Chlorine dioxide generator

Abstract

To provide a chlorine dioxide generator that is effective for sterilization or bacteriostasis and deodorant of microorganisms under the environment of a recessed form such as a drain port of a bathroom, a kitchen or the like which is always exposed to moisture, and a structure of which is simplified to reduce a manufacturing cost.SOLUTION: A chlorine dioxide generator installed to a drain port of a bathroom or a kitchen, in which chlorine dioxide generating agent containing chlorite, pH adjuster and water absorbent is housed in a container body made of a resin container, one or more pores are formed on the container body, an opening area per single pore is 0.02 to 15 mm2 or less, and water enters from the pore into the container body.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a chlorine dioxide generator, and more particularly to a chlorine dioxide generator that is installed in an environment that is constantly exposed to moisture. [Background technology]

[0002] Chlorine dioxide gas generators used in living spaces such as the interior of an ordinary home come in liquid, gel, granular, and other forms. Some require the user to mix the components immediately before use, while others require only an opening operation and no mixing. These are packaged in hard or soft containers for use (see Patent Documents 1 and 2, etc.). Chlorine dioxide generators are sold with labels claiming that users can disinfect, eliminate viruses, and deodorize their living spaces by placing the generator in their living spaces, such as indoors, or wearing it on their body. However, the safety and effectiveness of these air disinfectants for users of chlorine dioxide gas have not been fully verified (see Non-Patent Documents 1 and 2, etc.).

[0003] On the other hand, practical applications of chlorine dioxide gas include sterilization of safety cabinets and decontamination of biological clean rooms, and its effectiveness has been fully verified (see Patent Document 3, etc.). In other words, when the concentration and exposure time are controlled, chlorine dioxide gas can be said to be very effective.

[0004] Here, in areas referred to as drain manholes and drain outlets, including bathroom hair catchers, and drain manholes and drain outlets, including kitchen mesh baskets (hereinafter referred to as drain outlets, etc.), a slime called a biofilm forms due to the growth of microorganisms. Biofilms are unsightly in appearance and emit an unpleasant odor. Typically, scrubbing with a brush or the like removes the biofilm and improves the odor. However, brushing is time-consuming, and there are areas that cannot be reached with cleaning tools, so the growth of microorganisms and the odor cannot be suppressed.

[0005] Injecting pipe cleaners containing sodium hypochlorite, sodium hydroxide, surfactants, etc. cleans the appearance and eliminates odors due to their bactericidal and bleaching effects, but the effects are short-lived and there are safety issues with handling. Organic chlorine tablets are used as cleaning and disinfecting agents for kitchen drains. However, when hot water is poured onto the organic chlorine tablets, the strong chlorine odor can be unpleasant, and if the drain is submerged in water for a long time, the chlorine concentration can become very high.

[0006] In a relatively small enclosed space, sterilization or deodorization is possible by designing the amount of chlorine dioxide gas released in accordance with the volume of the space. Generally, to generate chlorine dioxide, the user must mix two highly storable chemicals before use (see Patent Documents 4 and 5, etc.). This involves the risk of handling chemicals and the inconvenience of handling them. According to Patent Documents 4 and 5, the two chemicals are contained in a container with a partition, and the user breaks the partition before use to mix the chemicals and generate chlorine dioxide gas. However, the complex structure inevitably leads to high manufacturing costs. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 11-278808 [Patent Document 2] Japanese Patent Application Publication No. 1-99559 [Patent Document 3] Patent No. 5639294 [Patent Document 4] Japanese Patent Application Laid-Open No. 2013-244994 [Patent Document 5] Japanese Patent Application Laid-Open No. 2006-335447 [Non-patent literature]

[0008] [Non-Patent Document 1] Hidekazu Nishimura, "Verification of the Practicality of Chlorine Dioxide Gas-Emitting Formulations That Claim to Inactivate Viruses - Inactivation of Airborne Influenza Viruses at Temperatures and Humidities Equivalent to Winter Indoors," Journal of Environmental Infection, 2016, Vol. 31, No. 5 [Non-patent document 2] Hidekazu Nishimura, "Verification of the influenza virus inactivation and Staphylococcus aureus killing ability of chlorine dioxide gas-emitting formulations - Examination on low-humidity environmental surfaces," Journal of Environmental Infection, 2017, Vol. 32, no. 3 Summary of the Invention [Problem to be solved by the invention]

[0009] After further intensive research, the inventors have completed a chlorine dioxide generator that is designed to continuously release chlorine dioxide in small, recessed spaces such as drains that are relatively small and constantly exposed to moisture within human living spaces, thereby maintaining the effects of sterilizing or stabilizing microorganisms and deodorizing.

[0010] The present invention has been made in consideration of the above points, and provides a chlorine dioxide generator that is effective in sterilizing or bacteriostasis of microorganisms and deodorizing in environments that are constantly exposed to moisture, such as bathrooms and kitchen drains, and that has a simplified structure and reduced manufacturing costs. [Means for solving the problem]

[0011] That is, the chlorine dioxide generator of the embodiment is a chlorine dioxide generator to be installed at a drain outlet, and a chlorine dioxide generator containing a chlorite, a pH adjuster, and a water absorbent is accommodated in a container body made of a molded thermoplastic resin, and one or more pores are formed in the container body, and the opening area of ​​each pore is 0.02 to 15 mm 2 The present invention is characterized by the following:

[0012] Furthermore, the container body of the chlorine dioxide generator is characterized in that it is formed by combining the openings of the first container body and the second container body.

[0013] Furthermore, the chlorine dioxide generator is characterized in that the pores are formed in either the first container or the second container, or in that there are two or more pores, and the pores are formed in both the first container and the second container.

[0014] Furthermore, the chlorine dioxide generator is characterized in that it is provided with a sealing member for sealing the pore on the container body side of the pore, a sealing pin for inserting into the pore to seal it, and a covering member for covering the pore.

[0015] Furthermore, the chlorine dioxide generator is characterized in that the pH adjuster is a solid organic acid.

[0016] Furthermore, the chlorine dioxide generator is characterized in that the water absorbing agent is a gelling agent.

[0017] Furthermore, the chlorine dioxide generator is characterized in that an extender is mixed with the chlorine dioxide generator.

[0018] Furthermore, the chlorine dioxide generator is characterized in that a desiccant is mixed with the chlorine dioxide generator. [Effects of the Invention]

[0019] The chlorine dioxide generator of the present invention is a chlorine dioxide generator to be installed at a drain outlet, and a chlorine dioxide generator containing a chlorite, a pH adjuster, and a water absorbent is contained in a container body made of a molded thermoplastic resin. One or more pores are formed in the container body, and the opening area of ​​each pore is 0.02 to 15 mm. 2 Since the thickness is less than 100 μm, it is effective in sterilizing or bacteriostasis of microorganisms and deodorizing in environments that are constantly exposed to moisture, such as bathrooms and kitchen drains, and furthermore, it is possible to reduce manufacturing costs by simplifying the structure. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a schematic side view of a chlorine dioxide generator according to an embodiment before use. [Figure 2] FIG. 10 is a partial cross-sectional view of a chlorine dioxide generator according to another embodiment. [Figure 3] FIG. 10 is a partial cross-sectional view of a chlorine dioxide generator according to still another embodiment. [Figure 4] FIG. 4 is a partially enlarged cross-sectional view of a pore and a sealing member. [Figure 5] FIG. 4 is a partially enlarged cross-sectional view of a fine hole and a sealing pin. [Figure 6] FIG. 2 is a partially enlarged cross-sectional view of a pore and a covering member. [Figure 7] FIG. 2 is a cross-sectional view showing the function of pores. [Figure 8] FIG. 1 is a schematic side view of a chlorine dioxide generator according to an embodiment in use. [Figure 9] FIG. 1 is a cross-sectional view showing the effect of pores during use. DETAILED DESCRIPTION OF THE INVENTION

[0021] The configuration of a chlorine dioxide generator 1 according to an embodiment will be described using the schematic side view of FIG. 1. The chlorine dioxide generator 1 of the illustrated embodiment has a container body 10 containing a powder, granule, crystalline, or tablet-like chlorine dioxide generating agent 15 for generating chlorine dioxide. The container body 10 of the embodiment is formed by bonding together a first container body 11 and a second container body 12. The first container body 11 and the second container body 12 are bonded together by a flange portion 14. Chlorine dioxide gas (ClO2) generated as a result of a chemical reaction of the chlorine dioxide generating agent 15 diffuses to the outside of the container body 10 (first container body 11 in the illustration) through pores 13 formed in the container body 10. Therefore, the surrounding area where the chlorine dioxide generator 1 is installed is exposed to the diffused chlorine dioxide gas, which affects surrounding mold and bacteria.

[0022] The chlorine dioxide generator 1 is intended to be installed in a recessed space with an open top, such as a bathroom or kitchen drain. Chlorine dioxide is a gas heavier than air. Therefore, by installing the chlorine dioxide generator 1 in a recessed space such as a drain, the chlorine dioxide concentration in and around the drain is higher than outside, and this concentration is likely to be maintained for a long period of time. As a result, chlorine dioxide acts on the inside (interior) of the drain and in the immediate vicinity, enhancing the disinfecting effect.

[0023] The chlorine dioxide generator 1 is expected to be installed in an environment that is almost always exposed to water. Specifically, it is expected to be installed in places such as a kitchen drain (inside the trash basket, above the bowl trap below the basket, or in the water next to the bowl trap), or a bathroom drain (on the wall near the hair catcher, above or inside the hair catcher, or in the water in the trap below the hair catcher).

[0024] In the case of a kitchen drain, wastewater from cooking various ingredients and wastewater from washing dishes pass through the drain. Wastewater contains a large amount of organic matter, which makes it easy for mold and bacteria to grow around the drain, causing bad odors and slime. In the case of a bathroom drain, water from the bathtub, wastewater from washing the body, soap, detergent, etc. pass through the drain. Therefore, the area around the bathroom drain also contains an excess of organic matter, making it easy for mold and bacteria to grow, causing bad odors and slime. In other words, the purpose of the chlorine dioxide generator 1 is to disinfect, bacteriostatic, or deodorize recessed spaces such as drains.

[0025] Therefore, the chlorine dioxide generator 1 is installed directly in a recessed space in an excessively moist environment such as a kitchen drain or a bathroom drain, etc. The chlorine dioxide gas emitted from the chlorine dioxide generator 1 is continuously maintained in the recessed space in an excessively moist environment such as a drain, thereby suppressing the growth of mold and bacteria.

[0026] 1 is composed of a first container body 11 and a second container body 12, and both the first container body 11 and the second container body 12 are molded bodies made of thermoplastic resin. The resin of the container body 10 is polyethylene, polypropylene, polystyrene, polyvinyl chloride resin, polyamide (so-called nylon resin), polyethylene terephthalate (PET resin), acrylonitrile styrene resin (AS resin), acrylonitrile butadiene styrene resin (ABS resin), etc.

[0027] The container body 10 is constantly exposed to water or warm water (or boiling water in some cases). It is also affected by chlorine dioxide generated inside. Therefore, the first container body 11 and the second container body 12 have a thickness of at least 0.2 mm, preferably 0.5 to 1.5 mm. Furthermore, polypropylene is preferably used from the viewpoint of temperature resistance. When molding the first container body 11 and the second container body 12, known molding methods such as injection molding, vacuum molding, and blow molding are used.

[0028] In the chlorine dioxide generator 1 of this embodiment, the first container body 11 and the second container body 12 are joined together by the flange portion 14. The joining may be by heat sealing or by bonding with an adhesive. The first container body 11 and the second container body 12 are joined together firmly enough that they will not separate during use.

[0029] In another embodiment of a chlorine dioxide generator 1A shown in the partial cross-sectional view of Fig. 2, its container body 10a is formed by screwing together a container and a lid having a male thread 31 and a female thread 32. In the chlorine dioxide generator 1A of Fig. 2, the opening 17 of the first container body 11a and the opening 18 of the second container body 12a are fitted together. Examples of container bodies 10a of this type include well-known screw-cap ointment containers. As will be described later, in the chlorine dioxide generator 1A of Fig. 2, pores 13 are formed in each of the first container body 11a and the second container body 12a. Also, reference numeral 21 in the figure denotes a sealing member.

[0030] In a chlorine dioxide generator 1B of yet another embodiment shown in a partial cross section in Fig. 3, its container body 10b is formed by fitting together return portions 33, 34 formed on both the first container body 12a and the second container body 12b. In the chlorine dioxide generator 1B of Fig. 3, the opening 17 of the first container body 11b and the opening 18 of the second container body 12b are fitted together. As will be described later, in the chlorine dioxide generator 1B of Fig. 3 as well, pores 13 are formed in each of the first container body 11b and the second container body 12b. Reference numeral 23 in the figure denotes a covering member.

[0031] The pores 13 are formed by forming using a mold during press molding or by drilling using laser light irradiation. The number of pores 13 is one or more and is appropriate depending on the size of the container body 10. For example, the pores 13 are formed at multiple locations, e.g., three to six locations, spaced apart in each of the first container body 11 and the second container body 12. Of course, the pores 13 are not limited to the top or bottom surface of the container body 10, but may also be formed on the side surfaces.

[0032] The pores 13 can be openings, since they serve as a passageway for water to enter the inside of the container body 10 and as a release port for the generated chlorine dioxide. Furthermore, the properties required of the pores 13 are that the chlorine dioxide generator 15 does not easily leak from the pores 13 (openings) during the manufacturing, sale, and use of the chlorine dioxide generator 1, and that when the chlorine dioxide generator 1 is installed in a drain or the like, the pores 13 can absorb a necessary and sufficient amount of water to form a solution for the reaction of the chlorine dioxide generator 15. Therefore, the shape of the pores 13 is not particularly limited. In addition to being circular or rectangular, the pores 13 may also be slits like those made by a laser or a sharp blade.

[0033] Considering the role of the pores 13, the opening area per pore is 0.02 to 15 mm 2 Preferably, 0.02 to 12.6 mm or less 2Even if the opening area of ​​each pore is small, a predetermined opening area can be achieved by adding multiple pores. The total opening area of ​​the pores 13 is adjusted depending on the size of the container body 10 itself, the amount of chlorine dioxide generator 15, the conditions of use, and the place of use.

[0034] The opening area of ​​each pore is 0.02 mm 2 If the opening area (opening volume) of the pores is less than 15 mm, the opening area (opening volume) of the pores is extremely small and is not sufficient for water to enter due to the influence of the surface tension of water. 2 If the temperature exceeds this range, the water can penetrate sufficiently, but the opening area of ​​the pores becomes large, so that the leakage of the swollen chlorine dioxide generating agent 15 from the pores becomes significant.

[0035] Here, the upper and lower limits of the opening area per pore are specified based on the need to simultaneously prevent water from entering and prevent the swollen chlorine dioxide generator from leaking from the pores. On the other hand, the upper limit of the total opening area (total value of the opening areas) is not clearly specified because the number of pores formed in the container body is an appropriate number.

[0036] Therefore, it is necessary to increase the opening area of ​​the pores to facilitate the infiltration of water through the pores while preventing the leakage of the chlorine dioxide generating agent through the wide opening of the pores. To address this, as shown in the schematic cross-sectional view of Fig. 2 and the partially enlarged cross-sectional view of Fig. 4, a sealing member 21 for sealing the pores is provided on the container body 10, 10a side of the pores 13, that is, on the internal space 16 side of the container body 10, 10a.

[0037] The sealing member 21 may be made of any material with excellent water absorption, such as paper, Japanese paper, water-soluble paper, or cellophane. It may also be made of cotton or synthetic fabric. The sealing member 21 functions satisfactorily as long as it prevents leakage of the chlorine dioxide generating agent 15 when the chlorine dioxide generator 1 (1A) is not in use. As shown in the figure, the sealing member 21 is attached to the pores 13 from the side of the internal space 16. During use, after the chlorine dioxide generator 1 is placed in a drain or the like, water enters the pores 13 from the outside of the chlorine dioxide generator 1. The water that penetrates and passes through the sealing member 21 reaches the internal space 16. Naturally, the sealing member 21 is also permeable to chlorine dioxide gas.

[0038] 2 and 4, as shown in the schematic cross-sectional view of Fig. 5, a sealing pin 22 is provided which is inserted into the pore 13 to seal the pore 13. When the chlorine dioxide generator 1 is used, the sealing pin 22 is pulled out to expose the pore 13. In the case of using the sealing pin 22, the opening area of ​​each pore can be increased, which is suitable when efficient water absorption into the pores is required.

[0039] Furthermore, as shown in the cross-sectional schematic diagram of FIG. 6, a covering member 23 is provided on the outside of the container body 10 (10a, 10b), i.e., on the outside of the first container body 11 (11a, 10b) in the drawing, to cover the pores 13 from the outside. As the covering member 23, an adhesive seal made of a film formed from PET resin, vinyl chloride resin, or the like, or a shrink-wrap film made of a thermoplastic resin such as polypropylene, or the like is used. The adhesive seal or shrink-wrap film is peeled off when the chlorine dioxide generator 1 is used to expose the pores 13. In addition, as the covering member 23, a film made of a water-soluble resin such as polyvinyl alcohol, or a seal made of water-soluble paper is used. In the case of a water-soluble resin film, it may be peeled off or left as is.

[0040] In the chlorine dioxide generator 1 shown in Fig. 1, the pores 13 are formed in the first container body 11 of the container main body 10. Of course, it is also possible to form the pores 13 in the second container body 12, as opposed to the illustrated example. Furthermore, the pores 13 may be formed in both the first container body 11 and the second container body 12 (see Figs. 2 and 3 above).

[0041] In particular, when the pore 13 is provided in the lower part of the container body 10 of the chlorine dioxide generator 1 (1A) (the second container body 12 side in FIG. 1), the sealing member 21, sealing pin 22, and covering member 23 are highly effective in suppressing leakage of the chlorine dioxide generator 15. In addition to the structure for sealing the pore shown in the figure, a cover member (not shown) that slides outside the pore may be provided so that the pore is opened during use.

[0042] The chlorine dioxide generator 15 contained in the container body 10 of the chlorine dioxide generator 1 is a composition containing chlorite, a pH adjuster, and a water absorbent. Furthermore, a bulking agent and a desiccant are blended into the chlorine dioxide generator 15. The total content of the chlorine dioxide generator 15 is 5 to 30 g depending on the volume of the installation location, and is contained in the container body 10.

[0043] Chlorite is an alkali metal salt of chlorous acid, such as sodium chlorite (NaClO2) or potassium chlorite (KClO2). Chlorite is in the form of a granular, powdered, or crystalline solid for ease of storage, transportation, sale, etc., of the chlorine dioxide generator 1.

[0044] The quantitative relationship between the chlorite (sodium chlorite) and the pH adjuster in the chlorine dioxide generator 15 is determined by their molar ratio. Chlorine dioxide gas is generated by the reaction between the chlorite and the pH adjuster. Here, the pH adjuster is a solid, not a liquid. Examples include inorganic solid acids with sulfonic groups introduced onto the surface of activated carbon, such as amidosulfuric acid (sulfamic acid). The pH adjuster may be any suitable one as long as it maintains the alkaline solution in the acidic to neutral range when the chlorite (sodium chlorite) is dissolved in water.

[0045] pH adjusters can include solid organic acids in addition to inorganic solid acids, making them acidifying agents. Solid organic acids include carboxylic acid compounds such as citric acid, oxalic acid, malic acid, succinic acid, and fumaric acid. These organic acids are weak acids with lower ionization rates than inorganic acids. Furthermore, they are used as food additives and are therefore safer to handle. Furthermore, because organic acids are weak acids, they react slowly with chlorite, resulting in long-lasting chlorine dioxide generation.

[0046] In the chlorine dioxide generator 1 of this embodiment, the chlorine dioxide generator 15 in the container body 10 is characterized in that it does not previously retain water as a solution required for the reaction inside the container body 10. Chlorite and pH adjuster become ions in the presence of water, and chlorite generates chlorine dioxide. Therefore, water remains essential. However, as described in the Background Art section, it is necessary to avoid contact with water before chlorine dioxide generation (before use) and to devise a way to contact water only when chlorine dioxide is to be generated during use. This is because, without this, it is impossible to control the generation of chlorine dioxide.

[0047] In contrast, as shown in the enlarged cross-sectional view of FIG. 7, the chlorine dioxide generator 1 of this embodiment has pores 13 formed in the container body 10. FIG. 7 shows the chlorine dioxide generator 1 immediately before use or immediately after installation at the use location. As mentioned above, the chlorine dioxide generator 1 is installed near a kitchen or bathroom drain. Therefore, the area around the chlorine dioxide generator 1 is constantly overhydrated. Water outside the container body 10 can infiltrate the internal space 16 of the container body 10 through the pores 13. This intrusion triggers the generation of chlorine dioxide from the chlorine dioxide generator 15. Furthermore, because the installation location is a high-humidity environment, even if water does not infiltrate the container body 10 for a long time, the reaction proceeds by absorbing water vapor. However, unless the device absorbs water as a solution, it cannot continuously and effectively emit chlorine dioxide gas. Therefore, the chlorine dioxide generator 1 must not only absorb water vapor but also absorb water in solution form.

[0048] A water-absorbing agent is also blended into the chlorine dioxide generator 15. The water-absorbing agent is blended in for the purpose of retaining water that has entered the container body 10 through the pores 13 inside the container body 10. Materials capable of absorbing water, such as cotton or hemp, are suitable as water-absorbing agents. Furthermore, a gelling agent is blended as a preferred water-absorbing agent. The gelling agent keeps the chlorine dioxide generator 15 homogeneous and viscous after swelling due to water absorption. Therefore, the solution becomes more viscous than when it is an aqueous solution. Therefore, it takes time for the generated chlorine dioxide gas to pass through, and the release of chlorine dioxide gas is slowed down. The gelling agent is selected from polymeric water-absorbing materials such as carboxymethyl cellulose, polyvinyl alcohol, agar (agarose), xanthan gum, guar gum, and polyacrylamide.

[0049] FIG. 8 is a schematic side view of the chlorine dioxide generator 1 in use. The gelling agent used as a water absorbent has swelled due to water that has entered the internal space 16 of the container body 10 through the pores 13. The swelling causes the volume of the chlorine dioxide generator 15 to expand. FIG. 9 is an enlarged cross-sectional view of the vicinity of the pores 13. The chlorine dioxide generator 15 expands due to the swelling of the gelling agent, and reaches the vicinity of the pores 13. Therefore, taking into account the amount of volumetric expansion of the chlorine dioxide generator 15, the filling amount of the chlorine dioxide generator 15 is limited to one-third to two-thirds, preferably one-half, of the volume of the internal space 16 of the container body 10. The swelling of the contents prevents the chlorine dioxide generator 15 from leaking out of the pores 13.

[0050] When generating chlorine dioxide gas, the presence of only chlorite and a pH adjuster in the presence of moisture is sufficient. However, the chlorine dioxide generator 1 must continue to generate chlorine dioxide gas gradually over a long period of time. Due to this requirement for sustained release, it is preferable to suppress the reaction between chlorite and the pH adjuster. Therefore, a bulking agent, which is a component not directly involved in the generation of chlorine dioxide gas, is added to mitigate the reaction.

[0051] Bulking agents include various salts such as Glauber's salt (anhydrous sodium sulfate), sodium chloride, and potassium chloride. Other examples include silicates and phosphates. Furthermore, bulking agents include minerals such as bentonite, talc, and zeolite. Typically, chlorites such as sodium chlorite are designated as hazardous substances. Therefore, safety during handling is a consideration. Therefore, bulking agents are also incorporated to limit the weight ratio of chlorites to the total components.

[0052] In addition, a desiccant is mixed into the chlorine dioxide generator 15. When unused, the chlorine dioxide generator 1 generates almost no chlorine dioxide due to moisture absorption, and can be stored as is. Typically, the chlorine dioxide generator 1 is packaged in a packaging material such as a resin film, distributed, and then displayed in stores. During this time, moisture may permeate the packaging material. Therefore, it is preferable to incorporate a desiccant to extend the shelf life of the chlorine dioxide generator 1 and prevent deterioration of the chlorine dioxide generator 15 itself. Silica gel is a good example of a desiccant. Montmorillonite, allophane, and zeolite are also used as desiccants. Here, zeolites and the like are used as both a desiccant and a bulking agent. Note that calcium oxide is not used as a desiccant because the chlorine dioxide generator 1 is intended for moisture absorption.

[0053] If necessary, an alkalizing agent is blended with the chlorine dioxide generator 15. The alkalizing agent is added to maintain the alkaline state of the chlorine dioxide generator 15 in a dry state before use. Maintaining the alkaline state suppresses the decomposition of chlorite. Examples of alkalizing agents include calcium hydroxide and sodium aluminate. [Example]

[0054] [Raw materials used] Preparation of chlorine dioxide generator 30% by weight of 80% sodium chlorite crystals (manufactured by Nippon Carlit Co., Ltd., Silbright 80), 12% by weight of a high-molecular-weight superabsorbent resin (Sunfresh ST-500D, manufactured by Sanyo Chemical Industries, Ltd.) of sodium polyacrylate superabsorbent polymer particles, 34% by weight of B-type silica gel (Toyota Chemical Industries, Ltd., B-type silica gel (mesh 30-80, 0.05-0.18 mm) A mixture was prepared by blending 24% by weight of anhydrous Glauber's salt (neutral anhydrous Glauber's salt, manufactured by Tosoh Corporation). Anhydrous citric acid was added in an amount of 0.06% by weight based on the total weight of the mixture, and the mixture was further mixed uniformly to prepare a chlorine dioxide generator.

[0055] Container body A PET resin seasoning container ("Resin Container I") was prepared, with a lid diameter of 51 mm, a bottom diameter of 40 mm, a total height of 29.2 mm, a thickness of 0.2 mm, and a capacity of 40 mL. Holes with a diameter of 0.2 to 0.3 mm were formed in the top surface (lid) or side of the container. The diameter was confirmed using a graduated magnifying glass.

[0056] [Creating a chlorine dioxide generator] The chlorine dioxide generator prepared above was filled into the resin container I to a volume (approximately 17 g) that was half the capacity of the container. At this time, five holes were formed on the top surface (lid) of the container and one hole was formed on the side surface (generator A).

[0057] A prototype chlorine dioxide generator (Generator A) was installed on top of a hair catcher (a net that catches hair, etc.) installed above the drain of a bathroom in a house. Three people took showers, etc. in the bathroom every day. Generator A was collected on the 20th, 29th, 36th, and 43rd days after installation, and the chlorine dioxide emission rate from Generator A was measured.

[0058] [Measurement of chlorine dioxide generation] The sample to be measured (generator A) was placed in a 4.5 L synthetic resin airtight container and sealed. It was left to stand for approximately one hour, with no sudden changes in ambient temperature. During this time, the gas inside the container was sampled at least twice, and the chlorine dioxide gas concentration was measured using a detector tube (Gastec Corporation, 23M). A plot of time on the horizontal axis and chlorine dioxide gas concentration on the vertical axis yields a straight line sloping upward to the right. The slope of the line, approximated by a linear equation, was used to calculate the number of milligrams of chlorine dioxide molecules emitted per hour (mg chlorine dioxide / hr) from the ideal gas equation of state. The median ambient air temperature during the standing time was used as the temperature to be substituted into the ideal gas equation of state. Table 1 shows the change in chlorine dioxide concentration over the cumulative number of days.

[0059] [Table 1]

[0060] Regarding the results of generator A, it was confirmed that chlorine dioxide was being generated for approximately one month to 40 days after the start of use. In addition, the hair catcher and drain outlet in the bathroom where it was installed were visually inspected. Compared to before the installation of generator A, the bathroom drain outlet was less slimy, and there was also a reduction in red yeast, black mold stains, and odors. Therefore, chlorine dioxide generators are effective when used in humid environments such as bathrooms that are constantly exposed to hot water.

[0061] [Measurement of water concentration of chlorine dioxide generation] From the amount of chlorine dioxide generated by Generator A after 43 days, the amount of chlorine dioxide in water can be estimated to be 0.015 ppm / L after immersion of Generator A for 1 hour, and 0.075 ppm / L after immersion for 5 hours. Therefore, we checked whether such theoretical values ​​could actually be reproduced by Generator A.

[0062] 1 L of ion-exchanged water was poured into an open container (a 2 L PET bottle with the body cut off), and Generator A, which had been in use for 43 days, was placed in it and allowed to sink to the bottom. At this point, a depression-like space had formed 5 cm above the water surface from the top of the open container. The chlorine dioxide concentration and pH in the water were measured over time. The diethylparaphenylenediamine (DPD) method, which is used to test tap water, was used to measure the chlorine dioxide concentration. The results are shown in Table 2.

[0063] [Table 2]

[0064] The actual measurement results of the water concentration of chlorine dioxide generated, as shown in Table 2, showed a concentration of 0.05 ppm after 5 hours of immersion, which is considered to be roughly in line with the theoretical value. Furthermore, the chlorine dioxide concentration was maintained even after approximately 190 hours of immersion. Additionally, the pH remained in the neutral to slightly acidic range. This pH range is considered to pose no risk to metal corrosion or adverse effects on the human body or skin. These results demonstrate that the chlorine dioxide generator is capable of continuously emitting chlorine dioxide even after 40 days of use. Furthermore, even when placed (submerged) in stored water, the chlorine dioxide concentration does not rise significantly, making it highly safe.

[0065] [Comparison of concentrations at each installation location] · Making a chlorine dioxide generator The chlorine dioxide generator prepared as described above was placed inside the resin container 1 so that its volume (approximately 12 g) was 1 / 3 of the capacity of the resin container I. At this time, three fine holes (generator B) were formed on the top surface (lid) of the resin container I. In order to measure the chlorine dioxide concentration at different locations, 24 mL of ion-exchanged water was placed in the generator B beforehand, and the generator B was sealed to start the reaction.

[0066] -Recreating the installation location A kitchen drain was simulated. A 2L soft drink container (a typical PET bottle) was cut horizontally at the body and 1L of water was poured into the bottom of the container. A sink drain basket (made of polyethylene, 100mm diameter, 40mm depth, 110mm diameter including flange) was placed at the cut end of the container. The bottom of the drain basket was 10mm away from the water surface. Two types of installation were carried out: an "in-basket installation" in which the aforementioned generator B was placed inside the drain basket, and a "floating installation" in which generator B was floated on the water surface below the drain basket.

[0067] For the "in-cage installation," the chlorine dioxide concentration was measured in the space above generator B and inside the cage, and in the area between directly below the cage and the water surface. For the "floating installation," the chlorine dioxide concentration was measured inside the cage and in the area between directly below the cage and the water surface. The chlorine dioxide concentration was measured by sampling the gas from the relevant area and using a chlorine dioxide gas detector (ATI, PortaSens II). Concentration measurements were taken 2.6 days and 5.8 days after the start of the reaction. The measurement results for chlorine dioxide gas concentration are shown in Table 3.

[0068] [Table 3]

[0069] The results in Table 3 show that chlorine dioxide generation was confirmed both inside the drain basket and when the device was floated on the water surface. Furthermore, when the device was installed floating, more water was supplied to generator B than when it was installed inside the basket, which accelerated the reaction and increased the amount of chlorine dioxide generated. Therefore, whether the device is installed directly in the drain of a kitchen or bathroom in a home or floated in a puddle of water inside the drain, it can be expected to have sterilizing, bacteriostatic and deodorizing effects.

[0070] [Confirmation of microbial suppression effect] A chlorine dioxide generator was prepared by reducing the amount of anhydrous citric acid to 0.006% by weight in the composition for preparing the chlorine dioxide generator described above. This was enclosed in a volume (approximately 12 g) that was 1 / 3 of the capacity of the resin container I. At this time, one small hole (0.6 mm in diameter) was formed on the top surface (lid) of the resin container I and one on the bottom surface (generator C).

[0071] First, 0.5 g of SCD agar powder was added to 560 mL of tap water and dissolved. A small amount of microbial clumps collected from a bathroom drain and grown on PDA agar medium was scraped with a platinum loop, suspended in 9 mL of sterile distilled water, and filtered through nonwoven fabric to obtain a filtrate. This filtrate was added to the aforementioned SCD agar-containing solution. The resulting liquid was a light, transparent brown color. This was poured into a PET bottle, sealed, opened and stirred once a day, and stored at room temperature for 14 days to obtain the raw wastewater solution. The raw wastewater solution emitted a strong putrid odor and numerous biofilm-like flakes precipitated.

[0072] The biofilm-like flakes adhering to the container containing the raw sewage liquid were dispersed and clouded by vigorously stirring. 100 mL of this was taken and added to a PET resin container measuring 90 mm on each side and 180 mm high, along with 900 mL of tap water, to make a total of approximately 1000 mL. Two of these were prepared to serve as simulated drainage outlets. The mixed liquid appeared slightly cloudy. Water was filled into a water bath and maintained at 24.5°C from morning to evening, with the heating turned off after evening to allow the liquid temperature to drop naturally. One of the two simulated drainage outlets was used as a control, and Generator C was floated in one of them, and the microbial concentration of the liquid was measured over a 10-day period.

[0073] Microbial concentration in the liquid A Komagome pipette was inserted into the container with the pseudo-drainage outlet, and the pipette was repeatedly sucked in and discharged to stir the liquid inside and suspend the flakes inside the container. 1 mL of the liquid was then sampled and serially diluted as necessary. 0.1 mL was then smeared onto an 85 mm diameter SCD agar plate and cultured in an incubator at 30 to 35°C for 1 to 3 days. After culturing, the number of colonies that appeared on the plate was counted, and a representative value was used.

[0074] When comparing the side where Generator C was not floated on the liquid surface and repeatedly heated, with the side where Generator C was floated on the liquid surface and repeatedly heated, the number of colonies on the side with Generator C was approximately 1 / 10 or less. Therefore, although it did not achieve complete sterilization of microorganisms, it was confirmed that it had the effect of inhibiting growth. Therefore, the use of the Generator is expected to have a bacteriostatic effect.

[0075] Additionally, odors caused by microbial growth were assessed using a six-level odor intensity rating system (see Table 4). On the side without generator C, a clear putrid odor was detected directly above the container from three days after the start (rated as 2 or 3 on a six-level odor intensity scale). On the side with generator C, no putrid odor was detected throughout the test period (rated as 0 on a six-level odor intensity scale). These results confirmed that the chlorine dioxide generator is also effective in suppressing unpleasant odors.

[0076] [Table 4]

[0077] [Comparison with full aperture] A 20 mL container for ointment (lid: polypropylene, body: polyethylene) was prepared. Three 2.0 mm diameter holes were drilled near the center of the lid. 7.3 g of the chlorine dioxide generator prepared above was filled into the container. Ion-exchanged water was added to the container so that the water absorption rate was 100% (15 mL), assuming a saturated water absorption of 15 mL, and the lid was closed (opening area: 37.7 mm). 2 In addition, after adding ion-exchanged water to achieve a water absorption rate of 100%, a comparison product was prepared without closing the lid (main body only) (opening area 962 mm 2 The opening diameter of the main body was 35.0 mm. Both containers (specimens) were placed in a 3 L sealed container, which was filled with rolled up newspaper to absorb the chlorine dioxide gas that was generated.

[0078] The sealed container was stored in an incubator at 45°C and the emission rate was measured over time. The cumulative emission amount (mg) was calculated by integrating the daily emission rate value (mg / h) and the elapsed time (h). The cumulative value was plotted on the vertical axis against the number of days elapsed converted to 20°C on the horizontal axis, creating a graph showing the change in the cumulative emission amount over time. The plotted values ​​on the graph are shown in Table 5.

[0079] [Table 5]

[0080] [Comparison results with full aperture] When comparing 100% water absorption over the 10-50 day period at 20°C, the cumulative chlorine dioxide gas emission rate drops to approximately half when the opening area is extremely large. This predicts that the sterilization, bacteriostasis, and deodorization effects will be reduced. Therefore, the maximum opening area can be set taking into account the desired total emission rate or the emission rate over time. Furthermore, the inventors have demonstrated that for the same water absorption rate, there is a positive correlation between the opening area and the emission rate three days after the emission rate stabilizes. It is easy to predict that the emission rate will be higher without the lid between 0 and 10 days compared to with the lid, and it is possible that the values ​​from 0 to 50 days will be similar. However, it is desirable to avoid making the opening too large to ensure stable chlorine dioxide emission.

[0081] [Comparison between steam and water] Four 0.95 mm diameter holes (opening area 2.83 mm) were drilled near the center of a 15 mL ointment container (lid: polypropylene, body: polyethylene). 2 ) 7.3 g of the chlorine dioxide generator prepared above was filled into the container. At this point, the saturated water absorption amount was 11 mL. After absorbing 11 mL of ion-exchanged water, the container was closed and placed in a 2 L sealed container, which was then filled with rolled-up newspaper to absorb the generated chlorine dioxide gas. The sealed container was then stored in an incubator at 25°C.

[0082] Four similarly sized holes were drilled in an ointment container of the same shape, and 7.3 g of the chlorine dioxide generator prepared above was filled into the container.The container was then placed in a similar 2 L sealed container without allowing it to absorb water, and a beaker containing an appropriate amount of saturated saline was placed next to the ointment container in the same sealed container, which was then sealed and stored in the same manner.

[0083] The samples were taken out after 1 day (1.2 days) and 3 days (2.6 days) and the diffusion rate was measured. Three samples were prepared for each and the average value was calculated. The diffusion rates (mg / h) for water vapor exposure only and 100% water absorption, converted to 20°C, are shown in Table 6.

[0084] [Table 6]

[0085] [Comparison of steam and water] In the case of a container that was not allowed to absorb water, the specimen under high humidity conditions at 25°C after one day turned yellowish, and the emission rate was 0.6 mg / h, a satisfactory value for demonstrating sterilization, bacteriostasis, and deodorization effects. After three days, it dropped to 0.04 mg / h and remained at around 0.03 mg / h without further increase. In the case of a container that was allowed to absorb water (100% water absorption), the emission rate gradually decreased from 1.5 mg / h. The cumulative total emission amount calculated by integrating the emission rate and the number of days elapsed was approximately seven times lower after 25 days at 20°C. Based on other experiments conducted by the inventors, an emission rate of approximately 0.02 mg / h is believed to be necessary to achieve sterilization, bacteriostasis, and deodorization effects in an actual drain. Therefore, it was found that the chlorine dioxide generator's absorption of water vapor alone through its pores is not sufficient to fully demonstrate sterilization, bacteriostasis, and deodorization effects; it must also absorb water in solution.

[0086] [Comparison of required water absorption amount] A 20 mL container for ointment (lid: polypropylene, body: polyethylene) was prepared, and 7.3 g of the prepared chlorine dioxide generator was filled into the container. A 0.6 mm diameter hole was formed near the center of both the lid and the body of the ointment container (Container Example 1, opening area 0.57 mm). 2As another example, four pores with a diameter of 0.95 mm were formed in the lid of an ointment container (Container Example 2, opening area 2.83 mm 2 ) In this way, two types of containers with different opening areas were prepared.

[0087] Furthermore, a comparison was made between an example in which the water absorption rate was set to 100% (saturation) at the initial stage and an example in which the water absorption rate was increased stepwise over the course of days to 1, 5, 10, 30, and 60%.

[0088] For the emission rate measurement, the water absorption rate was increased stepwise over a 5-day period to 1, 5, 10, 30, and 60%. At each step, ion-exchanged water was added and the sample was left to stand at room temperature for approximately 2 hours to measure the emission rate. The sample was then placed in a 45°C incubator for 2 hours (equivalent to 11.3 hours at 20°C), removed, and allowed to cool. The emission rate was also measured overnight, and ion-exchanged water was added and the same procedure was repeated. The temperature was converted to 20°C from the start, and the accelerated test was continued at 45°C until 16.9 days later, after which the accelerated test was continued at 35°C. The emission rate was measured over time, and the 20°C-converted progress was plotted on the horizontal axis, while the cumulative integral of the emission rate and the number of days elapsed was plotted on the vertical axis.

[0089] Table 7 shows the change over time in the amount of chlorine dioxide (mg) when converted to 20°C for Container Example 1 and Container Example 2, for the two systems of gradual water absorption and initial saturation.

[0090] [Table 7]

[0091] Although there is a difference in the amount of chlorine dioxide between Container Example 1 and Container Example 2, there is no significant difference in the total amount of chlorine dioxide emitted. In other words, even if the water absorption rate (% / L) is low and the solution water is absorbed little by little, or even if it becomes saturated early, there is little difference in the cumulative total amount of chlorine dioxide emitted, and it is expected to be effective in all aspects of sterilization, bacteriostasis, and deodorization. Therefore, to exert its effect, it is necessary to absorb water in solution, not absorb water vapor.

[0092] From a series of experiments, it was confirmed that a sufficient and sustainable amount of chlorine dioxide can be generated by absorbing water from the outside of the container, even if water (as a solution) is not kept inside the container when assembling the device. In particular, the lower limit of the total opening area of ​​the pores formed in the container (total value of the opening area) is 0.02 mm2, preferably 0.5 mm2. 2 In addition, taking into consideration that the chlorine dioxide generator sealed in the container is in powder form, the opening area per pore is 15 mm 2 It is desirable that the following:

[0093] [Pore size] Several types of containers were prepared, and pores of different shapes and opening areas were formed. The leakage of the chlorine dioxide generator, which is an internal component, from the pores and the quality of water absorption were then verified. The amount of leakage was measured by tapping the container lightly and measuring the amount that spilled.

[0094] Prototype example 1 is a "15cc ointment container", prototype example 2 is a "14cc PET resin container (condiment container)", prototype example 3 is a "15cc ointment container", prototype example 4 is a "20cc ointment container", prototype example 5 is a "14cc PET resin container (condiment container)", prototype example 6 is a "20cc ointment container", prototype example 7 is a "14cc PET resin container (condiment container)", prototype example 8 is a "20cc ointment container, nonwoven fabric used as a sealing member", and prototype example 9 is a "20cc ointment container, absorbent cotton used as a sealing member". Table 8 shows each prototype, its number of pores (number of openings), and total opening area (total value of opening area) (mm 2 ), leakage amount (mg), and water absorption rate (% / L) are shown. "Top" and "bottom" in the table refer to the orientation of the pores when measuring the water absorption rate. Prototype 1 is an example in which no pores are formed in the container. Prototype 4 is an example in which pores are formed on the top and bottom of the container. Prototypes 2, 3, 5 to 9 are examples in which pores are formed on one side of the container.

[0095] [Table 8]

[0096] As a result, leakage increases relative to the total opening area, but water absorption improves. Therefore, by using a sealing member, it is possible to achieve both leakage suppression and water absorption while increasing the total opening area. Considering the total opening area of ​​each prototype in the table, the upper limit of the opening area of ​​one pore is set at 15 mm, taking into account the results of prototypes 7, 8, and 9. 2 , preferably 12.6 mm 2 According to the inventor's experiment, the opening area of ​​one pore (circular, 4 mm diameter) is 12.6 mm 2 When the water content exceeds 100%, the chlorine dioxide generator swells due to water absorption, and the chlorine dioxide generator is blown out from the pores. Furthermore, it was confirmed that the chlorine dioxide generator inside the device flows out due to the flow of water that comes into contact with the device through the chlorine dioxide generator that has been blown out due to swelling. From this point of view, the upper limit of the opening area per pore is 15 mm 2 , preferably 12.6 mm 2 The following is the result.

[0097] [summary] The fabrication and testing of a chlorine dioxide generator confirmed its effectiveness when installed in kitchen and bathroom drains. Kitchen and bathroom drains are constantly in contact with hot and cold water and contain an excess of organic matter, creating an environment conducive to mold and bacterial growth. In such locations, the device diffuses chlorine dioxide in a sustained, localized manner, maintaining a chlorine dioxide concentration effective for sterilization and bacteriostasis over a long period of time. Therefore, mold and bacteria are almost always exposed to the chlorine dioxide emitted from the chlorine dioxide generator, achieving sterilization, bacteriostasis, and deodorization. In particular, the water required for the chlorine dioxide reaction is supplied externally, eliminating the need for a separate water storage structure. The device's structure is simple and easy to manufacture. Furthermore, no mixing is required at the start of use, making it safe and easy to operate, even for those without a chemical background. [Industrial Applicability]

[0098] The chlorine dioxide generator of the present invention slowly releases chlorine dioxide under mild conditions after being installed in kitchen and bathroom drains. Even in spaces where people are present (living spaces), the chlorine dioxide concentration at and near the drain can be maintained for a long period of time without causing any unpleasant odor of chlorine dioxide gas. Therefore, it is particularly effective in combating slime and other stains caused by microorganisms in environments with excessive moisture, such as recessed spaces. [Explanation of symbols]

[0099] 1, 1A, 1B Chlorine dioxide generator 10, 10a, 10b Container body 11,11a,11b 1st container body 12, 12a, 12b Second container body 13 pores 14 Flange 15 Chlorine dioxide generator 16 Interior Space 17 Opening of first container body 18 Opening of second container body 21 Sealing member 22 sealing pin 23 Covering material

Claims

1. A chlorine dioxide generator installed at a drain outlet, The chlorine dioxide generator is A chlorine dioxide generator containing a chlorite, a pH adjuster, and a water absorbent is accommodated in a container body made of a molded thermoplastic resin, The container body has one or more pores, and the opening area of ​​each pore is 0.02 to 15 mm ２ is A chlorine dioxide generator characterized by:

2. 2. The chlorine dioxide generator according to claim 1, wherein the container body is formed by combining the openings of a first container body and a second container body.

3. The chlorine dioxide generator according to claim 2, wherein the pores are formed in either the first container body or the second container body.

4. 3. The chlorine dioxide generator according to claim 2, wherein the number of the pores is two or more, and the pores are formed in both the first container body and the second container body.

5. 5. The chlorine dioxide generator according to claim 1, wherein a sealing member for sealing the pore is provided on the inner space side of the container body relative to the pore.

6. 5. The chlorine dioxide generator according to claim 1, further comprising a sealing pin that is inserted into the hole to seal it.

7. 5. The chlorine dioxide generator according to claim 1, further comprising a covering member for covering the pores.

8. 8. The chlorine dioxide generator according to claim 1, wherein the pH adjuster is a solid organic acid.

9. 9. The chlorine dioxide generator according to claim 1, wherein the water-absorbing agent is a gelling agent.

10. 10. The chlorine dioxide generator according to claim 1, wherein the chlorine dioxide generator contains an extender.

11. 11. The chlorine dioxide generator according to claim 1, wherein the chlorine dioxide generator contains a desiccant.

Images