JP2016088797A - Method for generating chlorine dioxide gas, kit for generating chlorine dioxide gas and gelatinous composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for generating chlorine dioxide gas by which chlorine dioxide gas can be sustainedly generated for a long period of time, a kit for generating chlorine dioxide gas, and a gel composition.SOLUTION: The method for generating chlorine dioxide gas is method for sustainedly generating chlorine dioxide gas from a gelated composition obtained by mixing chlorite aqueous solution with a gelation activator containing a gas generation regulator, a pH adjustor and a water-absorbing resin. The kit for generating chlorine dioxide gas is composed of an A agent containing chlorite aqueous solution, and a B agent containing gelation activator containing a gas generation regulator, a pH adjuster and a water-absorbing resin, and sustainedly generates chlorine dioxide gas by mixing the A agent and the B agent. The gel composition contains chlorite aqueous solution and a gelation activator containing a gas generation regulator, a pH adjustor and a water- absorbing resin, and sustainedly generates chlorine dioxide gas.SELECTED DRAWING: None

Description

  The present invention relates to a method for generating dilute chlorine dioxide gas used for environmental purification, sterilization or sterilization of bacteria or viruses, indoor (indoor or outdoor), outdoor or food, etc., antifungal, antiseptic, etc., chlorine dioxide The present invention relates to a gas generation kit and a gel composition.

Chlorine dioxide has a strong oxidizing power, and is used as a sanitizer in the fields of environmental purification, sterilization or sterilization of bacteria or viruses, deodorization, mold prevention, antiseptic indoors or outdoors such as homes and hospitals, foods, Widely used as bactericides, deodorants, fungicides, preservatives, or bleaches. For example, the government has approved the use of chlorine dioxide for hot water such as hot springs and super public baths (sterilization of Legionella), sterilization of pool water, sterilization of raw vegetables, addition to drinking water (iron, manganese) Etc.). In addition, as an environmental standard for chlorine dioxide gas in the atmosphere, TLV (Threshold Limit Values) announced in 2001 by ACGIH (American Industrial Hygiene Experts Council) is exposed to certain substances such as chlorine dioxide gas repeatedly every day. Sometimes it is an important indicator that most workers do not have adverse effects. TWA at 8 hours (time-weighted average, which is the concentration of certain substances such as chlorine dioxide gas) The sum of the product of the concentration and its duration divided by the total number of hours, for example 8 hours or 40 hours) is 0.1 ppm (0.28 mg / m ³ ), and STEL ( The short-term exposure limit, which is a 15-minute time-weighted average value that workers should not be exposed to at any time during work) pm (0.84 mg / m ³ ). Therefore, when chlorine dioxide gas is constantly generated in a room, the concentration of chlorine dioxide gas in the room needs to be equal to or less than the above TWA and STEL.

  Various powdery and granular compositions that generate chlorine dioxide gas have been developed for the above applications. For example, JP-A-61-48404 (Patent Document 1) discloses a composition in which a powder of chlorite or an aqueous solution of chlorite or stabilized chlorine dioxide is mixed or adsorbed on a basic solid substance. Discloses a method for slowly generating chlorine dioxide by contacting an acid or ester vapor.

  Japanese Patent Laid-Open No. 63-303905 (Patent Document 2) discloses that sodium chlorite scattered in the air or the volatilized product is dispersed in the air by irradiating the chlorite soda solution with ultrasonic waves. Disclosed is a method for preventing a chlorine dioxide gas generated by reacting with a gas from contacting an object to be treated.

  Japanese Patent Application Laid-Open No. 6-223985 (Patent Document 3) discloses a sterilizing / disinfecting method in which chlorine dioxide gas is adsorbed and held on a porous inorganic carrier, and a sterilizing / disinfecting method for releasing chlorine dioxide gas from the sterilizing / disinfecting agent. Disclose.

  Furthermore, Japanese Patent Application Laid-Open No. 11-278808 (Patent Document 4) discloses a pure chlorine dioxide solution having dissolved chlorine dioxide gas, chlorite and a pH adjuster as constituents, such a pure chlorine dioxide solution and a superabsorbent resin. Disclosed is a gel composition containing and continuously generating chlorine dioxide gas using such pure chlorine dioxide solution or gel composition.

  JP 2003-12424 A (Patent Document 5) discloses a chlorine dioxide composition containing calcined aggregate, water, and dissolved chlorine dioxide in order to control the amount of chlorine dioxide gas released. A chlorine dioxide composition comprising such a chlorine dioxide composition and further containing a gelling agent is disclosed.

  Japanese Patent Laid-Open No. 2005-29430 (Patent Document 6) discloses that gas generation control of powdered organic acid or inorganic acid and sepiolite is added to an aqueous chlorite solution in order to further extend the generation duration of chlorine dioxide gas. A chlorine dioxide gas generation method is disclosed in which an agent or such a gas generation regulator and a water-absorbing resin are added and gelled to continuously generate chlorine dioxide gas.

JP 61-48404 A JP-A 63-303905 JP-A-6-233985 JP-A-11-278808 JP 2003-12424 A JP 2005-29430 A

  Chlorine dioxide gas generation as disclosed in JP-A-61-48404 (Patent Document 1), JP-A-63-303905 (Patent Document 2) and JP-A-6-233985 (Patent Document 3) In general, a composition for a reaction proceeds by moisture in the air and gradually generates chlorine dioxide gas. Therefore, the generation rate of chlorine dioxide gas is not only dependent on moisture, but is remarkably large at the beginning of use, but the generation amount decreases with time. Also, since it is a solid, only the components on its surface are consumed for the generation of chlorine dioxide gas, so it is necessary to renew the surface by stirring the particles from time to time. To maintain the chlorine dioxide gas concentration at a certain level These compositions must be replaced and replenished from time to time. Further, the method of adsorbing chlorine dioxide gas on silica gel and driving it out with air requires equipment and labor, and is not easy in use.

  The gel composition disclosed in Japanese Patent Application Laid-Open No. 11-278808 (Patent Document 4) can generate chlorine dioxide gas continuously for a long time. It is difficult to adjust the gas transpiration rate, and for example, there is a problem that the transpiration rate increases as the temperature rises.

  A gel-like composition as disclosed in JP-A No. 2003-12424 (Patent Document 5) and JP-A No. 2005-29430 (Patent Document 6) is disclosed in JP-A No. 11-278808 (Patent Document 4). Compared to the gel-like composition as disclosed, the generation duration of chlorine dioxide gas can be further extended, but environmental purification, sterilization or sterilization of bacteria or viruses, indoor or outdoor such as home, hospital or From the viewpoint of deodorization of food, mold prevention, antiseptic, etc., it is required to further extend the generation duration of chlorine dioxide gas.

  An object of the present invention is to provide a method for generating chlorine dioxide gas, a kit for generating chlorine dioxide gas, and a gel-like composition.

  According to one aspect of the present invention, from a gelled composition obtained by adding a gelation activator containing a gas generation regulator, a pH regulator and a water absorbent resin to a chlorite aqueous liquid and gelling the gel, This is a method for generating chlorine dioxide gas that continuously generates chlorine dioxide gas.

  In the method for generating chlorine dioxide gas according to this aspect of the present invention, the gelation activator may further include a gas generation accelerator. The aqueous chlorite solution can be made alkaline with a pH of 9 or more and 13 or less. Alternatively, the aqueous chlorite solution can be enclosed in an airtight container before the gelling activator is added. Also, the gelling activator can be enclosed in an airtight container before being added to the aqueous chlorite solution.

  According to another aspect, the present invention comprises an agent A containing an aqueous chlorite solution and an agent B containing a gelation activator containing a gas generation regulator, a pH adjuster and a water absorbent resin. This is a chlorine dioxide gas generating kit that continuously generates chlorine dioxide gas by adding B agent to A agent.

  In the kit for generating chlorine dioxide gas according to this aspect of the present invention, the gelation activator contained in the agent B can further contain a gas generation accelerator. Moreover, the aqueous chlorite solution contained in the agent A can be made alkaline with a pH of 9 or more and 13 or less.

  According to yet another aspect, the present invention includes a chlorite aqueous liquid and a gelling activator including a gas generation regulator, a pH regulator, and a water absorbent resin, and continuously containing chlorine dioxide gas. It is a gel-like composition to be generated.

  In the gel composition according to this aspect of the present invention, the gelation activator can further include a gas generation accelerator.

  ADVANTAGE OF THE INVENTION According to this invention, the generation | occurrence | production method of chlorine dioxide gas, the kit for chlorine dioxide gas generation | occurrence | production, and a gel-like composition can be provided.

It is the schematic which shows the measuring method of the density | concentration of the chlorine dioxide gas generate | occur | produced from the gel-like composition.

[Embodiment 1: Method for generating chlorine dioxide gas]
A method for generating chlorine dioxide gas, which is an embodiment of the present invention, is obtained by adding a gelation activator containing a gas generation regulator, a pH adjuster and a water absorbent resin to an aqueous chlorite solution to obtain a gel. In this method, chlorine dioxide gas is continuously generated from the gel composition. The method for generating chlorine dioxide gas of the present embodiment is a gel obtained by gelation by adding a gelation activator containing a gas generation regulator, a pH regulator and a water absorbent resin to a chlorite aqueous liquid. From the composition, chlorine dioxide gas can be continuously generated over a very long time.

  In the method for generating chlorine dioxide gas of the present embodiment, it is defined as “addition of gelling activator to chlorite aqueous liquid”, but “addition of chlorite aqueous liquid to gelation activator” However, essentially the same effect can be obtained. That is, “adding the aqueous chlorite solution to the gelling activator” is equivalent to “adding the gelling activator to the aqueous chlorite solution”.

  In the method for generating chlorine dioxide gas of the present embodiment, from the viewpoint of promoting the generation and generation of chlorine dioxide gas in the initial stage (for example, after 0 to 1 hour) after adding the gelation activator to the aqueous chlorite solution, The gelling activator can further include a gas generation accelerator.

  In the method for generating chlorine dioxide gas of the present embodiment, the generation and generation of chlorine dioxide gas due to the decomposition of chlorite in the aqueous chlorite solution before the addition of the gelation activator is suppressed and stable for a long period of time. The pH of the aqueous chlorite solution is preferably 9 or more and 13 or less, preferably 10 or more and 12.5 or less, from the viewpoint of being able to preserve and stably generate chlorine dioxide gas by adding a gelation activator for a long time. More preferably, it is 11 or more and 12 or less.

  In the method for generating chlorine dioxide gas of the present embodiment, the generation and generation of chlorine dioxide gas due to the decomposition of chlorite in the aqueous chlorite solution before the addition of the gelling activator is suppressed for a long period of time. From the standpoint of stable storage and generation of chlorine dioxide gas stably for a long time by adding a gelation activator, an aqueous chlorite solution is used before the gelation activator is added. It is preferable to be enclosed in an airtight container.

  In the method for generating chlorine dioxide gas of the present embodiment, the gelation activator is chlorous acid from the viewpoint of suppressing deterioration of the gelation activator before being added to the aqueous chlorite solution and storing it stably for a long time. Before being added to the aqueous acid salt solution, it is preferably sealed in an airtight container.

(Aqueous chlorite liquid)
The aqueous chlorite liquid used in the method for generating chlorine dioxide gas of the present embodiment includes water containing chlorite as a main component (a solvent excluding solutes such as chlorite and / or dispersoids) and water. And / or a liquid having a water content in the dispersion medium of 50% by mass or more, the same shall apply hereinafter), and comprising a gas generation regulator, a pH regulator, a water absorbent resin and a gas production accelerator. A liquid that can dissolve and / or disperse the gelling activator including the gelling activator is added to form a gel-like composition, and chlorine dioxide gas is formed from the formed gel-like composition. It is a liquid that continuously generates water. Aqueous chlorite liquid is an aqueous solution or water dispersion from the viewpoint of generating chlorine dioxide gas safely, stably over a long period of time from a gel composition obtained by gelation with the addition of a gelling activator. A liquid is preferred.

The chlorite contained in the aqueous chlorite solution is not particularly limited as long as it is a chlorite that generates chlorine dioxide gas due to the presence of a pH adjuster described later. For example, sodium chlorite (NaClO) ₂ ), chlorites of group 1 elements (alkali metal elements) excluding hydrogen, such as 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 ), chlorite of group 2 elements such as magnesium chlorite (Mg (ClO ₂ ) ₂ ) Examples include acid salts. Among these, commercially available sodium chlorite is easily available and there is no problem in use.

  The aqueous chlorite solution can be obtained by dissolving a predetermined concentration of the above chlorite in the aqueous solution. When sodium chlorite is dissolved in an aqueous liquid, a commercially available 25% by mass sodium chlorite aqueous solution used as a bleaching agent in the liquid, or a 86% by mass, 80% by mass, or 79% by mass commercially available solid. Or 76% by mass is preferably used. The concentration of the aqueous chlorite solution is preferably less than 25% by mass, more preferably less than 15% by mass, and more preferably 10% by mass or less from the viewpoint of being easy to handle because it does not fall under the category of dangerous poisons and dangerous substances. Further preferred.

  The pH of the aqueous chlorite solution is from 9 to 13, preferably from 10 to 12.5, and more preferably from 11 to 12. Chlorine dioxide can be stored stably for a long period of time by suppressing generation and generation of chlorine dioxide gas due to decomposition of chlorite in chlorite aqueous solution before addition of gelling activator, and addition of gelling activator Gas can be generated stably for a long time.

  The aqueous chlorite salt solution preferably further contains an ant potting agent so that the pH is 9 or more and 13 or less. The alkali agent is not particularly limited as long as the chlorite aqueous solution exhibits alkalinity by being dissolved and / or dispersed in the chlorite aqueous solution, but a gelling activator is added. From the viewpoint of preventing the generation of chlorine dioxide gas even in an acidic atmosphere, sodium hydroxide (NaOH), potassium hydroxide (KOH), and the like are preferable. Potassium hydroxide does not react with carbon dioxide in the atmosphere like sodium hydroxide to form a salt such as sodium bicarbonate. It is easier to wet and penetrate during hydration than sodium hydroxide, and it is a gelling activator. It is particularly preferable because it can be easily mixed with each other and the formation of the gel composition is further promoted.

  The aqueous chlorite solution is preferably sealed in an airtight container before the gelling activator is added. By sealing the chlorite aqueous solution in an airtight container, the generation and generation of chlorine dioxide gas due to the decomposition of chlorite in the chlorite aqueous solution before the addition of the gelation activator is suppressed. Aqueous chlorite liquid can be stored stably for a long period of time, and chlorine dioxide gas can be stably generated for a long period of time by adding a gelation activator. Here, the airtight container refers to a container that does not transmit a gas such as water vapor, a liquid such as moisture, or a solid. From the viewpoint of low reactivity with the aqueous chlorite solution and stable storage of the aqueous chlorite solution for a long period of time, various plastic containers are preferred.

(Gas generation regulator)
The gas generation regulator used in the method for generating a chlorinated gas according to the present embodiment refers to the chlorine dioxide gas generated from the chlorite aqueous liquid due to the presence of the pH regulator, continuously from the gel composition for a long time. A regulator for generation. That is, the gas generation regulator retains at least part of the chlorine dioxide gas on the surface and / or inside when the amount of chlorine dioxide gas produced is large, and retains when the amount of chlorine dioxide gas produced is small or absent. By releasing the generated chlorine dioxide gas, the chlorine dioxide gas is continuously generated from the gel composition. Here, the gas generation regulator is a component of the gelation activator and is a solid.

  The gas generation regulator is not particularly limited in material and shape as long as it can efficiently disperse the generation of chlorine dioxide gas, but from the viewpoint of maintaining a large amount of chlorine dioxide gas, a porous material having a large surface area is preferable. It is preferably at least one selected from the group consisting of sepiolite, montmorillonite, diatomaceous earth, talc and zeolite. From the viewpoint of increasing the surface area, it is preferably powdery, granular and / or porous.

Of the gas generation regulators described above, sepiolite is preferable from the viewpoint of excellent retention and release of chlorine dioxide gas. Here, sepiolite is a natural mineral of magnesium silicate, the chemical composition formula is represented by Mg ₈ Si ₁₂ O ₃₀ (OH) ₄ (OH ₂ ) ₄ · 8H ₂ O, and its crystal structure is fibrous. The material has a large surface area with a large number of grooves on the surface and a large number of cylindrical tunnel structure clearances inside. Commercially available products include Miracle (trade name, manufactured by Omi Mining Co., Ltd.). An example of powdered diatomaceous earth is Celite (manufactured by Showa Chemical Co., Ltd.).

(PH adjuster)
The pH adjuster used in the method for generating chlorine dioxide gas of the present embodiment has a function of stably maintaining the pH atmosphere in the gel composition at a pH necessary for generating chlorine dioxide gas from chlorite. The pH adjuster is a constituent of the gelling activator and is a solid. Here, the pH atmosphere in the gel composition is not particularly limited, but is preferably 2 or more and 9 or less, more preferably 3 or more and 7 or less, from the viewpoint of stably generating chlorine dioxide gas stably for a long time.

  The pH adjuster is not particularly limited, but is a salt of a weak acid having an acid dissociation constant pKa of 2.5 or more and an acid dissociation constant pKa of 3.8 or more from the viewpoint of stably producing chlorine dioxide gas for a long time. At least one substance selected from the group consisting of a weak acid, an amphoteric compound having both acidic and alkaline functional groups, and a heterocyclic compound having a pyrimidine structure is preferred.

The acid dissociation constant pK _a of 2.5 or more salts of weak acids, sodium citrate is a salt of citric acid (pK _a1 is 2.90, pK _a2 is 4.35, pK _a3 is 5.69), apples Examples thereof include sodium malate which is a salt of an acid (pK _a1 is 3.23 and pK _a2 is 4.77). Here, there are three types of sodium citrate: monosodium citrate (monosodium citrate), disodium citrate (disodium citrate)) and trisodium citrate (trisodium citrate)). Of these, disodium citrate and trisodium citrate are more preferred. There are two types of sodium malate, monosodium malate (monosodium malate) and disodium malate (disodium malate), and among these, disodium malate is more preferred.

The acid dissociation constant pK _a of 3.8 or more weak, succinic acid (pK _a1 is 3.99, pK _a2 is 5.20), boric acid (pK _a1 is 9.23, pK _a2 is 12.74, pK _a3 is 13.52), and the like.

Examples of the amphoteric compounds include amino acids having a carboxyl group (COOH group) that is an acidic functional group and an amino group (NH ₂ group) that is an alkaline functional group. As amino acids, glycine having an alkyl chain, alanine, valine, leucine, and isoleucine, serine and trionine having a hydroxy group (OH group), asparagine and glutamine having an amide group (RCONH group), imino group (C = NH group) Or proline having CNHC group), phenylalanine having phenyl group (C ₆ H ₅ group), tyrosine and tryptophan, aspartic acid and glutamic acid having two or more carboxyl groups (COOH group), two or more amino groups (NH ₂ group) ) Lysine, arginine and the like.

  Examples of the heterocyclic compound having a pyrimidine structure include barbituric acid and orotic acid.

(Water absorbent resin)
The water absorbent resin used in the method for generating chlorine dioxide gas according to the present embodiment absorbs moisture to form a gel composition. The water-absorbing resin is a constituent element of the gelling activator and is a solid. For example, starch-based water-absorbing resins, cellulose-based water-absorbing resins, synthetic polymer-based water-absorbing resins are preferably used. Examples of starch-based water-absorbing resins include starch / polyacrylic acid resins (manufactured by Sanyo Chemical Co., Ltd., powder). Synthetic polymer-based water-absorbing resins include crosslinked polyacrylic acid resins, isobutylene / maleic acid resins, popal / There are a polyacrylate resin, a polyacrylate resin, and the like. Specifically, sodium polyacrylate is used.

(Gas generation accelerator)
In the method for generating chlorine dioxide gas according to the present embodiment, the gas generation accelerator that is optionally used is for promoting the generation of chlorine dioxide gas from chlorite in the presence of a pH adjuster. The gas generation accelerator is an optional component of the gelation activator and is not particularly limited as long as it is solid, but an organic acid used as a food additive is preferable from the viewpoint of high safety. As the organic acid, citric acid (pK _a1 is 2.90, pK _a2 is 4.35, pK _a3 is 5.69), malic acid (pK _a1 is 3.23, pK _a2 is 4.77), formic acid ( pK _a is 3.54), lactic acid (pK _a is 3.64), tartaric acid ((+) pK _a1 in body 2.87, pKa ₂ is 3.97: pK _a1 2.95 in meso, pK and carboxylic acids such that _a2 is 4.46).

Also, when the acid dissociation constant pK _a is used 2.5 or more salts of weak acids as pH adjusting agents, in view of enhancing the pH adjustment effect, the use of the conjugate acid of pH adjusting agent as a gas generating accelerator preferable. For example, when citrate is used as the pH adjuster, it is preferable to use citric acid as the gas generation accelerator, and when malate is used as the pH adjuster, malic acid is used as the gas generation accelerator. preferable.

(Gelling activator)
The gelation activator used in the method for generating chlorine dioxide gas of the present embodiment forms a gel-like composition by adding it to an aqueous chlorite solution, and chlorine dioxide gas is formed from the formed gel-like composition. Is generated continuously, and includes a gas generation regulator, a pH regulator and a water-absorbing resin. Further, the gelation activator can further include a gas generation accelerator from the viewpoint of promoting the generation and generation of the initial chlorine dioxide gas after the gelation activator is added to the aqueous chlorite solution. Here, from the viewpoint of forming a homogeneous gel composition, the gelation activator is composed of a chlorite, a gas generation regulator, a pH regulator, a water absorbent resin, and optionally a gas production accelerator. It is preferable to contain what was fully mixed.

  The gelling activator is preferably enclosed in an airtight container before being added to the aqueous chlorite solution. Before addition to the aqueous chlorite solution, the gelling activator is sealed in an airtight container, which prevents moisture from entering the atmosphere and prevents deterioration. Therefore, it can be stably stored for a long time. Here, the airtight container refers to a container that does not transmit a gas such as water vapor, a liquid such as moisture, or a solid, and examples thereof include various metal containers and various plastic containers.

[Embodiment 2: Kit for generating chlorine dioxide gas]
A kit for generating chlorine dioxide gas according to another embodiment of the present invention includes an agent A containing an aqueous chlorite solution, and a B containing a gelation activator containing a gas generation regulator, a pH adjuster and a water absorbent resin. And a kit that continuously generates chlorine dioxide gas by adding the B agent to the A agent. The kit for generating chlorine dioxide gas of this embodiment is composed of an agent A containing an aqueous chlorite solution and an agent B containing a gelation activator containing a gas generation regulator, a pH adjuster and a water absorbent resin. In addition, by adding the B agent to the A agent, chlorine dioxide gas can be continuously generated over a very long time from the gel composition obtained by gelation.

  In the kit for generating chlorine dioxide gas according to the present embodiment, “adding B agent to A agent” is prescribed, but even if “adding A agent to B agent” is essentially the same effect. . That is, “adding agent A to agent B” is equivalent to “adding agent B to agent A”.

  In the kit for generating chlorine dioxide gas of the present embodiment, the gel contained in the B agent from the viewpoint of promoting the generation and generation of the initial (for example, 0 to 1 hour) after the addition of the B agent to the A agent. The activation activator can further include a gas generation accelerator.

  In the kit for generating chlorine dioxide gas of the present embodiment, the generation and generation of chlorine dioxide gas due to the decomposition of chlorite in the aqueous chlorite solution in agent A before addition of agent B is suppressed for a long period of time. The pH of the aqueous chlorite solution contained in the agent A is preferably 9 or more and 13 or less from the viewpoint of stable storage and stable generation of chlorine dioxide gas for a long time by addition of the agent B. It is more preferably 12.5 or less, and further preferably 11 or more and 12 or less.

  It is preferable that A agent which is one element which comprises the kit for chlorine dioxide gas generation of this embodiment is enclosed with the airtight container before addition of B agent. Before the addition of B agent, the production and generation of chlorine dioxide gas due to decomposition of chlorite in chlorite aqueous solution in agent A is suppressed, and A agent containing chlorite aqueous solution is stable for a long time The chlorine dioxide gas can be stably generated for a long time by adding the B agent. Here, an airtight container refers to a container that does not allow gas such as water vapor, liquid such as water, and solids to pass through. The reactivity with the aqueous chlorite solution is low, and the aqueous chlorite solution is used for a long time. From the viewpoint of stable storage, various plastic containers are preferable.

  It is preferable that B agent which is another element which comprises the kit for chlorine dioxide gas generation of this embodiment is enclosed in the airtight container, before adding to A agent. Since the gelation activator in the agent B is sealed in an airtight container, moisture is prevented from being mixed in from the atmosphere, so that deterioration is prevented. The agent can be stored stably for a long period of time. Here, the airtight container refers to a container that does not transmit a gas such as water vapor, a liquid such as moisture, or a solid, and examples thereof include various metal containers and various plastic containers.

  In addition, the B agent is a chlorite, a gas generation regulator, and a pH regulator from the viewpoint of forming a homogeneous gel composition and generating chlorine dioxide gas continuously over an extremely long time. And a gelling activator in which the water-absorbing resin and, optionally, the gas generation accelerator are sufficiently mixed.

  The chlorine dioxide aqueous liquid, gas generation regulator, pH regulator, water absorbent resin, gas generation accelerator and gelation activator in the chlorine dioxide gas generation kit of this embodiment are the chlorine dioxide of Embodiment 1. Since it is the same as the chlorite aqueous liquid, gas generation regulator, pH regulator, water absorbent resin, gas generation accelerator and gelation activator in the gas generation method, it will not be repeated here.

  The specific form of the kit for generating chlorine dioxide gas of the present embodiment is not particularly limited, and an airtight container enclosing agent A (for example, a chlorite aqueous solution) and agent B (for example, a gas generation regulator, a form in which an airtight container enclosing a pH adjusting agent and a water-absorbing resin) is packaged together, or a container in which an agent A (for example, a chlorite aqueous solution) is encapsulated , And a combination of a packaged container in which a B agent (for example, a gelation activator including a gas generation regulator, a pH regulator and a water-absorbing resin) is enclosed, and the like.

[Embodiment 3: Gel composition]
Still another embodiment of the present invention is a gel composition comprising an aqueous chlorite liquid and a gelation activator comprising a gas generation regulator, a pH regulator and a water absorbent resin, and chlorine dioxide gas. It is a gel-like composition that continuously generates. Since the gel composition of the present embodiment includes a chlorite aqueous liquid and a gelling activator including a gas generation regulator, a pH regulator, and a water absorbent resin, the gel composition is oxidized from the gel composition. Chlorine gas can be generated continuously over an extremely long time.

  In the gel composition of the present embodiment, the viewpoint of promoting the generation of chlorine dioxide gas from the gel composition in the initial stage (for example, after 0 to 1 hour) after adding the gelation activator to the aqueous chlorite solution. Thus, the gelling activator may further include a gas generation accelerator.

  In the gel composition of this embodiment, according to the chlorine dioxide gas generation method of Embodiment 1, a gelation activator containing a gas generation regulator, a pH adjuster and a water absorbent resin is added to the aqueous chlorite solution. More specifically, using the chlorine dioxide gas generation kit of Embodiment 2, the agent A containing an aqueous chlorite solution is added to a gas generation regulator, a pH regulator, and It is gelled by adding a B agent containing a gelling activator containing a water absorbent resin.

In addition, the aqueous chlorite liquid, the gas generation regulator, the pH regulator, the water absorbent resin, the gas generation accelerator and the gelation activator in the gel composition of the present embodiment generate chlorine dioxide gas in the first embodiment. Since it is the same as the aqueous chlorite solution, gas generation regulator, pH regulator, water absorbent resin, gas production accelerator and gelation activator in the method, the gel composition of this embodiment is not repeated here. Although there is no particular limitation, from the viewpoint of continuously generating chlorine dioxide gas from the gel composition for an extremely long time, the chlorite component in the aqueous chlorite solution is 2. 5 mass% to 10 mass%, gas generation regulator is 1.5 mass% to 15 mass%, pH regulator is 2 mass% to 10 mass%, water absorbent resin is 2.5 mass% to 10 mass%, gas 0% to 5% by weight of formation accelerator, chlorite aqueous solution It is preferable that the aqueous liquid component in it is 50 mass%-90 mass%.

(Preparation of container)
Referring to FIG. 1, a plastic body having a capacity of 200 ml (average inner diameter 35.7 mm × height 50 mm, opening inner diameter 28 mm), and plastic having five drill holes having a diameter of 1.5 mm as opening holes 1w A number of containers 1 composed of a screw cap made of a screw were prepared.

(Preparation of aqueous chlorite solution)
A chlorite aqueous solution was prepared as follows. First, a 25 mass% sodium chlorite aqueous solution (25% sodium chlorite aqueous solution manufactured by Daiso Corporation) was diluted with pure water to prepare 1000 ml of an 8 mass% sodium chlorite aqueous solution. Next, 0.4 g of sodium hydroxide (a flake caustic soda manufactured by Kanto Denka Co., Ltd.) as an alkaline agent is added to 1000 ml of an 8% by mass sodium chlorite aqueous solution, and the pH of the chlorite aqueous solution is about 12. An 8 mass% sodium chlorite aqueous solution was prepared.

(Adjustment of gelling activator)
A gelation activator containing a gas generation regulator, a pH regulator, a water absorbent resin and a gas production accelerator was prepared as follows. First, 630 g of sepiolite powder (Omi Kogyo Miraclay P-150D) as a gas generation regulator, 975 g of trisodium citrate dihydrate powder (sodium citrate from Fuso Chemical Industries) as a pH regulator, and a water-absorbing resin 17.4 g of polyacrylic acid water-absorbing resin powder (Sunfresh ST-500D manufactured by Sanyo Chemical Co., Ltd.) and 585 g of citric acid powder (citric acid (crystal) manufactured by Fuso Chemical Industry Co., Ltd.) as a gas generation accelerator 3930 g of a gelling activator was prepared by mixing with

  Using the high-speed filling machine and the packaging machine, the gelation activator thus obtained was subjected to the packaging No. 1-No. A large number of each of the three types of 3 packages were prepared. One package No. 1 is filled with 13.1 g of gelling activator and one sachet no. 2 is filled with 19.65 g of gelation activator (that is, 1.5 times the amount of gelation activator of sachet No. 1). 3 was filled with 26.2 g of gelling activator (that is, twice as much gelling activator as sachet No. 1).

Example 1
After 46.9 g of the prepared aqueous chlorite solution was put in the main body of each of the three containers, the sachet No. 13.1 g of 1 gelling activator was added. Gelation was obtained in 1.5 minutes from the addition of the gelation activator to obtain a gel composition. Next, the main body of each container was closed with the screw cap of each container.

  Next, referring to FIG. 1, three containers 1 containing the gel composition were added to three beakers 2 having a capacity of 1.3 l (PYREX (registered trademark) IWAKI TE-32 ASAHI GLASS (AGC Asahi Glass)). ) At the bottom of each. Next, openings other than the spout of each beaker 2 were covered with a plastic film 3 (Saran Wrap (registered trademark) manufactured by Asahi Kasei Chemicals).

After a predetermined time elapsed from the addition of the gelling activator, the concentration of chlorine dioxide gas generated from the gel-like composition was measured by inserting the Kitagawa type detection tube 4 into the spout where the beaker 2 was released. The average of the actual measurement values for the three containers was corrected to 20 ° C. to obtain the chlorine dioxide gas concentration. Table 1 shows the elapsed time (hr), chlorine dioxide (ClO ₂ ) gas concentration (ppm), atmospheric temperature (° C.), and relative humidity (%) at that time.

(Example 2)
After putting 70.35 g (that is, 1.5 times the amount of Example 1) of the prepared aqueous chlorite solution into the main body of each of the three containers, 19.65 g of gelling activator 2 (ie 1.5 times the amount of Example 1) was added. Gelation was obtained in 2 minutes from the addition of the gelation activator to obtain a gel composition. Next, the screw lid cap of each container was closed on the main body of each container. In the same manner as in Example 1, the concentration of chlorine dioxide gas generated from the gel composition was measured after a predetermined time had elapsed from the addition of the gelling activator. Table 2 shows the elapsed time (hr), chlorine dioxide (ClO ₂ ) gas concentration (ppm), atmospheric temperature (° C.), and relative humidity (%) at that time.

(Example 3)
After 93.8 g (that is, twice the amount of Example 1) of the prepared chlorite aqueous solution was put in the main body of each of the three containers, 26.2 g of gelling activator 3 (ie twice the amount of Example 1) was added. Gelation was obtained in 2.5 minutes after the addition of the gelation activator to obtain a gel composition. Next, the main body of each container was closed with the screw cap of each container. In the same manner as in Example 1, the concentration of chlorine dioxide gas generated from the gel composition was measured after a predetermined time had elapsed from the addition of the gelling activator. Table 3 summarizes the elapsed time (hr), chlorine dioxide (ClO ₂ ) gas concentration (ppm), atmospheric temperature (° C.), and relative humidity (%).

Example 4
In each of the three containers, 60 g of the prepared aqueous chlorite solution (that is, about 1.28 times the amount of Example 1) was added. One gelling activator, 13.1 g (ie 1 volume of Example 1) was added. Gelation was obtained in 3 minutes from the addition of the gelation activator to obtain a gel composition. Next, the main body of each container was closed with the screw cap of each container. In the same manner as in Example 1, the concentration of chlorine dioxide gas generated from the gel composition was measured after a predetermined time had elapsed from the addition of the gelling activator. Table 4 shows the elapsed time (hr), chlorine dioxide (ClO ₂ ) gas concentration (ppm), atmospheric temperature (° C.), and relative humidity (%) at that time.

(Example 5)
After 90 g of the prepared aqueous chlorite solution (that is, about 1.92 times the amount of Example 1) was put in the main body of each of the three containers, 19.65 g of gelling activator 2 (ie 1.5 times the amount of Example 1) was added. Gelation was obtained in 3 minutes from the addition of the gelation activator to obtain a gel composition. Next, the main body of the container was closed with the screw cap of the container. In the same manner as in Example 1, the concentration of chlorine dioxide gas generated from the gel composition was measured after a predetermined time had elapsed from the addition of the gelling activator. Table 5 shows the elapsed time (hr), chlorine dioxide (ClO ₂ ) gas concentration (ppm), atmospheric temperature (° C.), and relative humidity (%) at that time.

(Example 6)
A gelation activator containing a gas generation regulator, a pH regulator and a water-absorbing resin (not containing a gas production accelerator) was prepared as follows. First, 2.1 g of sepiolite powder (Omi Kogyo Miracle P-150D) as a gas regulator and 5.2 g of trisodium citrate dihydrate powder (sodium citrate from Fuso Chemical Co., Ltd.) as a pH regulator, Then, 5.8 g of a polyacrylic acid-based water-absorbent resin powder (Sunfresh ST-500D manufactured by Sanyo Chemical Co., Ltd.) as a water-absorbing resin was filled in a plastic (polyethylene) chuck bag and mixed. In this way, three sachets containing 13.1 g of the gelling activator were prepared.

4. 46.9 g of the prepared aqueous chlorite solution (that is, 1 times the amount of Example 1) is placed in the main body of each of the three containers, and then the gelation activator of the prepared packaging is used. 1 g (ie 1 time the amount of Example 1) was added. Gelation was obtained in 2.5 minutes after the addition of the gelation activator to obtain a gel composition. Next, the main body of each container was closed with the screw cap of the container. In the same manner as in Example 1, the concentration of chlorine dioxide gas generated from the gel composition was measured after a predetermined time had elapsed from the addition of the gelling activator. Table 6 shows the elapsed time (hr), chlorine dioxide (ClO ₂ ) gas concentration (ppm), atmospheric temperature (° C.), and relative humidity (%) at that time.

(Example 7)
A gelation activator containing a gas generation regulator, a pH regulator and a water-absorbing resin (not containing a gas production accelerator) was prepared as follows. First, 2.1 g of sepiolite powder (Miraclay P-150D, manufactured by Omi Kogyo Co., Ltd.) as a gas generation regulator, 5.2 g of amino acid powder (glycine (food additive), Organic Synthetic Chemical Industry Co., Ltd.) as a pH regulator, and water absorption 5.8 g of a polyacrylic acid water-absorbing resin powder (Sanfresh ST-500D manufactured by Sanyo Kasei Co., Ltd.) as a functional resin was filled in a plastic (polyethylene) chuck bag and mixed. In this way, three sachets containing 13.1 g of the gelling activator were prepared.

4. 46.9 g of the prepared aqueous chlorite solution (that is, 1 times the amount of Example 1) is placed in the main body of each of the three containers, and then the gelation activator of the prepared packaging is used. 1 g (ie 1 time the amount of Example 1) was added. Gelation was obtained in 2.5 minutes after the addition of the gelation activator to obtain a gel composition. Next, the main body of each container was closed with the screw cap of each container. In the same manner as in Example 1, the concentration of chlorine dioxide gas generated from the gel composition was measured after a predetermined time had elapsed from the addition of the gelling activator. Table 7 summarizes the elapsed time (hr), chlorine dioxide (ClO ₂ ) gas concentration (ppm), atmospheric temperature (° C.), and relative humidity (%) at that time.

(Example 8)
A gelation activator containing a gas generation regulator, a pH regulator and a water-absorbing resin (not containing a gas production accelerator) was prepared as follows. First, 2.1 g of sepiolite powder (Miraclay P-150D manufactured by Omi Kogyo Co., Ltd.) as a gas generation regulator, 5.2 g of potassium citrate powder (potassium citrate M manufactured by Fuso Chemical Co., Ltd.) as a pH regulator, and water absorption 5.8 g of a polyacrylic acid water-absorbing resin powder (Sanfresh ST-500D manufactured by Sanyo Kasei Co., Ltd.) as a functional resin was filled in a plastic (polyethylene) chuck bag and mixed. In this way, three sachets containing 13.1 g of the gelling activator were prepared.

4. 46.9 g of the prepared aqueous chlorite solution (that is, 1 times the amount of Example 1) is placed in the main body of each of the three containers, and then the gelation activator of the prepared packaging is used. 1 g (ie 1 time the amount of Example 1) was added. Gelation was obtained in 2.5 minutes after the addition of the gelation activator to obtain a gel composition. Next, the main body of each container was closed with the screw cap of each container. In the same manner as in Example 1, the concentration of chlorine dioxide gas generated from the gel composition was measured after a predetermined time had elapsed from the addition of the gelling activator. Table 8 shows the elapsed time (hr), chlorine dioxide (ClO ₂ ) gas concentration (ppm), atmospheric temperature (° C.), and relative humidity (%) at that time.

  As shown in Tables 1 to 8, it is obtained by adding a gelation activator containing a gas generation regulator, a pH adjuster, a water absorbent resin, and preferably a gas production accelerator to a chlorite aqueous liquid to obtain a gel. From this gel composition, chlorine dioxide gas could be continuously generated over a very long time by the chlorine dioxide gas generating method for continuously generating chlorine dioxide gas.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  1 Plastic container containing gel composition, 1w opening hole, 2 beaker, 3 plastic film, 4 Kitagawa type detector tube.

Claims (10)

  A carbon dioxide gas that continuously generates chlorine dioxide gas from a gelled composition obtained by adding a gelation activator containing a gas generation regulator, a pH regulator and a water absorbent resin to an aqueous chlorite solution. Generation method of chlorine gas.   The method for generating chlorine dioxide gas according to claim 1, wherein the gelation activator further includes a gas generation accelerator.   The method for generating chlorine dioxide gas according to claim 1 or 2, wherein the aqueous chlorite solution is alkaline having a pH of 9 or more and 13 or less.   The generation of chlorine dioxide gas according to any one of claims 1 to 3, wherein the aqueous chlorite solution is sealed in an airtight container before the gelation activator is added. Method.   The method for generating chlorine dioxide gas according to any one of claims 1 to 3, wherein the gelling activator is enclosed in an airtight container before being added to the aqueous chlorite solution. .   The A agent containing an aqueous chlorite solution and the B agent containing a gelation activator containing a gas generation regulator, a pH adjuster and a water absorbent resin, and the B agent is added to the A agent Chlorine dioxide gas generation kit that continuously generates chlorine dioxide gas.   The said gelatinization activator contained in the said B agent is a kit for chlorine dioxide gas generation of Claim 6 which further contains a gas production | generation promoter.   The chlorine dioxide gas generating kit according to claim 6 or 7, wherein the aqueous chlorite solution contained in the agent A is alkaline having a pH of 9 or more and 13 or less.   A gel-like composition for continuously generating chlorine dioxide gas, comprising an aqueous chlorite solution and a gelation activator comprising a gas generation regulator, a pH regulator and a water absorbent resin.   The gel composition according to claim 9, wherein the gelation activator further includes a gas generation accelerator.

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