JP6684786B2 - Chlorine dioxide generator and chlorine dioxide generator - Google Patents

Description

  The present invention relates to a chlorine dioxide generating unit and a chlorine dioxide generating device. More specifically, a small chlorine dioxide generating unit, which utilizes a mechanism of generating chlorine dioxide by irradiating a drug containing solid chlorite with light having a wavelength in the visible region, and a chlorine dioxide generating unit. A chlorine dioxide generator provided with a unit. The present invention can be suitably mounted particularly on a vehicle (for example, a private car, a bus, a taxi, etc.) and other vehicles (for example, an airplane, a train, a ship, etc.). Further, since the chlorine dioxide generating unit of the present invention is small, it can be incorporated in air conditioning equipment such as a heating device, a cooling device, an air purifier, and a humidifier.

  2. Description of the Related Art Conventionally, there has been known an apparatus that irradiates an aqueous solution containing chlorite or a gelling agent containing chlorite with ultraviolet rays to generate chlorine dioxide (for example, Patent Document 1). However, the conventional chlorine dioxide production apparatus was not developed with the intention of being carried around, and there were many large-scale ones. Further, the conventional chlorine dioxide generator is a liquid containing chlorite, or a gel-like substance containing it is the main component (chlorine dioxide generation source), and if you dare to carry these, the main component is Alternatively, there was a problem that the waste liquid spilled. In addition, even if it is simply made smaller and portable, the problem caused by its small size, that is, the problem that chlorine dioxide generation is poor in sustainability (due to a shortage of the absolute amount of chlorite), newly occurs, and the problem continues. Was difficult to use.

  As a device that simultaneously solves the problems of "miniaturization" and "continuous use" of a chlorine dioxide generator, a cartridge with a predetermined structure contains a drug containing solid chlorite and is irradiated with ultraviolet rays. A device for generating chlorine dioxide is known (Patent Document 2).

JP, 2005-224386, A WO2011 / 118447

  The device described in Patent Document 2 is superior to the conventional chlorine dioxide generation device in that it is small in size and can be continuously used. However, the device is a device for generating chlorine dioxide by irradiating ultraviolet rays to an aqueous solution containing chlorite or a gelling agent containing chlorite in that solid chlorite is used as a chlorine dioxide generation source. There was a further problem in that the amount of chlorine dioxide generated was smaller than that of.

  Conventionally, when chlorine dioxide is generated by irradiating a drug containing solid chlorite with light, in order to generate chlorine dioxide more efficiently, ultraviolet light with higher energy is used among light of various wavelengths. It has been considered essential to use the light of the area.

  The present inventors have conducted extensive studies to increase the chlorine dioxide generation amount of an apparatus that uses a drug containing solid chlorite as a chlorine dioxide generation source. As a result, unexpectedly, when ultraviolet rays were irradiated to a drug containing solid chlorite, not only chlorine dioxide but also ozone was generated, and this ozone interferes with chlorine dioxide, and as a whole, it is generated. It has been found that the amount of chlorine dioxide present is less than the amount of ozone (see also Example 1 herein and Figure 3).

  Based on the above findings, the present inventors increase the amount of chlorine dioxide generated as a whole while suppressing the generation of ozone in a device that uses a chemical agent containing solid chlorite as a chlorine dioxide generation source. In order to do so, further studies were conducted. As a result, it is possible to reduce the amount of ozone generated by using light in the visible region instead of the ultraviolet ray which has been conventionally considered to be essential for generating chlorine dioxide from solid chlorite. , Succeeded in increasing the amount of chlorine dioxide that can be generated as a whole device.

  Furthermore, the present inventors have improved the device to compensate for the decrease in reactivity due to the use of light in the visible region, which has lower energy than ultraviolet light, and as a result, surprisingly, solid chlorite has been solidified. It has been found that the efficiency of chlorine dioxide generation is "synergistically" improved when a drug containing is irradiated with light from a plurality of light source parts.

  Further, the inventors of the present invention prevent the drug containing solid chlorite in the drug container from spilling by covering the drug container in the chlorine dioxide generating unit of the present invention with a breathable sheet. At the same time, it has been found that excessive drying or excessive wetting of the drug by aeration can be prevented, and the device can more stably release chlorine dioxide.

  By these ingenuities, the present inventors have found that the chlorine dioxide generation unit of the present invention, which is small in size but can release a practically sufficient amount of chlorine dioxide over an extremely long time, and We have completed a chlorine dioxide generator equipped with a unit.

That is, the present invention, in one embodiment thereof, is a chlorine dioxide generating unit,
The unit includes a medicine container and at least two light source units, and the light source unit is for generating light having a wavelength substantially in the visible region. A drug containing chlorite is stored, and the drug container is provided with one or more openings so that air can move inside and outside the drug container, The one or more openings of the medicine container are covered with a breathable sheet, and the medicine present inside the medicine container is irradiated with the light generated from the light source unit. The present invention relates to a chlorine dioxide generating unit, which is characterized by generating chlorine dioxide gas.

  Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, the drug storage unit and the at least two light source units are integrally arranged, and the at least two light source units are the drug storage units. The medicine stored in the container is irradiated with light from at least two directions.

  Further, the chlorine dioxide generating unit of the present invention is characterized in that, in one embodiment, the wavelength of the light to be irradiated is 360 nm to 450 nm.

  Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, the light source unit includes a lamp or a chip.

  In one embodiment, the chlorine dioxide generating unit of the present invention is characterized in that the chip is an LED chip.

  Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, the light source unit is a light source unit capable of intermittently irradiating light.

  Also, in the chlorine dioxide generating unit of the present invention, in one embodiment, the solid chlorite-containing agent comprises (A) a porous substance carrying chlorite, and (B) a metal. A drug containing a catalyst or a metal oxide catalyst.

  Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, the "chlorite-supporting porous substance" is obtained by impregnating a porous substance with an aqueous chlorite solution and further drying. It is characterized by being obtained by.

  Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, the metal catalyst or metal oxide catalyst is selected from the group consisting of palladium, rubidium, nickel, titanium, and titanium dioxide. To do.

Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, the porous substance is selected from the group consisting of sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, and perlite,
It is characterized in that the chlorite is selected from the group consisting of sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, and barium chlorite.

  Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, in the drug in the drug container, the mass ratio of the chlorite to the metal catalyst or the metal oxide catalyst is 1: 0. It is characterized in that it is 0.04 to 0.8.

  Further, the chlorine dioxide generating unit of the present invention is, in one embodiment, characterized in that the porous substance further carries an alkali agent.

  Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, the alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and lithium carbonate. It is characterized by

  Further, in the chlorine dioxide generating unit of the present invention, in one embodiment, a molar ratio of the chlorite and the alkaline agent in the agent is 1: 0.1 to 2.0. And

  Further, the unit for generating chlorine dioxide of the present invention, in one embodiment, the "porous substance carrying a chlorite and an alkaline agent" is a chlorite and an alkaline agent, simultaneously or sequentially, It is characterized by being obtained by impregnating a porous material and drying it.

Another embodiment of the present invention comprises a unit for generating chlorine dioxide according to any of the above,
Chlorine dioxide generator

  Further, the chlorine dioxide generating device of the present invention, in one embodiment, further comprises a blower unit for sending air to the medicine stored in the medicine storing unit in the chlorine dioxide generating unit, To do.

  Further, in the chlorine dioxide generator of the present invention, in one embodiment, the blower unit is a fan for taking in air from the outside to the inside of the chlorine dioxide generator, or from the inside to the outside of the chlorine dioxide generator. It is characterized by being a fan for discharging air into the air.

  Further, in the chlorine dioxide generator of the present invention, in one embodiment, at least one of the openings of the medicine container is present on a side surface of the medicine container, and the air sent from the air blower is: At least a part is characterized in that the drug is delivered through an opening existing on a side surface of the drug container.

  Moreover, in one embodiment, the chlorine dioxide generator of the present invention is characterized in that the relative humidity in the medicine container is maintained at 30 to 80% RH by the air sent from the air blower. .

  It goes without saying that any combination of the above-mentioned one or more features of the present invention from the viewpoint of a person skilled in the art without causing technical inconsistency is also included in the scope of the present invention.

  The chlorine dioxide generating unit of the present invention and the chlorine dioxide generating apparatus provided with the unit are small in size, but can discharge a practically sufficient amount of chlorine dioxide for an extremely long time. Therefore, it can be suitably used for mounting on a vehicle, for example. Further, since the chlorine dioxide generating unit of the present invention is small, it can be incorporated in air conditioning equipment such as a heating device, a cooling device, an air purifier, and a humidifier.

FIG. 1 shows a vertical cross-sectional view of a chlorine dioxide generating unit incorporating a drug containing solid chlorite. FIG. 2 shows a vertical cross-sectional view of a chlorine dioxide generation device incorporating the chlorine dioxide generation unit of FIG. FIG. 3 is a graph showing changes in measured values of chlorine dioxide concentration in the air and ozone concentration when the wavelength of the irradiation light is changed in the case of irradiating light to a drug containing solid chlorite. Is. FIG. 4 is a graph showing an average value of measured values in the ultraviolet region and an average value of measured values in the visible region among the measured values of the chlorine dioxide concentration and the ozone concentration in FIG. 3. FIG. 5 is a graph showing changes in the amount of chlorine dioxide generated depending on the shape of the metal catalyst or metal oxide catalyst mixed with the drug when the drug containing solid chlorite is irradiated with light. FIG. 6 shows the chlorine dioxide generation amount when the ratio of chlorite and titanium dioxide in a solid chlorite and a drug containing a metal catalyst or a metal oxide catalyst (titanium dioxide) is changed. Show changes. FIG. 7 shows the content of titanium dioxide in a drug containing solid chlorite and a metal catalyst or a metal oxide catalyst (titanium dioxide), and the maximum value of the chlorine dioxide concentration generated by visible light irradiation. Shows the relationship. FIG. 8 shows a change in the amount of chlorine dioxide generated when a drug containing a solid chlorite and a metal catalyst or a metal oxide catalyst (titanium dioxide) is continuously irradiated with visible light for a long time. FIG. 9 shows a perspective view, a top view, and a side view of a chlorine dioxide generation unit that is an embodiment of the present invention. FIG. 10 is a schematic view of a chlorine dioxide generation device incorporating a chlorine dioxide generation unit, which is an embodiment of the present invention. FIG. 11 shows a case in which the chlorine dioxide generating unit according to one embodiment of the present invention is irradiated with light from only one light source section (one side) to the medicine in the medicine storing section and two light source sections (both sides). ) Shows the amount of chlorine dioxide generated when irradiated with light. FIG. 12 is a diagram showing a chlorine dioxide generating unit according to an embodiment of the present invention in which a drug in a drug container is irradiated with light from only one light source (one side) and two light sources (both sides). ) Shows a diagram in which the ratio of the chlorine dioxide generation amount in the case of irradiation with light is plotted. It should be noted that when light is emitted from two light source units (both sides), the amount of chlorine dioxide generated is more than double that in the case where light is emitted from only one light source unit (one side). For the sake of illustration, a double value is used as the chlorine dioxide generation amount in the case of single-sided irradiation in order to obtain the ratio of chlorine dioxide generation amounts. FIG. 13 shows a case where light is emitted from two light source portions (both sides) in the chlorine dioxide generating unit which is one embodiment of the present invention, and light is emitted from only one light source portion (one side). It is a figure explaining that light can be efficiently made to reach | attain the medicine in a medicine storage part by comparison. FIG. 14 shows a change in the chlorine dioxide generation amount when the relative humidity in the chemical container is changed in the chlorine dioxide generating unit according to the embodiment of the present invention. Note that FIG. 14 shows data when light is emitted from only one light source unit (one surface). FIG. 15 shows the change over time in the chlorine dioxide generation amount when the relative humidity in the chemical container is changed in the chlorine dioxide generation unit which is one embodiment of the present invention. Note that FIG. 15 shows data obtained when light is emitted from two light source units (both sides). FIG. 16 is a chlorine dioxide generation amount in the case where the chlorine dioxide generating unit according to the embodiment of the present invention is intermittently irradiated with light from two light source portions (both sides) to the medicine in the medicine storing portion. Shows the change over time. In the figure, “10 s / 80 s” means that light irradiation is continued for 2 minutes from the start of irradiation, light is irradiated for 10 seconds (LED is turned on) after 2 minutes from the start of irradiation, and irradiation of light for 80 seconds is stopped ( Indicates that the cycle of turning off the LED) has been repeated. Similarly, in the figure, "20s / 80s" means that the light irradiation is continued for 2 minutes after the irradiation starts, the light is irradiated for 20 seconds (LED is turned on) after the irradiation starts for 2 minutes, and the irradiation of the light for 80 seconds is stopped. It shows that the cycle of turning off (LED is turned off) is repeated, and "30s / 80s" means to continue irradiating light for 2 minutes after starting irradiation, and irradiate light for 30 seconds after starting irradiation for 2 minutes (turning on LED) Then, the cycle of stopping the irradiation of light for 80 seconds (turning off the LED) is repeated. FIG. 17 shows an embodiment in the case where the chemical storage portion of the chlorine dioxide generation unit of the present invention is covered with a breathable sheet. FIG. 18 shows that in the chlorine dioxide generation device incorporating the medicine storage part shown in FIG. 17, most of the air flowing through the apparatus flows so as to trace the surface of the medicine storage part, and only a part of the air stores the medicine. We show that chlorine dioxide can be released stably by going back and forth between the inside and outside of the section.

  The present invention is, in one embodiment, a unit for generating chlorine dioxide, wherein the unit comprises a drug storage unit and at least two light source units, and the light source units substantially have a wavelength in the visible region. It is for generating light, the drug storage unit stores a drug containing solid chlorite, and the drug storage unit has air inside and outside the drug storage unit. One or more openings are provided for movement, and the one or more openings of the drug reservoir are covered by a breathable sheet, wherein the interior of the drug reservoir is The present invention relates to a chlorine dioxide generating unit, wherein chlorine dioxide gas is generated by irradiating the existing drug with the light generated from the light source unit.

  The chlorine dioxide generating unit of the present invention includes at least two light source units (for example, 2, 3, 4, 5, 6 or more light source units), and the positional relationship between the at least two light source units. Is not particularly limited as long as it is possible to irradiate a drug that is a source of chlorine dioxide with light from at least two directions (for example, 2, 3, 4, 5, 6 or more directions). Preferably, the at least two light source units are arranged symmetrically with respect to the drug that is a source of chlorine dioxide.

  As the light source used in the present invention, a conventionally known light source can be used as long as it emits light in the visible region alone or in the visible region. Therefore, the wavelength of light generated from the light source used in the present invention is not limited to the wavelength of light in the visible region (360 nm to 830 nm), and the wavelength of light in the ultraviolet region (to 360 nm) and light in the infrared region are not limited. The light may include the wavelength (830 nm to). However, when a drug containing solid chlorite is irradiated with light having a wavelength in the ultraviolet region, ozone is likely to be generated as a by-product, and the energy of light having a wavelength in the infrared region is weak. The amount of chlorine dioxide generated is small even when a drug containing salt is irradiated. Therefore, it is preferable that the light emitted from the light source used in the present invention substantially consists of light having a wavelength in the visible region. The light emitted from the light source used in the present invention is preferably light having a wavelength of 360 nm to 450 nm, more preferably light having a wavelength of 380 nm to 450 nm or 360 nm to 430 nm, and further preferably 380 nm to 430 nm. Most preferably, it is light.

  It can be confirmed that the wavelength of the light emitted from the light source is substantially included in the range of the specific wavelength region by measuring the wavelength or energy of the light emitted from the light source by a known measuring device.

  The light source used in the present invention is not particularly limited as long as it emits light having a wavelength in the visible region, for example, a lamp (incandescent lamp, LED lamp) that emits light in the visible region, a chip, a laser device, etc. Various ones can be used. From the viewpoint of the directivity of the light generated from the light source and the viewpoint of downsizing of the apparatus, it is preferable to use the light source in the form of a chip. Since the light source in the form of a chip has a narrow directivity, it is possible to efficiently irradiate an object to be irradiated with light without diffusing the light, and it is possible to improve the chlorine dioxide generation efficiency of the device. Further, from the viewpoint of limiting the wavelength of light emitted from the light source so that light in the ultraviolet region or infrared region is not included, it is preferable to use an LED that emits light in the visible region as the light source. In particular, the light source used in the present invention is most preferably an LED chip that emits light in the visible region, from the viewpoint of miniaturization of the device and the generation efficiency of chlorine dioxide.

  Further, the light source used in the present invention may be a light source capable of emitting light intermittently. For example, the light source used in the present invention may be a light source that repeats a cycle of irradiating light for a certain period of time and then stopping irradiation of the light for a certain period of time. The method of controlling the light source for intermittently irradiating the light is not particularly limited, and a method known to those skilled in the art can be used.

  The light source unit and the drug storage unit in the chlorine dioxide generator of the present invention may be arranged integrally or separately, but with respect to the drug stored in the drug storage unit. In order to efficiently irradiate the light generated from the light source unit, it is preferable that they are integrally arranged. Here, the light source unit and the medicine storage unit may be integrally arranged or connected in a non-separable manner, or may be integrally arranged or connected in a separable manner. When the light source unit and the medicine container are integrally arranged or connected in a separable manner, the medicine container may be a replaceable cartridge.

  The medicine container used in the present invention is not limited in its material and structure as long as it has one or a plurality of openings so that air can move between the inside and the outside. For example, by making the material of the medicine container (particularly, the surface of the medicine container directly irradiated with the light from the light source section) a known light-transmissive material, the light emitted from the light source section is prevented. It is possible to irradiate the medicine inside the medicine container. Preferably, the material of the drug container is made of a resin that substantially transmits light in the visible region, so that the light generated from the light source unit is not absorbed by the resin and the drug inside the drug container is irradiated. To be done. In the present specification, the resin that substantially transmits light having a wavelength in the visible region may be, for example, a resin that transmits 80% or more of the irradiated light having a wavelength in the visible region, and is preferably irradiated. It may be a resin that transmits 90% or more of the light having a wavelength in the visible region, and more preferably a resin that transmits 95% or more of the irradiated light having a wavelength in the visible region. Specifically, as the material of the surface of the medicine storage portion to which the light from the light source portion is directly irradiated, for example, a material made of acrylic, vinyl chloride, or PET can be used, but the material is not particularly limited to these. Not done.

  In addition, for example, the medicine container may be formed of a mesh plate having a mesh that does not cause the contained items to fall. According to such a configuration, the air outside the medicine container can move inside and outside the medicine container, and the light generated from the light source section passes through the mesh to reach the medicine inside the medicine container. Is irradiated.

  In addition, one or a plurality of openings of the medicine container in the present invention are covered with a breathable sheet. In the present specification, the “breathable sheet” allows a gas (eg, air, gas, humidity, etc.) to pass therethrough, but substantially allows a solid substance (eg, powdery substance, granular substance) to pass through. It means a sheet-like structure that does not allow it. The “breathable sheet” in the present invention may further have a property of not allowing a liquid (for example, water droplets) to substantially pass therethrough. The material of the breathable sheet in the present invention is not limited, but for example, a material formed into a sheet by adhering or intertwining fibers by a thermo-mechanical or chemical action, a microporous film (having a large number of very small holes). The film of the material that has it), or the material that is laminated by laminating multiple sheets, the material that enables the movement of gas, air, and humidity (water vapor) even if it is non-porous, and the strong repellency of high density fabric. Examples include coating-type materials that have been subjected to water treatment, or materials formed by combining these materials. More specifically, examples of the breathable sheet in the present invention include non-woven fabrics (Elves (registered trademark, manufactured by Unitika Ltd.), Axter (registered trademark, manufactured by Toray), Gore-Tex (registered trademark) and Exepol ( Registered trademark, manufactured by Mitsubishi Plastics Co., Ltd .: Use materials such as microporous polyolefin film and various non-woven fabrics that have excellent breathability, moisture permeability and waterproofness), Entrant E (registered trademark, manufactured by Toray), etc. You can The breathable sheet according to the present invention preferably has a heat-sealing property (heat-welding property) so that it can be easily attached to the medicine container.

The shape and thickness of the breathable sheet used in the present invention is such that the breathable sheet has a certain size above the boundary between the inside and the outside of the medicine container, which allows gas, air, and moisture to pass therethrough. A person skilled in the art can make an appropriate selection as long as the purpose of "not passing an object" can be achieved. For example, when a nonwoven fabric is used as the breathable sheet, the fabric weight is 15 to 120 g / m ² (preferably 40 to 100 g / m ² , more preferably 50 to 80 g / m ² ) and the thickness is 0.1 to 1. It is possible to use one having a thickness of 0.0 mm (preferably 0.2 to 0.5 mm, more preferably 0.2 to 0.4 mm).

  Examples of the chlorite used in the present invention include alkali metal chlorite and alkaline earth metal chlorite. Examples of the alkali metal chlorite include sodium chlorite, potassium chlorite, and lithium chlorite, and examples of the alkaline earth metal chlorite include calcium chlorite, magnesium chlorite, and hypochlorite. Examples include barium chlorate. Among them, sodium chlorite and potassium chlorite are preferable, and sodium chlorite is most preferable, from the viewpoint of easy availability. These chlorites may be used alone or in combination of two or more.

The solid chlorite used in the present invention may be supported on a porous material.
In the present invention, the solid chlorite is supported on the porous substance, and by reacting with light on the surface of the porous substance, compared to the case of using the solid chlorite as it is, less. Energy can trigger a reaction. That is, in the present invention, chlorine dioxide can be more efficiently generated by using a solid chlorite supported on a porous substance. The porous material used in the present invention can be used, for example, sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, etc., but in order not to decompose chlorite, it becomes alkaline when suspended in water. Those shown are preferable, palygorskite and sepiolite are more preferable, and sepiolite is particularly preferable.

  In the present invention, the method of supporting the chlorite salt on the porous substance is not particularly limited. For example, “a chlorite-supported porous substance” can be obtained by impregnating a porous substance with an aqueous chlorite solution and drying. The water content of the "porous substance supporting chlorite" is preferably 10% by weight or less, and more preferably 5% by weight or less.

  The "porous substance supporting chlorite" used in the present invention may have any particle size, but particularly preferably one having an average particle size of 1 mm to 3 mm. it can.

  The average particle size of the "porous substance supporting chlorite" in the present invention is, for example, by an optical microscope, the particle size of the "porous substance supporting chlorite" used is measured, and statistics are obtained. It can be calculated by performing processing and calculating the average value and standard deviation.

  The concentration of chlorite in the "porous substance supporting chlorite" used in the present invention is effective when it is 1% by weight or more, but when it exceeds 25% by weight, it corresponds to a deleterious substance. Therefore, it is preferably 1% by weight or more and 25% by weight or less, and more preferably 5% by weight or more and 20% by weight or less.

  The “solid chlorite-containing agent” used in the present invention may further contain a metal catalyst or a metal oxide catalyst. For example, the "drug containing solid chlorite" used in the present invention includes (A) a porous substance supporting chlorite, and (B) a metal catalyst or a metal oxide catalyst. It may be a drug containing.

  Examples of the metal catalyst or metal oxide catalyst used in the present invention include palladium, rubidium, nickel, titanium and titanium dioxide. Of these, titanium dioxide is particularly preferably used. Note that titanium dioxide may be simply referred to as titanium oxide or titania. The metal catalyst or metal oxide catalyst used in the present invention can be used in various forms such as powder and granules, and the chlorite in the drug and the metal catalyst or metal oxide catalyst can be used. Those skilled in the art can appropriately select a preferable form depending on the mixing ratio. For example, when the proportion of metal catalyst or metal oxide catalyst in the drug is relatively high, a granular metal catalyst or metal oxide catalyst can be selected, and the proportion of metal catalyst or metal oxide catalyst in the drug can be selected. A powdered metal catalyst or a metal oxide catalyst can be selected when the ratio is relatively low, but is not limited thereto.

  In the present specification, as a rough guide for the size of “powder” or “granular”, for example, “powder” means a solid substance having an average particle size of 0.01 mm to 1 mm, and The term “granular” refers to a solid material having an average particle diameter of 1 mm to 30 mm, but is not particularly limited.

  The mass ratio of chlorite to metal catalyst or metal oxide catalyst in the agent used in the present invention is chlorite: metal catalyst or metal oxide catalyst = 1: 0.04 to 0.8. , Preferably 1: 0.07 to 0.6, and more preferably 1: 0.07 to 0.5. In the drug, when the content of the metal catalyst or the metal oxide catalyst is more than 1 time the content of the chlorite salt, and the content of the metal catalyst or the metal oxide catalyst is 0 times the content of the chlorite salt. In any case of less than 0.04 times, the amount of chlorine dioxide generated upon irradiation with visible light can be reduced.

  The “chlorite-supported porous substance” used in the present invention may further support an alkaline agent.

  The alkaline agent used in the preparation of the agent of the present invention may be, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, rubidium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, Preferably sodium hydroxide can be used. By further supporting an alkaline agent on the “chlorite-supported porous material”, the pH of the drug used in the present invention can be adjusted, the stability of the drug itself is increased, and light irradiation is performed. It is possible to suppress the wasteful emission of chlorine dioxide when not stored.

  The amount of the alkaline agent used in the preparation of the drug of the present invention is appropriately 0.1 equivalent or more and 2.0 equivalents or less, preferably 0.1 equivalent or more and 1. equivalent to the chlorite (mol). It is 0 equivalent or less, and more preferably 0.1 equivalent or more and 0.7 equivalent or less. If it is less than 0.1 equivalent, the supported chlorite may be decomposed at room temperature, and if it exceeds 2.0 equivalent, stability is improved, but chlorine dioxide is less likely to be generated and the generation concentration is lowered, which is preferable. Absent.

  In the preparation of the drug of the present invention, the method of further supporting an alkaline agent on the "chlorite-supported porous material" is not particularly limited, and for example, the chlorite and the alkaline agent are simultaneously or sequentially added. Alternatively, a method of impregnating a porous material and drying it may be used. In the present specification, the intended composition may be obtained by "spraying and adsorbing" an aqueous chlorite solution and / or an alkaline agent onto a porous substance and drying the same. The term "spray adsorption" shall be included in the term "impregnation".

  In one embodiment, the present invention may be configured as a chlorine dioxide generation device including the chlorine dioxide generation unit of the present invention. The chlorine dioxide generation device of the present invention may further include a blower for sending air to the medicine stored in the medicine storage of the chlorine dioxide generation unit. The blower unit may be for taking in air from the outside of the device to the inside, or may be for discharging air from the inside of the device to the outside.

  In the chlorine dioxide generator of the present invention, the air blower for sending air to the medicine stored in the medicine storage may be, for example, a fan or an air pump, but is preferably a fan. By providing such a blower unit, more air can be supplied to the medicine inside the medicine storage unit. Since more air is supplied to the chemicals, the frequency of contact between the chemicals containing solid chlorite and the water content (water vapor) in the air increases, so chlorine dioxide is emitted from the solid chlorite irradiated with light. Is likely to occur.

  In the chlorine dioxide generator of the present invention, the relative humidity in the medicine container is adjusted to 30 to 80% RH (preferably 40 to 70% RH, more preferably 40 to 60% RH) by the air sent from the air blower. ) Can be adjusted. The amount of chlorine dioxide generated can be increased by adjusting the relative humidity in the medicine container within the above range.

  Further, in the chlorine dioxide generator of the present invention, as another method for supplying the water vapor in the air into the chemical container, a Peltier element (Peltier effect) for condensing and collecting water in the air is used. It can also be done (the disadvantage of the Peltier element, which causes infiltration and condensation of water vapor, can be used in reverse to increase the humidity).

  The method for controlling the relative humidity in the device is not particularly limited, and can be appropriately performed by those skilled in the art using known techniques. For example, a relative humidity is controlled by installing a hygrometer to measure the humidity inside the main body of the device and adjusting the amount of air blown from the air blower or adjusting the amount of moisture absorbed by the Peltier element while monitoring the amount of water. You may

  Further, since the chlorine dioxide generating unit of the present invention is small, it can be incorporated in home electric appliances and the like whose main purpose is not to generate chlorine dioxide. An apparatus in which the chlorine dioxide generating unit of the present invention is incorporated in a home electric appliance or the like whose main purpose is not to generate chlorine dioxide is also included in the "chlorine dioxide generating apparatus" of the present invention. For example, by incorporating the unit for generating chlorine dioxide of the present invention into an air conditioner such as a heating device, an air conditioner, an air purifier, a humidifier, etc., the chlorine dioxide in the chlorine dioxide generating unit can be removed by the effect of the wind emitted from the air conditioner. The generation is promoted, and chlorine dioxide can be efficiently diffused into the space by being placed on the air discharged from the air conditioning equipment into the space.

  The terminology used herein is used to describe a particular embodiment and is not intended to limit the invention.

  Further, the term “comprising” as used in the present specification is intended to mean that the described items (members, steps, elements, numbers, etc.) are present, unless the context clearly requires different understanding. It does not exclude the existence of other matters (members, steps, elements, numbers, etc.).

  Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein are to be interpreted as having a meaning consistent with the meaning herein and in the related art, unless otherwise defined, idealized, or excessively formal. It should not be construed in a conventional sense.

  Embodiments of the present invention may be described with reference to schematic diagrams, but in the case of schematic diagrams, they may be exaggerated for clarity of explanation.

  In the present specification, for example, when the expression “1 to 10%” is given, those skilled in the art will recognize that the expression is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%. Understand that it refers to an individual.

  In this specification, all numerical values used to indicate a component content or a numerical range are to be construed to include the meaning of the term “about” unless otherwise specified. For example, “10 times” is understood to mean “about 10 times” unless otherwise specified.

  The references cited in this specification are to be regarded as being incorporated herein in their entirety by their disclosure, and a person skilled in the art, according to the context of the present specification, can obtain the spirit of the present invention. And without departing from the scope, the relevant disclosures in those prior art documents are understood to be incorporated as part of this specification.

  In the following, the invention will be explained in more detail with reference to examples. However, the invention may be embodied in various forms and should not be construed as limited to the examples set forth herein.

Example 1 Change in Chlorine Dioxide Generation Rate with Wavelength of Irradiating Light In this example, a test was conducted using the chlorine dioxide generation unit and the chlorine dioxide generation apparatus shown in FIGS. 1 and 2.

  FIG. 1 is a vertical cross-sectional view showing the internal structures of a medicine storage portion and a light source portion of the chlorine dioxide generation unit used in this embodiment. As shown in FIG. 1, the chlorine dioxide generating unit 10 includes a medicine container 11 and a light source unit (LED chip 12 and operation board 13) for generating light in the visible region. The medicine container 11 contains a test medicine 14. The medicine container 11 is provided with an opening 16 so that air can move inside and outside. The chlorine dioxide generating unit 10 includes a tube 15 for guiding air outside the device into the device.

  The air introduced from the tube 15 is supplied into the medicine container 11 through the opening 16. The water vapor contained in the supplied air is taken up by the chlorite salt in the test chemical 14. The light in the visible region generated from the light source unit passes through the bottom surface of the medicine container 11 and is applied to the test medicine 14 existing inside the medicine container 11. The chlorite containing water vapor reacts with the irradiated light to generate chlorine dioxide. Titanium dioxide contained in the test chemical 14 together with chlorite accelerates the reaction of generating chlorine dioxide from chlorite when irradiated with light in the visible region. The generated chlorine dioxide is discharged to the outside through the opening 16.

  FIG. 2 is a vertical cross-sectional view showing the overall structure of the chlorine dioxide generator used in this example. As shown in FIG. 2, the chlorine dioxide generation device 20 includes a chlorine dioxide generation unit 21 inside. The device body 22 of the chlorine dioxide generator 20 includes an air supply port 23 for introducing air outside the device into the device, and an air outlet 25 for discharging air inside the device to the outside of the device. Further, the chlorine dioxide generator 20 is provided with a fan 24 inside in order to efficiently introduce air into the inside of the device.

  By driving the fan 24, air is introduced into the inside of the apparatus main body 22 from the air supply port 23. The introduced air passes through the chlorine dioxide generating unit 21 installed inside the apparatus and is discharged from the air discharge port 25. In the chlorine dioxide generation unit 21, chlorine dioxide is generated by a mechanism similar to that of the device shown in FIG. 1, so the air discharged from the air discharge port 25 contains chlorine dioxide.

  70 g of a 10 wt% sodium chlorite aqueous solution was spray-adsorbed on 100 g of sepiolite and dried, and then 20 g of a 10 wt% sodium hydroxide aqueous solution was spray-adsorbed and dried. To this, 20 g of powdery titanium dioxide prepared by subjecting titanium powder to a firing treatment was mixed to obtain a test chemical used in this example.

  The above-mentioned chemicals were stored in the chemical storage part in the chlorine dioxide generator shown in FIG. Air was introduced into the medicine container at 1 L / min from the opening of the medicine container, and the LED chip was irradiated with light to the medicine in the medicine container. The wavelength of the light emitted from the LED chip was changed every 2 nm from 80 nm to 430 nm, and the chlorine dioxide concentration and ozone concentration contained in the air discharged from the chlorine dioxide generator were measured. In this example, the chlorine dioxide generator was stored in a chamber of about 7 liters, and the chlorine dioxide concentration and the ozone concentration were measured by measuring the chlorine dioxide concentration and the ozone concentration in the chamber. .. The results are shown in FIGS. 3 and 4. In this test, a frequency counter (MCA3000, Tektronix), a spectrum analyzer (BSA, Agilent Technologies), a wavelength sweep light source (TSL-510, Suntec), an ultraviolet integrating photometer (UIT-250, Ushio). Denki Co., Ltd.) and an ultraviolet integrated photometer receiver (VUV-S172, UVD-C405, USHIO INC.) Were used.

  FIG. 3 is a graph showing actually measured values of chlorine dioxide concentration and ozone concentration in air at various wavelengths of light, and FIG. 4 is a measurement in the ultraviolet region (80 nm to 358 nm) of the above measured values. It is a graph which compared the average value of the value and the average value of the measured value in a visible region (360 nm-430 nm). In addition, in FIG. 4, the average values of the measured values of chlorine dioxide in the ultraviolet region and the visible region are approximately 2.25 ppm and approximately 4.87 ppm, respectively, and the average values of the measured values of ozone in the ultraviolet region and the visible region are approximately respectively. The values were 7.04 ppm and about 3.04 ppm.

  As shown in Fig. 3, when the wavelength of the light irradiating the drug is moved from the ultraviolet region to the visible region, the ozone concentration in the air becomes maximum in the ultraviolet region and decreases from the ultraviolet region to the visible region. It has been shown. On the other hand, it was surprisingly shown that the concentration of chlorine dioxide in the air increased from the ultraviolet region to the visible region. From this result, a person skilled in the art can use the wavelength range preferably used in the present invention beyond the upper limit of 430 nm of the measurement range of the present embodiment, for example, at a wavelength of at least about 450 nm without any problem. Understand that

  Further, as shown in FIG. 4, comparing the average values of the ozone concentration and the chlorine dioxide concentration in the air in the ultraviolet region and the visible region, the ozone concentration decreased to about 43% from the ultraviolet region to the visible region. On the other hand, the chlorine dioxide concentration increased to about 213% from the ultraviolet region to the visible region.

  That is, by irradiating solid chlorite and a mixture of a metal catalyst or a metal oxide catalyst with light in the visible region, chlorine dioxide is generated much more efficiently than with irradiation with light in the ultraviolet region. I found out that I could make it happen.

Example 2: Change in chlorine dioxide generation amount depending on the shape of catalyst Sample 1 used in this example is the same as Example 1 except that granular titanium dioxide (prepared by baking titanium) was used. The drug was prepared by the method. In Samples 2 and 3 used in this example, drugs were prepared in the same manner as in Example 1.

  The chemicals (Samples 1 to 3) prepared by the above method were stored in the chemical storage unit of the chlorine dioxide generator described in Example 1, respectively. For Sample 1 and Sample 2, air was introduced into the device at 1 L / min from the opening of the drug storage unit, and 405 nm light was emitted from the LED chip of the light source unit. For sample 3, only air was introduced into the device at 1 L / min from the opening of the medicine container, and light was not irradiated. The concentration of chlorine dioxide contained in the air discharged from the apparatus was measured 11 hours after the start of irradiation. The measurement results for each of Samples 1 to 3 are shown in FIG.

  As shown in FIG. 5, the case where granular titanium dioxide was mixed in the drug (Sample 1) was more efficient than the case where powdery titanium dioxide was mixed in the drug (Sample 2). It has been found that chlorine can be generated.

Example 3: Examination of content ratio of chlorite and titanium dioxide in drug After spraying and adsorbing 70 g of 10 wt% sodium chlorite aqueous solution on 100 g of sepiolite and further drying, spraying 20 g of 10 wt% sodium hydroxide aqueous solution. Adsorbed and dried. Powdered titanium dioxide was mixed with this in various amounts to prepare a test drug used in this example. The test chemical was irradiated with visible light using the same chlorine dioxide generator and irradiation method as in Example 1, and the chlorine dioxide concentration was also measured in the same manner as in Example 1.

FIG. 6 is a diagram showing a change in the amount of chlorine dioxide generated when the ratio of chlorite and titanium dioxide in the composition of the present invention is changed. As shown in FIG. 6, the content (wt%) of titanium dioxide in the drug, the mass ratio of chlorite to titanium dioxide in the drug, and the dioxide contained in the air one hour after the start of visible light irradiation. Table 1 shows the relationship with the chlorine concentration (ppm). FIG. 7 shows the relationship between the content of titanium dioxide in the drug of the present invention and the maximum value of the chlorine dioxide concentration generated by irradiation with visible light.

  As shown in FIGS. 6, 7 and Table 1, the amount of chlorine dioxide generated when the test drug was irradiated with visible light was such that the mass ratio of titanium dioxide to chlorite in the drug was 0 to about 0. It was shown that it increased as it increased to 3, and gradually decreased when the mass ratio of titanium dioxide to chlorite exceeded about 0.3. Further, it has been shown that when the mass ratio of titanium dioxide to chlorite in the composition exceeds about 1.0, the amount of chlorine dioxide generated is lower than that in the case where titanium dioxide is not mixed.

  FIG. 8 is a diagram showing changes in the amount of chlorine dioxide generated when the test drug of this example was continuously irradiated with visible light for a long time. As shown in FIG. 8, even when observed for a long time, the mixing ratio (mass ratio) of chlorite and titanium dioxide in the test drug was 1: 1 as in the results shown in FIGS. 6 and 7. In the case of 0.04 to 0.8 (preferably 1: 0.07 to 0.6, more preferably 1: 0.07 to 0.5), compared with the case where the mixing ratio is set to other range. It was confirmed that the high concentration chlorine dioxide was continuously released.

Example 4 Examination of Sandwich Structure of Light Source Part A test was conducted on the effectiveness of the sandwich structure of the light source part in the present invention. In this example, an experiment was conducted using the chlorine dioxide generation unit shown in FIG. 9 and the chlorine dioxide generation device shown in FIG.

  FIG. 9 is a diagram showing the internal structure of the chlorine dioxide generating unit 30, which is an embodiment of the present invention. As shown in FIG. 9, the chlorine dioxide generating unit 30 of the present invention includes a drug container 32 and a light source unit (electronic substrate 33 and LED chip 34) for generating light in the visible region. The medicine container 32 contains a medicine containing solid chlorite therein. The medicine container 32 is provided with openings (gas generating port 31, air introducing port 36) so that air can move inside and outside.

  The air introduced from the air introduction unit 36 is supplied to the inside of the medicine storage unit 32. The water vapor contained in the supplied air is taken in by the test drug contained in the drug container 32. The light in the visible region generated from the light source unit passes through the exterior portion 35 of the medicine container 32 and is applied to the medicine contained in the medicine container 32. The test agent containing water vapor reacts with the irradiated light to generate chlorine dioxide. The generated chlorine dioxide is discharged to the outside through the gas generating port 31.

  FIG. 10 is a diagram showing the internal structure of the chlorine dioxide generator 40, which is an embodiment of the present invention. As shown in FIG. 10, the chlorine dioxide generation device 40 of the present invention is provided with a chlorine dioxide generation unit (LED chip mounting substrate 41 and chemical storage 42) which is one embodiment of the present invention. The chlorine dioxide generation device further includes a blower fan 44 inside, and by driving the blower fan 44, air is supplied to the inside of the chlorine dioxide generation unit. By adjusting the drive of the blower fan 44, it is possible to adjust the relative humidity in the medicine container in the chlorine dioxide generating unit.

  By driving the blower fan 44, air is supplied from the air introduction port of the chlorine dioxide generating unit to the inside of the medicine container. The water vapor contained in the supplied air is taken in by the test drug contained in the drug container. Light in the visible region generated from the light source unit passes through the exterior of the medicine container and is applied to the medicine contained in the medicine container. The test agent containing water vapor reacts with the irradiated light to generate chlorine dioxide. The generated chlorine dioxide is released to the outside through the gas generating port.

70 g of a 10 wt% sodium chlorite aqueous solution was spray-adsorbed on 100 g of sepiolite and dried, and then 20 g of a 10 wt% sodium hydroxide aqueous solution was spray-adsorbed and dried. Approximately 1.8 g of powdery titanium dioxide was mixed with this to obtain a test chemical used in this example. The prepared test chemical was stored in the chemical storage of the chlorine dioxide generating unit shown in FIG. 9, and visible light was irradiated from the ^two light source sections (100 mm ² each). This test was conducted in a chamber of 1 m ³ , and the temperature in the chamber was about 26 ° C and the relative humidity was about 40%. In the comparative example, the test was performed in the same manner as in the example except that the one-sided (single-sided) light source section was used for irradiation with visible light.

  FIG. 11 shows the results of measuring the changes over time in the chlorine dioxide concentration in the chamber in the examples and comparative examples. Further, FIG. 12 shows the ratio of chlorine dioxide concentration in the chamber between the example and the comparative example at each time from the start of irradiation. Note that, in FIG. 12, when the light is emitted from two light source units (both sides), the amount of chlorine dioxide generated is twice as compared with the case where the light is emitted from only one light source unit (one side). In order to show the above, the chlorine dioxide generation amount in the case of single-sided irradiation is set to a double value in order to obtain the ratio of the chlorine dioxide generation amount.

  As shown in FIGS. 11 and 12, when the visible light is emitted from the two light source parts (both sides), surprisingly, compared with the case where the visible light is emitted from only one light source (one side), It was shown that the amount of chlorine dioxide generated was more than doubled. Further, as shown in FIG. 12, it was also shown that the value of the ratio of the chlorine dioxide generation amount in the example to the chlorine dioxide generation amount in the comparative example further increased with the passage of time.

  The above results can be explained by FIG. That is, since the light intensity exponentially decreases when the light passes through the medium, it is difficult for the light to reach the inside and the inside of the drug by irradiation from only one side, and the light is efficiently emitted to the entire drug. Irradiation is difficult. However, by irradiating the drug with light from two directions (or two or more directions), it becomes possible to supply the amount of light necessary for the reaction to the inside of the drug and efficiently generate chlorine dioxide. It became possible to do.

Example 5: Study on Relative Humidity of Chemical Storage Section Using the chlorine dioxide generation unit shown in FIG. 9 and the chlorine dioxide generation apparatus shown in FIG. 10, chlorine dioxide generation by relative humidity inside the chemical storage section The change in quantity was examined.

  The same conditions as in Example 4 were used for the drug stored in the drug storage unit, the visible light irradiation method, and the chlorine dioxide concentration measurement. The relative humidity inside the medicine container was adjusted by controlling the amount of air supplied to the medicine container (that is, the amount of water vapor supplied to the medicine) by driving a blower fan. The relationship between the relative humidity in the drug container and the chlorine dioxide concentration in the chamber is shown in FIGS. 14 and 15. FIG. 14 shows a value obtained by averaging chlorine dioxide concentrations measured multiple times during light irradiation for 0.5 hours to 2 hours and its standard deviation, and FIG. 15 shows a temporal change in chlorine dioxide concentration in the chamber. Show.

  As shown in FIG. 14, the amount of chlorine dioxide generated is increased by adjusting the relative humidity in the medicine container to 30 to 80% RH (preferably 50 to 70% RH, more preferably 40 to 60% RH). It was shown that it is possible. If the relative humidity in the medicine container is less than 30%, the amount of water necessary for the reaction to generate chlorine dioxide from chlorite is insufficient, and if the relative humidity is higher than 80%, it is generated in the condensed water. Since chlorine dioxide dissolves, the amount of chlorine dioxide released as a gas is considered to decrease.

  Further, as shown in FIG. 15, by adjusting the relative humidity in the medicine container to 30 to 80% RH (preferably 40 to 70% RH, more preferably 40 to 60% RH), the relative humidity is less than 30%. Compared to the case of 1, the concentration of chlorine dioxide released can be maintained high even after the time from the start of irradiation. Even when the relative humidity is set to 20%, the concentration of chlorine dioxide at the beginning of the irradiation is considered to be high because the drug itself before the irradiation starts contains a certain amount of water.

Example 6: Examination of usefulness of intermittent irradiation The usefulness of intermittent irradiation of visible light in the present invention was examined using the chlorine dioxide generating unit shown in FIG.

  The same conditions as in Example 4 were used for the measurement of the drug stored in the drug storage unit and the chlorine dioxide concentration. Intermittent irradiation of visible light from the light source unit was performed by switching ON / OFF of the LED and alternately performing visible light irradiation and stopping. Specifically, intermittent irradiation was performed under the following conditions (1) to (3).

(1) Repeat the cycle of irradiating light for 2 minutes from the start of irradiation, irradiating light for 10 seconds (turning on the LED) and stopping irradiation of light for 80 seconds (turning off the LED) after 2 minutes from the start of irradiation. It was
(2) Repeat the cycle of continuously irradiating light for 2 minutes from the start of irradiation, and irradiating light for 20 seconds (turning on the LED) and stopping irradiation for 80 seconds (turning off the LED) after 2 minutes from the start of irradiation. It was
(3) Repeat the cycle of continuously irradiating light for 2 minutes after the start of irradiation, and irradiating light for 30 seconds (turning on the LED) and stopping irradiation for 80 seconds (turning off the LED) after 2 minutes from the start of irradiation. It was
The results of this test are shown in FIG. The “relative ClO ₂ gas concentration” in the graph of FIG. 16 represents the relative value of the chlorine dioxide concentration at each time when the chlorine dioxide concentration 2 minutes after the start of irradiation is 1.

  As shown in FIG. 16, in the present invention, visible light is intermittently irradiated from the light source unit, and the balance between the irradiation time and the stop time in the intermittent irradiation is adjusted, whereby chlorine dioxide having a desired concentration can be generated. .

  Further, in the present invention, the intermittent irradiation of visible light from the light source section could prevent the release of a relatively high concentration of chlorine dioxide at the beginning of irradiation. When visible light continues to be emitted from the light source (that is, when intermittent irradiation is not performed), for example, as shown in the graph of FIG. 6, the chlorine dioxide generation concentration reaches a maximum at the beginning of irradiation and then gradually decreases. That is, in the present invention, chlorine dioxide can be more stably released by intermittently irradiating the light source with visible light.

  Furthermore, as a matter of course, when intermittently irradiating visible light from the light source unit, solid chlorite, which is a chlorine dioxide supply source, is compared with the case of continuously irradiating visible light from the light source unit. It is possible to suppress the consumption amount of the contained drug. That is, in the present invention, the usable period of the chlorine dioxide generating unit can be extended by using a light source capable of intermittently irradiating visible light.

Example 7: Examination of Use of Breathable Sheet in Medicine Storage Section 1
In the chlorine dioxide generator of the present invention, for example, as shown in FIG. 10, in order to supply water (steam) to the solid drug contained in the drug container, and / or by using chlorine dioxide gas, Since it spreads over a wide range, air may be actively blown into the medicine container by a blower fan. However, depending on the amount of air blown into the medicine container, the humidity of the air, etc., the medicine may be excessively dried, the generation efficiency of chlorine dioxide may be reduced, or the medicine may be excessively wet.

  Therefore, as shown in FIG. 17, the opening of the medicine container is covered with a breathable sheet (Exepol (registered trademark) (manufactured by Mitsubishi Plastics Co., Ltd. is used in this embodiment), and the structure of the present invention An experiment to drive a chlorine generator was tried. As a result, most of the air sent into the device of the present invention flows so as to trace the surface of the drug container, and only a part of the air moves back and forth between the inside and outside of the drug container, thereby blowing in the drug container. The state of the solid drug could be stabilized irrespective of the change in the amount of water and the humidity of the air. That is, by using the breathable sheet, it was possible to stabilize the chlorine dioxide generation efficiency while maintaining the chlorine dioxide diffusing capacity of the device of the present invention (FIG. 18). Furthermore, by covering the opening of the medicine container with a breathable sheet, the medicine will not spill out of the medicine container even if the force of the air to be sent is increased, and the practicality of the device can be further improved. did it.

Example 8: Examination of Use of Breathable Sheet in Medicine Storage Part 2
In Example 7 described above, the same experiment was performed using a nonwoven fabric (Elves (registered trademark, manufactured by Unitika Ltd.)) as the breathable sheet. As a result, most of the air sent into the device of the present invention flows so as to trace the surface of the drug container, and only a part of the air moves back and forth between the inside and outside of the drug container, thereby blowing in the drug container. The state of the solid drug could be stabilized irrespective of the change in the amount of water and the humidity of the air. That is, by using the non-woven fabric, the chlorine dioxide generation efficiency could be stabilized while maintaining the chlorine dioxide diffusing capacity of the device of the present invention (FIG. 18). Furthermore, by covering the opening of the drug container with a non-woven fabric, the drug does not spill out of the drug container even when the force of the air to be fed is increased, and the practicality of the device can be further improved. .

10 Chlorine Dioxide Generation Unit 11 Chemical Storage 12 LED Chip 13 Operation Base 14 Chemical 15 Tube 16 Opening 20 Chlorine Dioxide Generator 21 Chlorine Dioxide Generation Unit 22 Device Main Body 23 Air Supply Port 24 Fan 25 Air Discharge Port 30 Chlorine Dioxide Generation unit 31 Gas generation port 32 Chemical storage part 33 Electronic substrate 34 LED chip 35 Exterior part 36 Air introduction port 40 Chlorine dioxide generator 41 LED chip mounting substrate 42 Chemical storage part 43 Housing part 44 Blower fan 51 Transparent resin plate 52 Medicine storage section 53 Breathable sheet 54 LED chip mounting substrate 55 Medicine storage section 56 Blower fan

Claims (18)

A unit for generating chlorine dioxide,
The unit includes a medicine container and at least two light sources,
The light source unit is for generating light having a wavelength substantially in the visible region,
The drug storage unit stores a drug containing solid chlorite,
The medicine container is provided with one or a plurality of openings so that air can move inside and outside the medicine container,
The one or more openings of the medicine container are covered with a breathable sheet,
Here, the drug present inside the drug container is irradiated with the light generated from the light source unit to generate chlorine dioxide gas ,
The solid chlorite-containing drug is a drug containing (A) a chlorite-supported porous material, and (B) a metal catalyst or a metal oxide catalyst,
In the medicine in the medicine container, the mass ratio of the chlorite and the metal catalyst or the metal oxide catalyst is 1: 0.04 to 0.8, wherein
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 1,
The drug storage unit and the at least two light source units are integrally arranged, and the at least two light source units emit light from at least two directions with respect to the drug stored in the drug storage unit. Illuminating,
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 1 or 2,
The wavelength of the irradiation light is 360 nm to 450 nm,
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 3,
The light source unit comprises a lamp or a chip,
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 4,
The chip is an LED chip,
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 4 or 5,
The light source unit is a light source unit that can emit light intermittently,
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 1 ,
The "chlorite-supported porous substance" is characterized in that it is obtained by impregnating a porous substance with an aqueous chlorite solution and further drying.
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 1 ,
Wherein the metal catalyst or metal oxide catalyst is selected from the group consisting of palladium, rubidium, nickel, titanium, and titanium dioxide,
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 1 ,
The porous material is selected from the group consisting of sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, and perlite,
For generating chlorine dioxide, wherein the chlorite is selected from the group consisting of sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, and barium chlorite. unit. The chlorine dioxide generating unit according to claim 1 ,
Wherein the porous material further carries an alkaline agent,
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 10 ,
The chlorine dioxide generating unit, wherein the alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and lithium carbonate. The chlorine dioxide generating unit according to claim 10 or 11 , wherein
The molar ratio of the chlorite and the alkaline agent is 1: 0.1 to 2.0,
Chlorine dioxide generation unit. The chlorine dioxide generating unit according to claim 10 ,
The above-mentioned “porous substance supporting chlorite and an alkaline agent” is obtained by impregnating a porous substance with a chlorite and an alkaline agent at the same time or sequentially and drying. ,
Chlorine dioxide generation unit. A unit for chlorine dioxide generation according to any one of claims 1 to 13 ,
Chlorine dioxide generator. The chlorine dioxide generator according to claim 14 , wherein
In the chlorine dioxide generating unit, further comprising an air blower for sending air to the medicine stored in the medicine storage,
Chlorine dioxide generator. The chlorine dioxide generator according to claim 15 , wherein
The blower unit is a fan for taking in air from the outside to the inside of the chlorine dioxide generator, or a fan for discharging air from the inside of the chlorine dioxide generator to the outside. ,
Chlorine dioxide generator. The chlorine dioxide generator according to claim 15 or 16 , wherein
At least one of the openings of the medicine container is present on a side surface of the medicine container,
The air sent from the air blower is at least partially sent to the medicine through an opening existing on a side surface of the medicine container.
Chlorine dioxide generator. The chlorine dioxide generator according to any one of claims 15 to 17 ,
The relative humidity in the medicine container is maintained at 30 to 80% RH by the air sent from the blower.
Chlorine dioxide generator.