Sustained-release chlorine dioxide gas generating set and method thereof

Abstract

The present invention relates to a method for generating chlorine dioxide gas in a sustained-release manner for a long period of time without generating dangerous high-concentration gas. When the slow-release chlorine dioxide gas generation method according to the present invention is used, the purpose of long-term disinfection can be achieved by generating chlorine dioxide gas at a low concentration until alternating swarms without hurting bees in order to manage the infection of swarms.

Description

Technical Field

[0001] This application claims priority to Korean Patent Application No. 10-2022-0141844, filed on October 28, 2022, and Korean Patent Application No. 10-2023-0054371, filed on April 25, 2023, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a chlorine dioxide generating kit and method for generating chlorine dioxide gas in a sustained-release manner over several months.

Background Art

[0003] It is well known that chlorine dioxide is generated when ultraviolet rays are irradiated onto an aqueous solution or gel agent containing sodium chlorite (Patent Document 1: Japanese Published Patent Gazette No. 2005-224386, published on August 25, 2005). However, when ultraviolet rays are irradiated onto an aqueous solution in which sodium chlorite is dissolved in pure water, the reaction is too slow, and the amount of chlorine dioxide generated is too low to produce a concentration of chlorine dioxide sufficient for disinfection or sterilization. Also, it is well known that chlorine dioxide is generated when sodium chlorite comes into contact with an acid such as citric acid (Patent Document 2: Korean Patent Granted Gazette No. 10-1807966, granted on December 5, 2017), but the method of bringing sodium chlorite into contact with citric acid cannot be interrupted once the reaction starts, and if sulfuric acid or hydrochloric acid is used instead of citric acid, it is dangerous and there is a risk of explosion due to an excessive rapid reaction. Therefore, a method for safely producing chlorine dioxide gas at a low concentration is needed.

[0004] It is well known that bees play an important role in the pollination of plants and thus play an important role in maintaining the ecosystem. However, bees are very vulnerable to diseases caused by pathogens such as fungi, bacteria, and viruses, and chemical substances such as pesticides and insecticides for control purposes aimed at increasing crop productivity act on bees instead, frequently causing great harm to bee colonies. In particular, recently, a phenomenon called colony collapse disorder (CCD) of bees has occurred in the United States, Canada, Europe, South America, and Asia, etc. Although the cause of this colony collapse disorder has not been clearly identified, it is known to be caused by the combined action of various diseases spreading among bees and the emergence of pathogens such as pests, bacteria, and viruses. Therefore, there is a need to develop a disinfectant that is harmless to bees themselves and does not remain in honey and has excellent disinfection effects.

[0005] Korean Patent No. 10-1315260 (Patent Document 3, authorized on September 30, 2013) discloses a disinfection device using chlorine dioxide gas for preventing or treating infectious diseases such as sacbrood disease. Since chlorine dioxide explodes at a concentration of more than 10% and cannot be stored or transported, according to the disclosure in the above patent, stable chlorine dioxide stabilized by reacting with an alkaline salt reacts with ultraviolet light to generate chlorine dioxide gas and has an excellent disinfection effect. However, the above device includes an electronic device and failed in the commercialization process due to difficult management.

[0006] In addition, the existing method of adding citric acid to an aqueous solution of sodium chlorite explosively generates chlorine dioxide. However, as chlorine dioxide dissolves in the aqueous solution, the generated gas is slowly released. Therefore, there is a problem that the gas generation amount decreases and the gas generation ends in about 2 weeks at the longest (see Figure 4 ). Therefore, there is a need to develop a method and kit that can stably generate chlorine dioxide gas at a low concentration for a long time without including an electronic device.

Summary of the Invention

[0007]

Technical Problem

[0008] As described above, there is a need to develop a safe and easy-to-use disinfection method for preventing or treating infectious diseases of bees. In particular, bees are different from other livestock. When an infectious disease occurs, it is impossible to only isolate the diseased bees, nor is it possible to completely remove the pathogens from the infected bees. Therefore, for the infection management of the bee colony, it is necessary to create an environment that can disinfect the entire bee colony and maintain the above environment for more than 60 days, which is the average lifespan of bees, so that the bee colony can be passed on without being infected by pathogens.

[0009] Therefore, the present inventors made several efforts to develop a method and device for managing bee colonies that are easy to use and can continuously produce chlorine dioxide gas for a long time. As a result, it was confirmed that when an organic compound containing a hydroxyl (-OH group) and an organic acid are added to a gel composition containing sodium chlorite, chlorine dioxide is generated at a low concentration for a long time, thus completing the present invention.

[0010] Therefore, an object of the present invention is to provide a sustained-release chlorine dioxide gas generation kit, comprising (a) a chlorite; (b) a sugar; (c) a gelling agent or thickening agent; and (d) an acid.

[0011] Another object of the present invention is to provide a method for delaying the generation of chlorine dioxide gas, comprising: Step a), putting a preparation containing a chlorite into a container; and Step b), adding a powder containing a sugar and an acid to the above container.

[0012]

Technical Solution

[0013] According to an embodiment of the present invention, the present invention provides a sustained-release chlorine dioxide gas generation kit, comprising

[0014] (a) chlorite; (b) sugar; (c) gelling agent or thickening agent; and (d) acid.

[0015] The above-mentioned chlorite of the present invention is characterized in that chlorine dioxide gas is continuously generated in the long term by reacting with sugar. The types of the above-mentioned sugar can be those listed in Table 1 below, but are not limited thereto. However, the start of the reaction between the above-mentioned (a) chlorite and (b) sugar is too slow, so there is a problem that the reaction start time cannot be specified. And if the chlorite and sugar are stirred accordingly, there is a risk of explosion with the reaction rate out of control.

[0016] Therefore, the inventor of the present invention further includes (d) acid in the chlorine dioxide gas generation kit containing (a) chlorite, (b) sugar, and (c) gelling agent or thickening agent, so that the reaction with chlorite can be quickly started. As a result, chlorine dioxide gas is rapidly generated by the reaction of acid and chlorite, and the chlorine dioxide gas promotes the reaction between chlorite and sugar. That is, the kit of the present invention is characterized in that in the composition of the kit, the acid can control the time point of the chlorine dioxide gas generation reaction by quickly reacting with chlorite, and the above-mentioned gelling agent or thickening agent can delay the generation of chlorine dioxide to generate chlorine dioxide gas in a sustained-release manner in the long term.

[0017] In an example of the present invention, the above-mentioned chlorite is one or more selected from the group consisting of sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, magnesium chlorite, and barium chlorite, but is not limited thereto.

[0018] In an example of the present invention, based on the total weight of the composition of the kit containing the above-mentioned (a) to (d) except for the container, the above-mentioned chlorite can be contained in a weight of 1% to 15%, 1% to 10%, 1% to 9%, 1% to 8%, 1% to 7%, 1% to 6%, 1% to 5%, 2% to 15%, 2% to 10%, 2% to 9%, 2% to 8%, 2% to 7%, 2% to 6%, 2% to 5%, 3% to 15%, 3% to 10%, 3% to 9%, 3% to 8%, 3% to 7%, 3% to 6%, 3% to 5%, 4% to 15%, 4% to 10%, 4% to 9%, 4% to 8%, 4% to 7%, 4% to 6%, 4% to 5%, 5% to 15%, 5% to 10%, 5% to 9%, 5% to 8%, 5% to 7%, or 5% to 6%, but is not limited thereto.

[0019] In an example of the present invention, the above-mentioned chlorite is a precursor substance of chlorine dioxide gas.

[0020] The preparation containing the above-mentioned chlorite can be provided in the form of an aqueous solution or in the form of a gel, but from the aspect of controlling the generation rate of chlorine dioxide gas, the form of a gel is preferred.

[0021] In one example of the present invention, the above sugar can be a monosaccharide, a disaccharide, a sugar alcohol or a combination thereof. Specifically, the kit of the present invention can contain a monosaccharide and a disaccharide, or can contain a monosaccharide, a disaccharide and a sugar alcohol.

[0022] In one example of the present invention, the above monosaccharide can be glucose, fructose, galactose or a combination thereof.

[0023] In one example of the present invention, based on the total weight of the composition of the kit containing the above (a) to (d) except for the container, the above monosaccharide can be contained in a weight of 0.05% to 5%, 0.05% to 4%, 0.05% to 3.5%, 0.05% to 3%, 0.05% to 2.5%, 0.05% to 2%, 0.05% to 1.5%, 0.05% to 1%, 0.05% to 0.9%, 0.05% to 0.8%, 0.05% to 0.7%, 0.05% to 0.6%, 0.05% to 0.5%, 0.05% to 0.4%, 0.05% to 0.35%, 0.05% to 0.3%, 0.05% to 0.25%, 0.05% to 0.2%, 0.1% to 5%, 0.1% to 4%, 0.1% to 3.5%, 0.1% to 3%, 0.1% to 2.5%, 0.1% to 2%, 0.1% to 1.5%, 0.1% to 1%, 0.1% to 0.9%, 0.1% to 0.8%, 0.1% to 0.7%, 0.1% to 0.6%, 0.1% to 0.5%, 0.1% to 0.4%, 0.1% to 0.35%, 0.1% to 0.3%, 0.1% to 0.25% or 0.1% to 0.2%, but not limited thereto.

[0024] In one example of the present invention, the above disaccharide can be sucrose, maltose, trehalose, lactose or a combination thereof.

[0025] In one example of the present invention, based on the total weight of the composition of the kit containing the above (a) to (d) except for the container, the above disaccharide can be contained in a weight of 1% to 10%, 1% to 9%, 1% to 8%, 1% to 7%, 1% to 6%, 1% to 5%, 1% to 4%, 2% to 10%, 2% to 9%, 2% to 8%, 2% to 7%, 2% to 6%, 2% to 5%, 2% to 4%, 3% to 10%, 3% to 9%, 3% to 8%, 3% to 7%, 3% to 6%, 3% to 5% or 3% to 4%, but not limited thereto.

[0026] In an example of the present invention, the above-mentioned disaccharide is the main reactant that causes the main reaction after the initial reaction of chlorous acid and monosaccharide.

[0027] In an example of the present invention, the above-mentioned sugar alcohol can be ethylene glycol, glycerol, erythritol, sorbitol, mannitol, xylitol, inositol or a combination thereof.

[0028] In a specific example of the present invention, based on the total weight of the set containing the above (a) to (d) except for the container, the above-mentioned sugar alcohol can be contained in a weight of 1% to 10%, 1% to 9%, 1% to 8%, 1% to 7%, 1% to 6%, 1% to 5%, 1% to 4%, 2% to 10%, 2% to 9%, 2% to 8%, 2% to 7%, 2% to 6%, 2% to 5%, 2% to 4%, 3% to 10%, 3% to 9%, 3% to 8%, 3% to 7%, 3% to 6%, 3% to 5% or 3% to 4%, but not limited thereto.

[0029] In an example of the present invention, the above-mentioned sugar alcohol is the main reactant that causes the main reaction after the initial reaction of chlorous acid and monosaccharide.

[0030] In an example of the present invention, the above-mentioned gelling agent or thickening agent can include agar, konjac powder, carrageenan, pectin, gelatin, starch, locust bean gum, tara gum, guar gum, gellan gum, xanthan gum, tamarind gum, gum arabic, cellulose gum, sodium caseinate, sodium alginate, dextran, dextrin, carboxymethyl cellulose or a combination thereof.

[0031] In a specific example of the present invention, based on the total weight of the composition of the set containing the above (a) to (d) except for the container, the gelling agent or thickening agent can be contained in an amount of 1% to 10%, 1% to 9%, 1% to 8%, 1% to 7%, 1% to 6%, 1% to 5.5%, 1% to 5%, 1% to 4%, 1% to 3%, 1% to 2%, 1% to 1.5%, 1.1% to 10%, 1.1% to 9%, 1.1% to 8%, 1.1% to 7%, 1.1% to 6%, 1.1% to 5.5%, 1.1% to 5%, 1.1% to 4%, 1.1% to 3%, 1.1% to 2%, 1.1% to 1.5%, 1.2% to 10%, 1.2% to 9%, 1.2% to 8%, 1.2% to 7%, 1.2% to 6%, 1.2% to 5.5%, 1.2% to 5%, 1.2% to 4%, 1.2% to 3%, 1.2% to 2%, 1.2% to 1.5%, 1.3% to 10%, 1.3% to 9%, 1.3% to 8%, 1.3% to 7%, 1.3% to 6%, 1.3% to 5.5%, 1.3% to 5%, 1.3% to 4%, 1.3% to 3%, 1.3% to 2%, 1.3% to 1.5%, 1.5% to 10%, 1.5% to 9%, 1.5% to 8%, 1.5% to 7%, 1.5% to 6%, 1.5% to 5.5%, 1.5% to 5%, 1.5% to 4%, 1.5% to 3%, 1.5% to 2%, 2% to 10%, 2% to 9%, 2% to 8%, 2% to 7%, 2% to 6%, 2% to 5.5%, 2% to 5%, 2% to 4%, 2% to 3%, 3% to 10%, 3% to 9%, 3% to 8%, 3% to 7%, 3% to 6%, 3% to 5.5%, 3% to 5%, 3% to 4%, 4% to 10%, 4% to 9%, 4% to 8%, 4% to 7%, 4% to 6%, 4% to 5.5%, 4% to 5%, 5.5% to 10%, 5.5% to 9%, 5.5% to 8%, 5.5% to 7% or 5.5% to 6%, 5% to 10%, 5% to 9%, 5% to 8%, 5% to 7%, 5% to 6% or 5% to 5.5% by weight, but not limited thereto.

[0032] In one example of the present invention, the gelling agent or thickening agent is a delaying agent that delays the reaction with chlorite.

[0033] In one example of the present invention, the set contains a gelling promoter.

[0034] In a specific example of the present invention, the gelling promoter is magnesium chloride, potassium chloride, calcium chloride, sodium chloride or a combination thereof.

[0035] In one example of the present invention, the acid is an organic acid, an inorganic acid or a mixture thereof.

[0036] In a specific example of the present invention, the above-mentioned organic acids include lactic acid, acetic acid, formic acid, citric acid, oxalic acid, ascorbic acid, glucuronic acid, maleic acid, succinic acid, benzoic acid, tartaric acid, fumaric acid, propionic acid, glutamic acid, aspartic acid, butyric acid, or a combination thereof, but is not limited thereto.

[0037] In a specific example of the present invention, the above-mentioned inorganic acids include hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, or a combination thereof, but is not limited thereto.

[0038] In a specific example of the present invention, based on the total weight of the composition of the set including the above (a) to (d) excluding the container, the above-mentioned acids can be included in a weight of 0.001% to 2%, 0.001% to 1.5%, 0.001% to 1%, 0.001% to 0.5%, 0.001% to 0.4%, 0.001% to 0.3%, 0.001% to 0.2%, 0.001% to 0.1%, 0.005% to 2%, 0.005% to 1.5%, 0.005% to 1%, 0.005% to 0.5%, 0.005% to 0.4%, 0.005% to 0.3%, 0.005% to 0.2%, 0.005% to 0.1%, 0.01% to 2%, 0.01% to 1.5%, 0.01% to 1%, 0.01% to 0.5%, 0.01% to 0.4%, 0.01% to 0.3%, 0.01% to 0.2%, 0.01% to 0.1%, 0.05% to 2%, 0.05% to 1.5%, 0.05% to 1%, 0.05% to 0.5%, 0.05% to 0.4%, 0.05% to 0.3%, 0.05% to 0.2%, or 0.05% to 0.1%, but is not limited thereto.

[0039] In an example of the present invention, the above-mentioned chlorine dioxide gas generation set of the present invention may include: a first agent containing (a) chlorite; a second agent containing (b) sugar and (c) a gelling agent or thickening agent; and a third agent containing (d) an acid. But is not limited thereto.

[0040] In other examples of the present invention, the above-mentioned chlorine dioxide gas generation set may include: a first agent containing (a) chlorite and (c) a gelling agent or thickening agent; and a second agent containing (b) sugar, (c) a gelling agent or thickening agent, and (d) an acid. But is not limited thereto.

[0041] In the above example, when the first agent contains (a) chlorite and (c) a gelling agent or thickening agent, the gelling agent or thickening agent functions to stabilize the chlorite.

[0042] In the above example, when the second dose contains (b) sugar, (c) a gelling agent or thickening agent, and (d) an acid, the gelling agent or thickening agent functions to delay the reaction of the acid with chlorite to generate chlorine dioxide.

[0043] In a specific example of the present invention, the above chlorine dioxide gas generating kit may include: (a) chlorite; (b) glucose and sucrose; (c) agar, starch, and xanthan gum; and (d) ascorbic acid.

[0044] In one example of the present invention, the above kit is for disinfection, deodorization, or pesticide removal of an article, but is not limited thereto.

[0045] The preparation containing chlorite of the present invention can be provided in a state in a loading container.

[0046] In one example of the present invention, the above sugar is provided in a powder form.

[0047] In one example of the present invention, the above gelling agent or thickening agent is provided in a powder or gel form.

[0048] In one example of the present invention, the above acid is provided in a powder or liquid form.

[0049] As demonstrated in the examples of the present invention, when the constituent preparations of the chlorine dioxide generating kit of the present invention come into contact, chlorine dioxide gas starts to be generated after several hours.

[0050] The concentration of the above chlorine dioxide gas remains at a concentration of 0.5 ppm to 1 ppm between the first day and the third day, and can remain at a concentration of 0.03 ppm to 0.05 ppm for more than 60 days after the third day.

[0051] The chlorine dioxide of the present invention does not generate trihalomethanes produced in the water purification process of drinking water shown by the US Environmental Protection Agency, and thus it is confirmed that it can be used as a safe bactericidal disinfectant. It is also used in the sterilization and disinfection of Bacillus anthracis. The above chlorine dioxide is also a disinfectant of grade A-1, which is the safest standard among the food additives of the World Health Organization, and is known in the US Food and Drug Administration and the Korea Food and Drug Safety Department to be able to be used for sterilization purposes in the washing of fruits, vegetables, food containers, etc.

[0052] The chlorine dioxide of the present invention is different from other chlorine-based disinfectants such as hypochlorous acid (Lorsheen) and chloramine, and does not produce toxic by-products such as trihalomethanes, haloacetonitriles, haloacetic acids, iodates, bromates, aldehydes, ketones, and benzene during the disinfection process, and thus has the characteristic of high safety.

[0053] Moreover, chlorine dioxide of the present invention has excellent disinfection effects against various bacteria and viruses (Morino et al., Letters in Applied Microbiology 53, 628–634, 2011).

[0054] According to another embodiment of the present invention, there is provided a method for delayed generation of chlorine dioxide gas, comprising: step a) putting a preparation containing chlorite into a container; and step b) adding a powder containing sugar and an acid to the above container.

[0055] In an example of the present invention, the dosage form of the preparation containing chlorite contained in the above container may be liquid or gel-like.

[0056] In an example of the present invention, the preparation containing chlorite contained in the above container may contain pure water.

[0057] In an example of the present invention, the above i) the preparation contained in the container, ii) the powder, or iii) the preparation and the powder contained in the container further contain a gelling agent or a thickening agent.

[0058] In an example of the present invention, a lid capable of being opened and closed is provided on the above container, and a hole capable of ejecting the chlorine dioxide gas generated in the container is provided on the lid.

[0059] In an example of the present invention, a lid capable of being opened and closed may be provided on the above hole.

[0060] In an example of the present invention, the above method for generating chlorine dioxide gas can be used under the temperature condition of 10°C to 50°C.

[0061] In an example of the present invention, the replacement cycle of the preparation used in the above method for generating chlorine dioxide gas is 2 to 3 months. The above set used in the method of the present invention is characterized in that the duration is more than 60 days which is the average lifespan of bees, and it can be used until the replacement with an uninfected bee colony.

[0062] In an example of the present invention, the above chlorine dioxide gas disinfects bacterial, viral or fungal pathogens of bees.

[0063] In an example of the present invention, the above chlorine dioxide gas removes herbicides. The above herbicides are mancozeb, ethylenethiourea, tebuconzole, azoxystrobin, dimethomorph, methamidophos or a combination thereof, but not limited thereto.

[0064]

Effects of the Invention

[0065] The present invention provides a kit and method for reducing the initially high gas generation of existing ones and generating chlorine dioxide gas with a long-term sustained-release type and a short storage period. When using the chlorine dioxide generation kit and generation method of the present invention, chlorine dioxide gas can be produced in the long term without the harmfulness caused by high concentrations, and chlorine dioxide gas can be safely produced until the infected bee generations in the entire bee colony are replaced, thereby achieving the purpose of sterilizing or disinfecting space and things.

Description of the Drawings

[0066] Figure 1 A photograph showing the addition of a second agent in powder form (glucose and xanthan gum) and a third agent in powder form (ascorbic acid) to a container containing the first agent (agar gel containing sodium chlorite) of the kit of the present invention.

[0067] Figure 2 A graph showing the results of measuring the chlorine dioxide concentration from 3 hours after the addition of the first agent (agar gel containing sodium chlorite), the second agent (glucose and xanthan gum), and the third agent (ascorbic acid) of the present invention to the 77th day.

[0068] Figure 3 A graph showing the preparation for the purpose of disinfecting a 100-cubic-meter space by increasing the ratios of the first agent (agar gel containing sodium chlorite), the second agent (glucose and xanthan gum), and the third agent (ascorbic acid) and generating chlorine dioxide at a concentration of 1 ppm or more on the 120th day.

[0069] Figure 4 Showing the case of generating chlorine dioxide gas using citric acid in the prior art, the gas generation stops at most after 14 days at room temperature.

[0070] Figure 5 Showing a preparation example of the sustained-release chlorine dioxide generation kit product of the present invention.

Detailed Description

[0071] Hereinafter, the present invention will be described in more detail through examples. It should be self-evident to those of ordinary skill in the technical field to which the present invention pertains that these examples are only used to more specifically illustrate the present invention, and according to the gist of the present invention, the scope of the present invention is not limited to these examples.

[0072]

Examples

[0073] Throughout this specification, unless otherwise stated, "%" representing the concentration of a specific substance represents (weight / weight)% in the case of solid / solid, (weight / volume)% in the case of solid / liquid, and (volume / volume)% in the case of liquid / liquid.

[0074]

Example 1: Chlorine Dioxide Generation Test 1 - Adding Organic Matter

[0075] To confirm the reactivity and hazard of organic matter with sodium chlorite, organic matter in Table 1 was added to a 23% aqueous solution of sodium chlorite, and the reactivity was observed at room temperature to refrigerated temperature. The types and reactivity results of the organic matter are shown in Table 1.

[0076]

Table 1

[0077]

[0078] Organic matter with a fast reaction rate (+++++) starts to generate chlorine dioxide gas relatively quickly and reacts relatively quickly within hours to days after adding the organic matter. Organic matter with a medium reaction rate (+++) starts to generate chlorine dioxide gas between days and dozens of days after adding the organic matter, and the reaction proceeds slower than that of organic matter with a fast reaction rate. Organic matter with a slow reaction rate (+) is difficult to determine the starting point of the reaction. Even when the reaction starts, careful observation is required to observe the generation of a trace amount of chlorine dioxide gas.

[0079] Moreover, although the starting point of the reaction varies with the type of organic matter and cannot be determined, once the chlorine dioxide gas generation reaction starts, the reaction rate of substances with a fast reaction is fast, while substances with a slow reaction continuously generate gas during the slow reaction process.

[0080]

Example 2: Chlorine Dioxide Generation Test 2 - Adding Organic Matter and Organic Acid

[0081] The inventor confirmed through Example 1 above that when sodium chlorite reacts in an aqueous solution state, when adding glucose with a fast reaction rate, the reaction starts within 7 to 20 days and continues to react, showing the characteristic of a slow reaction compared with the existing method of generating chlorine dioxide by adding organic acid to chlorite.

[0082] That is, in the case of adding organic matter, although chlorine dioxide gas can be generated at a non-hazardous level concentration for a long time, in this case, the start of the reaction is too slow to determine the starting point of the reaction, thus confirming its inapplicability. Therefore, a small amount of organic acid was added to promote the start of the reaction.

[0083] As an example, the inventor of the present invention used alkaline-resistant agar containing 0.3 g of sodium chlorite as the first agent to prepare 35 ml of a gel solid, used 0.5 g of glucose powder and 0.5 g of xanthan gum as the second agent, and used 0.02 g of ascorbic acid as the third agent to coat the surface of the gel. As a result, the surface of the agar gel began to react, and the entire gel began to slowly release chlorine dioxide gas.

[0084] In order to measure the concentration of chlorine dioxide generated by the above chlorine dioxide generation method, the inventor of the present invention manufactured a 125 L chamber (length × width × height: 50 cm × 50 cm × 50 cm) and added citric acid and glucose powder to sodium chlorite agar by the above method to generate chlorine dioxide gas, and measured the concentration of chlorine dioxide every 7 days for a total of 77 days (11 weeks) starting from 1 hour later.

[0085] A photograph of adding the second agent in powder form and the third agent in powder form to the container containing the first agent of the kit of the present invention is as Figure 1 shown.

[0086] Moreover, the results of measuring the chlorine dioxide concentration for 77 days are as Figure 2 shown.

[0087] As Figure 2 shown, when the first agent, the second agent, and the third agent of the chlorine dioxide generation kit of the present invention come into contact, it is confirmed that chlorine dioxide gas begins to be generated after several hours, the measured concentration is at most 0.5 ppm, the concentration gradually decreases within several days, and by the 77th day, the measured concentration is about 0.03 ppm to 0.05 ppm.

[0088] In an infected bee colony, the time from egg to adult is about 22 days, and the lifespan of an adult is about 35 days. Therefore, if the entire bee colony is to be disinfected, long-term disinfection for more than 60 days is required. From the above results, it is confirmed that if the kit of the present invention is used to generate chlorine dioxide gas, chlorine dioxide equivalent to more than 60 days of the bee colony alternation cycle can be generated for a long time at a low concentration of chlorine dioxide gas without damaging bees, thereby preventing the spread of infectious diseases in the entire bee colony and achieving a sufficient disinfection effect.

[0089]

Example 3: Chlorine Dioxide Generation Test 3

[0090] In order to confirm how the amount of chlorine dioxide generated changes with different addition ratios of the first agent, the second agent, and the third agent, the inventor of the present invention conducted a chlorine dioxide generation test under the conditions shown in Table 2.

[0091]

Table 2: 100 ml of water + 1.5 g of agar + 10 ml of sodium chlorite (NaClO2) (23% aqueous solution)

[0092]

[0093]

[0094] In Table 2 above, water, agar, and sodium chlorite solution were mixed to prepare a gel, and citric acid, glucose, and xanthan gum were prepared in powder form and coated on the surface of the gel.

[0095] As shown in Table 2 above, no chlorine dioxide occurred in the control group. In Example 3-1 with only glucose added as an organic substance, chlorine dioxide gas temporarily occurred from the sixth day and then gradually occurred from the 14th day.

[0096] In Example 3-2 and Example 3-3 containing citric acid, the occurrence of chlorine dioxide was observed on the first day, but chlorine dioxide only occurred until the 6th day, and no further occurrence of chlorine dioxide was confirmed thereafter. On the other hand, in Example 3-3 with xanthan gum also added, the amount of chlorine dioxide generated was more than that in the example with only citric acid added.

[0097] In both Example 3-4 containing citric acid and glucose and Example 3-5 containing citric acid with the dose of glucose reduced to 0.5 g and 0.5 g of xanthan gum added, the occurrence of chlorine dioxide was observed from the first day, and the occurrence of chlorine dioxide was continuously observed until the 30th day. However, compared with Example 3-5 with 0.5 g of glucose and 0.5 g of xanthan gum added respectively, Example 3-4 with only 1 g of glucose added had more chlorine dioxide initially, and the amount of occurrence decreased relatively sharply. On the contrary, it was confirmed that in Example 3-5 with 0.5 g of glucose and 0.5 g of xanthan gum added respectively, although the initial amount of chlorine dioxide gas generated was low, it maintained a relatively high concentration of occurrence for a long time.

[0098] From the above results, it can be seen that in the present invention, the organic acid as the third agent and the organic substance as the second agent react with sodium chlorite respectively to generate chlorine dioxide gas. Thus, it can be known that the amount of chlorine dioxide gas generated varies with the amounts of the organic acid and the organic substance added.

[0099] Moreover, it can be seen that organic acids such as citric acid have the effect of initiating the chlorine dioxide generation reaction. It can be known that in Table 1, organic substances such as glucose with a fast reaction rate, when an organic substance is added to initiate the reaction, the reaction between glucose and sodium chlorite is accelerated and chlorine dioxide gas is generated faster.

[0100] In the case of adding organic substances such as xanthan gum with a slow mixing reaction rate and glucose, chlorine dioxide gas is generated for a long time at a lower concentration than when only glucose is added. From this, it is confirmed that glucose reacts quickly first, and xanthan gum starts to react slowly later. Therefore, it can be known that the chlorine dioxide generation kit and method of the present invention can easily adjust the reaction rate and the usage time of the kit by adjusting the mixing ratio of the organic substance with a fast reaction and the organic substance with a slow reaction.

[0101] The present inventor prepared for the purpose of disinfecting a 100 cubic meter space by increasing the doses of the first agent, the second agent, and the third agent under the same proportional conditions as in Examples 3-5 above. As Figure 3 shown, in the chlorine dioxide gas preparation kit prepared on December 13, 2021, chlorine dioxide gas with a concentration of 1 ppm can still be generated on April 12, 2022, after 4 months (120 days).

[0102] On the other hand, Figure 4 For the existing method of generating chlorine dioxide gas using citric acid and an aqueous solution of sodium chlorite, it is shown that the gas generation stops after at most 14 days at room temperature.

[0103]

Example 4: Preparation of a Sustained-Release Chlorine Dioxide Generation Kit

[0104] The present inventor prepared a sustained-release chlorine dioxide generation kit product with the composition shown in Table 3 and Table 4 below.

[0105] Composition of the Sustained-Release Chlorine Dioxide Generation Kit Product (BeeO2)

[0106]

Table 3: Composition of the Solid Substance (85 ml) Containing Sodium Chlorite and a Gelling Agent

[0107] Component Name Unique Number (such as CAS No etc.) Mixing Ratio (%) Use (Function) Pure Water 7732-18-5 81-82 Dilution Sodium Chlorite 7758-19-2 5.0-6.0 Precursor Agar 9002-18-0 1.2-1.3 Gelation

[0108]

Table 4: Composition of the Powder Additive (11 g) Containing Sugar, a Gelling Agent / Thickener, and Acid

[0109] Ascorbic Acid 50-81-7 0.01-0.1 Trigger Glucose 50-99-7 0.2-0.3 Initial Reagent Starch 9005-25-8 0.2-0.3 Delayed Reagent Sucrose 57-50-1 5.0-6.0 Main Reagent Xanthan Gum 11138-66-2 5.5-6.0 Delayed Reagent

[0110] The present inventor prepared a kit with the composition shown in Table 3 and Table 4 above and used it to generate chlorine dioxide gas. As a result, it was confirmed that the kit with the composition shown in Table 3 and Table 4 generated chlorine dioxide gas for more than 3 months at room temperature. However, the temperature inside the beehive is about 35 °C, which is higher than room temperature. Therefore, the chlorine dioxide gas generation time was shortened to about 9 to 10 weeks.

[0111] Therefore, in order to generate gas for more than 3 months in an environment with an air temperature of about 35°C, the present inventor took out glucose from the powder additive and added agar to delay the reaction. As a result, an attempt was made to prepare a sustained-release chlorine dioxide generating kit with the compositions shown in Tables 5 and 6 and use it to generate chlorine dioxide gas.

[0112] Compared with the kits with the compositions shown in Tables 3 and 4, the overall reaction rate of the kits with the compositions shown in Tables 5 and 6 is slower. As a result, it can be confirmed that even in a beehive with a relatively high temperature, the gas generation time of chlorine dioxide remains more than 3 months.

[0113]

Table 5: Composition of the solid (85 ml) containing sodium chlorite and a gelling agent

[0114]

[0115] Pure Water 7732-18-5 81-82 Dilution Sodium Chlorite 7758-19-2 5.0-6.0 Precursor Agar 9002-18-0 1.2-1.3 Gelation

[0116]

Table 6: Composition of the powder additive (11 g) containing sugar, a gelling agent / thickener, and an acid

[0117] Component Name Unique Number (such as CAS No etc.) Mixing Ratio (%) Use (Function) Ascorbic Acid 50-81-7 0.1-0.3 Trigger Starch 9005-25-8 2-3 Delayed Reagent Sucrose 57-50-1 50-70 Main Reagent Agar 9002-18-0 15-25 Delayed Reagent Xanthan Gum 11138-66-2 15-25 Delayed Reagent

[0118] The above products are prepared for use in sterilizing and deodorizing enclosed spaces such as shoe cabinets at normal temperature and articles such as empty beehives.

[0119] A product photo of the present invention is as Figure 5 shown. The usage method is to remove the sealed packaging of the container containing the solid containing pure water, sodium chlorite, and agar, put into the container the powder additive containing ascorbic acid, glucose, starch, sucrose, and xanthan gum packaged in the attached strip bag, and then cover the lid. The reaction result is the generation of chlorine dioxide gas.

[0120] Small holes are formed in the lid of the above container. Therefore, even when the lid is covered, the chlorine dioxide gas slowly sprays out to the outside through the above holes.

[0121] The above has described in detail specific parts of the present invention. However, those of ordinary skill in the technical field to which the present invention pertains should understand that these specific descriptions are only preferred examples, and the scope of the present invention is not limited to these contents.

Claims

1. A slow-release chlorine dioxide gas generation set, characterized in that, Comprising: (a) Chlorite; (b) Sugar; (c) A gelling agent or thickening agent; and (d) Acid.

2. The slow-release chlorine dioxide gas generation set according to claim 1, characterized in that, The above-mentioned chlorite is one or more selected from the group consisting of sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, magnesium chlorite, and barium chlorite.

3. The slow-release chlorine dioxide gas generation set according to claim 1, characterized in that, The above-mentioned sugar is a monosaccharide, disaccharide, sugar alcohol, or a combination thereof.

4. The slow-release chlorine dioxide gas generation set according to claim 1, characterized in that, The above-mentioned monosaccharide is glucose, fructose, galactose, or a combination thereof.

5. The slow-release chlorine dioxide gas generation set according to claim 1, characterized in that, The above-mentioned disaccharide is sucrose, maltose, trehalose, lactose, or a combination thereof.

6. The slow-release chlorine dioxide gas generation set according to claim 1, characterized in that, The above-mentioned sugar alcohol is ethylene glycol, glycerol, erythritol, sorbitol, mannitol, xylitol, inositol, or a combination thereof.

7. The slow-release chlorine dioxide gas generation set according to claim 1, characterized in that, The above-mentioned gelling agent or thickening agent is agar, konjac powder, carrageenan, pectin, gelatin, starch, locust bean gum, tara gum, guar gum, gellan gum, xanthan gum, tamarind gum, gum arabic, cellulose gum, sodium caseinate, sodium alginate, dextran, dextrin, carboxymethyl cellulose, or a combination thereof.

8. The slow-release chlorine dioxide gas generation set according to claim 1, characterized in that, The above-mentioned acid is an organic acid, inorganic acid, or a mixture thereof.

9. The slow-release chlorine dioxide gas generation set according to claim 8, characterized in that, The above-mentioned organic acids include lactic acid, acetic acid, formic acid, citric acid, oxalic acid, ascorbic acid, glucuronic acid, maleic acid, succinic acid, benzoic acid, tartaric acid, fumaric acid, propionic acid, glutamic acid, aspartic acid, butyric acid, or a combination thereof.

10. The slow-release chlorine dioxide gas generation set according to claim 8, characterized in that, The above-mentioned inorganic acids include hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, or a combination thereof.

11. The slow-release chlorine dioxide gas generation set according to claim 1, characterized in that, The above-mentioned kit is for disinfection, deodorization, or pesticide removal of articles.

12. A method for delaying the generation of chlorine dioxide gas, characterized in that, Comprising: Step a), putting a preparation containing chlorite into a container; And Step b), adding a powder containing sugar and acid to the above-mentioned container.

13. The method for delaying the generation of chlorine dioxide gas according to claim 12, characterized in that, The dosage form of the preparation contained in the above-mentioned container is liquid or gel-like.

14. The method for delaying the generation of chlorine dioxide gas according to claim 12, characterized in that, i) The preparation contained in the container, ii) The powder, or iii) The preparation and powder contained in the container contain a gelling agent or thickening agent.

15. The method for delayed generation of chlorine dioxide gas according to claim 12, characterized in that, A lid that can be opened and closed is provided on the above-mentioned container, and a hole for ejecting the chlorine dioxide gas generated in the container is provided on the lid.

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