JP2024089221A - Method for producing chlorine dioxide-containing water, method for spraying chlorine dioxide-containing water, and kit for spraying chlorine dioxide-containing water - Google Patents

Abstract

To provide a method for producing chlorine dioxide-containing water which can be stored for a long time in the form of a pack and can be used as a liquid by producing chlorine dioxide-containing water during use.SOLUTION: A method for producing chlorine dioxide-containing water includes a step for preparing a chlorine dioxide-generating agent pack including a chlorine dioxide-generating agent and a gas-liquid permeable container which contains the chlorine dioxide-generating agent and permeates water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide, and a step for producing the chlorine dioxide-containing water by bringing the chlorine dioxide-generating agent pack into contact with water.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing chlorine dioxide-containing water, a method for spraying chlorine dioxide-containing water, and a chlorine dioxide-containing water spray kit.

Chlorine dioxide solutions containing chlorine dioxide are provided as disinfectants or deodorants because the strong oxidizing action of chlorine dioxide can sterilize or decompose malodorous components. Patent Document 1 (International Publication WO 2008/111358) discloses a stabilizing composition for chlorine dioxide, which is characterized in that the composition is a combination of a chlorite and a pH adjuster, and the pH adjuster is a buffering acid or its salt (e.g., phosphoric acid or its salt) that provides a pH of 2.5 to 6.8 in a 5% aqueous solution at 25°C. Patent Document 2 (International Publication WO 2009/093540) discloses a chlorine dioxide solution composition whose solutes consist of dissolved chlorine dioxide and a chlorite.

Furthermore, Patent Document 3 (JP 2012-245434 A) discloses a chlorine dioxide gas generator pack including a chlorine dioxide gas generator containing a mixture of chlorite powder, gas generation regulator powder, moisture absorbent powder, water-absorbent resin powder, and activator powder, and a gas-permeable membrane container that contains the chlorine dioxide gas generator and is permeable to water vapor and chlorine dioxide gas, and a method for manufacturing the same.

International Publication No. 2008/111358 International Publication No. 2009/093540 JP 2012-245434 A

The chlorine dioxide liquid compositions disclosed in Patent Documents 1 and 2 contain dissolved chlorine dioxide, and therefore have a short storage period of about one month from production to the start of use. The chlorine dioxide gas generator pack disclosed in Patent Document 3 can be stored for an extremely long period of six months or more, preferably one year or more, as long as it is stored in an airtight container, but has a problem in that it cannot be applied or sprayed as a liquid, because it generates chlorine dioxide gas directly from a solid powder.

The present invention aims to provide a method for producing chlorine dioxide-containing water that can be stored in a pack for a long period of time (e.g., six months or more) and that can be used as a liquid by producing chlorine dioxide-containing water when in use, a method for spraying chlorine dioxide-containing water, and a chlorine dioxide-containing water spray kit.

A method for producing chlorine dioxide-containing water according to one embodiment of the present invention includes the steps of preparing a chlorine dioxide generator pack including a chlorine dioxide generator and a gas-liquid permeable container that contains the chlorine dioxide generator and is permeable to water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide, and producing chlorine dioxide-containing water by contacting the chlorine dioxide generator pack with water.

A method for spraying chlorine dioxide-containing water according to another embodiment of the present invention includes the steps of preparing a chlorine dioxide generator pack including a chlorine dioxide generator and a gas-liquid permeable container that contains the chlorine dioxide generator and is permeable to water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide, producing chlorine dioxide-containing water by contacting the chlorine dioxide generator pack with water, and spraying the chlorine dioxide-containing water.

According to yet another embodiment of the present invention, a chlorine dioxide-containing water spray kit includes a chlorine dioxide generator pack including a chlorine dioxide generator and a gas-liquid permeable container that contains the chlorine dioxide generator and is permeable to water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide, and a sprayer that sprays the chlorine dioxide-containing water obtained by contacting the chlorine dioxide generator pack with water.

The present invention provides a method for producing chlorine dioxide-containing water, a method for spraying chlorine dioxide-containing water, and a chlorine dioxide-containing water spray kit that can be stored in a pack for a long period of time and can produce chlorine dioxide-containing water at the time of use and use it as a liquid agent.

FIG. 1 is a flow chart showing an example of a method for producing chlorine dioxide-containing water or a method for spraying chlorine dioxide-containing water according to the present invention. 2 is a schematic diagram showing an example of a chlorine dioxide generator pack used in the present invention and a method for producing the same, in which (A) shows an example of a film for a gas-liquid permeable container, and (B) shows an example of a chlorine dioxide generator pack in which a chlorine dioxide generator is stored in a gas-liquid permeable container. FIG. 3 is a schematic diagram showing an example of a method for storing a chlorine dioxide generator pack used in the present invention. FIG. 4 is a schematic diagram showing an example of a sprayer for storing chlorine dioxide-containing water obtained by contacting the chlorine dioxide generator pack used in the present invention with water. FIG. 5 is a chart showing an example of a chlorine dioxide-containing water spray kit according to the present invention. FIG. 6 is a graph showing the daily changes in the average values of the chlorine dioxide concentration, sodium chlorite, and pH of unused chlorine dioxide-containing water after the production of chlorine dioxide-containing water in Example 1. 7 is a schematic diagram showing a room where Example 2 was carried out, in which (A) shows the installation location of a circulator in the room, the spraying position and spraying direction of chlorine dioxide-containing water, and (B) shows the measurement position of chlorine dioxide gas concentration in the room. FIG. 8 is a graph showing the change over time in chlorine dioxide gas concentration after spraying of chlorine dioxide-containing water in a room in Example 2. FIG. 9 is a graph showing the daily changes in the average values of the chlorine dioxide concentration, sodium chlorite, and pH of the chlorine dioxide-containing water during use after production of the chlorine dioxide-containing water in Example 3.

<Embodiment 1>
Referring to FIG. 1, a method M1 for producing chlorine dioxide-containing water, which is an embodiment of the present invention, includes a step S1 of preparing a chlorine dioxide generator pack including a chlorine dioxide generator and a gas-liquid permeable container for storing the chlorine dioxide generator and allowing water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide to pass therethrough, and a step S2 of producing chlorine dioxide-containing water by contacting the chlorine dioxide generating pack with water.

The method for producing chlorine dioxide-containing water of this embodiment includes the above steps S1 and S2, so that the chlorine dioxide generator pack 1 shown in FIG. 2 prepared in step S1 can be stored for a long period of time, such as six months or more, by storing it in an airtight container 30 shown in FIG. 3. In addition, in step S2, the chlorine dioxide generator pack can be brought into contact with water at the time of use to produce chlorine dioxide-containing water.

<1> Step of Preparing Chlorine Dioxide Generator Pack The step of preparing a chlorine dioxide generator pack includes a sub-step of receiving or manufacturing a chlorine dioxide generator pack, and a sub-step of storing the chlorine dioxide generator pack.

[Chlorine dioxide generator pack]
2, the chlorine dioxide generator pack 1 prepared in step S1 includes a chlorine dioxide generator 10 and a gas-liquid permeable container 20 that contains the chlorine dioxide generator 10 and allows water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide to pass through. When the chlorine dioxide generator pack 1 comes into contact with water, the water molecules in the water permeate the gas-permeable container 20 as water vapor (gas) and water (liquid) to generate chlorine dioxide gas and/or dissolved chlorine dioxide that is present in the water, and the generated chlorine dioxide gas permeates out of the gas-liquid permeable container 20 and dissolves in water to become dissolved chlorine dioxide, and/or the generated dissolved chlorine dioxide permeates out of the gas-liquid permeable container 20 to produce chlorine dioxide-containing water.

{Chlorine dioxide generator}
The chlorine dioxide generator 10 includes a chlorite powder, an activator powder, a chlorine dioxide generation regulator powder, a moisture absorbent powder, a water-absorbent resin powder, etc. Since the chlorine dioxide generator 10 includes these powders, the chlorite powder and the activator powder can be gradually reacted in the presence of moisture to gradually generate the chlorine dioxide gas and/or the dissolved chlorine dioxide.

(Chlorite powder)
The chlorite powder is a powder of chlorite, and is not particularly limited as long as it reacts with the activator powder in the presence of moisture to generate the chlorine dioxide gas and/or the dissolved chlorine dioxide, and examples thereof include alkali metal chlorite powders such as sodium chlorite (NaClO ₂ ) powder, potassium chlorite (KClO ₂ ) powder, and lithium chlorite (LiClO ₂ ) powder, and alkaline earth metal chlorite such as calcium chlorite (Ca(ClO ₂ ) ₂ ) powder, magnesium chlorite (Mg(ClO ₂ ) ₂ ) powder, and barium chlorite (Ba(ClO ₂ ) ₂ ) powder. Among these, sodium chlorite powder is designated as a food additive, so it is highly safe, easy to obtain, and has few restrictions on use.

(Activator powder)
The activator powder refers to a powder that reacts with chlorite in the presence of moisture to generate the chlorine dioxide gas and/or the dissolved chlorine dioxide, and is not particularly limited, and inorganic acid powder, organic acid powder, bleaching powder, isocyanuric acid powder, etc. are used. Among these, organic acid powder is preferably used from the viewpoint of easy handling. Examples of organic acid powder include carboxylic acid powder such as citric acid powder, malic acid powder, acetic acid powder, formic acid powder, lactic acid powder, tartaric acid powder, and oxalic acid powder.

(Chlorine dioxide generation regulator powder)
The chlorine dioxide generation regulator powder refers to a powder for gradually and continuously generating the chlorine dioxide gas and/or the dissolved chlorine dioxide generated by the reaction of the chlorite powder and the activator powder in the presence of moisture, thereby producing chlorine dioxide-containing water.That is, when the amount of the chlorine dioxide gas and/or the dissolved chlorine dioxide generated is large, the chlorine dioxide generation regulator powder holds at least a part of the chlorine dioxide gas and/or the dissolved chlorine dioxide on its surface and/or inside, and when the amount of the chlorine dioxide gas and/or the dissolved chlorine dioxide generated decreases or disappears, it releases the chlorine dioxide gas and/or the dissolved chlorine dioxide that it has held, thereby gradually and continuously generating the chlorine dioxide gas and/or the dissolved chlorine dioxide from the chlorine dioxide generator.

The chlorine dioxide generation regulator powder is not particularly limited in material and shape as long as it can efficiently disperse the generation of the chlorine dioxide gas and/or the dissolved chlorine dioxide, but from the viewpoint of being able to hold a large amount of the chlorine dioxide gas and/or the dissolved chlorine dioxide, it is preferable that it is porous with a large surface area, and is preferably at least one selected from the group consisting of sepiolite, montmorillonite, diatomaceous earth, talc and zeolite. Also, from the viewpoint of increasing the surface area, it is preferable that it is powdery, granular, flat, fibrous and/or porous. Among the above gas generation regulators, sepiolite is preferable from the viewpoint of excellent retention and release of the chlorine dioxide gas and/or the dissolved chlorine dioxide. Here, sepiolite is a natural mineral of _{magnesium silicate} salt, and its chemical formula is said to be _Mg8Si12O30 ( _OH2 ) ₄ (OH) _4.8H2O . Its crystal structure is fibrous, and it has many grooves on its surface and many clearances with _cylindrical tunnel structures inside, making it a substance with an extremely large surface area.

(Moisture absorbent powder)
The moisture absorbent powder refers to a powder that absorbs water molecules in water as water vapor and/or water through the gas-liquid permeable container 20 and supplies the moisture to the chlorine dioxide generator 10, and has the function of generating the chlorine dioxide gas and/or the dissolved chlorine dioxide by the reaction between the chlorite powder and the activator powder. The moisture absorbent powder is not particularly limited, but from the viewpoint of high hygroscopicity, calcium chloride (CaCl ₂ ) powder, sodium chloride (NaCl) powder, magnesium oxide (MgO) powder, etc. are preferred.

(Water-absorbent resin powder)
The water-absorbent resin powder refers to a resin powder that absorbs and retains the moisture supplied to the chlorine dioxide generator 10 by the moisture absorbent powder to promote the reaction between the chlorite powder and the activator powder in the chlorine dioxide generator 10, and by retaining the chlorine dioxide gas and/or the dissolved chlorine dioxide generated by the reaction between the chlorite powder and the activator powder in the presence of absorbed moisture, it also has a function of regulating the generation of the chlorine dioxide gas and/or the dissolved chlorine dioxide from the chlorine dioxide generator 10, similar to the chlorine dioxide generation regulator powder. The water-absorbent resin powder is not particularly limited as long as it absorbs and retains moisture to generate the chlorine dioxide gas and/or the dissolved chlorine dioxide from the chlorine dioxide generator 10 and retains the generated chlorine dioxide gas and/or the dissolved chlorine dioxide, but from the viewpoint of high retention of the chlorine dioxide gas and/or the dissolved chlorine dioxide, starch-based water-absorbent resin powder, cellulose-based water-absorbent resin powder, synthetic polymer-based water-absorbent resin powder, etc. are preferred. The starch-based water-absorbent resin powder includes starch/polyacrylic acid-based resin (powder, manufactured by Sanyo Chemical Industries, Ltd.), and the synthetic polymer-based water-absorbent resin includes crosslinked polyacrylic acid-based resin powder, isobutylene/maleic acid-based resin powder, popar/polyacrylate-based resin powder, polyacrylate-based resin powder, and specifically, sodium polyacrylate powder is used.

Here, the chlorine dioxide generator 10 is not particularly limited, but from the viewpoint of continuously generating the chlorine dioxide gas and/or the dissolved chlorine dioxide, it is preferable that the chlorite powder is 1.5% by mass to 15% by mass, the chlorine dioxide generation regulator powder is 8% by mass to 50% by mass, the moisture absorbent powder is 1.5% by mass to 15% by mass, the water absorbent resin powder is 8% by mass to 50% by mass, and the activator powder is 1.5% by mass to 15% by mass, respectively, calculated on a pure product basis. Note that, from the viewpoint of not being a toxic or deleterious substance, it is preferable that the ratio of the mass of the chlorite to the total mass of the chlorine dioxide generator is 25% by mass or less.

{Gas-liquid permeable container}
The gas-liquid permeable container 20 is a container that hermetically stores the chlorine dioxide generator 10 and is permeable to water vapor and chlorine dioxide gas, which are gases, and water and dissolved chlorine dioxide, which are liquids. The gas-liquid permeable container 20 is not particularly limited as long as it is permeable to the above gases and liquids, but from the viewpoint of suppressing the sudden generation of the chlorine dioxide gas and/or the dissolved chlorine dioxide at the beginning of the contact between the chlorine dioxide generating pack 1 and water, it is possible to apply a water-repellent treatment and/or a waterproof treatment that is effective only for a predetermined period after contact with water. As the gas-liquid permeable container 20, for example, a gas-permeable membrane such as Type A-1 to A-5 (Japanese Paper Type) and Type B-1 to B-2 (Film Type) of Typical properties of POWSTO manufactured by ENEOS Techno Materials Co., Ltd. is preferably formed into a bag by sealing the outer edge of the membrane.

[Sub-process of receiving or manufacturing chlorine dioxide generator pack]
Referring to FIG. 2, the chlorine dioxide generator pack 1 may be received, with or without payment, or may be manufactured as follows.

The chlorine dioxide generator pack 1 can be manufactured by mixing chlorite powder, activator powder, chlorine dioxide generation regulator powder, moisture absorbent powder, and water-absorbent resin powder to prepare the chlorine dioxide generator 10, and storing the resulting chlorine dioxide generator 10 in a gas-liquid permeable container 20.

In order to reduce the contact between the chlorite powder and the activator during mixing and to suppress or prevent the generation of chlorine dioxide gas before use, it is preferable to mix the chlorite powder and the chlorine dioxide generation regulator powder to prepare agent A 10a, mix the moisture absorbent, water-absorbent resin powder, and activator powder to prepare agent B 10b, and then mix agent A 10a and agent B 10b. Furthermore, agent A 10a and agent B 10b may be mixed in a gas-liquid permeable container 20. There are no particular limitations on the method for mixing the powders, but shaking mixing, ultrasonic mixing, stirring mixing, high-speed mixing, etc. are suitable from the viewpoint of homogeneous mixing.

Also, referring to FIG. 2, the method of storing the chlorine dioxide generator 10 in the gas-liquid permeable container 20 is not particularly limited, but from the viewpoint of efficient sealing with good yield, it is preferable to fold the film for the gas-liquid permeable container 20 (hereinafter also referred to as the film for the gas-liquid permeable container) in half as shown in FIG. 2(A), seal a certain area 20s from the outer edge of two of the three sides 20e other than the folded side 20b as shown in FIG. 2(B) to form a bag-shaped gas-liquid permeable container 20, store the chlorine dioxide generator 10 (A agent 10a and B agent 10b when A agent and B agent are mixed in the gas-liquid permeable container 20) in the gas-liquid permeable container 20 from one side of the opening, and seal a predetermined area 20s from the outer edge of the one side of the opening. In addition, the preparation of the chlorine dioxide generator 10 and its storage in the gas-liquid permeable container 20 are preferably carried out in a dry atmosphere with a relative humidity of 35% or less or in a vacuum in order to suppress or prevent the inclusion of water vapor (moisture), which is water molecules in the air.

[Sub-step of storing chlorine dioxide generator pack]
Since the chlorine dioxide generator pack 1 allows not only water but also moisture (water vapor) in the air to permeate into the permeable container 20, if the pack is left in the air for a long period of time before contacting it with water to produce chlorine dioxide-containing water, chlorine dioxide gas is gradually and continuously generated, and the production capacity of chlorine dioxide-containing water is reduced or lost. To solve this problem, the chlorine dioxide generator pack 1 that has been acquired or manufactured is stored in the airtight container 30 until the step S2 of producing chlorine dioxide-containing water. This allows the chlorine dioxide generator pack 1 to be stored for a long period of time of six months or more, preferably one year or more.

Referring to FIG. 3, the chlorine dioxide generator pack 1 is stored in an airtight container 30. There is no particular restriction on the method of storing the chlorine dioxide generator pack 1 in the airtight container 30, but from the viewpoint of suppressing or preventing the intrusion of moisture (water vapor) in the air, a method of storing the chlorine dioxide generator pack 1 through the opening of the airtight container 30 and then sealing the opening is preferable. Here, the airtight container 30 is not particularly limited, but from the viewpoint of easy sealing by sealing and high airtightness, an aluminum-containing container that can be heat-sealed is preferable, for example, an aluminum laminate film in which an aluminum foil and a plastic film are laminated, and an aluminum vapor deposition film in which aluminum is vapor-deposited on a plastic film, etc. are preferably mentioned. There is no particular restriction on the material of the plastic film as long as it can be heat-sealed and has high airtightness, and PE (polyethylene), PP (polypropylene), PET (polyethylene terephthalate), etc. are preferably mentioned.

<2> Step of producing chlorine dioxide-containing water With reference to Fig. 2 and Fig. 4, the chlorine dioxide-containing water 2c can be produced by contacting the chlorine dioxide generator pack 1 with the water 2w. Specifically, when the chlorine dioxide generator pack 1 is contacted with the water 2w, the chlorine dioxide generator 10 in the chlorine dioxide generator pack 1 absorbs and takes in the moisture that has permeated the water 2w into the gas-liquid permeable container 20 as water vapor and/or water using the moisture absorbent powder, and the water absorbent resin powder absorbs the moisture, causing the chlorite powder and the activator powder to react gradually to gradually produce chlorine dioxide gas, and/or the generated chlorine dioxide gas dissolves in the moisture to gradually produce dissolved chlorine dioxide. The generated chlorine dioxide gas and/or dissolved chlorine dioxide are held by the water absorbent resin powder and the chlorine dioxide generation regulator powder, so that chlorine dioxide gas and/or dissolved chlorine dioxide are gradually and continuously generated. The generated chlorine dioxide gas permeates out of the gas-liquid permeable container 20 and dissolves in the water 2w to become dissolved chlorine dioxide, and/or the generated dissolved chlorine dioxide permeates out of the gas-liquid permeable container 20, thereby obtaining chlorine dioxide-containing water 2c.

There are no particular limitations on the water 2w as long as it does not interfere with the generation, generation, and dissolution of chlorine dioxide gas into water. Pure water, distilled water, ion-exchanged water, as well as spring water, groundwater, well water, tap water, etc. can be suitably used. There are no particular limitations on the chlorine dioxide concentration of the chlorine dioxide-containing water 2c, but from the viewpoint of being effective for sterilization and/or deodorization, it is preferably 100 ppm or more, more preferably 150 ppm or more, and even more preferably 200 ppm or more, and from the viewpoint of suppressing loss due to gasification of chlorine dioxide, it is preferably 8000 ppm or less, more preferably 2000 ppm or less, and even more preferably 500 ppm or less. The chlorine dioxide concentration and chlorite concentration of the chlorine dioxide-containing water 2c are measured by iodometric titration.

<Embodiment 2>
Referring to FIG. 1, a method M2 for spraying chlorine dioxide-containing water, which is another embodiment of the present invention, includes a step S1 of preparing a chlorine dioxide generator pack including a chlorine dioxide generator and a gas-liquid permeable container for storing the chlorine dioxide generator and allowing water vapor, chlorine dioxide gas, water and dissolved chlorine dioxide to pass through, a step S2 of producing chlorine dioxide-containing water by contacting the chlorine dioxide generating pack with water, and a step S3 of spraying the chlorine dioxide-containing water.

The method M2 for spraying chlorine dioxide-containing water of this embodiment includes the above steps S1, S2, and S3, and therefore allows the chlorine dioxide generator pack to be stored in an airtight container for a long period of time, such as six months or more, and when in use, the chlorine dioxide generator pack is brought into contact with water to produce chlorine dioxide-containing water, which can then be repeatedly sprayed at a stable concentration.

The process S1 of preparing a chlorine dioxide generator pack and the process S2 of producing chlorine dioxide-containing water in this embodiment are the same as the process S1 of preparing a chlorine dioxide generator pack <1> and the process S2 of producing chlorine dioxide-containing water in embodiment 1, respectively, and therefore will not be described again.

<3> Step of spraying chlorine dioxide-containing water With reference to Figures 2 and 4, the chlorine dioxide-containing water 2c obtained as described above is sprayed. There is no particular limitation on the method of spraying the chlorine dioxide-containing water 2c, and any type of system such as a trigger type, a pressurized type, or a pressure accumulation type, and any type of power such as manual or electric, may be used, and for example, a manual trigger type sprayer 3 shown in Figure 4 may be used. The trigger type sprayer 3 includes, for example, a head portion 3a and a bottle portion 3b.

When using the sprayer 3 shown in FIG. 4, the chlorine dioxide generator pack 1 and water 2w are stored in the bottle part 3b, and then the head part 3a is attached to the bottle part 3b. In the bottle part 3b, the chlorine dioxide generator pack 1 and the water 2w come into contact with each other, and as described in the above-mentioned <2> Step of producing chlorine dioxide-containing water, chlorine dioxide-containing water 2c is obtained. By pulling the lever of the head part 3a, the chlorine dioxide-containing water 2c is sprayed into the atmosphere. The sprayed chlorine dioxide-containing water 2c comes into contact with harmful components such as bacteria or bad odors in the atmosphere, and has a sterilizing or deodorizing effect due to the strong oxidizing action of the dissolved chlorine dioxide therein. Furthermore, the dissolved chlorine dioxide in the sprayed chlorine dioxide-containing water is vaporized into chlorine dioxide gas, which is diffused into the atmosphere. Such chlorine dioxide gas comes into contact with harmful components such as bacteria or bad odors in the atmosphere, and has a sterilizing or deodorizing effect due to its strong oxidizing action.

The chlorine dioxide concentration of the chlorine dioxide-containing water 2c is not particularly limited, but from the viewpoint of being effective for sterilization and/or deodorization, it is preferably 100 ppm or more, more preferably 150 ppm or more, and even more preferably 200 ppm or more, and from the viewpoint of suppressing loss due to gasification of chlorine dioxide, it is preferably 8000 ppm or less, more preferably 2000 ppm or less, and even more preferably 500 ppm or less. The chlorine dioxide concentration and chlorite concentration of the chlorine dioxide-containing water 2c are measured by iodometric titration.

There are no particular restrictions on the concentration of chlorine dioxide gas released into the atmosphere, but from the viewpoint of being effective for sterilization or deodorization, a concentration of 10 ppb or more is preferable, and from the viewpoint of reducing the burden on the environment, a concentration of 0.1 ppm (100 ppb) or less is preferable. The concentration of chlorine dioxide gas in the atmosphere is measured using a gas detection sensor when it is less than 0.5 ppm, and using a Kitagawa detector tube when it is 0.5 ppm or more.

<Embodiment 3>
1 to 5, a chlorine dioxide-containing water spray kit K1, which is yet another embodiment of the present invention, includes a chlorine dioxide generator pack 1, P1 including a chlorine dioxide generator 10 and a gas-liquid permeable container 20 for storing the chlorine dioxide generator and allowing water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide to pass through, and a sprayer 3, P2 for spraying chlorine dioxide-containing water 2c obtained by contacting the chlorine dioxide generating pack 1 with water 2w.

The chlorine dioxide-containing water spray kit of this embodiment includes the above-mentioned chlorine dioxide generator pack and the above-mentioned sprayer, and during use, the chlorine dioxide generator pack is brought into contact with water to produce chlorine dioxide-containing water, and the chlorine dioxide-containing water can be repeatedly sprayed at a stable concentration.

[Chlorine dioxide generator pack]
The chlorine dioxide generator pack 1, P1 included in the chlorine dioxide-containing water spray kit of this embodiment is the same as the chlorine dioxide generator pack 1 described in embodiment 1, so the description thereof will not be repeated.

[Sprayer]
The sprayer 3, P2 included in the chlorine dioxide-containing water spray kit of this embodiment may be of any type, such as a trigger type, a pressurized type, or a pressure-accumulating type, and may be of any power, such as a manual or electric type, as with the sprayer 3 described in the second embodiment, but from the viewpoint of high convenience as a kit, a manual trigger type sprayer 3 shown in Fig. 4 is preferable. The trigger type sprayer 3 includes, for example, a head part 3a and a bottle part 3b. There is no particular limitation on the sprayer 3 as long as it can reliably enclose the chlorine dioxide-containing water 2c to be stored, and for example, one made of polyethylene is preferable.

In addition to the chlorine dioxide generator pack P1 and sprayer P2, the chlorine dioxide-containing water spray kit K1 of this embodiment preferably further includes an airtight container 30, P1A for storing the chlorine dioxide generator pack 1. By including the chlorine dioxide generator pack P1, the sprayer P2, and the airtight container P1A, the chlorine dioxide-containing water spray kit K1 can store the chlorine dioxide generator pack for a long period of time, such as six months or more, in the airtight container, and when in use, can produce chlorine dioxide-containing water by contacting the chlorine dioxide generator pack with water, and can repeatedly spray the chlorine dioxide-containing water at a stable concentration.

[Airtight container]
3, the airtight container 30 of this embodiment is the same as the airtight container described in the first embodiment, and therefore the description thereof will not be repeated.

[Example 1]
Chlorine dioxide-containing water was produced according to the following procedure, and the dissolved chlorine dioxide concentration, the dissolved sodium chlorite concentration, and the pH of the produced chlorine dioxide-containing water were examined for changes over time.

(1) Production of chlorine dioxide-containing water Referring to FIG. 4, 250 g of water 2w (tap water) was placed in the bottle portion 3b (capacity 300 ml) of a 300 ml polyethylene manual trigger sprayer (T-95 C7S N/N LB=180, manufactured by Tasman Co., Ltd.) which is the sprayer 3, and then 105 specimens were prepared by placing a chlorine dioxide generator pack 1 therein. Referring to FIG. 2, the chlorine dioxide generator pack 1 used here was a gas-liquid permeable container containing the following chlorine dioxide generator. The gas-liquid permeable container 20 was a 100 mm wide x 80 mm long gas-liquid permeable container film (Typical properties of A POWSTO Type B-2 was folded in half in the width direction, and two of the three sides 20e other than the folded side 20b were heat-sealed in a region 20s 10 mm from the outer edge to obtain a gas-liquid-permeable container 20. The following chlorine dioxide generator 10 was then placed in the gas-liquid-permeable container 20, and a region 20s 10 mm from the outer edge of one side of the opening was then heat-sealed. Here, the gas-liquid-permeable membrane was treated to be water-repellent so as to be water-impermeable for one day (24 hours) after contact with water. The chlorine dioxide generator was 0.31 g of chlorite powder. The powder mixture was 80% by mass sodium chlorite powder (manufactured by Nippon Carlit Co., Ltd.), 1.29 g of sepiolite (Miraclair P-150, manufactured by Omi Mining Co., Ltd.) as a gas generation regulator powder, 0.28 g of calcium chloride H powder for food additives (manufactured by Tomita Pharmaceutical Co., Ltd.) as a moisture absorbent powder, 1.13 g of acrylate-based water absorbent resin powder (Sunfreffu ST-500D, manufactured by Sanyo Chemical Industries Co., Ltd.) as a water absorbent resin powder, and 0.28 g of malic acid powder (manufactured by Fuso Chemical Co., Ltd.) as an activator powder.

(2) Measurement of daily changes in the concentration of dissolved chlorine dioxide, the concentration of dissolved sodium chlorite, and the pH of the chlorine dioxide-containing water after production The 105 samples produced were left standing in two rooms at our company, (i) indoors (3-27°C) or (ii) in a constant temperature room (20°C). One day, two days, three days, four days, five days, six days, seven days, eight days, nine days, ten days, fifteen days, twenty days, twenty-five days, and thirty days after production (meaning contact between the chlorine dioxide generator pack and water, the same applies below), three samples were taken out from each of the rooms (i) and (ii), and the dissolved chlorine dioxide concentration, dissolved sodium chlorite concentration, and pH of the chlorine dioxide-containing water of each sample were measured. The dissolved chlorine dioxide concentration and the dissolved sodium chlorite concentration were measured by iodometric titration, and the pH was measured by a pH meter (Portable pH/ORP meter D-72 manufactured by Horiba, Ltd.). The results are shown in Tables 1 to 3. Furthermore, the daily changes in the average values of the dissolved chlorine dioxide concentration, the dissolved sodium chlorite concentration, and the pH of the chlorine dioxide-containing water of each of the samples (i) and (ii) are summarized in FIG. 6.

Referring to FIG. 6, the average value of the dissolved chlorine dioxide concentration of the chlorine dioxide-containing water was 100 ppm or more three days after production in both cases (i) and (ii). When the dissolved chlorine dioxide concentration of the chlorine dioxide-containing water is 100 ppm or more, the bactericidal effect and/or deodorizing effect of spraying the chlorine dioxide-containing water becomes large, so in this embodiment, spraying after three days or more have passed since production is recommended. Note that, referring to Table 1, the dissolved chlorine dioxide concentration of the chlorine dioxide-containing water of No. 1 in (i) and No. 3 in (ii) was less than 100 ppm after three days and was 100 ppm or more after four days. From this, taking into account the variation depending on the sample, spraying after four days or more have passed since production is more recommended in this embodiment. The number of days from production until the dissolved chlorine dioxide concentration in the chlorine dioxide-containing water reaches 100 ppm or more can be shortened by reducing or eliminating the water-repellent and/or waterproofing treatment of the gas-liquid permeable container and/or by increasing the contact efficiency between the chlorine dioxide generator pack and water (for example, by shaking the chlorine dioxide pack in water).

The average dissolved chlorine dioxide concentration in the chlorine dioxide-containing water reached a maximum (approximately 270 ppm) 15 to 25 days after production in the case of (i), and a maximum (approximately 290 ppm) 5 to 8 days after production in the case of (ii), and remained stable and high up to 30 days after production in both cases (i) and (ii). From this, it is believed that in this embodiment, the bactericidal effect and/or deodorizing effect of spraying the chlorine dioxide-containing water is large for at least 30 days after production.

[Example 2]
In our company's room (width 2930 mm x depth 3370 mm x height 2200 mm, air conditioner set temperature 20°C) shown in Figures 7(A) and (B) (door closed), chlorine dioxide-containing water was sprayed six times from the No. 1 specimen (dissolved chlorine dioxide concentration 299 ppm) in the case of (ii) in Example 1, which was produced 7 days ago, and the chlorine dioxide gas concentration was measured immediately after spraying (0 hours), 1 hour, 2 hours, 3 hours, and 4 hours later. The measurement points were the four measurement points (1) to (4) shown in Figure 7(B). The chlorine dioxide gas concentration was measured using XPS-7II (sensor: XDS-7C4 ClO ₂ 500 ppb) manufactured by Shin Cosmos Electric Co., Ltd. The circulator used was KCF-MKM151-W manufactured by Iris Ohyama Co., Ltd. The results are summarized in Figure 8.

Referring to Figure 8, at all four measurement points (1) to (4) and their average, the chlorine dioxide gas concentration was 0 ppb one hour or more after spraying. In other words, it was found that the room can be used comfortably one hour or more after spraying, even in a room with the door closed.

[Example 3]
Chlorine dioxide-containing water was produced on January 11, 2022 using the same procedure as in Example 1, and while standing indoors (3 to 27 ° C.) as in Example 1 (i), 39 samples were sprayed five times per business day (company business days, i.e., weekdays excluding Saturdays, Sundays, and holidays, the same below) from January 11 to March 11, 2022, and 21 samples were sprayed nine times per business day from January 11 to February 10, 2022. (a) For the 39 samples that were sprayed five times, three samples were taken out 5 days, 10 days, 15 days, 20 days, 25 days, 30 days, 36 days, 40 days, 45 days, 50 days, 55 days, and 60 days after the date of production, and the dissolved chlorine dioxide concentration, dissolved sodium chlorite concentration, and pH of the chlorine dioxide-containing water of each sample were measured in the same manner as in Example 1. In addition, for the 21 samples (b) that were sprayed 9 times, three samples were taken out 5, 10, 15, 20, 25, and 30 days after the date of manufacture, and the dissolved chlorine dioxide concentration, dissolved sodium chlorite concentration, and pH of the chlorine dioxide-containing water of each sample were measured in the same manner as in Example 1. The results are shown in Tables 4 to 6. The daily changes in the average values of the dissolved chlorine dioxide concentration, dissolved sodium chlorite concentration, and pH of the chlorine dioxide-containing water of each sample (a) and (b) are summarized in Figure 9.

Referring to FIG. 9, (a) in the case of five sprays, the dissolved chlorine dioxide concentration was stable in the range of 201 to 308 ppm, and the pH was stable in the range of 5.44 to 5.79, from 5 to 60 days after the date of manufacture. (b) in the case of nine sprays, the dissolved chlorine dioxide concentration was stable in the range of 174 to 311 ppm, and the pH was stable in the range of 5.48 to 5.94, from 5 to 30 days after the date of manufacture. From this, it was found that the chlorine dioxide-containing water of this embodiment can be stably used for up to 30 days, preferably up to 60 days, from the date of manufacture, when sprayed and used every business day from the date of manufacture.

The embodiments and examples disclosed herein are illustrative in all respects and should not be considered limiting. The scope of the present invention is indicated by the claims rather than the embodiments and examples described above, and is intended to include all modifications within the scope of the claims and meanings equivalent thereto.

1 Chlorine dioxide generator pack, 2c Chlorine dioxide-containing water, 2w Water, 3 Sprayer, 10 Chlorine dioxide generator, 10a Agent A, 10b Agent B, 20 Gas-liquid permeable container, 20s, 20t Sealing part, 30 Airtight container, 30r Zipper part.

Claims (8)

Preparing a chlorine dioxide generator pack including a chlorine dioxide generator and a gas-liquid permeable container that contains the chlorine dioxide generator and is permeable to water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide;
and producing chlorine dioxide-containing water by contacting the chlorine dioxide generator pack with the water. The method for producing chlorine dioxide-containing water according to claim 1, wherein the dissolved chlorine dioxide concentration in the chlorine dioxide-containing water is 100 ppm or more. Preparing a chlorine dioxide generator pack including a chlorine dioxide generator and a gas-liquid permeable container that contains the chlorine dioxide generator and is permeable to water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide;
producing chlorine dioxide-containing water by contacting the chlorine dioxide generator pack with the water;
A method for spraying chlorine dioxide-containing water, comprising the step of spraying the chlorine dioxide-containing water. The method for spraying chlorine dioxide-containing water according to claim 3, wherein the dissolved chlorine dioxide concentration in the chlorine dioxide-containing water is 100 ppm or more. The method for spraying chlorine dioxide-containing water according to claim 3 or claim 4, wherein the step of producing the chlorine dioxide-containing water is carried out in a spray container. A chlorine dioxide generator pack including a chlorine dioxide generator and a gas-liquid permeable container that contains the chlorine dioxide generator and is permeable to water vapor, chlorine dioxide gas, water, and dissolved chlorine dioxide;
and a sprayer for spraying the chlorine dioxide-containing water obtained by contacting the chlorine dioxide generator pack with the water. The chlorine dioxide-containing water spray kit according to claim 6, further comprising an airtight container for housing the chlorine dioxide generator pack. The chlorine dioxide-containing water spray kit according to claim 6 or 7, wherein the dissolved chlorine dioxide concentration of the chlorine dioxide-containing water is 100 ppm.

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