸性次亜塩素酸水で、３分間浸漬処理することで効果的に除菌できることを確認した。また、この除菌効果は４８時間安定していた。 <Example 4: Disinfection of cut vegetables with slightly acidic hypochlorous acid water containing fine bubbles>
Using the slightly acidic hypochlorous acid water containing fine bubbles in Example 1, the cut vegetables were sterilized. For sterilization, immerse mizuna or shredded cabbage cut into approximately 5 cm length in the slightly acidic hypochlorous acid water containing fine bubbles for 3 minutes, wash it with sterile water, Each sample was put in a bag, and three samples were prepared and stored in a refrigerator. Similarly, 25 g of untreated specimens were placed in a sterile plastic bag of stomacher, and 3 bags were stored in a refrigerator. One specimen stored in the refrigerator was taken out and immediately returned to room temperature (about 15 ° C.), 225 ml of sterilized physiological saline was added, homogenized with a stomacher for 30 seconds, and the viable cell count was examined. Similarly, the viable cell count of each specimen stored for 24 hours and 48 hours in a refrigerator was measured. The tryptic soy agar medium (Eiken Chemical Co., Ltd.) was used as a general bacterium, and the EC colimark agar medium (Eiken Chemical Co., Ltd.) was used as an Escherichia coli / Coliform group. The treated water of mizuna had an effective chlorine concentration of 50 ppm and pH 5.2, and the treated water after the treatment for 3 minutes had an effective chlorine concentration of 50 ppm and pH 5.4. The shredded cabbage treated water had an effective chlorine concentration of 48 ppm and a pH of 5.4, and after the treatment, it exhibited an effective chlorine of 45 ppm and a pH of 5.5. The results are shown in Table 3.

As shown in Table 3, 10 ³ to 10 ⁵ general bacteria are detected in 1 g of cut vegetables, but it is effective by soaking for 3 minutes with slightly acidic hypochlorous acid water containing fine bubbles. It was confirmed that sterilization was possible. This sterilization effect was stable for 48 hours.

<Example 5: UV absorption spectrum of slightly acidic hypochlorous acid water containing fine bubbles stored for 40 days>
All UV absorption spectra of finely acid-containing slightly acidic hypochlorous acid water stored at 10 ° C. to 60 ° C. for 40 days showed weak absorption near 236 nm, and the pH was adjusted to 9.5 with a dilute sodium hydroxide solution. The absorption spectrum newly showed maximum absorption near 292.4 nm. As actual data, the UV absorption spectrum of a slightly acidic hypochlorous acid aqueous solution containing fine bubbles stored at 60 ° C. for 40 days is shown below. FIG. 4 shows a microbubble-containing slightly acidic hypochlorous acid aqueous solution stored at 60 ° C. for 40 days and pH 6.4. 5 shows a solution obtained by adjusting the solution of FIG. 4 to pH 9.5, and FIG. 6 shows a UV absorption spectrum obtained by adjusting the pH 9.5 solution of FIG. 5 again to pH 6.0 with hydrochloric acid. From these spectra, it is understood that in the slightly acidic region, the absorption is weak in the vicinity of 236 nm, and the maximum absorption is 292.4 nm on the alkali side (the UV absorption spectra of the 10 ° C. to 50 ° C. storage solutions are all the same). Result). The UV absorption spectrum was measured using a Hitachi auto-recorded spectrophotometer U-3210. These findings were consistent with the hypochlorous acid and hypochlorite ions in the literature values (Shuji Nakagawa et al., Analytical Sciences 14: 691-698, 1998). The chlorine component of the slightly acidic hypochlorous acid water containing fine bubbles stored in a sealed state was identified as hypochlorous acid.

表４の如く、微酸性次亜水は３０℃では次亜塩素酸は１日後には４７％程度に減少し、４日後には殆どが消失していたことが分かる。 <Example 6: Stability in an open system of microacid-containing slightly acidic hypochlorous acid water>
Tapper containing finely acid-containing slightly acidic hypochlorous acid water (effective chlorine concentration 200 ppm, pH 5.7) and slightly acidic hypochlorous acid (effective chlorine concentration 171 ppm, pH 5.4) prepared in the same manner as the stability in the above-mentioned sealed system 600 ml each was dispensed to the wear and covered with aluminum foil, and then stored in a 10 ° C. and 30 ° C. incubator to examine changes over time. The results are shown in Table 4.

As shown in Table 4, it can be seen that the slightly acidic hypochlorous acid was reduced to about 47% after 1 day at 30 ° C. and almost disappeared after 4 days.

  On the other hand, the slightly acidic hypochlorous acid water containing fine bubbles remained 98.5% after 4 days after storage at 10 ° C., and 77.5% remained at 30 ° C. From the UV spectrum analysis shown in FIG. 7 and FIG. 8, when stored in an open system at 10 degrees for 4 days, a mixture of hypochlorous acid and hypochlorite ions was recognized. In storage at 30 ° C. for 4 days, the presence of hypochlorite ions was confirmed. These results show that when carbon dioxide is dissolved in electrolytic hyposulfite (or sodium hypochlorite solution) and adjusted to slightly acidic, the chlorine component becomes hypochlorous acid, and as the carbon dioxide is released, hypochlorous acid is released. This suggests that it changes to an acid ion. On the other hand, the slightly acidic hypochlorous acid adjusted to be slightly acidic with an organic acid such as acetic acid has been decomposed in an open system.

<Example 7: Bactericidal effect by spraying humidified spray of finely acid-containing slightly acidic hypochlorous acid water>
Microbubble-containing micro acidity in a humidifier (ultrasonic type: manufactured by Apics International, Inc., ultrasonic humidifier AHD-010 and manufactured by CCP, steam fan type humidifier KX-235m) Operate with chlorous acid water (effective chlorine concentration 28ppm, pH 5.1). After collecting the mist-like mist generated from the spray port in a plastic bag, it was measured on the drips with a crawl test paper (for measurement of 10 to 50 ppm) manufactured by Advantech Toyo Co., Ltd. As shown in Table 5, the ultrasonic humidifier confirmed an effective chlorine concentration of about 20 ppm, but the steam fan type could detect only about 1 ppm.

これらの結果は、これまでに開示された技術では、特開２００３‐１５３９８９号（特許第３８２０４６２号）に、有効塩素濃度８０ｐｐｍ、ｐＨ２．５７〜２．５８の電解水に界面活性剤を添加して超音波加湿器で噴霧すると、噴霧された霧粒子有効塩素濃度は０．０２〜０．０５ｐｐｍで、新たに発明された噴霧装置でも、有効塩素濃度８０〜９０ｐｐｍを噴霧して、検出される有効塩素濃度は０．１９〜０．３４ｐｐｍであることを示している。従って、本発明の微細気泡含有微酸性次亜塩素酸水を超音波加湿器で噴霧する有用性は、先行技術より著しく改善されていることを立証している。 In addition, Staphylococcus aureus cultured overnight at 37 ° C in Soybean casein digest medium (manufactured by Nippon Shinyaku Co., Ltd.)
aureus) 209P JC-1 was washed with physiological saline to prepare a 1.3 × 10 ⁷ / ml bacterial solution. Next, ^two circles with an area of 25 cm ² are drawn on an aluminum tray, 0.1 ml of the bacterial solution is spread in the two circles, and air-dried in a clean bench (Hitachi, PCV-750AP). . Subsequently, a Petan Check 25 standard agar medium (trade name, manufactured by Eiken Chemical Co., Ltd.) was stamped on one circle to make an untreated section. This tray was hung in a clean bench. Place the ultrasonic humidifier AHD-010 in the clean bench, spray fine water-containing slightly acidic hypochlorous acid water (effective chlorine concentration 28ppm, pH 5.1) for 3 minutes, and put it on the mist released from the humidifier. I was confirmed to be surrounded. Subsequently, a Petan Check 25 standard agar medium (trade name, manufactured by Eiken Chemical Co., Ltd.) was stamped on one remaining circle on the tray to form a treatment zone. The two Petan Check 25 standard agar media (trade name, manufactured by Eiken Chemical Co., Ltd.) were cultured overnight at 37 ° C. As shown in Table 5 below, the microbe-containing microacidic hypochlorous acid water sterilization effect by the humidifier spray shows that the number of bacteria cannot be measured (infinite) on the untreated Petcheck 25 standard agar medium. Although growth was recognized, the growth of 135 colonies of Staphylococcus aureus was measured on the Petan Check 25 standard agar medium in the treatment area sprayed with microbubble-containing slightly acidic hypochlorous acid water.

These results show that, in the technology disclosed so far, a surfactant is added to electrolyzed water having an effective chlorine concentration of 80 ppm and a pH of 2.57 to 2.58 in JP2003-153898 (Patent No. 3820462). When sprayed with an ultrasonic humidifier, the sprayed fog particles have an effective chlorine concentration of 0.02 to 0.05 ppm, and even with a newly invented spray device, an effective chlorine concentration of 80 to 90 ppm is sprayed and detected. It shows that the effective chlorine concentration is 0.19 to 0.34 ppm. Therefore, the usefulness of spraying the microbubble-containing slightly acidic hypochlorous acid water of the present invention with an ultrasonic humidifier proves to be significantly improved over the prior art.

<Effects of spraying chrysanthemum with sprayed fine chrysanthemum hypochlorous acid containing fine bubbles>
In order to keep cut flowers for a long time, it is said that the quality of landing is the most important point. In addition, as a factor that hinders the landing of cut flowers, rot of cut flower stems due to bacterial growth and blockage of conduits are cited. In order to solve this problem, antibacterial agents such as silver nitrate and aluminum sulfate, bacteriostatic agents, freshness-preserving agents to which organic acids are added, or STS (silver thiosulfate complex salt) that has an ethylene generation inhibitory activity involved in senescence of cut flowers Is commercially available as a cut flower life prolonging agent. On the other hand, Japanese Patent No. 3078791 and Japanese Patent Application Laid-Open No. 2000-109401 disclose techniques relating to the long-lasting effect of hypochlorous acid water generated by electrolyzing a solution of salt, potassium chloride or hydrochloric acid. In the former, when cut flowers are immersed in electrolyzed water having a pH of 3 or less and containing 10 to 50 ppm of hypochlorous acid, the carnation is 1.4 to 1.6 times that of the control zone in which the groundwater is ikebana water. The rose is 1.75 times the same as a commercially available freshness-preserving agent. In the latter technique, it is described that hypochlorous acid water having an effective chlorine concentration of 10 ppm and pH 6.2 has almost the same effect as a commercially available drug solution using roses. The slightly acidic hypochlorous acid water containing fine bubbles of the present invention is also effective in promoting the landing of spray chrysanthemums, which was confirmed by experiments.

<Example 8>
Using Vietnamese white spray chrysanthemums (hereinafter referred to as chrysanthemum cut flowers), the following treatment was performed.
Pumped water treatment: Three treatment zones were prepared: a control zone (tap water), an effective chlorine concentration of 10 ppm for fine acidic hypochlorite water containing fine bubbles, and a 20 ppm zone. Each treatment was carried out in a plastic bucket (length 40 cm x width 30 cm x depth 35 cm), 7 L of finely acid-containing slightly acidic hypochlorous acid water (effective chlorine concentration 10 ppm and 20 ppm, pH 5.0). ) Was injected respectively. Three sets of chrysanthemum flowers as test materials were used as one set, and three sets were inserted into each treatment area. As a control, 7L of tap water was used for the same treatment. During the experiment, the bucket was allowed to stand at room temperature (about 15 ° C.) under natural light conditions.
Measurement of landing amount of chrysanthemum cut flower: The landing amount was evaluated by subtracting the weight after 4 and 8 days from the cut flower weight at the start of the experiment. That is, if the value of the subtraction weight is small, it is determined that the landing amount is large.
Measurement of effective chlorine concentration and pH: An effective chlorine concentration measuring device AQ-102P manufactured by Shibata Kagakusha and a pH meter SK-620PH manufactured by Sato Keiki were used.
Microorganism measurement: The inner surface of a plastic bucket is petan-checked. General bacteria are Petan Check 25 Tryptosoy Agar (trade name, manufactured by Eiken Chemical Co., Ltd.) ES colimark agar medium (trade name, manufactured by Eiken Chemical Co., Ltd.) was used.

表６によれば、スプレー菊水揚げ実験に使用した微細気泡含有微酸性次亜水の有効塩素濃度は数日を経過すると低下する傾向が見られ、それに伴ってｐＨも変化するが、８日程度では、なお、有効な濃度を保っていることが分かる。 The results of Example 8 are shown below.

According to Table 6, the effective chlorine concentration of microbubble-containing slightly acidic hyponitrous acid used in the spray chrysanthemum landing experiment tends to decrease after a few days, and the pH also changes accordingly, but about 8 days. It can be seen that the effective concentration is maintained.

（切り花重量減少量は、室温（約１５℃）条件下で測定した。）

表７によれば、対照区は４日後減少量Ｂ／Ａが１３％を超え、８日後になると減少量Ｃ／Ａが１６．３％を示す。これに対して、本発明の微細気泡含有の微酸性次亜塩素酸水による場合１０ｐｐｍで４日後減少量Ｂ／Ａが９．６％、８日後減少量Ｃ／Ａは１２．７％、２０ｐｐｍでは４日後減少量Ｂ／Ａが１２．９％、８日後減少量Ｃ／Ａは１６．６％であった。これらにより、本発明の微細気泡含有の微酸性次亜塩素酸水を切り花に使用することによって、延命効果を図れることが分かる。 Furthermore, the change in the amount of cut flower weight of slightly acidic hypochlorous acid water containing fine bubbles was measured, and the results are shown.

(The cut flower weight loss was measured under room temperature (about 15 ° C.) conditions.)

According to Table 7, the amount of decrease B / A after 4 days exceeds 13% in the control group, and the amount of decrease C / A shows 16.3% after 8 days. On the other hand, in the case of the slightly acidic hypochlorous acid water containing fine bubbles of the present invention, the decrease amount B / A after 4 days is 9.6% at 10 ppm, and the decrease amount C / A after 8 days is 12.7%, 20 ppm. The decrease B / A after 4 days was 12.9%, and the decrease C / A after 8 days was 16.6%. From these, it can be seen that the life-prolonging effect can be achieved by using the finely acid-containing slightly acidic hypochlorous acid water of the present invention for cut flowers.

<Example 9: Bactericidal effect by spray of slightly acidic hypochlorous acid water containing fine bubbles>
Using the slightly acidic hypochlorous acid water containing fine bubbles shown in Example 1, which was stored at 20 ° C. for 110 days (effective chlorine concentration 52 ppm, pH 6.2), about 600,000 cm ³ (frontage 132 × It sprayed for 3 minutes to the sealed space of depth 67x 72cm in height, and the environment of effective chlorine concentration 30ppm and pH 6.4 was formed. Two days after the spraying, the falling bacteria were tested by a dropping method in which a soy bean, casein, digest agar plate was opened for 30 minutes. As a result, 0 to 2 bacteria were detected per plate. In addition, since carbon dioxide gas may escape after spraying and the pH may rise slightly, it is determined that pH 5.0 to 6.9 is an effective range.

Recently, many infectious diseases such as influenza and norovirus have occurred, and various drugs and quasi-drugs have been commercialized as countermeasures. However, the slightly acidic hyponitrous acid has the characteristics that the effective chlorine is deactivated quickly after use and the rapid effect of sterilizing power, and according to the present invention, the pH is adjusted with a mixed gas of carbon dioxide gas and nitrogen gas, By generating nano-microbubbles, it was confirmed that the thermal stability can be remarkably improved until the time of use, as seen in the above-mentioned examples, so that it can be used for a wide range of applications.

It is a block diagram which shows an example of the apparatus used for implementation of the manufacturing method of the micro acid-containing slightly acidic hypochlorous acid water which concerns on this invention. It is sectional drawing which shows an example of the nozzle used for an apparatus same as the above. It is sectional drawing which shows an example of the member with which the nozzle of FIG. 2 is mounted | worn. It is a chart figure which shows the UV absorption spectrum of the data which preserve | saved 40 days of the slightly acidic hypochlorous acid water containing fine bubbles of this invention at 60 degreeC. It is front explanatory drawing which shows an example. Similarly, it is a chart showing a UV absorption spectrum after adjusting the sample of FIG. 4 to pH 9.5. FIG. 6 is a chart showing a UV absorption spectrum after adjusting the sample of FIG. 5 to pH 6.0 again. It is a chart which shows the UV spectrum of the fine bubble containing slightly acidic hypochlorous acid water which preserve | saved the fine bubble containing slightly acidic hypochlorous acid water of this invention by 10 degreeC and the open system for 4 days. It is a chart which similarly shows the UV spectrum of the microbubble containing slightly acidic hypochlorous acid water containing 30 degreeC and an open system for 4 days preservation | save. It is a chart figure which similarly shows the UV spectrum of 10 ppm of effective chlorine concentration, pH 6.7, and landing 8th day. Similarly, it is a chart showing the UV spectrum of effective chlorine concentration 20 ppm, pH 6.7, landing 8th day.

DESCRIPTION OF SYMBOLS 10 Apparatus used for implementation of the manufacturing method of the slightly acidic hypochlorous acid water containing a fine bubble 11 Pump 12 Gas intake path 13 Liquid intake path 14 Air flow regulator 15 Carbon dioxide cylinder 16 Gas source 17 Control valve 18 Sterilizer production | generation part DESCRIPTION OF SYMBOLS 19, 21 Piping 20 Mixing tank 22 Fine bubble production | generation nozzle 23 Fine bubble mixing liquid tank 24 Inlet 25 Collision wall surface 26 Nozzle hole 27 Nozzle case 28 Plate surface 29 Fine hole 30 Compression expansion member 31 Stirring member 32 Gap 33 Slits 34, 35 Stirring means B Microbubble

Claims (3)

A method of manufacturing a slightly acidic hypochlorous acid water containing fine bubbles dissolved carbon dioxide gas and nitrogen gas,
A step of mixing carbon dioxide gas and nitrogen gas with a pump in an electrolytic hypochlorous acid or sodium hypochlorite aqueous solution diluted to a desired effective chlorine concentration to prepare pH 5-6 hypochlorous acid water,
Resulting the hypochlorous acid solution of slightly acidic conducts the microbubble generator, by injecting a fine bubble generating nozzle, to produce the following fine-bubble particle size 50μm in the hypochlorous acid solution method for producing a slightly acidic hypochlorous acid water which is characterized in that a step. Carbon dioxide gas and nitrogen gas are mixed using a pump with electrolytic hypochlorous acid or sodium hypochlorite aqueous solution diluted to a desired effective chlorine concentration to prepare pH 5-6 hypochlorous acid water ,
By passing the obtained slightly acidic hypochlorous acid water through a microbubble generator and spraying it from a microbubble generating nozzle, microbubbles having a particle diameter of 50 μm or less are generated, and the next containing microbubbles Producing chlorite water,
The hypochlorous acid water is adjusted to an effective chlorine concentration of 5 to 20 ppm and pH is 5.0 to 6.7, poured into a bucket, and cut flowers are inserted into the slightly acidic hypochlorous acid water containing the fine bubbles for landing. A method of using slightly acidic hypochlorous acid water characterized by that. Carbon dioxide gas and nitrogen gas are mixed using a pump with electrolytic hypochlorous acid or sodium hypochlorite aqueous solution diluted to a desired effective chlorine concentration to prepare pH 5-6 hypochlorous acid water ,
By passing the obtained slightly acidic hypochlorous acid water through a microbubble generator and spraying it from a microbubble generating nozzle, microbubbles having a particle diameter of 50 μm or less are generated, and the next containing microbubbles Producing chlorite water,
The hypochlorous acid solution, by spraying in a closed space existing object or it with spray means, to form an effective chlorine concentration 10 to 30 ppm, PH5.0～6.9 environment, the target A method of using slightly acidic hypochlorous acid water characterized by sterilizing a product or the enclosed space.

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