Chlorine dioxide generator

Abstract

To provide a chlorine dioxide generator capable of obtaining a stable generation amount of chlorine dioxide gas for a long period from immediately after the start of use and maintaining the concentration of chlorine dioxide in a space within a substantially fixed range.SOLUTION: A chlorine dioxide generator contains a chlorite-supporting inorganic porous body (A) in which the chlorite is supported on the inorganic porous body, 2-oxoglutaric acid and / or succinic anhydride (B), a deliquescent inorganic salt (C), and a desiccant (D).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a chlorine dioxide generator that generates chlorine dioxide gas. [Background technology]

[0002] Chlorine dioxide gas is a strong oxidizing agent, and its oxidizing power is used as a disinfectant, bleach, and deodorizer that breaks down malodorous components. Sterilization and disinfection methods using chlorine dioxide gas have the advantages of being less toxic and safer than methods using chlorine, hypochlorite, hydrogen peroxide, etc., and of not causing any unpleasant feeling because it does not have the strong irritating odor that chlorine has. In addition, chlorine dioxide gas has a high oxidizing power per unit, and while it shows excellent disinfection and disinfection effects against spores, mold, bacteria, viruses, etc., it also has the advantage of not producing carcinogens. On the other hand, chlorine dioxide gas is unstable and difficult to store at a constant concentration for a long period of time. Conventionally, the mainstream method for generating chlorine dioxide was to mix and react chlorite with acid, but although a large amount of chlorine dioxide is generated at first, the amount of generated chlorine dioxide gradually decreases, and it is difficult to continuously release chlorine dioxide for a long period of time, and chlorite in an aqueous solution state has low storage stability and decomposes over time.

[0003] As a method for continuously generating chlorine dioxide for a long period of time, a method using a pH adjuster such as sodium dihydrogen phosphate, a method of gelling an aqueous solution of chlorine dioxide with a gelling agent such as agar, gelatin, superabsorbent resin, etc. Based on these proposals, products that provide a sterilizing and disinfecting effect in the air as a stationary bottle-type preparation, and products that provide a sterilizing and disinfecting effect near the user's face as a body-worn preparation that can be hung around the neck like a name tag or inserted in a pocket as a pen-type preparation are commercially available. These commercially available products, particularly body-worn formulations, generate chlorine dioxide in amounts that are at the detection limit only 10 cm away, as reported in Non-Patent Document 1 below. That is, chlorine dioxide generators still have the problem that they generate an extremely small amount of chlorine dioxide gas and do not fully exert their sterilizing and disinfecting effects. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Environmental Infection, Vol. 32, No. 4, pp. 222-226, 2017 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to provide a chlorine dioxide generator which can generate a stable amount of chlorine dioxide gas over a long period of time from immediately after the start of use and can maintain the chlorine dioxide concentration in the space within a substantially constant range. [Means for solving the problem]

[0006] As a result of intensive research into solving the above problems, the present inventors have found that by employing a combination of a chlorite-supported inorganic porous material and 2-oxoglutaric acid and / or succinic anhydride, it is possible to suppress the initial generation concentration of chlorine dioxide and obtain stable generation of chlorine dioxide gas over a long period of time, and have thus completed the present invention.

[0007] In detail, the present invention relates to the following items. 1. A chlorine dioxide generator comprising a chlorite-supported inorganic porous material (A) in which chlorite is supported on an inorganic porous material, 2-oxoglutaric acid and / or succinic anhydride (B), a deliquescent inorganic salt (C), and a desiccant (D). 2. The chlorine dioxide generator according to 1., which contains anhydrous magnesium sulfate as the component (D). Effect of the Invention

[0008] The chlorine dioxide generator of the present invention is excellent in safety because it can generate a stable amount of chlorine dioxide immediately after use by combining a chlorite-supporting inorganic porous material with 2-oxoglutaric acid and / or succinic anhydride. Furthermore, the chlorine dioxide generating agent of the present invention is extremely useful since it can maintain the amount of chlorine dioxide generated within a substantially constant range for a long period of time. [Brief description of the drawings]

[0009] [Figure 1] Photographs showing SCDLP agar medium for checking the bacterial counts of the control, Example 2, one bag of commercial product A, two bags of commercial product A, and commercial product B after the "On Mask" test was completed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in detail below. <Component (A)> The chlorine dioxide generator of the present invention comprises, as component (A), a chlorite-supported inorganic porous material in which a chlorite is supported on an inorganic porous material. Chlorite salts such as sodium chlorite are known to have the danger of ignition due to impact, etc., due to their nature, and are registered internationally as oxidizing substances.The inorganic porous body in the present invention is not involved in the reaction that generates chlorine dioxide gas from chlorite salt, but by supporting chlorite salt on the inorganic porous body, the danger of ignition, etc. is reduced, and it is no longer necessary to treat it as an oxidizing solid, making it easier to handle it as a substance.

[0011] Chlorite in the present invention is the main raw material for generating chlorine dioxide gas.Chlorite that can be used in the present invention can be, for example, alkali metal chlorite and alkaline earth metal chlorite.As alkali metal chlorite, for example, sodium chlorite, potassium chlorite, lithium chlorite can be included, and as alkaline earth metal chlorite, for example, calcium chlorite, magnesium chlorite, barium chlorite can be included.Among them, alkali metal chlorite is preferred as it is widely used and low-cost, and sodium chlorite is more preferred.

[0012] The type of inorganic porous material in the present invention is not particularly limited, and any known porous carrier can be used. The inorganic porous body of the present invention is preferably one in which 2.5 to 5 parts by mass of pure water is added to 1 part by mass of the inorganic porous body, the mixture is shaken to leach the contained components into the water, and the pH value of the leachate measured with a glass electrode is 7 or more, and an inorganic porous body exhibiting a neutral or alkaline pH of 7.1 or more is more preferred. The inorganic porous body of the present invention may be a fired body obtained by adding a flux such as sodium carbonate or sodium hydrogen carbonate to a base inorganic porous body and firing the mixture. For example, flux-calcined diatomaceous earth obtained by adding a flux to diatomaceous earth and firing the mixture may be used. The shape of the inorganic porous material in the present invention is not particularly limited and can be arbitrarily selected from granular, powdery, fibrous, etc. In general, granular or powdery materials are preferably used because they are easily available and inexpensive. The granular or powdered inorganic porous material preferably has an average particle size in the range of about 0.01 to 10 mm, more preferably in the range of 0.025 to 3 mm, and even more preferably in the range of 0.03 to 0.1 mm. Note that the average particle size in this specification means the 50% particle size (median size). The inorganic porous body of the present invention has a BET specific surface area of ​​10 to 300 m 2 / g range is preferred.

[0013] The method of supporting chlorite on the inorganic porous body in the present invention is not particularly limited. For example, a chlorite solution is prepared by dissolving chlorite in a solvent, and the inorganic porous body is immersed in the chlorite solution to impregnate it, or a method of spraying the chlorite solution on the inorganic porous body can be exemplified. There are no particular conditions for the spraying method as long as it can be sprayed evenly, but a method of uniformly spraying the chlorite solution while stirring the inorganic porous body in a mixing device is simple. After impregnating or spraying the chlorite solution, the inorganic porous body is dried to firmly support the chlorite. The drying method is not particularly limited, but examples include drying with a fluidized dryer or a tray dryer. The drying conditions are also not particularly limited, but the drying is performed at 30 to 130 ° C, preferably 70 to 100 ° C, for 0.5 to 48 hours, preferably 3 to 8 hours. By this drying, the moisture content relative to the entire chlorite-supporting inorganic porous material is preferably set to 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The above-mentioned chlorite solution may be an aqueous solution when the chlorite used is water-soluble, but may also contain an organic solvent capable of dissolving chlorite.In addition, the concentration of chlorite is not limited and may be appropriately set.For example, the concentration of sodium chlorite in aqueous solution is preferably about 25% by mass.

[0014] In the present invention, the chlorite-supporting inorganic porous material has a chlorite content, i.e., a ratio of chlorite when the total of the inorganic porous material and chlorite is taken as 100 mass%, preferably in the range of 1 to 50 mass%, more preferably in the range of 5 to 40 mass%, and even more preferably in the range of 10 to 35 mass%. The content of the chlorite in the chlorine dioxide generator of the present invention is preferably in the range of 1 to 25 mass%, and more preferably in the range of 5 to 20 mass%, when the entire chlorine dioxide generator is taken as 100 mass%. The chlorite-supporting inorganic porous material in the present invention is not limited to one type, and two or more types of chlorite-supporting inorganic porous materials in which different inorganic porous materials and chlorite are combined may be used in combination.

[0015] <Ingredient (B)> The chlorine dioxide generator of the present invention contains 2-oxoglutaric acid and / or succinic anhydride as component (B). The component (B) in the present invention is a component that reacts with a chlorite in the presence of water to generate chlorine dioxide. The chlorine dioxide generator of the present invention, by combining component (A) and component (B), exhibits extremely excellent effects, such as significantly improving the amount of chlorine dioxide generated immediately after the start of use and providing a stable amount of chlorine dioxide generated over a long period of time, compared with a chlorine dioxide generator not containing component (B). These effects of the combination of components (A) and (B) in the present invention were newly discovered by the present inventors through numerous experiments. As component (B) of the present invention, an embodiment in which 2-oxoglutaric acid is used alone or 2-oxoglutaric acid and succinic anhydride are used in combination is preferred, and it is more preferred that 2-oxoglutaric acid is used alone. The content of component (B) in the chlorine dioxide generator of the present invention is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.1 to 30 mass%, further preferably in the range of 0.2 to 10 mass%, particularly preferably in the range of 0.3 to 5 mass%, and most preferably in the range of 0.5 to 3 mass%, when the entire chlorine dioxide generator is taken as 100 mass%. This preferable content range applies when the chlorine dioxide generator of the present invention does not contain any substance having an acidic group other than the following component (B).

[0016] The chlorine dioxide generator of the present invention preferably contains a substance having an acidic group in addition to 2-oxoglutaric acid and / or succinic anhydride, which are component (B). The substance having an acidic group means a component that has an oxidizing effect on chlorite and reacts with chlorite in the presence of water to generate chlorine dioxide. The substance having an acidic group is not particularly limited in type, but examples thereof include substances having functional groups such as a carboxy group, a sulfo group, a hydroxy group, etc. in the molecular structure. Among them, substances that exhibit a pH value of 8 or less in water are preferable, and specific examples thereof include aldoses such as glucose, xylose, mannose, and galactose, and ketoses such as fructose. In addition, examples of substances having an acidic group include organic acids and smectite group minerals. Examples of organic acids include citric acid, succinic acid, maleic acid, gluconic acid, glucono delta lactone, gluconolactone, glycine, alginic acid, stearic acid, iconitic acid, adipic acid, glucose, etc. In addition, although the charge between layers of smectite group minerals differs depending on the type of constituent elements, they have a common feature of having a cation exchange capacity, and examples of such minerals include activated clay, saponite, montmorillonite, beidellite, stevensite, hectorite, etc. In the chlorine dioxide generator of the present invention, when 2-oxoglutaric acid and / or succinic anhydride, which is component (B), is used in combination with a substance having an acidic group, the content of the substance having an acidic group is preferably in the range of 1 to 35 mass%, more preferably in the range of 10 to 30 mass%, and even more preferably in the range of 15 to 25 mass%, when the entire chlorine dioxide generator is taken as 100 mass%. When the chlorine dioxide generator of the present invention contains a substance having an acidic group, the content of component (B) is preferably in the range of 0.01 to 10 mass%, more preferably in the range of 0.05 to 5 mass%, and further preferably in the range of 0.1 to 3 mass%, when the entire chlorine dioxide generator is taken as 100 mass%.

[0017] <Component (C)> The chlorine dioxide generator of the present invention contains a deliquescent inorganic salt as component (C). In the present invention, the deliquescent inorganic salt refers to an inorganic metal salt having a property that the water vapor partial pressure of a saturated aqueous solution of the inorganic salt at 20°C is lower than the water vapor partial pressure (7.9 mmHg) of the atmosphere at 20°C and a relative humidity of 45% that comes into contact with the inorganic salt. The deliquescent inorganic salt in the present invention absorbs moisture in the air and spontaneously dissolves to change into an aqueous solution. The moisture absorbed by the inorganic salt promotes the reaction of the chlorite with 2-oxoglutaric acid and / or succinic anhydride, or the combination of 2-oxoglutaric acid and / or succinic anhydride with a substance having an acidic group, thereby generating chlorine dioxide. Examples of the component (C) in the present invention include sodium chloride, calcium chloride, sodium hydrogen sulfide, magnesium chloride, aluminum chloride, manganese sulfate, calcium nitrate, potassium carbonate, potassium acetate, zinc chloride, etc. Among these deliquescent inorganic salts, sodium chloride, calcium chloride, and magnesium chloride are preferred in view of low cost and ease of handling. As component (C) in the present invention, these deliquescent inorganic salts can be used alone or in combination of two or more. The content of component (C) in the chlorine dioxide generator of the present invention is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 1 to 40 mass%, and further preferably in the range of 5 to 30 mass%, when the entire chlorine dioxide generator is taken as 100 mass%. The higher the content ratio of the deliquescent inorganic salt, the faster the chlorine dioxide gas generation rate becomes, and the time until the chlorine dioxide gas concentration in the usage space reaches a predetermined value may be shortened. When the humidity in the space is high, the deliquescent inorganic salt deliquesces quickly, increasing the rate of generation of chlorine dioxide gas. Conversely, when the humidity is low, the deliquescent process is delayed, decreasing the rate of generation of chlorine dioxide gas. Therefore, it is preferable to appropriately adjust the content of component (C) of the present invention depending on the purpose, application, environment of use, etc. of use.

[0018] <Ingredient (D)> The chlorine dioxide generator of the present invention contains a desiccant as component (D). The component (D) in the present invention is a component that is blended for the purpose of absorbing moisture in the chlorine dioxide generator before use and improving storage stability. Since the chlorine dioxide generator of the present invention generates chlorine dioxide gas by the reaction of the components (A) and (B) in the presence of water, the reaction can be prevented by keeping the chlorine dioxide generator dry, and the stability during storage can be improved. Examples of the component (D) of the present invention include (anhydrous) magnesium sulfate, silica gel, zeolite, etc. As the zeolite, crystalline zeolite is preferable. As the component (D) of the present invention, one or more of these desiccants can be used in combination. The deliquescent inorganic salts, which are component (C) of the present invention, include substances such as calcium chloride and magnesium chloride that have deliquescent properties and a drying function. Although these substances are not included in component (D) of the present invention, when calcium chloride or magnesium chloride is used as component (C) of the present invention, it is preferable because they also exhibit a drying function. As described above, the chlorine dioxide generator of the present invention is one in which the amount of chlorine dioxide generated is significantly improved immediately after the start of use by combining component (A) and component (B). That is, since component (A) and component (B) of the present invention are highly reactive, it is preferable to contain (anhydrous) magnesium sulfate as component (D) in order to improve stability during storage. When (anhydrous) magnesium sulfate is used as component (D) of the present invention, (anhydrous) magnesium sulfate may be used alone or in combination with one or more other drying agents, but an embodiment in which (anhydrous) magnesium sulfate is used in combination with one or more other drying agents is preferred. The content of component (D) in the chlorine dioxide generator of the present invention is preferably in the range of 5 to 35 mass%, more preferably in the range of 7 to 30 mass%, and further preferably in the range of 10 to 30 mass%, when the entire chlorine dioxide generator is taken as 100 mass%.

[0019] The chlorine dioxide generator of the present invention can be blended with other materials as long as they do not impair the properties of the chlorine dioxide generator. For example, water-absorbing resins such as sodium polyacrylate and fragrances can be blended. The water-absorbing resin is a copolymer crosslinked body mainly made of sodium polyacrylate, and can hold water 10 to 1000 times its own weight. By adding this water-absorbing resin, the water deliquesced by the deliquescent inorganic salt agent can be held in the chlorine dioxide generator, and the water can be dispersed in the chlorine dioxide generator. In the chlorine dioxide generating agent of the present invention, the water absorbent resin can be used in the range of 0 to 5 mass % assuming that the entire chlorine dioxide generating agent is 100 mass %.

[0020] <Preparation of chlorine dioxide generator> The chlorine dioxide generator of the present invention can be prepared by weighing out the components (A) to (D) in a predetermined ratio and mixing them. Any mixing method can be used as long as it can mix uniformly, and examples of the mixing method include a V-type mixer or a container rotation and rocking mixer. The mixing time depends on the amount to be mixed and the performance of the mixer used, but for example, when using a container rotation and rocking mixer, a mixing time of 20 to 40 minutes is appropriate for mixing 100 kg. The chlorine dioxide generator of the present invention may be in the form of a powder or granule, or may be molded into a cylindrical shape by tableting, or may be molded into other shapes.

[0021] The chlorine dioxide generator of the present invention is preferably stored in a dry state cut off from contact with water vapor so as to prevent the generation reaction of chlorine dioxide gas, and can be stored for a long time by sealing it in a container made of a material that is impermeable to water vapor. The shape of the container is not particularly limited, and examples include box-shaped, bottle-shaped, bag-shaped, nameplate-shaped, and pen-shaped. Even if the container is not completely sealed to maintain a dry state, long-term storage is also possible by packaging it together with a desiccant. The material of the container can be arbitrarily selected from materials that are impermeable to water vapor or have low water vapor permeability. Specific examples include metal, oriented polypropylene, non-oriented polypropylene, polyester, low-density polyethylene, high-density polyethylene, ethylene vinyl alcohol resin (EVOH), etc. These materials include those with a water vapor permeability of 30 (g / m 2 Specific examples of the material include aluminum-deposited polyethylene film and laminated materials of metal foil and resin film. The chlorine dioxide generator of the present invention sealed in the container can be stored for a long period of time and can be easily transported during distribution.

[0022] When the chlorine dioxide generator of the present invention stored in a container is opened and exposed to the atmosphere, it absorbs water vapor from the atmosphere, causing the deliquescent inorganic salt of component (C) to deliquesce, providing moisture to the chlorite and 2-oxoglutaric acid and / or succinic anhydride of component (B), and chlorine dioxide gas is generated by contact with the water. The chlorine dioxide generator of the present invention, by combining component (A) and component (B), can greatly improve the amount of chlorine dioxide generated immediately after the start of use, and can provide a stable amount of chlorine dioxide generated over a long period of time, thereby demonstrating excellent sterilizing and disinfecting effects. EXAMPLES

[0023] The present invention will be specifically described below using examples and comparative examples. <Preparation of component (A)> (1) Inorganic porous material As an inorganic porous material, it has an average particle size of 7μm and a BET specific surface area of ​​20m 2 / g diatomaceous earth, average particle size 12μm, BET specific surface area 4m 2 / g perlite, average particle size 0.2 μm, BET specific surface area 10 m 2 / g kaolin was used. 2.5 parts by mass of pure water was added to 1 part by mass of these inorganic porous bodies and shaken for 30 minutes. The pH value of the leachate was measured with a glass electrode. The pH value was 8 for diatomaceous earth, 7 for perlite, and 7 for kaolin. (2) Chlorite solution As a chlorite solution, a 25% by mass aqueous solution of sodium chlorite was prepared. (3) Preparation of chlorite-supported inorganic porous material 100 parts by mass of each of the inorganic porous bodies (1) above was sprayed with 100 parts by mass of an aqueous sodium chlorite solution to impregnate the bodies, and then dried at 70° C. for 6 hours to obtain inorganic porous bodies supporting chlorite. The content of sodium chlorite in the obtained chlorite-supporting inorganic porous material was 55 mass % for all of diatomaceous earth, perlite, and kaolin. Furthermore, the moisture content in each of the chlorite-supporting inorganic porous materials was less than 5 mass % for all of diatomaceous earth, perlite, and kaolin.

[0024] <Examples 1 to 3> (1) Preparation of chlorine dioxide generator of Example 1 The chlorine dioxide generator of Example 1 was prepared based on the composition shown in Table 1 by weighing out the chlorite-supported diatomaceous earth (A) obtained in the above "Preparation of component (A)", 2-oxoglutaric acid (B), calcium chloride, sodium chloride (C), silica gel (D), and glucose other than component (B), and mixing them for 20 minutes in a container rotary rocking type mixer. In addition, the numbers in parentheses in the column for component (A) in Table 1 indicate the content of sodium chlorite in the chlorine dioxide generator. (2) Preparation of chlorine dioxide generator of Example 2 The chlorine dioxide generator of Example 2 was prepared based on the composition shown in Table 1 by weighing out the chlorite-supported diatomaceous earth (A) obtained in the above "Preparation of component (A)", 2-oxoglutaric acid (B), calcium chloride and sodium chloride (C), silica gel and (anhydrous) magnesium sulfate (D), and glucose other than component (B), and mixing them for 20 minutes in a container rotary rocking type mixer. (3) Preparation of chlorine dioxide generator of Example 3 The chlorine dioxide generator of Example 3 was prepared based on the composition shown in Table 1 by weighing out the chlorite-supported diatomaceous earth (A) obtained in the above "Preparation of component (A)", succinic anhydride (B), calcium chloride and sodium chloride (C), silica gel and (anhydrous) magnesium sulfate (D), and glucose other than component (B), and mixing them for 20 minutes in a container rotary rocking type mixer.

[0025] <Comparative Examples 1 to 10> (1) Production of chlorine dioxide generators of Comparative Examples 1 to 10 The chlorine dioxide generators of Comparative Examples 1 to 10 are examples that do not contain the component (B) of the present invention. The substances having acidic groups used were activated clay, gluconolactone, glucose, and succinic acid. As component (C), magnesium chloride was used in addition to calcium chloride and sodium chloride. As component (D), in addition to (anhydrous) magnesium sulfate and silica gel, crystalline zeolite (trade name "Molecular Sieve") and zeolite were used. Based on the compositions shown in Table 1, chlorine dioxide generators of Comparative Examples 1 to 10 were produced in the same manner as the chlorine dioxide generators of Examples 1 to 3.

[0026] <Evaluation method> 30 g of each of the chlorine dioxide generators prepared in Examples 1 to 3 and Comparative Examples 1 to 10 was placed in a waterproof and moisture-permeable nonwoven fabric based on polyethylene / polypropylene and sealed by heat sealing, which was then placed in a storage bag made of a multi-layer film in which aluminum was vapor-deposited to a thickness of 9 μm on one side of a 12 μm-thick polyethylene film, and the opening of the storage bag was heat-sealed to seal it. The chlorine dioxide generators sealed in the storage bag were stored at room temperature for 3 months. The "reactivity during use" of the chlorine dioxide generator after three months was evaluated using the following method.

[0027] (1) Reactivity during use The storage bag was opened and the chlorine dioxide gas generation status of the chlorine dioxide generator taken out was evaluated. The chlorine dioxide generators of Examples 1 to 3 and Comparative Examples 1 to 10 were weighed out in an amount of 10 g and placed in a sample container made of low-density polyethylene. The sample container had an open top and an opening area of ​​706 mm 2 It is. Each sample container containing the chlorine dioxide generator was placed in a high-density polyethylene chamber with an internal volume of 16 L, and the chamber was sealed while maintaining a temperature of 25°C and a humidity of 45%, and the chlorine dioxide gas concentration in the chamber was measured 30 and 60 minutes after placement in the chamber. The measured values ​​are shown in Table 1. In addition, each chlorine dioxide generator after the measurement was left in the sample container in contact with the air at room temperature for one month. After leaving it for one month, the chlorine dioxide gas concentration was measured in a sealed small chamber after 30 minutes and 60 minutes in the same manner. Each measured value is shown in Table 1. To evaluate the reactivity during use, the chlorine dioxide gas concentration was measured using a chlorine dioxide gas measuring device made by Gastec Co., Ltd. (automatic gas sampling device GSP-300FT-2 and gas detector tubes 23M and 23L).

[0028] [Table 1]

[0029] As shown in Table 1, it was confirmed that the chlorine dioxide generators of Examples 1 to 3, which are specific examples of the chlorine dioxide generators of the present invention containing 2-oxoglutaric acid or succinic anhydride as component (B), can generate stable amounts of chlorine dioxide not only 30 minutes and 60 minutes after being placed in the chamber, but also 30 minutes and 60 minutes after being left for one month, compared to the chlorine dioxide generators of Comparative Examples 1 to 10 that do not contain component (B), and thus have high reactivity during use. In particular, it was confirmed that the chlorine dioxide generators of Examples 2 and 3, which use 2-oxoglutaric acid or succinic anhydride as component (B) in combination with anhydrous magnesium sulfate as component (D), are more stable immediately after use and generate a high amount of chlorine dioxide than the chlorine dioxide generator of Example 1 that does not contain component (D), and thus have even better reactivity during use. From the above results, it has become clear that the chlorine dioxide generator of the present invention can obtain a stable amount of chlorine dioxide generated immediately after use, and furthermore, can maintain the amount of chlorine dioxide generated within a roughly constant range for a long period of time.

[0030] (2) Safety In order to evaluate the safety of the chlorine dioxide generators of Examples 1 to 3 and Comparative Examples 1 to 10, which are specific examples of the chlorine dioxide generators of the present invention, a mixture of 0.02 g of each chlorine dioxide generator and 0.02 g of red phosphorus was sandwiched between brass cylinders with a diameter of 70 mm, and then the cylinder was struck from above to observe whether or not it ignited. This striking test was carried out once to three times. It was confirmed that all of the chlorine dioxide generators of Examples 1 to 3 and Comparative Examples 1 to 10, which are specific examples of the chlorine dioxide generator of the present invention, did not ignite, making it clear that the chlorine dioxide generator of the present invention is excellent in safety. When the above safety test was conducted on commercially available product A, it was confirmed that the product caught fire.

[0031] (3) Sterilizing property The disinfecting properties of the chlorine dioxide generator of the present invention were evaluated in two cases: when it was assumed that the agent would be used in the same manner as a commercially available body-worn preparation (hanging use), and when it was assumed that the mask would be disinfected when it was removed (on-mask use). Testing Method The test method for "hanging use" was to have a mannequin wear the mask and attach the following bacterial fabric to the mask. Test specimens that had been in use (opened) for 24 hours were placed on a stand 5 cm below the lower limit of the mask and exposed for 3 and 6 hours, after which the bacterial fabric was removed and the bacterial count was confirmed using the method described below. The "On Mask" test method consisted of attaching the following bacterial fabric to a mask, placing the test specimens 24 hours after the start of use (opening) on ​​top of the mask, and exposing them for 1 hour. The bacterial fabric was then removed and the bacterial count was confirmed using the method described below. The "bacterial cloth" used in the test was a nonwoven fabric with general viable bacteria collected from the environment attached. In detail, the general viable bacteria collected in advance were cultured on a standard agar medium (36°C, 48 hours), and the grown colonies were picked up, and the bacteria were multiplied by adding bouillon to physiological saline, and then counted again on the standard agar medium. This was diluted to 10 3 The solution was prepared to about 100% and used as the bacterial solution for testing. 1 mL of this bacterial solution was dropped onto a nonwoven fabric and allowed to dry naturally. This was used as the "bacterial cloth" for each test. To confirm the number of bacteria after the test, the collected "bacterial cloth" was placed in 5 mL of purified water, thoroughly squeezed, and the squeezed water was appropriately diluted and cultured on SCDLP agar medium, and the number of bacteria (CFU / mL) was counted. Test specimens As test specimens, the chlorine dioxide generator of Example 2 (1.5 g) in a sealed waterproof and moisture-permeable nonwoven bag based on polyethylene / polypropylene, which was opened and taken out of the storage bag, and a commercially available chlorine dioxide generator (1 bag of commercially available product A: 1.5 g, 2 bags of commercially available product A (1.5 g x 2 = 3.0 g), and one pen-shaped commercially available product B) were used. The two commercially available products A and B were used in their original product form. The "hanging use" test was conducted using two bags of commercial product A, and the "on-mask" test was conducted using one and two bags of commercial product A. The confirmed bacterial counts (CFU / mL) at the end of each test are summarized in Table 2 below. Figure 1 shows a photograph of the SCDLP agar medium used to check the bacterial count after the "On Mask" test was completed. In Table 1 and FIG. 1, the one in which no test sample was used is referred to as "Control", and the test samples are referred to as "Example 2", "1 bag of commercial product A", "2 bags of commercial product A", and "Commercial product B", respectively.

[0032] [Table 2]

[0033] As shown in Table 2, Example 2, which is a specific example of the chlorine dioxide generator of the present invention, was confirmed to exhibit extremely significant sterilization properties compared to commercially available products in sterilization tests assuming use in the same manner as commercially available body-worn preparations (hanging use) and sterilization of a mask when the mask is removed (on-mask use). From these results, it became clear that the chlorine dioxide generator of the present invention is capable of obtaining a stable amount of chlorine dioxide generated immediately after use, and furthermore, is capable of maintaining the amount of chlorine dioxide generated within a roughly constant range for a long period of time, and therefore has extremely excellent disinfecting properties.

Claims

1. A chlorine dioxide generator comprising: (A) a chlorite-supported inorganic porous material in which a chlorite is supported on an inorganic porous material; (B) 2-oxoglutaric acid and / or succinic anhydride; (C) a deliquescent inorganic salt; and (D) a desiccant.

2. The chlorine dioxide generator according to claim 1, comprising anhydrous magnesium sulfate as the component (D).

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