Sustained-release chlorine dioxide gas generation kit and method

Abstract

This invention relates to a method for generating chlorine dioxide gas in a sustained-release manner over a long period of time without generating dangerous high-concentration gases. By using the sustained-release chlorine dioxide gas generation method of this invention, chlorine dioxide gas can be produced at low concentrations without harming bees for infection control of bee colonies, and the purpose of disinfection can be achieved over a long period of time, until the bee colony changes.

Description

Detailed Description of the Invention

[0001] [Technical Field] This patent application claims priority to Korean Patent Application No. 10-2022-0141844, filed with the Korean Intellectual Property Office on October 28, 2022, and Korean Patent Application No. 10-2023-0054371, filed with the Korean Intellectual Property Office on April 25, 2023, and the disclosure of the patent applications is incorporated herein by reference.

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

[0003] [Background Art] Conventionally, it is well known that chlorine dioxide is generated when an aqueous solution or gel agent containing sodium chlorite is irradiated with ultraviolet light (Patent Document 1: Japanese Unexamined Patent Publication No. 2005-224386, published on August 25, 2005). However, when an aqueous solution obtained by dissolving sodium chlorite in pure water is irradiated with ultraviolet light, the reaction is too slow and the production amount of chlorine dioxide is small, so it was impossible to generate chlorine dioxide at a concentration sufficient for disinfection or sterilization. Also, it is well known that chlorine dioxide is generated when sodium chlorite is brought into contact with an acid such as citric acid (Patent Document 2: Korean Registered Patent Publication No. 10-1807966, registered on December 5, 2017). However, the method of bringing sodium chlorite into contact with citric acid cannot be interrupted once the reaction starts, and it is dangerous to use sulfuric acid or hydrochloric acid instead of citric acid. In the event that the reaction proceeds excessively, there is a risk of explosion. Therefore, a method for safely producing chlorine dioxide gas at a low concentration was needed.

[0004] As is well known, honeybees play a crucial role in plant pollination and are essential for maintaining ecosystems. However, honeybees are highly vulnerable to diseases caused by various pathogens such as fungi, bacteria, and viruses. Furthermore, chemical substances such as pesticides and insecticides used to improve crop productivity often end up harming honeybee colonies. In particular, a phenomenon called colony collapse disorder (CCD) has recently occurred in the United States, Canada, Europe, South America, and Asia. While the exact cause of such colony collapse disorder is unclear, it is known to be caused by a combination of factors, including various diseases prevalent among honeybees and the emergence of pests, bacteria, and viral pathogens. Therefore, there is a need to develop disinfectants that are harmless to honeybees, do not leave residues in honey, and have excellent disinfecting effects.

[0005] Korean Patent No. 10-1315260 (Patent Document 3, registered September 30, 2013) discloses a disinfection device for the prevention and treatment of infectious diseases such as gall rot using chlorine dioxide gas. Because chlorine dioxide explodes at concentrations of 10% or higher, making storage and transportation impossible, the patent disclosed that chlorine dioxide gas can be safely generated and exhibit excellent disinfection effects by reacting stabilized chlorine dioxide, which is stabilized by reacting it with an alkaline salt, with ultraviolet light. However, because the device includes electrical components, it was difficult to manage and failed to be commercialized.

[0006] Furthermore, conventional methods of adding citric acid to a chlorous acid solution produce a very explosive generation of chlorine dioxide. However, the amount of gas generated decreases as the gas produced by the dissolving chlorine dioxide in the solution is gradually released, and gas generation ceases after about two weeks at most (see Figure 4). Therefore, there is a need to develop a method and kit that does not require electrical equipment and can generate chlorine dioxide gas stably at low concentrations over a long period of time.

[0007] [Overview of the prefecture] [Problems the invention aims to solve] As mentioned above, there is a need to develop safe and long-term usable disinfection methods for preventing or treating infectious diseases in honeybees. In particular, unlike other livestock, when an infectious disease outbreak occurs, it is not possible to isolate only the infected bees, and it is impossible to remove all causative agents from infected bees. Therefore, in order to manage infections in honeybee colonies, it is necessary to create an environment in which the entire honeybee colony can be disinfected, and to maintain this environment for more than 60 days, which is the average lifespan of a bee, thereby inducing a generational turnover of bee colonies that are not infected with pathogens.

[0008] Therefore, the inventors have diligently researched and developed a method and apparatus for producing chlorine dioxide gas safely and sustainably over a long period of time, while being easy to use, for the management of honeybee colonies. As a result, they confirmed that chlorine dioxide is produced at low concentrations for a long period of time when an organic substance containing a hydroxyl group (-OH group) and an organic acid are added to a gel composition containing sodium chlorite, and thus completed the present invention.

[0009] Therefore, the object of the present invention is to provide a sustained-release chlorine dioxide gas generating kit comprising (a) chlorite, (b) sugars, (c) a gelling agent or thickening agent, and (d) an acid.

[0010] Another object of the present invention is to provide a method for delayed generation of chlorine dioxide gas, comprising the steps of a) adding a powder containing sugars and an acid to a container containing a preparation containing chlorite.

[0011] [Means for solving the problem] According to one aspect of the present invention, the present invention provides a chlorine dioxide gas generation kit comprising: (a) chlorites, (b) sugars, (c) gelling agents or thickeners, and (d) acids.

[0012] The chlorite salt of the present invention is characterized by its ability to react with sugars to generate chlorine dioxide gas over a long period of time. The type of sugar may be, but is not limited to, those shown in Table 1 below. However, the reaction between (a) chlorite salt and (b) sugar has the problem that the reaction start time cannot be determined because the reaction starts too late. If the chlorite salt and sugar are stirred, the reaction rate cannot be controlled, and there is a risk of explosion.

[0013] Therefore, the inventors have further added (d) an acid to a chlorine dioxide gas generation kit containing (a) a chlorite, (b) sugars, and (c) a gelling agent or thickener, so that the acid can react with the chlorite more quickly. As a result, chlorine dioxide gas was rapidly generated by the reaction of the acid with the chlorite, and the chlorine dioxide gas further promoted the reaction between the chlorite and the sugars. In other words, among the components of the kit, the acid reacts rapidly with the chlorite to control the timing of the chlorine dioxide gas generation reaction, and the gelling agent or thickener delays the generation of chlorine dioxide, allowing for sustained-release generation of chlorine dioxide gas over a long period of time.

[0014] In one embodiment of the present invention, the 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.

[0015] In one embodiment of the present invention, the chlorite may be present in an amount of 1-15%, 1-10%, 1-9%, 1-8%, 1-7%, 1-6%, 1-5%, 2-15%, 2-10%, 2-9%, 2-8%, 2-7%, 2-6%, 2-5%, 3-15%, 3-10%, 3-9%, 3-8%, 3-7%, 3-6%, 3-5%, 4-15%, 4-10%, 4-9%, 4-8%, 4-7%, 4-6%, 4-5%, 5-15%, 5-10%, 5-9%, 5-8%, 5-7%, or 5-6% by weight, based on the total weight of the composition of the kit including (a) to (d) excluding the container.

[0016] In one embodiment of the present invention, the chlorite is a precursor of chlorine dioxide gas.

[0017] The formulation containing the chlorite salt of the present invention may be provided in the form of an aqueous solution or in the form of a gel, but the gel form is preferred in terms of controlling the chlorine dioxide gas generation reaction rate.

[0018] In one embodiment of the present invention, the sugars may be monosaccharides, disaccharides, sugar alcohols, or combinations thereof. Specifically, the kit of the present invention may contain monosaccharides and disaccharides, or monosaccharides, disaccharides, and sugar alcohols.

[0019] In one embodiment of the present invention, the monosaccharides may be glucose, fructose, galactose, or a combination thereof.

[0020] In one embodiment of the present invention, the monosaccharides are present in amounts of 0.05-5%, 0.05-4%, 0.05-3.5%, 0.05-3%, 0.05-2.5%, 0.05-2%, 0.05-1.5%, 0.05-1%, 0.05-0.9%, 0.05-0.8%, 0.05-0.7%, 0.05-0.6%, 0.05-0.5%, 0.05-0.4%, 0.05-0.35%, and 0.05-0.3%, based on the total weight of the kit containing (a) to (d), excluding the container. It may, but is not limited to, be included in amounts of 0.05-0.25%, 0.05-0.2%, 0.1-5%, 0.1-4%, 0.1-3.5%, 0.1-3%, 0.1-2.5%, 0.1-2%, 0.1-1.5%, 0.1-1%, 0.1-0.9%, 0.1-0.8%, 0.1-0.7%, 0.1-0.6%, 0.1-0.5%, 0.1-0.4%, 0.1-0.35%, 0.1-0.3%, 0.1-0.25%, or 0.1-0.2% by weight.

[0021] In one embodiment of the present invention, the disaccharide may be sucrose, maltose, trehalose, lactose, or a combination thereof.

[0022] In one embodiment of the present invention, the disaccharide may 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% based on the total weight of the kit containing the above (a) to (d) excluding the container, but is not limited thereto.

[0023] In one embodiment of the present invention, the disaccharide is a main reactant that drives the main reaction after chlorous acid initially reacts with the monosaccharide.

[0024] In one embodiment of the present invention, the sugar alcohol may be ethylene glycol, glycerol, erythritol, sorbitol, mannitol, xylitol, inositol, or a combination thereof.

[0025] In a specific embodiment of the present invention, the sugar alcohol may 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% based on the total weight of the kit containing the above (a) to (d) excluding the container, but is not limited thereto.

[0026] In one embodiment of the present invention, the sugar alcohol is a main reactant that drives the main reaction after chlorite initially reacts with the monosaccharide.

[0027] In one embodiment of the present invention, the gelling agent or thickening agent may 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.

[0028] In a specific embodiment of the present invention, the gelling agent or thickening agent may be contained in a weight 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% based on the total weight of the kit containing (a) to (d) excluding the container, but is not limited thereto.

[0029] In one embodiment of the present invention, the gelling agent or thickening agent is a delay reaction agent that delays the reaction with chlorite.

[0030] In one embodiment of the present invention, the kit contains a gelling accelerator.

[0031] In a specific embodiment of the present invention, the gelling accelerator may be magnesium chloride, potassium chloride, calcium chloride, sodium chloride, or a combination thereof, but is not limited thereto.

[0032] In one embodiment of the present invention, the acid is an organic acid, an inorganic acid, or a mixture thereof.

[0033] In specific embodiments of the present invention, the organic acid includes, but is not limited to, 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 combinations thereof.

[0034] In specific embodiments of the present invention, the inorganic acid includes, but is not limited to, hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, or a combination thereof.

[0035] In specific embodiments of the present invention, the acid is present in amounts of 0.001-2%, 0.001-1.5%, 0.001-1%, 0.001-0.5%, 0.001-0.4%, 0.001-0.3%, 0.001-0.2%, 0.001-0.1%, 0.005-2%, 0.005-1.5%, 0.005-1%, 0.005-0.5%, 0.005-0.4%, 0.005-0.3%, and 0. It may, but is not limited to, be included in amounts of 0.05-0.2%, 0.005-0.1%, 0.01-2%, 0.01-1.5%, 0.01-1%, 0.01-0.5%, 0.01-0.4%, 0.01-0.3%, 0.01-0.2%, 0.01-0.1%, 0.05-2%, 0.05-1.5%, 0.05-1%, 0.05-0.5%, 0.05-0.4%, 0.05-0.3%, 0.05-0.2%, or 0.05-0.1% by weight.

[0036] In one embodiment of the present invention, the chlorine dioxide gas generation kit of the present invention may consist of, but is not limited to, (a) a first agent containing a chlorite; (b) a second agent containing sugars and (c) a gelling agent or thickener; and (d) a third agent containing an acid.

[0037] In other embodiments of the present invention, the chlorine dioxide gas generating kit may consist of, but is not limited to, a first component comprising (a) a chlorite and (c) a gelling agent or thickening agent; and a second component comprising (b) sugars, (c) a gelling agent or thickening agent, and (d) an acid.

[0038] In the above embodiment, when the first agent contains (a) a chlorite and (c) a gelling agent or thickening agent, the gelling agent or thickening agent plays a role in stabilizing the chlorite.

[0039] In the above embodiment, when the second agent contains (b) sugars, (c) a gelling agent or thickener, and (d) an acid, the gelling agent or thickener plays a role in delaying the reaction in which the acid reacts with chlorous acid to generate chlorine dioxide.

[0040] In a specific embodiment of the present invention, the chlorine dioxide gas generation kit may contain (a) chlorite, (b) glucose and sucrose, (c) agar, starch and xanthan gum, and (d) ascorbic acid.

[0041] In one embodiment of the present invention, the kit is for disinfecting, deodorizing, or removing pesticides from articles, but is not limited thereto.

[0042] The preparation containing the chlorite of the present invention may be provided in a container.

[0043] In one embodiment of the present invention, the sugars are provided in powder form.

[0044] In one embodiment of the present invention, the gelling agent or thickening agent is provided in the form of a powder or a gel.

[0045] In one embodiment of the present invention, the acid is provided in powder or liquid form.

[0046] As demonstrated by the embodiments of the present invention, when the constituent formulations of the chlorine dioxide generation kit of the present invention are brought into contact with the gas, chlorine dioxide gas is generated after several hours.

[0047] The concentration of chlorine dioxide gas is maintained at 0.5 to 1 ppm for the first 1 to 3 days, and can be maintained at 0.03 to 0.05 ppm for more than 60 days after the 3rd day.

[0048] The chlorine dioxide of the present invention has been approved by the U.S. Environmental Protection Agency as a safe disinfectant because it does not produce trihalomethanes, which are carcinogenic substances, during the treatment of drinking water. It has also been used for the sterilization and disinfection of anthrax bacteria. Furthermore, the chlorine dioxide has been given the A-1 grade, the safest standard among food additives, by the World Health Organization, and has been approved by the U.S. Food and Drug Administration and the Korea Food and Drug Administration as a disinfectant for use in washing fruits, vegetables, food containers, etc.

[0049] Unlike other chlorine-based disinfectants such as hypochlorous acid (Lux) and chloramine, the chlorine dioxide of the present invention does not generate toxic byproducts such as trihalomethanes, haloacetonitrile, haloacetic acid, iodates, bromates, aldehydes, ketones, and benzene during the disinfection process, and is characterized by its high safety.

[0050] Furthermore, the chlorine dioxide of the present invention has excellent disinfectant effects against various bacteria and viruses (Morino et al., Letters in Applied Microbiology 53, 628-634, 2011).

[0051] According to another aspect of the present invention, the present invention provides a method for delayed generation of chlorine dioxide gas, comprising the steps of a) adding a powder containing sugars and an acid to a container containing a preparation containing a chlorite.

[0052] In one embodiment of the present invention, the dosage form of the preparation containing chlorite contained in the container may be liquid or gel.

[0053] In one embodiment of the present invention, the preparation containing chlorite contained in the container includes purified water.

[0054] In one embodiment of the present invention, i) the preparation contained in the container, ii) the powder, or iii) the preparation and powder contained in the container further comprises a gelling agent or a thickening agent.

[0055] In one embodiment of the present invention, the container is equipped with a lid that can be opened and closed, and the lid is equipped with a hole from which chlorine dioxide gas generated inside the container is ejected.

[0056] In one embodiment of the present invention, the hole may also be equipped with a stopper that can be opened and closed.

[0057] In one embodiment of the present invention, the method for generating chlorine dioxide gas is used under ambient temperature conditions of 10 to 50°C.

[0058] In one embodiment of the present invention, the replacement cycle for the formulation used in the method for generating chlorine dioxide gas is 2 to 3 months. The kit used in the method of the present invention has the characteristic that it can be used until a new generation of bees that is not infected with pathogens takes over, as its duration is 60 days or more, which is the average lifespan of honeybees.

[0059] In one embodiment of the present invention, the chlorine dioxide gas is used to disinfect bacteria, viruses, or fungal pathogens in honeybees.

[0060] In one embodiment of the present invention, the chlorine dioxide gas removes a herbicide. The herbicide is, but is not limited to, mancozeb, ethylenethiourea, tebuconazole, azoxystrobin, dimethomorph, methamidophos, or a combination thereof.

[0061] [Effects of the invention] This invention presents a kit and method for generating chlorine dioxide gas in a sustained-release manner over a long period of time, while suppressing the high initial gas generation of conventional methods and reducing the short storage period. When using the chlorine dioxide generation kit and method of this invention, chlorine dioxide gas can be produced for a long period of time without the harmful effects of high concentrations, thus enabling the safe production of chlorine dioxide gas throughout a bee colony until the generational change of infected bees, thereby achieving the objective of sterilization or disinfection of spaces and objects.

[0062] [Brief description of the drawing] [Figure 1] This is a photograph of a container containing the first component of the kit of the present invention (agar gel containing sodium chlorite) to which the second component in powder form (glucose and xanthan gum) and the third component in powder form (ascorbic acid) have been added.

[0063] [Figure 2] This figure shows the results of measuring the chlorine dioxide concentration from 3 hours to 77 days after adding the second agent (glucose and xanthan gum) and the third agent (ascorbic acid) to the first agent (sodium chlorite-containing agar gel) of the present invention.

[0064] [Figure 3] This figure shows that chlorine dioxide was still being generated at a concentration of 1 ppm or higher even after 120 days, after manufacturing a solution with increased ratios of the first agent (sodium chlorite-containing agar gel), the second agent (glucose and xanthan gum), and the third agent (ascorbic acid) for the purpose of disinfecting a 100 cubic meter space.

[0065] [Figure 4] This figure shows that when conventional chlorine dioxide gas generation using citric acid is implemented, gas generation is interrupted at room temperature up to 14 days later.

[0066] [Figure 5] This figure shows an example of the manufacturing process for the sustained-release chlorine dioxide generation kit product of the present invention.

[0067] [Modes for carrying out the invention] The present invention will be described in more detail below using examples. These examples are merely for the purpose of illustrating the present invention in more detail, and it will be obvious to those with ordinary skill in the art that the scope of the present invention is not limited to these examples, as is the gist of the invention.

[0068] Examples Throughout this specification, unless otherwise specified, the percentages "%" used to indicate the concentration of a particular substance refer to (weight / weight)% for solid / solid, (weight / volume)% for solid / liquid, and (volume / volume)% for liquid / liquid.

[0069] Example 1: Chlorine dioxide generation test 1 - Addition of organic matter To confirm the reactivity and hazards of different types of organic matter with sodium chlorite, the organic substances listed in Table 1 were added to a 23% aqueous solution of sodium chlorite, and the reactivity was observed at room temperature or refrigerated temperature. The types of organic matter and the reactivity results are shown in Table 1.

[0070] [Table 1] JPEG2026510540000003.jpg95169

[0071] Organic compounds with a fast reaction rate (+++++) began generating chlorine dioxide gas relatively quickly, within a few hours or days after addition, and the reaction proceeded relatively rapidly. Organic compounds with an intermediate reaction rate (+++) began generating chlorine dioxide gas within a few days or tens of days after addition, and the reaction proceeded more slowly compared to the fast-reacting organic compounds. With slow-reacting (+) organic compounds, it was difficult to pinpoint the timing of the reaction's onset, and even after the reaction began, the generation of chlorine dioxide gas could only be observed in minute quantities through close observation.

[0072] Furthermore, while the reaction initiation time differed depending on the type of organic matter, it was not possible to identify a common point at which the reaction began. However, once the chlorine dioxide gas generation reaction started, fast-reacting substances reacted quickly, while slow-reacting substances reacted slowly, resulting in a longer duration of gas generation.

[0073] Example 2: Chlorine dioxide generation test 2 - Addition of organic matter and organic acid From Example 1, the inventors confirmed that when sodium chlorite is reacted in an aqueous solution, adding glucose, which has a fast reaction rate, causes the reaction to begin after 7 to 20 days. Once the reaction begins, it continues, but the reaction proceeds more slowly compared to the conventional method of generating chlorine dioxide by adding an organic acid to a chlorite salt.

[0074] In other words, adding organic matter allowed for the generation of chlorine dioxide gas at non-toxic concentrations over a long period of time. However, in this case, the reaction started too late, and the timing of the reaction's initiation could not be determined, making it impractical. Therefore, it was decided to add a small amount of organic acid to accelerate the reaction's initiation.

[0075] In one embodiment, the inventors prepared a 35 ml gel solid using alkali-resistant agar containing 0.3 g of sodium chlorite as the first agent; 0.5 g of glucose powder and 0.5 g of xanthan gum as the second agent; and 0.02 g of ascorbic acid as the third agent, which were applied to the surface of the agar gel. As a result, a gradual reaction occurred on the surface of the agar gel, and the entire gel gradually began to release chlorine dioxide gas.

[0076] To measure the concentration of chlorine dioxide generated by the chlorine dioxide generation method described above, the inventors prepared a 125L chamber (50cm wide x 50cm long x 50cm high), added citric acid and glucose powder to sodium chlorite agar gel so that chlorine dioxide gas would be generated using the method described above, and measured the concentration of chlorine dioxide every 7 days from 1 hour until the 77th day (11 weeks).

[0077] Figure 1 shows a photograph of a container containing the first component of the kit of the present invention, to which the second component and the third component in powder form have been added.

[0078] Furthermore, the results of measuring the chlorine dioxide concentration over 77 days are shown in Figure 2.

[0079] As shown in Figure 2, when the first, second, and third agents of the chlorine dioxide generation kit of the present invention come into contact, chlorine dioxide gas is generated after several hours, and a maximum concentration of 0.5 ppm is measured. The concentration gradually decreases within several days, and it was confirmed that the concentration was measured at around 0.03 to 0.05 ppm until day 77.

[0080] In an infected bee colony, it takes approximately 22 days for an egg to develop into an adult, and the lifespan of an adult is approximately 35 days. Therefore, disinfecting an entire bee colony requires a long period of more than 60 days. Based on the above results, it was confirmed that by generating chlorine dioxide gas using the kit of the present invention, it is possible to generate chlorine dioxide gas at a low concentration without harming the bees, while simultaneously generating chlorine dioxide for a long period of more than 60 days, which is the generation cycle of a bee colony. This prevents the spread of infectious diseases throughout the bee colony and achieves a sufficient disinfection effect.

[0081] Example 3: Chlorine dioxide generation test 3 The inventors conducted a chlorine dioxide generation test under the conditions shown in Table 2 to confirm how the amount of chlorine dioxide generated changes depending on the addition ratio of the first, second, and third agents.

[0082] [Table 2] JPEG2026510540000005.jpg76169

[0083] 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 applied to the gel surface.

[0084] As shown in Table 2 above, no chlorine dioxide was generated in the control group, and in Example 3-1, where only glucose was added as the organic substance, chlorine dioxide gas was temporarily generated on the 6th day after addition, and then the generation of chlorine dioxide gas increased rapidly from the 14th day onwards.

[0085] In Examples 3-2 and 3-3, which contained citric acid, the generation of chlorine dioxide was observed from day 1, but it was not generated until day 6, and no further generation of chlorine dioxide was confirmed thereafter. On the other hand, in Example 3-3, in which xanthan gum was further added, it was found that a larger amount of chlorine dioxide was generated compared to the example in which only citric acid was added.

[0086] In both Example 3-4, which contained citric acid and glucose, and Example 3-5, which contained citric acid but reduced the amount of glucose to 0.5 g and added 0.5 g of xanthan gum, the generation of chlorine dioxide was observed from day 1 and continued until day 30. However, in Example 3-4, which added 1 g of glucose alone, the initial amount of chlorine dioxide generated was higher compared to Example 3-5, which added 0.5 g each of glucose and xanthan gum, and the amount generated decreased relatively rapidly. On the other hand, in Example 3-5, which added 0.5 g each of glucose and xanthan gum, the initial amount of chlorine dioxide gas generated was low, but it was confirmed that the amount generated was maintained at a relatively higher concentration for a long period of time.

[0087] From the above results, it was found that in the present invention, the third agent, an organic acid, and the second agent, an organic substance, each react with sodium chlorite to generate chlorine dioxide gas. Therefore, it was found that the amount of chlorine dioxide gas generated varies depending on the amount of organic acid and organic substance added.

[0088] Furthermore, it was found that organic acids such as citric acid have the effect of initiating the chlorine dioxide generation reaction, and that organic substances such as glucose, which showed a fast reaction rate in Table 1, accelerate the reaction between glucose and sodium chlorite when the reaction is initiated by the addition of an organic acid, thereby generating chlorine dioxide gas more quickly.

[0089] When an organic substance with a relatively slow reaction rate, such as xanthan gum, is mixed with glucose and added, chlorine dioxide gas is generated at a lower concentration and for a longer period of time compared to when glucose alone is added. This confirms that glucose reacts quickly, while xanthan gum reacts later. Therefore, it was found that the reaction rate and the usage period of the chlorine dioxide generation kit and method of the present invention can be easily adjusted by adjusting the mixing ratio of the slow-reacting organic substance to the fast-reacting organic substance.

[0090] The inventors manufactured a solution for disinfecting a 100 cubic meter space by increasing the volumes of the first, second, and third agents under the ratio conditions described in Examples 3-5 above. As shown in Figure 3, the chlorine dioxide gas production kit manufactured on December 13, 2021, was still able to generate chlorine dioxide gas at a concentration of 1 ppm on April 12, 2022, four months (120 days) later.

[0091] On the other hand, Figure 4 illustrates the conventional method of generating chlorine dioxide gas using citric acid and sodium chlorite aqueous solution, showing that gas generation occurs for up to 14 days at room temperature before being interrupted.

[0092] Example 4: Manufacturing of a sustained-release chlorine dioxide generation kit The inventors manufactured a sustained-release chlorine dioxide generation kit product with the configurations shown in Tables 3 and 4 below.

[0093] <Components of the sustained-release chlorine dioxide generation kit product (BeeO2)>

[0094] [Table 3]

[0095] [Table 4]

[0096] The inventors manufactured kits with the configurations shown in Tables 3 and 4 above and used them to generate chlorine dioxide gas. As a result, it was confirmed that the kits with the configurations shown in Tables 3 and 4 generated chlorine dioxide gas for more than 3 months at room temperature, but because the temperature inside the beehive was about 35°C, which is higher than room temperature, the generation period of chlorine dioxide gas was slightly shortened to 9 to 10 weeks.

[0097] Therefore, in order to generate gas for more than three months in an environment where the temperature reaches approximately 35°C, the inventors removed glucose from the powder additive and added agar to delay the reaction. As a result, sustained-release chlorine dioxide generation kit products with the configurations shown in Tables 5 and 6 were manufactured, and chlorine dioxide gas was generated using the kits.

[0098] The kits with the configurations shown in Tables 5 and 6 exhibited slower overall reaction rates compared to the kits with the configurations shown in Tables 3 and 4. As a result, it was confirmed that the chlorine dioxide gas generation period could be maintained for more than three months even in beehives at high temperatures.

[0099] [Table 5]

[0100] [Table 6]

[0101] The aforementioned product was manufactured as a disinfectant and deodorizer for use in enclosed spaces such as shoe cabinets at room temperature, and for use with items such as empty beehives.

[0102] A photograph of the product of the present invention is shown in Figure 5. To use the product, remove the sealed packaging from the container containing the solid material comprising purified water, sodium chlorite, and agar, add the powder additive packaged in the attached stick envelope containing ascorbic acid, glucose, starch, sucrose, and xanthan gum into the container, and close the lid. As a result of this reaction, chlorine dioxide gas is generated.

[0103] The lid of the container has small holes formed in it, and even when the lid is closed, chlorine dioxide gas is gradually ejected from these holes to the outside of the container.

[0104] Although specific parts of the present invention have been described in detail above, it is clear to those with ordinary skill in the art that such specific descriptions are merely preferred examples and that the scope of the present invention is not limited thereto. [Brief explanation of the drawing]

[0105] [Figure 1] This is a photograph showing a container containing the first component of the present invention (agar gel containing sodium chlorite) to which the second component (glucose and xanthan gum) in powder form and the third component (ascorbic acid) in powder form have been added. [Figure 2] This figure shows the results of measuring the chlorine dioxide concentration from 3 hours to 77 days after adding the second agent (glucose and xanthan gum) and the third agent (ascorbic acid) to the first agent (sodium chlorite-containing agar gel) of the present invention. [Figure 3] This figure shows that chlorine dioxide was still being generated at a concentration of 1 ppm or higher even after 120 days, after manufacturing a solution with increased ratios of the first agent (sodium chlorite-containing agar gel), the second agent (glucose and xanthan gum), and the third agent (ascorbic acid) for the purpose of disinfecting a 100 cubic meter space. [Figure 4] This figure shows that when conventional chlorine dioxide gas generation using citric acid is implemented, gas generation is interrupted at room temperature up to 14 days later. [Figure 5] This figure shows an example of the manufacturing process for the sustained-release chlorine dioxide generation kit product of the present invention.

Claims

1. The following is included in the sustained-release chlorine dioxide gas generating kit: (a) chlorites, (b) sugars, (c) gelling agents or thickeners, and (d) acids.

2. The sustained-release chlorine dioxide gas generating kit according to claim 1, wherein the 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 sustained-release chlorine dioxide gas generating kit according to claim 1, wherein the sugars are monosaccharides, disaccharides, sugar alcohols, or combinations thereof.

4. The sustained-release chlorine dioxide gas generating kit according to claim 1, wherein the monosaccharide is glucose, fructose, galactose, or a combination thereof.

5. The sustained-release chlorine dioxide gas generating kit according to claim 1, wherein the disaccharide is sucrose, maltose, trehalose, lactose, or a combination thereof.

6. The sustained-release chlorine dioxide gas generating kit according to claim 1, wherein the sugar alcohol is ethylene glycol, glycerol, erythritol, sorbitol, mannitol, xylitol, inositol, or a combination thereof.

7. The sustained-release chlorine dioxide gas generating kit according to claim 1, wherein the gelling agent or thickening agent comprises agar, konjac powder, carrageenan, pectin, gelatin, starch, locus bean gum, tara gum, guar gum, gellan gum, xanthan gum, tamarind gum, gum arabic, cellulose gum, sodium caseinate, sodium alginate, dextran, dextrin, carboxymethylcellulose, or a combination thereof.

8. The sustained-release chlorine dioxide gas generating kit according to claim 1, wherein the acid is an organic acid, an inorganic acid, or a mixture thereof.

9. The sustained-release chlorine dioxide gas generating kit according to claim 8, wherein the organic acid includes 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 sustained-release chlorine dioxide gas generating kit according to claim 8, wherein the inorganic acid includes hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, or a combination thereof.

11. The kit is for disinfecting, deodorizing, or removing pesticides from articles, as described in claim 1.

12. a) A method for delayed generation of chlorine dioxide gas, comprising the step of adding a powder containing sugars and an acid to a container containing a preparation containing chlorite.

13. The method for delayed generation of chlorine dioxide gas according to claim 12, wherein the dosage form of the preparation contained in the container is liquid or gel.

14. i) a preparation contained in a container, ii) a powder, or iii) a preparation and powder contained in a container, each comprising a gelling agent or a thickening agent, according to claim 12, for the delayed generation of chlorine dioxide gas.

15. The method for delayed generation of chlorine dioxide gas according to claim 12, wherein the container is provided with a lid that can be opened and closed, and the lid is provided with a hole that allows the chlorine dioxide gas generated in the container to be ejected.

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