JP6961550B2 - Chlorine dioxide gas generation and extinction method and chlorine dioxide gas generation and extinction kit - Google Patents

Description

The present invention provides treatment of allergens such as pollen, dust, husks and fungi, treatment of harmful substances such as pathogens, viruses and harmful chemicals (eg tobacco smoke, formaldehyde), environmental purification, and shop. The present invention relates to a method for generating and extinguishing chlorine dioxide gas and a kit for generating and extinguishing chlorine dioxide gas, which are widely used for deodorizing, mold prevention and antiseptic of domestic and foreign foods.

Chlorine dioxide (ClO ₂ ) has a strong oxidizing power, so it treats allergens such as pollen, dust, skin dust and fungi, pathogens, viruses and harmful chemicals (eg tobacco smoke, formaldehyde). Widely used for treatment of harmful substances such as, environmental purification, indoor / outdoor and food deodorization, antifungal and antiseptic. A method for continuously generating useful chlorine dioxide used in such a wide range of applications and a composition for that purpose have been proposed.

For example, Japanese Patent Application Laid-Open No. 11-278808 (Patent Document 1) describes a pure chlorine dioxide solution containing dissolved chlorine dioxide gas, chlorite and a pH adjuster as constituents, the pure chlorine dioxide solution and a highly water-absorbent resin. We propose a gel-like composition containing, an effervescent composition containing the pure chlorine dioxide solution and a foaming agent, and a container for containing the pure chlorine dioxide solution, the gel-like composition, and the effervescent composition. ..

Further, Japanese Patent Application Laid-Open No. 2005-29430 (Patent Document 2) contains an organic acid or an inorganic acid, a powdery gas generation regulator or gas generation regulator, and a water-absorbent resin in an aqueous chlorite solution. We propose a method for generating chlorine dioxide gas, which is added and gelled to continuously generate chlorine dioxide gas.

Japanese Unexamined Patent Publication No. 11-278808 Japanese Unexamined Patent Publication No. 2005-29430

According to JP-A-11-278808 (Patent Document 1) and JP-A-2005-29430 (Patent Document 2), a method for continuously generating chlorine dioxide gas has been proposed, but chlorine dioxide generated is generated. Since the gas has a strong pungent odor, the pungent odor caused by chlorine dioxide gas after use has become a problem. For this reason, in places where many people gather (for example, indoors, in automobiles, etc.), treatment of allergens such as pollen, dust, skin dust, and fungi, pathogens, viruses, and harmful chemical substances (for example, tobacco smoke, formaldehyde, etc.) ), Etc., environmental purification, indoor / outdoor and food deodorization, antifungal and antiseptic, etc., it is necessary to evacuate people not only during use but also after use. There were problems and many restrictions.

An object of the present invention is to provide a method for generating and extinguishing chlorine dioxide gas and a kit for generating and extinguishing chlorine dioxide gas, which can solve the above problems by extinguishing the generated chlorine dioxide gas after use.

According to a certain aspect, the present invention has a gas generation step of generating chlorine dioxide gas by bringing an agent A containing chlorite and an agent B containing a gas generating agent into contact with each other, and reducing chlorine dioxide to chlorine dioxide gas. This is a method for generating and extinguishing chlorine dioxide gas, which comprises a gas extinguishing step of extinguishing chlorine dioxide gas by bringing an agent C containing an agent into contact with the agent.

In the method for generating and extinguishing chlorine dioxide gas in such an aspect of the present invention, the chlorine dioxide reducing agent may contain at least one selected from the group consisting of hydrogen peroxide, erythorbic acid and salts thereof, and ascorbic acid and salts thereof. can.

According to another aspect, the present invention is composed of an agent A containing a chlorite, an agent B containing a gas generating agent, and an agent C containing a chlorine dioxide reducing agent. It is a kit for generating and extinguishing chlorine dioxide gas, which generates chlorine dioxide gas by contacting the chlorine dioxide gas and extinguishes the chlorine dioxide gas by contacting the C agent with the chlorine dioxide gas.

In the chlorine dioxide gas generation and extinction kit in such an aspect of the present invention, the chlorine dioxide reducing agent may contain at least one selected from the group consisting of hydrogen peroxide, erythorbic acid and salts thereof, and ascorbic acid and salts thereof. can.

According to the present invention, it is possible to provide a method for generating and extinguishing chlorine dioxide gas and a kit for generating and extinguishing chlorine dioxide gas, which can reduce the irritating odor caused by the chlorine dioxide gas after use by extinguishing the generated chlorine dioxide gas after use. ..

FIG. 1 is a flowchart showing a method of generating and extinguishing chlorine dioxide gas.

<Embodiment 1: Method of generating and extinguishing chlorine dioxide gas>
With reference to FIG. 1, in the method for generating and extinguishing chlorine dioxide gas according to an embodiment of the present invention, chlorine dioxide gas is produced by bringing an agent A containing chlorite and an agent B containing a gas generating agent into contact with each other. The gas generating step S10 to generate the chlorine dioxide gas and the gas extinguishing step S20 for extinguishing the chlorine dioxide gas by bringing the C agent containing the chlorine dioxide reducing agent into contact with the chlorine dioxide gas are provided. The chlorine dioxide gas generation / extinction method of the present embodiment includes the gas generation step S10 and the gas extinction step S20, so that the generated chlorine dioxide gas can be extinguished after use. The pungent odor caused by chlorine dioxide gas can be reduced. As a result, the evacuation of people after using chlorine dioxide gas can be released at an early stage. Here, the use of chlorine dioxide gas is not particularly limited as long as it is effectively used for the treatment of the object to be treated, and the chlorine dioxide gas is used for treatment of allergens such as pollen, dust, skin dust, and fungi, pathogens, and so on. Includes widespread use in the treatment of harmful substances such as viruses, harmful chemicals (eg tobacco smoke, formaldehyde), environmental purification, indoor and outdoor and food deodorization, antifungal and antiseptic.

For chlorine dioxide gas, the US Occupational Safety and Health Administration (OSHA) has set an exposure limit of 0.1 ppm for 8 hours a day (PEL-TWA: time-weighted average). In Japan, there is no standard value for exposure limits, but it is assumed to be a provisional safety standard for space disinfection with chlorine dioxide gas. From these facts, it is considered that it is necessary to reduce the concentration of chlorine dioxide gas to 0.1 ppm or less in order to release the evacuation of people after using chlorine dioxide gas.

[Gas generation process]
The gas generation step S10 is a step of generating chlorine dioxide gas by bringing the agent A containing chlorite and the agent B containing a gas generating agent into contact with each other. By the gas generation step S10, chlorine dioxide gas to be used can be efficiently generated.

(Agent A)
Agent A contains chlorite. The agent A is not particularly limited as long as it contains chlorite, but is a liquid containing chlorite from the viewpoint of efficiently contacting agent B, which will be described later, to efficiently generate chlorine dioxide gas. It is preferable, and an aqueous solution containing chlorite is more preferable. Here, the aqueous liquid means that the solvent and / or the dispersion medium excluding the solute and / or the dispersoid such as chlorite is the main component of water (the content of water in the solvent and / or the dispersion medium is 50 mass by mass). % Or more) means an aqueous solution and / or an aqueous dispersion. From the above viewpoint, the liquid A is more preferably an aqueous liquid containing chlorite, and particularly preferably an aqueous chlorite liquid.
The chlorite contained in the agent A is not particularly limited as long as it is a chlorite that generates chlorine dioxide gas by contact with the gas generating agent contained in the agent B, which will be described later. For example, sodium chlorite ( Chlorite of Group 1 elements (alkali metal elements) excluding hydrogen such as NaClO ₂ ), potassium chlorite (KClO ² ), lithium chlorite (LiClO _{2 ), calcium chlorite (Ca (ClO 2)} ) ₂ ), Strontium chlorite (Sr (ClO ₂ ) ₂ ), Barium chlorite (Ba (ClO ₂ ) ₂ ), Magnesium chlorite (Mg (ClO ₂ ) ₂ ) Examples include chlorite. Among these, commercially available sodium chlorite is easily available and there is no problem in use. The agent A may contain a substance other than chlorite as long as it does not inhibit the generation of chlorine dioxide gas in contact with the agent B described later and does not generate harmful by-products. good. Examples of the substance other than the chlorite contained in the agent A include alkalis such as sodium hydroxide (NaOH). For example, Sylbrite (Silbrite 80 manufactured by Carlit Japan Co., Ltd.) containing 80% by mass or more of NaClO _{2 is preferably used as the agent A.}

The aqueous chlorite solution is obtained by dissolving and / or dispersing at least one of the above chlorites in an aqueous solvent and / or dispersion medium at a predetermined concentration. When sodium chlorite is dissolved in water, a commercially available 25% by mass sodium chlorite aqueous solution used as a bleaching agent for liquids and a commercially available 86% by mass, 80% by mass, 79% by mass for solids A product or a 76% by mass product is preferably used. The concentration of the aqueous chlorate solution is preferably 25% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, from the viewpoint that it does not correspond to a toxic substance or a dangerous substance and is easy to handle. More preferred.

(Agent B)
Agent B contains a gas generating agent. The agent B is not particularly limited as long as it contains a gas generating agent, but is preferably a liquid containing a gas generating agent from the viewpoint of efficiently contacting the agent A and efficiently generating chlorine dioxide gas. , An aqueous liquid containing a gas generating agent is more preferable. Here, the aqueous liquid means that the solvent and / or the dispersion medium excluding the solute and / or the dispersoid such as a gas generating agent is mainly composed of water (the content of water in the solvent and / or the dispersion medium is 50% by mass). The above) means an aqueous solution and / or an aqueous dispersion. From the above viewpoint, the liquid B is more preferably an aqueous solution containing a gas generating agent or an aqueous dispersion containing a gas generating agent, and particularly preferably an aqueous solution of a gas generating agent or an aqueous dispersion of a gas generating agent.

The gas generating agent contained in the agent B is not particularly limited as long as it is a gas generating agent that generates chlorine dioxide gas by contact with the chlorite contained in the agent A described above. For example, an inorganic acid such as hydrochloric acid. , Organic acids such as citric acid, lactic acid, malic acid and the like. Among these, hydrochloric acid, citric acid, etc. are easily available and there is no problem in use. The agent B may contain a substance other than the gas generating agent as long as it does not inhibit the generation of chlorine dioxide gas in contact with the above agent A and does not generate harmful by-products. ..

The gas generating agent aqueous liquid is obtained by dissolving and / or dispersing at least one of the above gas generating agents in an aqueous solvent and / or a dispersion medium at a predetermined concentration. When hydrochloric acid is dissolved in water, a commercially available hydrochloric acid (35% by mass product) is diluted with water, and an aqueous hydrochloric acid solution of 5% by mass or more and 15% by mass or less is preferably used. When citric acid is dissolved in water, an aqueous citric acid solution of 20% by mass or more and 40% by mass or less is preferably used. Here, the diluted water is not particularly limited as long as it does not inhibit the generation of chlorine dioxide gas, but purified water such as distilled water, ion-exchanged water, and RO (reverse osmosis) water is preferable from the viewpoint of having few impurities.

(Contact between agent A and agent B)
When the agent A and the agent B come into contact with each other, the chlorite contained in the agent A reacts with the gas generating agent contained in the agent B to generate chlorine dioxide gas. The ratio of the A agent and the B agent in contact with each other is not particularly limited, but from the viewpoint of efficiently reacting and efficiently generating chlorine dioxide gas, (chlorite contained in the A agent): (B). The gas generating agent contained in the agent) is preferably in the range of 1: 3 to 3: 1 when the gas generating agent is hydrochloric acid, and 1: 2 to 4: when the gas generating agent is citric acid. The range up to 1 is preferable.

The method of contacting the agent A and the agent B is not particularly limited as long as the chlorite contained in the agent A and the gas generating agent contained in the agent B are brought into contact with each other so as to react with each other. When both the agent and the agent B are solid, an aqueous solvent (meaning a solvent having a water content of 50% by mass or more, the same applies hereinafter) and / or an aqueous dispersion medium (a water content of 50% by mass or more). A method of mixing the agent A and the agent B by adding a dispersion medium (the same applies hereinafter) can be mentioned. When either the agent A or the agent B is an aqueous liquid (aqueous solution and / or aqueous dispersion) and the other is a solid, a method of mixing the aqueous liquid and the solid can be mentioned. When both Agent A and Agent B are aqueous liquids, a method of mixing both aqueous liquids can be mentioned. From the viewpoint of efficiently generating chlorine dioxide gas by efficiently reacting the chlorite contained in the A agent with the gas generating agent contained in the B agent, either the A agent or the B agent is aqueous. It is preferably a solution, and more preferably an aqueous solution.

[Gas extinction process]
The gas extinguishing step S20 is a step of extinguishing the chlorine dioxide gas by bringing the C agent containing the chlorine dioxide reducing agent into contact with the chlorine dioxide gas. By efficiently extinguishing the chlorine dioxide gas after being generated and used by the gas extinguishing step S20, the pungent odor due to the chlorine dioxide gas after use can be reduced.

(C agent)
The C agent used for extinguishing chlorine dioxide gas after use contains a chlorine dioxide reducing agent. Agent C is not particularly limited as long as it contains a chlorine dioxide reducing agent, but is a liquid containing a chlorine dioxide reducing agent from the viewpoint of efficiently contacting chlorine dioxide gas and efficiently extinguishing chlorine dioxide gas. Is preferable, and an aqueous liquid containing a chlorine dioxide reducing agent is more preferable. Here, the aqueous liquid means that the solvent and / or the dispersion medium excluding the solute and / or the dispersoid such as the chlorine dioxide reducing agent is mainly composed of water (the content of water in the solvent and / or the dispersion medium is 50 mass by mass). % Or more) means an aqueous solution and / or an aqueous dispersion. From the above viewpoint, the solution C is preferably an aqueous solution containing a chlorine dioxide reducing agent, and more preferably an aqueous solution of a chlorine dioxide reducing agent.

The chlorine dioxide reducing agent contained in Agent C is not particularly limited as long as it is a chlorine dioxide reducing agent that eliminates chlorine dioxide gas by reducing chlorine dioxide, and hydrogen peroxide, erythorbic acid and its salts, ascorbic acid and its salts. Examples include salt. Since it has a high ability to reduce chlorine dioxide, it has a high ability to suppress the pungent odor of chlorine dioxide gas, the toxicity of the chlorine dioxide reducing agent itself is low, and there is no generation of toxic substances when reducing chlorine dioxide, making it safe. From a high point of view, the chlorine dioxide reducing agent preferably contains at least one selected from the group consisting of hydrogen peroxide, erythorbic acid and salts thereof, and ascorbic acid and salts thereof. Further, as the chlorine dioxide reducing agent, hydrogen peroxide is more preferable, and the ability to reduce chlorine dioxide is higher, and the chlorine dioxide reducing agent is said to be more preferable from the viewpoint of higher safety due to the absence of generation of toxic substances when reducing chlorine dioxide. From the viewpoint of higher safety due to the chlorine dioxide reducing agent itself being a food additive, at least one selected from the group consisting of erythorbic acid and its salt, and ascorbic acid and its salt is preferable. Here, the erythorbic acid salt is not particularly limited as long as it does not inhibit the reduction of chlorine dioxide, but an alkali metal erythorbic acid salt such as sodium erythorbate and potassium erythorbate is preferable from the viewpoint of easy availability. The ascorbic acid salt is not particularly limited as long as it does not inhibit the reduction of chlorine dioxide, but an alkali metal ascorbic acid salt such as sodium ascorbate or potassium ascorbate is preferable from the viewpoint of easy availability. Further, ascorbic acid includes D-form D-ascorbic acid and L-form L-ascorbic acid (vitamin C), which are enantiomers of each other, and L-ascorbic acid is more preferable from the viewpoint of easy availability. The agent C may contain a substance other than the chlorine dioxide reducing agent as long as the elimination of chlorine dioxide gas is not inhibited by reducing chlorine dioxide and as long as no harmful by-products are generated. ..

Here, sodium sulfite and sodium thiosulfate, which are generally used as reducing agents, are not preferable because they may generate toxic sulfur dioxide gas, sulfite gas, hydrogen sulfide gas, etc. in a weakly acidic atmosphere. Hydroxylamine hydrochloride, which is a strong reducing agent, is not preferable because it has high vapor toxicity and has a risk of explosion when heated to a high temperature.

The chlorine dioxide reducing agent aqueous solution is obtained by dissolving and / or dispersing at least one of the above chlorine dioxide reducing agents in an aqueous solvent and / or a dispersion medium at a predetermined concentration. When hydrogen peroxide is dissolved in water, a hydrogen peroxide aqueous solution (hydrogen peroxide solution) having a mass of 1% by mass or more and 5% by mass or less is preferably used. When erythorbic acid or a salt thereof is dissolved in water, an aqueous solution of erythorbic acid or a salt thereof in an amount of 1% by mass or more and 5% by mass or less is preferably used. When ascorbic acid or a salt thereof is dissolved in water, an aqueous solution of ascorbic acid or a salt thereof in an amount of 1% by mass or more and 5% by mass or less is preferably used.

(Contact between chlorine dioxide gas and agent C)
Chlorine dioxide gas is generated by the contact between the agent A and the agent B. The generated chlorine dioxide gas is released into the air and used for the treatment of substances to be treated (allergens, harmful substances, etc.). By bringing the chlorine dioxide gas after use into contact with the agent C, the chlorine dioxide gas can be eliminated by reduction and the pungent odor caused by the chlorine dioxide gas can be reduced. In particular, when a large amount of chlorine dioxide gas is generated after use, the irritating odor caused by the chlorine dioxide gas can be greatly reduced by the contact between the generated chlorine dioxide gas and the agent C. As a result, the evacuation of people after using chlorine dioxide gas can be released at an early stage.

The ratio of the generated chlorine dioxide gas to the agent C is not particularly limited, but from the viewpoint of efficiently extinguishing the chlorine dioxide gas (chlorine dioxide generated by the contact between the agent A and the agent B) :( The chlorine dioxide reducing agent contained in the agent C) is preferably in the range of 100: 1 to 1: 3 and preferably in the range of 50: 1 to 2: 3 in terms of molar ratio. The wide range of suitable molar ratios of the chlorine dioxide reducing agent contained in the C agent to the chlorine dioxide generated by the contact between the A agent and the B agent is the size of the space for generating and extinguishing the chlorine dioxide gas. This is because the contact efficiency between the chlorine dioxide gas and the chlorine dioxide reducing agent differs greatly depending on the type. The larger the space for generating and extinguishing chlorine dioxide gas, the greater the diffusion of chlorine dioxide gas and chlorine dioxide reducing agent into the space and the greater adsorption to the wall, resulting in higher contact efficiency between chlorine dioxide gas and chlorine dioxide reducing agent. Therefore, the preferable molar ratio of the chlorine dioxide reducing agent contained in the agent C to the chlorine dioxide generated by the contact between the agent A and the agent B increases. Further, since hydrogen peroxide has a smaller reducing power of chlorine dioxide than erythorbic acid and its salt and ascorbic acid and its salt, the dioxide contained in the C agent with respect to the chlorine dioxide generated by the contact between the A agent and the B agent. The suitable molar ratio of the chlorine reducing agent increases.

The method of contacting the generated chlorine dioxide gas with the agent C is not particularly limited, but it is generated from the viewpoint of efficiently contacting the generated chlorine dioxide gas and then efficiently extinguishing the chlorine dioxide gas. A method in which the C agent is brought into contact with the chlorine dioxide gas scattered in the air in the form of a mist, for example, a method in which the C agent is sprayed on the chlorine dioxide gas is preferable. From the above viewpoint, the agent C is preferably an aqueous solution containing a chlorine dioxide reducing agent, and more preferably an aqueous solution of a chlorine dioxide reducing agent.

The number of times the generated chlorine dioxide gas and the C agent are brought into contact with each other is not particularly limited, but from the viewpoint of efficiently contacting the generated chlorine dioxide gas and then efficiently contacting the chlorine dioxide gas emitted into the air to efficiently extinguish the chlorine dioxide gas. It is preferably times. In particular, it is preferable that the larger the space in which the chlorine dioxide gas exists and the higher the concentration of the chlorine dioxide gas, the greater the number of times of contact with the agent C.

<Embodiment 2: Kit for extinguishing chlorine dioxide gas generation>
With reference to FIG. 1, a chlorine dioxide gas generation and extinction kit according to another embodiment of the present invention contains an agent A containing a chlorite, an agent B containing a gas generating agent, and a chlorine dioxide reducing agent. It is composed of agent C, and chlorine dioxide gas is generated by contacting agent A and agent B, and chlorine dioxide gas is extinguished by contacting agent C with chlorine dioxide gas. The chlorine dioxide gas generation and extinction kit of the present embodiment is composed of the above agents A, B, and C, and by contacting them in a certain order, the generated chlorine dioxide gas is extinguished after use. Therefore, the irritating odor caused by chlorine dioxide gas after use can be reduced. Here, the use of chlorine dioxide gas is not particularly limited as long as it is effectively used for the treatment of the object to be treated, and the chlorine dioxide gas is used for treatment of allergens such as pollen, dust, skin dust, and fungi, pathogens, and so on. Includes widespread use in the treatment of harmful substances such as viruses, harmful chemicals (eg tobacco smoke, formaldehyde), environmental purification, indoor and outdoor and food deodorization, antifungal and antiseptic.

Agents A, B, and C constituting the chlorine dioxide gas generation and extinction kit of the present embodiment, chlorine dioxide gas generated by contact between agent A and agent B, and chlorine dioxide gas generated by contact with agent C. Since the extinction of chlorine dioxide gas is the same as the agent A, the agent B, and the agent C, the gas generation step, and the gas extinction step described in the method for generating and extinguishing chlorine dioxide gas of the first embodiment, those explanations are repeated. No.

(Example 1)
In this example, agents A and B are used in an air circulation atmosphere by operating the air conditioner "inside" in a passenger car (Tesla Model S) that has a foul odor such as cigarettes, which is strongly recognized by all three panelists. ClO ₂ gas (chlorine dioxide gas, the same shall apply hereinafter) was generated by contact with, and ClO ₂ gas was extinguished _{by contact between the generated ClO 2 gas and the agent C.}

1. 1. Preparation of ClO ₂ gas generation and extinction kit 10 g of 25 mass% sodium chlorite aqueous solution as agent A, 17 g of 10 mass% hydrochloric acid aqueous solution as agent B, and 300 g of 2.5 mass% sodium erythorbate aqueous solution as agent C And prepared. The reason why the amount of C agent is 300 g is to put it in a trigger type atomizer for spraying, and _{the amount of C agent required to extinguish ClO 2} gas and reduce its concentration to 0.1 ppm or less is as described later. It was a very small amount.

2. _{Generation of ClO 2} gas due to contact between Agent A and Agent B Agent A in an inverted quadrangular pyramid-shaped PET (polyethylene terephthalate) container with a bottom surface of 58 mm x 58 mm, an opening surface of 83 mm x 83 mm, and a height of 30 mm. The total amount of the agent B and the total amount of the agent B were mixed and brought into contact with each other to generate _{ClO 2 gas.} Table 1 summarizes the elapsed time from the time when the agent A and the agent B were brought into contact with each other and _{the concentration of ClO 2 gas in the passenger car.} The concentration of ClO ₂ gas was measured using a Kitagawa type detector tube for concentrations of 1.0 ppm or more, and No. 1 of the Gastec low concentration detector tube for concentrations less than 1.0 ppm. 23M or No. It was measured using 23 L. The concentration of ClO ₂ gas was measured by inserting the measuring unit of the detector tube into the passenger car while ensuring the airtightness inside the passenger car.

3. 3. After measuring the ClO ₂ gas concentration at after 90 minutes when contacted by mixing with ClO ₂ gas annihilation above A agent and the B agent by contact with generated ClO ₂ gas and C agents, ClO ₂ generated Agent A and agent B after contact were taken out from the inside of the passenger car in which gas remained, and agent C contained in the trigger type atomizer was sprayed 5 times (4.75 g in total) in the passenger car. Table 1 shows _{the ClO 2} gas concentration in the passenger car after 95 minutes have passed from the time when the agent A and the agent B were brought into contact with each other (that is, 5 minutes after the spraying of the agent C). As shown in Table 1, _{the concentration of ClO 2} gas at this time is 0.05 ppm, which is the allowable exposure concentration in the 8-hour exposure (PEL-TWA) set by the US Occupational Safety and Health Administration (OSHA). It was less than 1 ppm. At this time, the _{pungent odor caused by the ClO 2} gas in the passenger car was reduced to the extent that all three panelists recognized it very slightly but did not feel any discomfort. At this time, the bad odor caused by cigarettes in the passenger car was not recognized by all three panelists and disappeared. The drain odor of the air conditioner was not recognized by all three panelists and disappeared.

(Example 2)
In this embodiment, A is performed in an air circulation atmosphere by operating the air conditioner at "medium (display value 24)" in a passenger car (Toyota Aqua) that has a foul odor such as cigarettes, which is strongly recognized by all three panelists. _{The ClO 2} gas was generated by the contact between the agent and the agent B, and the _{ClO 2} gas was extinguished by the contact between the _{generated ClO 2 gas and the agent C.}

1. 1. Preparation of ClO ₂ gas generation and extinction kit 10 g of 25 mass% sodium chlorite aqueous solution as agent A, 17 g of 10 mass% hydrochloric acid aqueous solution as agent B, and 2.5 mass% L-ascorbic acid aqueous solution as agent C 300 g and so on were prepared. Here, the reason why the amount of C agent is 300 g is to put it in a trigger type atomizer for spraying, and _{the amount of C agent required to extinguish ClO 2} gas and reduce its concentration to 0.1 ppm or less will be described later. It was an extremely small amount.

2. _{Generation of ClO 2} gas by contact between Agent A and Agent B In a PET container of the same shape and size as in Example 1, the total amount of Agent A and the total amount of Agent B are mixed and brought into contact with each other to make ClO ₂ Generated gas. Table 2 summarizes the elapsed time from the time when the agent A and the agent B were brought into contact with each other and _{the concentration of ClO 2 gas in the passenger car.} The concentration of ClO ₂ gas was measured using a Kitagawa type detector tube for concentrations of 1.0 ppm or more, and No. 1 of the Gastec low concentration detector tube for concentrations less than 1.0 ppm. 23M or No. It was measured using 23 L. The concentration of ClO ₂ gas was measured by inserting the measuring unit of the detector tube into the passenger car while ensuring the airtightness inside the passenger car.

3. 3. After measuring the ClO ₂ gas concentration at after 90 minutes when contacted by mixing with ClO ₂ gas annihilation above A agent and the B agent by contact with generated ClO ₂ gas and C agents, ClO ₂ generated Agent A and agent B after contact were taken out from the inside of the passenger car in which gas remained, and agent C contained in the trigger type atomizer was sprayed 5 times (4.75 g in total) in the passenger car. Table 2 shows _{the ClO 2} gas concentration in the passenger car 95 minutes after the contact by mixing the A agent and the B agent (that is, 5 minutes after the spraying of the C agent). As shown in Table 2, _{the concentration of ClO 2} gas at this time is 0.05 ppm, which is the allowable exposure concentration in the 8-hour exposure (PEL-TWA) set by the US Occupational Safety and Health Administration (OSHA). It was less than 1 ppm. At this time, the _{pungent odor caused by the ClO 2} gas in the passenger car was reduced to the extent that all three panelists recognized it very slightly but did not feel any discomfort. At this time, the bad odor caused by cigarettes in the passenger car was not recognized by all three panelists and disappeared. The drain odor of the air conditioner was not recognized by all three panelists and disappeared.

(Example 3)
^{In this example, in a 6 tatami room (capacity 21.7 m 3} : 2.93 m x 3.37 m x 2.2 m), which is strongly recognized by all three panelists and has a foul odor due to formaldehyde, agents A and B are used. The ClO ₂ gas was generated by the contact and the ClO ₂ gas was extinguished _{by the contact between the generated ClO 2 gas and the agent C.}

1. 1. Preparation of ClO ₂ gas generation and extinction kit 18 g of 25 mass% sodium chlorite aqueous solution as agent A, 30 g of 30 mass% citric acid aqueous solution as agent B, and 2.5 mass% sodium erythorbate aqueous solution as agent C 300 g and so on were prepared. The reason why the amount of C agent is 300 g is to put it in a trigger type atomizer for spraying, and _{the amount of C agent required to extinguish ClO 2} gas and reduce its concentration to 0.1 ppm or less is as described later. It was a small amount.

2. _{Generation of ClO 2} gas by contact between Agent A and Agent B In a PET container of the same shape and size as in Example 1, the total amount of Agent A and the total amount of Agent B are mixed and brought into contact with each other to make ClO ₂ Generated gas. Table 3 summarizes the elapsed time from the time when the agent A and the agent B were brought into contact with each other and _{the concentration of ClO 2 gas in the 6 tatami mat room.} The concentration of ClO ₂ gas was measured using a Kitagawa type detector tube for concentrations of 1.0 ppm or more, and No. 1 of the Gastec low concentration detector tube for concentrations less than 1.0 ppm. 23M or No. It was measured using 23 L.

3. 3. _{Extinction of ClO 2} gas by contact between the generated ClO ₂ gas and agent C The _{generated ClO 2} gas remains 6.25 hours after the contact by mixing the above agent A and agent B. Agent A and agent B after contact were taken out from the above 6 tatami room, and agent C placed in the trigger type atomizer was sprayed 35 times (33.25 g in total) in the above 6 tatami room (referred to as primary spraying of agent C). ,same as below). Here, the primary spraying of the C agent was carried out in the following manner. The 6 tatami mat room is divided into a front area, a middle area, and a back area of the same size from the entrance door to the back, and spreads uniformly from the front side to the back side of the back area. Spray at different places 10 times each so that it spreads evenly from the front side to the back side of the middle area, and spray 10 times each so that it spreads evenly from the back side to the front side of the front area. Sprayed in different places. _{The ClO 2} gas concentration in the 6 tatami room is shown in the table after 7.25 hours have passed since the contact was made by mixing the A agent and the B agent (that is, 1 hour after the first spraying of the C agent). As shown in 3, it was reduced to 0.75 ppm.

Next, 7.5 hours after the contact by mixing the A agent and the B agent, the C agent was sprayed 10 times (9.5 g in total) in the 6 tatami room (secondary of the C agent). The same applies to spraying). Here, the secondary spray of the C agent is sprayed four times at different locations so as to spread uniformly from the front side to the back side of the inner region, and spread evenly from the front side to the back side of the middle region. Was sprayed three times at different locations, and sprayed three times at different locations so as to spread evenly from the back side to the front side of the table area. _{The ClO 2} gas concentration in the 6 tatami room is shown in the table after 8.5 hours have passed since the contact was made by mixing the A agent and the B agent (that is, 1 hour after the secondary spraying of the C agent). As shown in 3, it was reduced to 0.10 ppm and reduced to 0.1 ppmm, which is the upper limit of the allowable exposure concentration in the 8-hour exposure (PEL-TWA) set by the US Occupational Safety and Health Administration (OSHA).

Further, after 8.75 hours had passed from the time when the A agent and the B agent were brought into contact with each other, the C agent was sprayed twice (1.9 g in total) in the 6 tatami room (the C agent). The same applies hereinafter as the tertiary spray). Here, the tertiary spraying of the C agent was carried out in the following manner. The above 6 tatami mat room is divided into a front side area and a back side area of the same size area from the entrance door to the back, and sprayed once from the front side to the back side of the back side area, and the front side area It was sprayed once from the back side to the front side. _{The ClO 2} gas concentration in the 6 tatami room is 9.0 hours after the contact by mixing the A and B agents (that is, 0.25 hours after the third spraying of the C agent). As shown in Table 3, it was reduced to 0.05 ppm, which was 0.1 ppm or less, which is the allowable exposure concentration at the 8-hour exposure (PEL-TWA) set by the US Occupational Safety and Health Administration (OSHA). At this time, the _{pungent odor caused by the ClO 2} gas in the 6 tatami mat room was reduced to the extent that all three panelists recognized it very slightly but did not feel any discomfort. At this time, the bad odor caused by formaldehyde in the 6 tatami mat room was not recognized by all three panelists and disappeared. The drain odor of the air conditioner was not recognized by all three panelists and disappeared.

(Example 4)
^{In this example, in a 6 tatami room (capacity 21.7 m 3} : 2.93 m x 3.37 m x 2.2 m), which is strongly recognized by all three panelists and has a foul odor due to formaldehyde, agents A and B are used. The ClO ₂ gas was generated by the contact and the ClO ₂ gas was extinguished _{by the contact between the generated ClO 2 gas and the agent C.}

1. 1. Preparation of ClO ₂ gas generation and extinction kit 18 g of 25 mass% sodium chlorite aqueous solution as agent A, 30 g of 30 mass% citrate aqueous solution as agent B, and 3.0 mass / volume% (w / by volume) of agent C Also referred to as v%. 300 g of a hydrogen peroxide aqueous solution (Oxidol manufactured by Kenei Pharmaceutical Co., Ltd.) of 3 g of hydrogen peroxide in a 100 mL aqueous solution was prepared. The reason why the amount of C agent is 300 g is to put it in a trigger type atomizer for spraying, and _{the amount of C agent required to extinguish ClO 2} gas and reduce its concentration to 0.1 ppm or less is as described later. It was a very small amount.

2. _{Generation of ClO 2} gas by contact between Agent A and Agent B In a PET container of the same shape and size as in Example 1, the total amount of Agent A and the total amount of Agent B are mixed and brought into contact with each other to make ClO ₂ Generated gas. Table 4 summarizes the elapsed time from the time when the agent A and the agent B were brought into contact with each other and _{the concentration of ClO 2 gas in the 6 tatami mat room.} The concentration of ClO ₂ gas was measured using a Kitagawa type detector tube for concentrations of 1.0 ppm or more, and No. 1 of the Gastec low concentration detector tube for concentrations less than 1.0 ppm. 23M or No. It was measured using 23 L.

3. 3. _{Disappearance of ClO 2} gas by contact between the generated ClO ₂ gas and agent C The _{generated ClO 2} gas remains after 6.33 hours have passed from the time of contact by the above mixing of agent A and agent B. Agent A and agent B after contact were taken out from the above 6 tatami room, and agent C placed in the trigger type atomizer was sprayed 35 times (25.9 g in total) in the above 6 tatami room (referred to as primary spraying of agent C). ,same as below). Here, the primary spraying of the C agent was carried out in the following manner. The 6 tatami mat room is divided into a front area, a middle area, and a back area of the same size from the entrance door to the back, and spreads uniformly from the front side to the back side of the back area. Spray at different places 10 times each so that it spreads evenly from the front side to the back side of the middle area, and spray 10 times each so that it spreads evenly from the back side to the front side of the front area. Sprayed in different places. _{The ClO 2} gas concentration in the 6 tatami room is 7.35 hours after the contact by mixing the A and B agents (that is, 1.02 hours after the primary spraying of the C agent). As shown in Table 4, the concentration was reduced to 1.40 ppm.

Next, after 7.75 hours had passed from the time when the A agent and the B agent were brought into contact with each other, the C agent was sprayed 10 times (7.4 g in total) in the 6 tatami room (secondary of the C agent). The same applies to spraying). Here, the secondary spray of the C agent is sprayed four times at different locations so as to spread uniformly from the front side to the back side of the inner region, and spread evenly from the front side to the back side of the middle region. Was sprayed three times at different locations, and sprayed three times at different locations so as to spread evenly from the back side to the front side of the table area. _{The ClO 2} gas concentration in the 6 tatami room is 8.85 hours after the contact by mixing the A and B agents (that is, 1.1 hours after the secondary spraying of the C agent). , As shown in Table 4, it was reduced to 0.55 ppm.

Further, after 9.0 hours had passed from the time when the A agent and the B agent were brought into contact with each other, the C agent was sprayed 10 times (7.4 g in total) in the 6 tatami room (the third spray of the C agent). The same applies below). Here, the tertiary spray of the C agent is sprayed four times at different locations so as to spread uniformly from the front side to the back side of the back area, and spread evenly from the front side to the back side of the middle area. Was sprayed three times at different locations, and sprayed three times at different locations so as to spread evenly from the back side to the front side of the table area. _{The ClO 2} gas concentration in the 6 tatami room is 10.0 hours after the contact between the A agent and the B agent (that is, 1.0 hour after the third spraying of the C agent). , As shown in Table 4, it was reduced to 0.23 ppm.

Further, after 10.05 hours had passed from the time when the agent A and the agent B were brought into contact with each other, the agent C was sprayed 10 times (7.4 g in total) in the above 6 tatami mat room of the agent C (the fourth order of the agent C). The same applies to spraying). Here, the fourth spray of the C agent is sprayed four times at different locations so as to spread uniformly from the front side to the back side of the back area, and spread evenly from the front side to the back side of the middle area. Was sprayed three times at different locations, and sprayed three times at different locations so as to spread evenly from the back side to the front side of the table area. _{The ClO 2} gas concentration in the 6 tatami room is 11.0 hours after the contact by mixing the A and B agents (that is, 0.95 hours after the fourth spraying of the C agent). As shown in Table 4, the concentration was reduced to 0.05 ppm, which was 0.1 ppm or less, which is the allowable exposure concentration at the 8-hour exposure (PEL-TWA) set by the US Occupational Safety and Health Administration (OSHA). At this time, the _{pungent odor caused by the ClO 2} gas in the 6 tatami mat room was reduced to the extent that all three panelists recognized it very slightly but did not feel any discomfort. At this time, the bad odor caused by formaldehyde in the 6 tatami mat room was not recognized by all three panelists and disappeared. The drain odor of the air conditioner was not recognized by all three panelists and disappeared.

As shown in Table 1-4 with respect to Example 1-4, it is composed of an agent A containing a chlorite, an agent B containing a gas generating agent, and an agent C containing a chlorine dioxide reducing agent. to generate ClO ₂ gas by contacting the a agent and the B agent, the ClO ₂ gas, ClO ₂ gas generated annihilation kit to extinguish the ClO ₂ gas by contacting the C agent, as well as chlorite A gas generation step of generating _{ClO 2} gas by contacting Agent A containing a gas generating agent with Agent B containing a gas generating agent, _{and ClO 2} gas by contacting Agent C containing a chlorine dioxide reducing agent with ClO ₂ gas. According to the method for generating and extinguishing _{ClO 2} gas, which comprises a gas extinguishing step for _{extinguishing the generated ClO 2} gas, the pungent odor caused by _{the ClO 2 gas after use can be reduced by extinguishing the generated ClO 2} gas after use. Therefore, _{after using ClO 2} gas, there is no problem such as evacuation of people, and even in indoors where many people gather and in automobiles, treatment of allergens such as pollen, dust, skin dust, fungi, and pathogenic bacteria _{ClO 2} gas can be widely used for treatment of harmful substances such as viruses, harmful chemical substances (for example, tobacco smoke, formaldehyde), environmental purification, deodorization, antifungal and antiseptic treatment.

As shown in the above Examples 1-4, by the ClO ₂ gas generated by contacting the C agent, thereby eliminating the ClO ₂ gas, it was possible to reduce the irritating odor due to ClO ₂ gas.

The embodiments and examples disclosed this time should be considered to be exemplary and not restrictive in all respects. The scope of the present invention is shown by the scope of claims rather than the above description, and it is intended to include all modifications within the meaning and scope equivalent to the scope of claims.

S10 gas generation step, S20 gas extinction step.

Claims (2)

A gas generation step of generating chlorine dioxide gas by contacting agent A, which is an aqueous liquid containing 25% by mass or less of chlorite, with agent B, which is an aqueous liquid containing a gas generating agent.
By contacting the chlorine dioxide gas with Agent C, which is an aqueous liquid containing a chlorine dioxide reducing agent of 1% by mass or more and 5% by mass or less, the chlorine dioxide gas is extinguished and the concentration of the remaining chlorine dioxide gas is reduced to 0. It is equipped with an extinction step of 1 ppm or less.
The chlorine dioxide reducing agent, e Risorubin acid and its salts and ascorbic acid and at least generation disappearance process of chlorine dioxide gas containing one of selected from the group consisting of a salt thereof,. Agent A, which is an aqueous liquid containing 25% by mass or less of chlorite, Agent B, which is an aqueous liquid containing a gas generating agent, and an aqueous liquid containing 1% by mass or more and 5% by mass or less of a chlorine dioxide reducing agent. Consists of a certain C agent
The chlorine dioxide reducing agent comprises at least one member selected from the group consisting of d Risorubin acid and its salts and ascorbic acid and its salts,
Chlorine dioxide gas is generated by bringing the agent A and the agent B into contact with each other.
A kit for generating and extinguishing chlorine dioxide gas, in which the chlorine dioxide gas is extinguished by bringing the agent C into contact with the chlorine dioxide gas, and the concentration of the remaining chlorine dioxide gas is 0.1 ppm or less.

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