JPWO2016194884A1 - Method to inactivate airborne microorganisms in space - Google Patents

Abstract

A method for supplying a sufficient amount of chlorine dioxide gas to a space to inactivate suspended microorganisms is provided. A method of deactivating suspended microorganisms in a space, comprising: (1): (A) a porous material supporting chlorite and (B) a metal catalyst or a metal oxide catalyst. Preparing a solid drug, wherein the mass ratio of the chlorite to the metal catalyst or metal oxide catalyst in the solid drug is 1: 0.04-0.8; (2): irradiating the solid drug with visible light; and (3): supplying chlorine dioxide gas generated from the solid drug to a space where airborne microorganisms exist. I will provide a.

Description

  The present invention relates to a method for inactivating suspended microorganisms in a space using low concentration chlorine dioxide gas.

  Chlorine dioxide gas is a safe gas for animal organisms at low concentrations (for example, 0.3 ppm or less), but even at such low concentrations, it has a deactivating effect on microorganisms such as bacteria, fungi, and viruses, It is known to have a deodorizing action and the like. Because of these characteristics, chlorine dioxide gas has attracted particular attention in applications such as deodorization, sterilization, virus removal, antifungal and antiseptic during environmental purification and food transportation.

  As described above, chlorine dioxide gas is safe for animal bodies at low concentrations and can be used for various purposes. For example, a method for inactivating respiratory viruses and the like using low-concentration chlorine dioxide gas has been proposed (for example, Patent Document 1). However, since chlorine dioxide gas can be harmful to the animal's body at high concentrations and there is a danger of explosion, development of a method for stably generating chlorine dioxide gas has been studied for practical use. .

  Conventionally, a method of generating chlorine dioxide by adding an acid to a chlorite aqueous solution or solid chlorite is known. However, in such a method, it is difficult to control the reaction, and a high concentration of chlorine dioxide gas is often generated unintentionally depending on the environmental conditions and the conditions of the added acid.

  Therefore, a method of generating chlorine dioxide by irradiating a gel composition comprising chlorite and a water-absorbing resin with ultraviolet rays (for example, Patent Document 2), or a porous carrier containing chlorite and an alkali agent. A method of generating chlorine dioxide by using the stabilized chlorine dioxide impregnated and dried and bringing the stabilized chlorine dioxide agent into contact with air has been proposed (for example, Patent Document 3).

WO / 2007/061092 JP-A-2005-224386 JP 2011-173758 A

  In order to put into practical use a method using chlorine dioxide gas in order to inactivate suspended microorganisms in the space, the present inventors have repeatedly studied a method for stably generating chlorine dioxide. As a result, although the methods described in Patent Document 2 and Patent Document 3 can control the generation of chlorine dioxide, the generation efficiency of chlorine dioxide is poor and a practical amount of chlorine dioxide is stably generated. I realized there was a problem that it was difficult.

  Furthermore, the present inventors, for example, in the method of generating chlorine dioxide that irradiates solid or gel chlorite with ultraviolet rays, as in the invention described in Patent Document 2, is the cause of poor generation efficiency of chlorine dioxide. Investigated. Then, unexpectedly, when a drug containing solid chlorite is irradiated with ultraviolet rays, not only chlorine dioxide but also ozone is generated, and this ozone is generated as a whole by interfering with chlorine dioxide. We have found that the amount of chlorine dioxide is decreasing (see also Example 1 and FIG. 3 herein).

  Based on the above findings, the present inventors have increased the amount of chlorine dioxide generated as a whole while suppressing the generation of ozone in a method of using a composition containing solid chlorite as a chlorine dioxide generation source. In order to make it happen, further examination was repeated. As a result, the amount of ozone generated is reduced by using light in the visible region (visible light) instead of ultraviolet light, which was previously considered essential for generating chlorine dioxide from solid chlorite. As a whole, the amount of chlorine dioxide generated was successfully increased to a practical level. Furthermore, the amount of chlorine dioxide generated from chlorite by mixing a metal catalyst or metal oxide oxide to compensate for the decrease in reactivity caused by using light in the visible region, which has lower energy than ultraviolet light. As a result, the present invention has been completed.

That is, the method of the present invention, in one embodiment, is a method for inactivating suspended microorganisms in space,
(1): (A) preparing a solid drug containing a porous material supporting chlorite and (B) a metal catalyst or a metal oxide catalyst;
Here, the mass ratio of the chlorite and the metal catalyst or metal oxide catalyst in the solid drug is 1: 0.04 to 0.8;
(2): irradiating the solid drug with visible light; and
(3): A method comprising: supplying chlorine dioxide gas generated from the solid drug to a space where airborne microorganisms exist.

  In one embodiment of the method of the present invention, the step (3) comprises the step of “supplying chlorine dioxide gas generated from the solid drug to a space where floating microorganisms are present, and chlorine dioxide gas in the space. The concentration is a step in which an animal can survive but the suspended microorganism is inactivated.

  In one embodiment, the method of the present invention is characterized in that the animal can survive, but the concentration at which the suspended microorganism is inactivated is 0.00001 ppm to 0.3 ppm.

  In one embodiment, the method of the present invention supplies the chlorine dioxide gas into the space when the chlorine dioxide gas concentration in the space is 0.1 ppm to 0.3 ppm in the step (3). The time is 0.5 minutes to 480 minutes.

  In one embodiment, the method of the present invention is characterized in that the floating microorganism is a floating virus or a floating bacterium.

  Moreover, in one embodiment, the method of the present invention is characterized in that the wavelength of visible light irradiated in the step (2) is 360 nm to 450 nm.

  In one embodiment, the method of the present invention is characterized in that the metal catalyst or metal oxide catalyst is selected from the group consisting of palladium, rubidium, nickel, titanium, and titanium dioxide.

  In one embodiment of the method of the present invention, the porous material is selected from the group consisting of sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, and pearlite, and the chlorite is chlorite. It is characterized by being selected from the group consisting of sodium acid, potassium chlorite, lithium chlorite, calcium chlorite, and barium chlorite.

  In one embodiment of the method of the present invention, the “porous material supporting chlorite” is obtained by impregnating a porous material with chlorite and further drying. Features.

  In one embodiment, the method of the present invention is characterized in that the porous material further carries an alkali agent.

  In one embodiment, the method of the present invention is characterized in that the alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and lithium carbonate. And

  Moreover, the method of this invention is characterized by the molar ratio of the said chlorite and the said alkali agent being 1: 0.1-2.0 in one embodiment.

  Further, in one embodiment of the method of the present invention, the “porous material carrying a chlorite and an alkali agent” is the same as that described above, wherein the chlorite and the alkali agent are simultaneously or sequentially converted into a porous material. It is obtained by impregnating and drying.

  In one embodiment of the method of the present invention, the water content of the porous material is 10% by weight or less.

In another embodiment, the method of the present invention is a method for inactivating suspended microorganisms in space, comprising:
(1): a step of preparing a unit for generating chlorine dioxide having the following configuration;
The unit includes a medicine container and at least two light sources.
The light source unit is for generating light having a wavelength in a visible region substantially,
In the medicine container, a medicine containing solid chlorite is housed,
The medicine container is provided with one or more openings so that air can move inside and outside the medicine container,
Here, chlorine dioxide gas is generated by irradiating the medicine existing inside the medicine storage part with the light generated from the light source part; and
(2): Supplying chlorine dioxide gas generated from the chlorine dioxide generating unit to a space where floating microorganisms are present.

  In one embodiment of the method of the present invention, the medicine storage part and the at least two light source parts are integrally arranged, and the at least two light source parts are stored in the medicine storage part. The medicine is irradiated with light from at least two directions.

  In one embodiment, the method of the present invention is characterized in that the wavelength of the irradiated light is 360 nm to 450 nm.

  In one embodiment, the method of the present invention is characterized in that the light source unit includes a lamp or a chip.

  In one embodiment, the method of the present invention is characterized in that the chip is an LED chip.

  In one embodiment of the method of the present invention, the light source unit is a light source unit capable of intermittently irradiating light.

  In one embodiment of the method of the present invention, the agent containing the solid chlorite is (A) a porous material supporting chlorite, and (B) a metal catalyst or metal oxidation. It is a chemical | medical agent containing a physical catalyst.

  In one embodiment, the method of the present invention is obtained by impregnating a porous material with a chlorite aqueous solution and further drying the “porous material supporting chlorite”. It is characterized by.

  In one embodiment, the method of the present invention is characterized in that the metal catalyst or metal oxide catalyst is selected from the group consisting of palladium, rubidium, nickel, titanium, and titanium dioxide.

  In one embodiment of the method of the present invention, the porous material is selected from the group consisting of sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, and pearlite, and the chlorite is chlorite. It is characterized by being selected from the group consisting of sodium acid, potassium chlorite, lithium chlorite, calcium chlorite, and barium chlorite.

  In one embodiment of the method of the present invention, in the drug in the drug container, the mass ratio of the chlorite to the metal catalyst or metal oxide catalyst is 1: 0.04 to 0. .8.

  In one embodiment, the method of the present invention is characterized in that the porous material further carries an alkali agent.

  In one embodiment, the method of the present invention is characterized in that the alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and lithium carbonate. And

  Moreover, the method of this invention is characterized by the molar ratio of the said chlorite in the said chemical | medical agent and the said alkali agent being 1: 0.1-2.0 in one embodiment.

  Further, in one embodiment of the method of the present invention, the “porous material carrying a chlorite and an alkali agent” is the same as that described above, wherein the chlorite and the alkali agent are simultaneously or sequentially converted into a porous material. It is obtained by impregnating and drying.

  Moreover, the method of this invention is implemented using the chlorine dioxide generator provided with the unit for chlorine dioxide generation in any one of said in another embodiment.

  Moreover, the chlorine dioxide generation apparatus used for the method of this invention is further equipped with the ventilation part for sending air to the chemical | medical agent accommodated in the said chemical | medical agent storage part in the said chlorine dioxide generation unit in one embodiment. It is characterized by that.

  In one embodiment, the chlorine dioxide generator used in the method of the present invention is a fan for the air blower to take in air from the outside to the inside of the chlorine dioxide generator, or of the chlorine dioxide generator. It is a fan for discharging air from the inside to the outside.

  Moreover, the chlorine dioxide generator used for the method 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 is sent from the blower. The air is sent to the medicine at least partially through an opening existing on a side surface of the medicine storage section.

  Moreover, the chlorine dioxide generator used for the method of this invention WHEREIN: In one embodiment, the relative humidity in the said chemical | medical agent storage part is kept at 30-80% RH by the air sent from the said ventilation part. Features.

  Needless to say, any combination of one or more of the features of the present invention described above from the viewpoint of those skilled in the art so as not to technically contradict is also included in the scope of the present invention.

  According to the method of the present invention, a practical amount of chlorine dioxide can be generated stably. In addition, the amount of chlorine dioxide generated can be easily adjusted by adjusting the amount of light to be irradiated. These effects have made it possible to stably supply chlorine dioxide gas into the space at a concentration at which animals can survive but the suspended microorganisms are inactivated.

FIG. 1 shows a longitudinal cross-sectional view of a unit for generating chlorine dioxide incorporating a drug containing solid chlorite. FIG. 2 is a longitudinal sectional view of a chlorine dioxide generator incorporating the chlorine dioxide generating unit of FIG. FIG. 3 is a graph showing changes in measured values of chlorine dioxide concentration and ozone concentration in the air when the wavelength of the irradiated light is changed in the case of irradiating light to a medicine containing solid chlorite. It 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 actually measured values of the chlorine dioxide concentration and the ozone concentration in FIG. 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 light is irradiated to the drug containing solid chlorite. FIG. 6 shows the amount of chlorine dioxide generated when the ratio of chlorite and titanium dioxide in a chemical containing solid chlorite and a metal catalyst or metal oxide catalyst (titanium dioxide) is changed. Showing change. FIG. 7 shows the content of titanium dioxide in a chemical containing solid chlorite and a metal catalyst or metal oxide catalyst (titanium dioxide), and the maximum value of the chlorine dioxide concentration generated by visible light irradiation. The relationship is shown. FIG. 8 shows changes in the amount of chlorine dioxide generated when a chemical containing solid chlorite and a metal catalyst or metal oxide catalyst (titanium dioxide) is continuously irradiated with visible light. FIG. 9 shows a perspective view, a top view, and a side view of a chlorine dioxide generating unit according to an embodiment of the present invention. FIG. 10 is a schematic view of a chlorine dioxide generator incorporating a unit for generating chlorine dioxide, which is an embodiment of the present invention. FIG. 11 shows a case in which light is emitted from only one light source part (one side) and two light source parts (both sides) in the chlorine dioxide generation unit according to one embodiment of the present invention. ) Shows a comparison of the amount of chlorine dioxide generated with light irradiation. FIG. 12 shows a case in which light is emitted from only one light source part (one side) and two light source parts (both sides) in the chlorine dioxide generation unit according to one embodiment of the present invention. The figure which plotted the ratio of the amount of chlorine dioxide generation with the case where light is irradiated from FIG. In addition, when light is emitted from two light source parts (both sides), the amount of chlorine dioxide generated is more than twice that when light is emitted from only one light source part (one side). For the sake of illustration, the chlorine dioxide generation amount in the case of single-sided irradiation for taking the ratio of the chlorine dioxide generation amount uses a double value. FIG. 13 shows a case where light is emitted from only two light sources (one side) when light is emitted from two light sources (both sides) in the chlorine dioxide generating unit according to an embodiment of the present invention. It is the figure explaining that light can be efficiently delivered to the chemical | medical agent in a chemical | medical agent storage part by comparison. FIG. 14 shows a change in the amount of chlorine dioxide generated when the relative humidity in the medicine container is changed in the chlorine dioxide generation unit according to the embodiment of the present invention. In addition, in FIG. 14, the data at the time of irradiating light from only one light source part (one side) are shown. FIG. 15 shows changes over time in the amount of chlorine dioxide generated when the relative humidity in the medicine container is changed in the chlorine dioxide generation unit according to the embodiment of the present invention. In addition, in FIG. 15, the data at the time of irradiating light from two light source parts (both surfaces) are shown. FIG. 16 shows the amount of chlorine dioxide generated when light is intermittently irradiated from two light source parts (both sides) to the medicine in the medicine storage part in the chlorine dioxide generation unit according to one embodiment of the present invention. The changes over time are shown. In the figure, “10s / 80s” means that 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 is repeated. Similarly, in the figure, “20s / 80s” means that irradiation continues for 2 minutes from the start of irradiation, irradiation for 20 seconds (LED is turned on) after 2 minutes from the start of irradiation, and irradiation of light for 80 seconds is stopped. (30 s / 80 s) indicates that light irradiation is continued for 2 minutes from the start of irradiation, and light is irradiated for 30 seconds after the start of irradiation (LED is turned on). It shows that the cycle of stopping light irradiation for 80 seconds (LED OFF) was repeated. FIG. 17 shows a schematic diagram of an experiment for inactivating suspended microorganisms in the space using the method of the present invention. FIG. 18 shows the change in virus titer in the air of the chamber with a chlorine dioxide concentration of about 0.05 ppmv. FIG. 19 shows the change in virus titer in the air of the chamber where the chlorine dioxide concentration was about 0.1 ppmv. FIG. 20 shows the change in virus titer in the air of the chamber with a chlorine dioxide concentration of about 0.3 ppmv. FIG. 21 shows the change in virus titer in the air of the chamber with a chlorine dioxide concentration of about 0.3 ppmv. FIG. 22 shows a schematic diagram of the experiment of Example 9. FIG. 23 shows the results of the experiment of Example 9. FIG. 24 shows a schematic diagram of the experiment of Example 10. FIG. 25 shows the results of the experiment of Example 10.

In one embodiment, the method of the present invention is a method for inactivating suspended microorganisms in space, comprising:
(1): (A) preparing a solid drug containing a porous material supporting chlorite and (B) a metal catalyst or a metal oxide catalyst;
Here, the mass ratio of the chlorite and the metal catalyst or metal oxide catalyst in the solid drug is 1: 0.04 to 0.8;
(2): irradiating the solid drug with visible light; and
(3): supplying chlorine dioxide gas generated from the solid drug to a space where airborne microorganisms are present.

  The space to which the present invention can be applied is not particularly limited, and can be applied to any space that can be in a closed state or an open state. For example, according to the present invention, chlorine dioxide gas can be supplied at a concentration at which the animal can survive but the suspended microorganisms are inactivated. Therefore, the present invention can be applied to a space where an animal exists. More specifically, the present invention can be applied to living spaces (eg, residences, offices), medical institutions (eg, hospital waiting rooms, examination rooms, treatment rooms, operating rooms, anterior rooms, hospital rooms), research institutions (eg, , University laboratories, front rooms), disaster medical facilities (eg, disaster containers, tents), public facilities (eg, stations, airports, schools), vehicles (eg, private cars, buses, trains, airplanes) Can be applied within.

The floating microorganism in the method of the present invention broadly means a microorganism that can float in the space,
Examples include airborne viruses, airborne bacteria, and airborne fungi. Airborne viruses include enveloped or non-enveloped viruses such as varicella / zoster virus, influenza virus (human, bird, swine, etc.), herpes simplex virus, adenovirus, enterovirus, rhinovirus, human papillomavirus (human) Papillomavirus), box virus, coxsackie virus, herpes simplex virus, cytomegalovirus, EB virus, adenovirus, papilloma virus, JC virus, parvovirus, hepatitis B virus, hepatitis C virus, lassa virus, feline calicivirus, Norovirus, Sapovirus, Coronavirus, SARS virus, Rubella virus, Mumps virus, Measles virus, RS virus, Poliovirus, Coxsackie virus , Echovirus, Marburg virus, Ebola virus, yellow fever virus, Bunyaviridae virus, rabies virus, reoviridae virus, rotavirus, human immunodeficiency virus, human T lymphophilic virus, simian immunodeficiency virus, STLV Etc. In addition, as floating bacteria, Gram-positive bacteria or Gram-negative bacteria, such as Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, Escherichia coli, Streptococcus, Neisseria gonorrhoeae, syphilis, meningococcus, tuberculosis, acid-fast bacilli, Examples include Klebsiella (Klebsiella pneumoniae), Salmonella, Clostridium botulinum, Proteus, Bordetella pertussis, Serratia, Vibrio parahaemolyticus, Citrobacter, Acinetobacter, Campylobacter, Enterobacter, Mycoplasma, Chlamydia, Clostridium and the like. Furthermore, examples of the floating fungi include Aspergillus, ringworm, Malassezia, and Candida.

  When chlorine dioxide gas is supplied into the space using the method of the present invention, the chlorine dioxide gas concentration in the space is preferably a concentration at which, for example, animals can survive but the suspended microorganisms are inactivated. In the present invention, the animal can survive, but the chlorine dioxide gas concentration at which suspended microorganisms are deactivated may be, for example, 0.00001 ppm to 0.3 ppm, preferably 0.0001 ppm to 0.3 ppm. It may be 0.001 ppm to 0.3 ppm, more preferably 0.01 ppm to 0.3 ppm, and most preferably 0.1 ppm to 0.3 ppm.

  Although the time for supplying chlorine dioxide gas into the space using the method of the present invention is not particularly limited, the supply time may be appropriately adjusted according to the chlorine dioxide gas concentration to be supplied. For example, when the chlorine dioxide gas concentration in the space is set to 0.00001 ppm to 0.01 ppm, there is no problem even if the chlorine dioxide gas is continuously supplied. When the chlorine dioxide gas concentration in the space is 0.01 ppm to 0.1 ppm, the time for supplying the chlorine dioxide gas into the space is preferably 10 minutes to 480 minutes, and preferably 15 minutes to 90 minutes. More preferably, it is more preferably 15 minutes to 60 minutes. When the chlorine dioxide gas concentration in the space is 0.1 ppm to 0.3 ppm, the time for supplying the chlorine dioxide gas to the space is preferably 0.5 minutes to 480 minutes, preferably 1 minute to 60 minutes is more preferable, and 2 minutes to 15 minutes is even more preferable.

  Examples of the chlorite used in the method of 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. Examples of the alkaline earth metal chlorite include calcium chlorite, magnesium chlorite, Barium chlorate is mentioned. Of these, sodium chlorite and potassium chlorite are preferable and sodium chlorite is most preferable from the viewpoint of easy availability. These chlorites may be used individually by 1 type, and may use 2 or more types together.

  The porous material used in the method of the present invention can be used, for example, sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, etc., but when suspended in water in order not to decompose chlorite. Those showing alkalinity are preferred, palygorskite and sepiolite are more preferred, and sepiolite is particularly preferred.

  In the method of the present invention, a porous material supporting chlorite is used, but the method for supporting chlorite on the porous material is not particularly limited. For example, the “porous material supporting chlorite” can be obtained by impregnating a porous material with a chlorite aqueous solution and drying it. The water content of the “porous material supporting chlorite” is preferably 10% by weight or less, and more preferably 5% by weight or less.

  The “porous material supporting chlorite” used in the method of the present invention may have any particle size, but particularly those having an average particle size of 1 mm to 3 mm are suitable. Can be used for

  The average particle size of the “porous material supporting chlorite” in the method of the present invention is measured, for example, by measuring the particle size of the “porous material supporting chlorite” used by an optical microscope, It can be calculated by performing statistical processing and calculating an average value and a standard deviation.

  The concentration of chlorite in the “porous material supporting chlorite” used in the method of the present invention is effective at 1% by weight or more, but when it exceeds 25% by weight, it becomes a deleterious substance. Since it corresponds, 1 to 25 weight% is preferable and it is more preferable that it is 5 to 20 weight%.

  Examples of the metal catalyst or metal oxide catalyst used in the method of the present invention include palladium, rubidium, nickel, titanium, and titanium dioxide. Of these, titanium dioxide is particularly preferably used. Titanium dioxide is sometimes 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. A person 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 ratio of metal catalyst or metal oxide catalyst in the drug When is relatively low, a powdery metal catalyst or a metal oxide catalyst can be selected, but is not limited thereto.

  In the present specification, as an approximate standard for the size of “powder” or “granular”, for example, powder refers to a solid having an average particle diameter of 0.01 mm to 1 mm, “Granular” means a solid 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 solid drug used in the method of the present invention is chlorite: metal catalyst or metal oxide catalyst = 1: 0.04. It may be -0.8, Preferably it may be 1: 0.07-0.6, More preferably, it may be 1: 0.07-0.5. In the drug, when the content of the metal catalyst or metal oxide catalyst exceeds 1 times the content of chlorite and when the content of metal catalyst or metal oxide catalyst is 0% of the content of chlorite In any case of less than .04 times, the amount of chlorine dioxide generated when irradiated with visible light can be reduced.

  The “porous material carrying chlorite” used in the method of the present invention may further carry an alkali agent.

  The alkaline agent used in the preparation of the drug used in the method of the present invention is, 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 alkali agent on the “porous material supporting chlorite”, 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. Unnecessary chlorine dioxide emission during storage can be suppressed.

  The amount of the alkaline agent used in the preparation of the drug used in the method of the present invention is suitably 0.1 equivalent or more and 2.0 equivalent or less with respect to chlorite (mol), preferably 0.1 The amount is not less than 1.0 equivalent and not more than 1.0 equivalent, more preferably not less than 0.1 equivalent and not more than 0.7 equivalent. If it is less than 0.1 equivalent, the supported chlorite may be decomposed even at room temperature, and if it exceeds 2.0 equivalent, stability is improved, but chlorine dioxide is less likely to be generated and the generated concentration is decreased, which is preferable. Absent.

  In the preparation of the drug used in the method of the present invention, the method of further supporting an alkali agent on the “porous material supporting chlorite” is not particularly limited, but for example, chlorite and alkali agent, A method of impregnating and drying the porous material simultaneously or sequentially may be used. In the present specification, the target composition may be obtained by “spray-adsorbing” a chlorite aqueous solution and / or an alkaline agent on a porous material and drying, but in this specification, The term “spray adsorption” is intended to be included in the term “impregnation”.

In another embodiment, the method of the present invention is a method for inactivating suspended microorganisms in space, comprising:
(1): a step of preparing a unit for generating chlorine dioxide having the following configuration;
The unit includes a medicine container and at least two light sources.
The light source unit is for generating light having a wavelength in a visible region substantially,
In the medicine container, a medicine containing solid chlorite is housed,
The medicine container is provided with one or more openings so that air can move inside and outside the medicine container,
Here, chlorine dioxide gas is generated by irradiating the medicine existing inside the medicine storage part with the light generated from the light source part; and
(2): providing a chlorine dioxide gas generated from the chlorine dioxide generating unit to a space where floating microorganisms are present.

  The unit for generating chlorine dioxide used in the method 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 at least two light source units. The positional relationship is particularly limited as long as it can irradiate light from at least two directions (for example, 2, 3, 4, 5, 6 or more directions) with respect to the drug that is a generation source of chlorine dioxide. Not. Preferably, the at least two light source units are arranged at symmetrical positions with respect to the medicine that is a generation source of chlorine dioxide.

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

  The fact that the wavelength of light generated from the light source is substantially included in the range of the specific wavelength region can be confirmed by measuring the wavelength and energy of the light generated from the light source with a known measuring device.

  The light source used in the method of the present invention is not particularly limited as long as it generates light having a wavelength in the visible region. For example, a lamp (incandescent lamp, LED lamp), chip, or laser device that generates light in the visible region. Various things can be used. From the viewpoint of directivity of light generated from the light source and from the viewpoint of miniaturization of the apparatus, it is preferable to use a chip 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 the object to be irradiated without diffusing light, and to improve the chlorine dioxide generation efficiency of the apparatus. Further, from the viewpoint of limiting the wavelength of light generated from the light source and not including light in the ultraviolet region or infrared region, it is preferable to use an LED that generates 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 generates light in the visible region from the viewpoint of downsizing the apparatus and the generation efficiency of chlorine dioxide.

  Moreover, the light source used in the method of the present invention may be a light source capable of intermittently irradiating light. For example, the light source used in the method of the present invention may be a light source that repeats a cycle of irradiating light for a certain time and then stopping light irradiation for a certain time. A method for controlling the light source for intermittently irradiating light is not particularly limited, and a person skilled in the art can use a known method. That is, in the method of the present invention, the step of irradiating the solid drug with visible light may be a step of intermittently irradiating the solid drug with visible light.

  The light source part and the medicine storage part of the chlorine dioxide generation unit used in the method of the present invention may be arranged integrally or separately, but are stored in the medicine storage part. In order to efficiently irradiate the light generated from the light source unit to the medicine that is present, it is preferable that the medicines are integrally disposed. Here, the light source unit and the medicine storage unit may be integrally disposed or connected in an inseparable manner, or may be integrally disposed or connected in a separable manner. When the light source unit and the medicine storage unit are integrally arranged or connected in a separable manner, the medicine storage unit may be a replaceable cartridge.

  The medicine container used in the method of the present invention is not limited in its material and structure as long as one or a plurality of openings are provided so that air can move inside and outside. For example, by using a known light-transmitting material as the material of the medicine container (particularly the surface directly irradiated with light from the light source part in the medicine container), the light emitted from the light source part can be reduced. It is possible to irradiate the medicine inside the medicine container. Preferably, the material of the medicine container is made of a resin that substantially transmits light in the visible region, so that the light generated from the light source part is not absorbed by the resin but irradiated to the medicine inside the medicine container. Is 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 light having a wavelength in the visible region that is irradiated. Further, it may be a resin that transmits 90% or more of light having a wavelength in the visible region, and more preferably a resin that transmits 95% or more of light having a wavelength in the visible region that is irradiated. Specifically, as a material for a surface directly irradiated with light from the light source unit in the medicine storage unit, for example, an acrylic material, a vinyl chloride material, or a PET material can be used. Not.

  In addition, for example, the medicine container can be configured by a mesh plate having a mesh that prevents the stored items from falling down. According to such a configuration, the air outside the medicine container can move between the inside and outside of the medicine container, and the light generated from the light source part passes through the mesh to the medicine inside the medicine container. Irradiated.

  Moreover, the 1 or several opening part of the chemical | medical agent storage part used in the method of this invention may be covered with the air permeable sheet. In this specification, a “breathable sheet” allows gas (eg, air, gas, moisture, etc.) to pass therethrough but substantially passes a solid substance (eg, powdery object, granular object). It means a sheet-like structure that is not allowed. The “breathable sheet” in the present invention may further have a property of substantially not allowing liquid (for example, water droplets) to pass therethrough. The material of the breathable sheet in the present invention is not limited. For example, a material formed into a sheet shape by bonding or intertwining fibers by a thermal, mechanical or chemical action, a microporous film (many very small pores) A single material or a stack of multiple materials, a non-porous material that can move gas, air, and moisture (water vapor), and a high-density fabric. Examples thereof include a coating-type material subjected to water treatment, or a material formed by combining these materials. More specifically, as the breathable sheet in the present invention, for example, non-woven fabric (Elves (registered trademark, manufactured by Unitika Co., Ltd.), Axter (registered trademark, manufactured by Toray Industries, Inc.)), Gore-Tex (registered trademark) and Excel ( Registered trademark, manufactured by Mitsubishi Plastics Co., Ltd .: Uses a material with excellent breathability, moisture permeability, and waterproof properties combining microporous polyolefin film and various non-woven fabrics, etc., and entrant E (registered trademark, manufactured by Toray Industries, Inc.) Can do. In addition, in order to make it easy to attach the air permeable sheet in this invention to a chemical | medical agent storage part, it is desirable to provide the heat seal property (thermal welding property).

The shape and thickness of the air permeable sheet used in the medicine storage section is such that the gas permeable sheet allows gas, air, and moisture to permeate at the boundary between the inside and outside of the medicine storage section. Those skilled in the art can appropriately select the object as long as the object of “not allowing the object to pass” can be achieved. For example, when a nonwoven fabric is used as the breathable sheet, the basis 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. A thickness of 0.0 mm (preferably 0.2 to 0.5 mm, more preferably 0.2 to 0.4 mm) can be used.

  In one embodiment, the method of the present invention may be carried out using a chlorine dioxide generator comprising the chlorine dioxide generating unit of the present invention. The chlorine dioxide generator used in the method of the present invention may further include a blower for sending air to the medicine stored in the medicine storage of the chlorine dioxide generating unit. The air blowing section may be for taking in air from the outside to the inside of the apparatus, or may be for discharging air from the inside of the apparatus to the outside.

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

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

  In the chlorine dioxide generator used in the method of the present invention, another method for supplying water vapor in the air into the medicine container is a Peltier element (Peltier element) that condenses and collects moisture in the air. (Effect) can also be used (the disadvantages of Peltier elements that cause intrusion and condensation of water vapor can be reversed and used to increase humidity).

  The method for controlling the relative humidity in the apparatus is not particularly limited, and can be appropriately performed by those skilled in the art using known techniques. For example, a relative humidity can be controlled by adjusting the amount of air blown from the blower unit or adjusting the amount of moisture absorbed by the Peltier element while monitoring the amount of moisture provided in the device body. It's okay.

  Moreover, since the unit for generating chlorine dioxide used in the method of the present invention is small, the method of the present invention can also be implemented by incorporating it into household appliances that do not mainly generate chlorine dioxide. For example, the present invention can also be implemented by incorporating a unit for generating chlorine dioxide used in the method of the present invention into a home appliance that does not mainly generate chlorine dioxide and supplying chlorine dioxide gas. For example, by incorporating a unit for generating chlorine dioxide used in the method of the present invention into an air conditioning facility such as a heating device, a cooling device, an air cleaner, a humidifier, etc., a chlorine dioxide generating unit is produced by the effect of the wind released from the air conditioning facility The generation of chlorine dioxide in the air can be promoted, and the chlorine dioxide can be efficiently diffused into the space on the wind released from the air conditioning equipment to the space.

  The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting of the invention.

  In addition, the term “comprising” as used in this specification intends that there is a matter (a member, a step, an element, a number, or the like) described unless the context clearly requires different understanding. It does not exclude the presence of other items (members, steps, elements, numbers, etc.).

  Unless otherwise defined, 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. Terms used herein should be construed as having a meaning consistent with the meaning in this specification and the related technical field, unless otherwise defined, idealized, or overly formal. It should not be interpreted in a general 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 this specification, for example, when expressed as “1 to 10%”, those skilled in the art will recognize that the expression is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%. Understand what it refers to individually.

  In this specification, any numerical value used to indicate component content or numerical range is to be interpreted as including the meaning of the term “about” unless otherwise indicated. For example, “10 times” is understood to mean “about 10 times” unless otherwise specified.

  References cited in this specification are to be regarded as the entire disclosure of which is hereby incorporated by reference, and those skilled in the art will recognize the spirit of the invention in accordance with the context of this specification. And without departing from the scope, the relevant disclosures in those prior art documents are incorporated and understood as part of the present specification.

In the following, the present invention will be described in more detail with reference to examples. However, the invention can be embodied in various ways and should not be construed as limited to the embodiments set forth herein.

Example 1: Change in chlorine dioxide generation amount depending on the wavelength of light to be irradiated In this example, a test was performed using the chlorine dioxide generation unit and the chlorine dioxide generator shown in FIGS. 1 and 2.

  FIG. 1 is a longitudinal sectional view showing an internal structure of a medicine storage part and a light source part of a unit for generating chlorine dioxide 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) that generates light in the visible region. The medicine container 11 includes a test medicine 14. The medicine container 11 includes an opening 16 so that air can move inside and outside. The unit 10 for generating chlorine dioxide includes a tube 15 for guiding air outside the apparatus into the apparatus.

  Air introduced from the tube 15 is supplied to the inside of the medicine container 11 through the opening 16. Water vapor contained in the supplied air is taken into chlorite in the test agent 14. The light in the visible region generated from the light source unit passes through the bottom surface of the drug container 11 and is irradiated to the test drug 14 present inside the drug container 11. Chlorite containing water vapor reacts with the irradiated light to generate chlorine dioxide. Titanium dioxide contained in the test agent 14 together with chlorite promotes 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 longitudinal sectional view showing the entire structure of the chlorine dioxide generator used in this example. As shown in FIG. 2, the chlorine dioxide generator 20 includes a chlorine dioxide generating unit 21 therein. The apparatus main body 22 of the chlorine dioxide generator 20 includes an air supply port 23 for introducing air outside the apparatus into the apparatus, and an air discharge port 25 for discharging air inside the apparatus to the outside of the apparatus. Further, the chlorine dioxide generator 20 includes a fan 24 in order to efficiently introduce air into the apparatus.

  By driving the fan 24, air is introduced from the air supply port 23 into the apparatus main body 22. 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 generating unit 21, chlorine dioxide is generated by the same mechanism as that of the apparatus shown in FIG. 1, and therefore the air discharged from the air outlet 25 contains chlorine dioxide.

  After 70 g of 10 wt% sodium chlorite aqueous solution was sprayed and adsorbed on 100 g of sepiolite and dried, 20 g of 10 wt% aqueous sodium hydroxide solution was further adsorbed and dried. This was mixed with 20 g of powdered titanium dioxide prepared by subjecting titanium powder to a baking treatment to obtain a test agent used in this example.

  The drug was stored in the drug container in the chlorine dioxide generator shown in FIG. Air was introduced into the drug container from the opening of the drug container at 1 L / min, and light was applied to the drug in the drug container from the LED chip. The wavelength of light emitted from the LED chip was changed every 2 nm from 80 nm to 430 nm, and the chlorine dioxide concentration and the 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 FIG. 3 and FIG. In this test, a frequency counter (MCA3000, Tektronix), a spectrum analyzer (BSA, Agilent Technologies), a wavelength sweep light source (TSL-510, Suntech), a UV integrated light meter (UIT-250, Ushio) Electric Co., Ltd.), and a UV integrated light meter receiver (VUV-S172, UVD-C405, USHIO INC.).

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

  As shown in FIG. 3, when the wavelength of 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 chlorine dioxide concentration in the air increases from the ultraviolet region to the visible region. From this result, a person skilled in the art can use the wavelength range suitably used in the present invention without problems even at a wavelength of at least about 450 nm, for example, exceeding the upper limit of the measurement range of the present example, 430 nm. I can understand that.

  Furthermore, as shown in FIG. 4, when comparing the average values of ozone concentration and 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, irradiating solid chlorite and a mixture of metal catalysts or metal oxide catalysts with visible light produces chlorine dioxide much more efficiently than ultraviolet light. I found out that

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

  Each of the drugs (samples 1 to 3) prepared by the above method was stored in the drug container of the chlorine dioxide generator described in Example 1. For sample 1 and sample 2, air was introduced into the apparatus at 1 L / min from the opening of the medicine container, and 405 nm light was irradiated from the LED chip of the light source. For sample 3, air was only introduced into the apparatus at 1 L / min from the opening of the medicine container, and no light was 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 is mixed in the drug (sample 1) is more efficient than the case where powdery titanium dioxide is mixed in the drug (sample 2). It has been found that chlorine can be generated.

Example 3: Examination of the content ratio of chlorite and titanium dioxide in the drug After 70 g of 10 wt% sodium chlorite aqueous solution was spray-adsorbed on 100 g of sepiolite and dried, another 20 g of 10 wt% sodium hydroxide aqueous solution was sprayed. Adsorbed and dried. To this, powdery titanium dioxide was mixed in various amounts to obtain a test agent used in this example. The test drug 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 graph showing changes in the amount of chlorine dioxide generated when the ratio of chlorite and titanium dioxide in the composition of the present invention is changed. 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 1 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 concentration of chlorine dioxide generated by visible light irradiation.

  As shown in FIGS. 6 and 7 and Table 1, the amount of chlorine dioxide generated when the test drug is irradiated with visible light is such that the mass ratio of titanium dioxide to chlorite in the drug is 0 to about 0.001. 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. Furthermore, it was 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 when titanium dioxide is not mixed.

  FIG. 8 is a diagram showing a change in the amount of chlorine dioxide generated when the test drug of this example is continuously irradiated with visible light for a long time. As shown in FIG. 8, even when observed over a long period of time, the mixing ratio (mass ratio) of chlorite and titanium dioxide in the test drug is 1: When 0.04 to 0.8 (preferably 1: 0.07 to 0.6, more preferably 1: 0.07 to 0.5), the mixing ratio is compared with other ranges. As a result, it was confirmed that high concentration of chlorine dioxide could be released stably.

Example 4 Examination of Sandwich Structure of Light Source Unit The effectiveness of the sandwich structure of the light source unit in the present invention was tested. In this example, an experiment was performed using the unit for generating chlorine dioxide shown in FIG. 9 and the chlorine dioxide generator shown in FIG.

  FIG. 9 is a diagram showing the internal structure of the unit 30 for generating chlorine dioxide, 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 medicine container 32 and a light source unit (electronic substrate 33 and LED chip 34) that generates light in the visible region. The medicine container 32 contains a medicine containing solid chlorite inside. The medicine container 32 includes openings (a gas generation port 31 and an air introduction port 36) so that air can move inside and outside.

  The air introduced from the air introduction part 36 is supplied into the medicine storage part 32. The water vapor contained in the supplied air is taken into the test medicine stored in the medicine storage section 32. The light in the visible region generated from the light source unit passes through the exterior portion 35 of the medicine storage unit 32 and is applied to the medicine stored in the medicine storage unit 32. 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 31.

  FIG. 10 is a view 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 generator 40 of this invention is equipped with the unit for a chlorine dioxide generation (LED chip mounting substrate 41 and chemical | medical agent storage part 42) which is one Embodiment of this invention inside. The chlorine dioxide generator further includes a blower fan 44 inside, and supplies air into the chlorine dioxide generation unit by driving the blower fan 44. By adjusting the driving of the blower fan 44, the relative humidity in the medicine container in the chlorine dioxide generating unit can be adjusted.

  By driving the blower fan 44, air is supplied from the air inlet of the chlorine dioxide generating unit to the inside of the medicine container. The water vapor contained in the supplied air is taken into the test drug stored in the drug storage unit. The light in the visible region generated from the light source part is transmitted through the exterior part of the medicine storage part, and is applied to the medicine stored in the medicine storage part. 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.

After 70 g of 10 wt% sodium chlorite aqueous solution was sprayed and adsorbed on 100 g of sepiolite and dried, 20 g of 10 wt% aqueous sodium hydroxide solution was further adsorbed and dried. This was mixed with about 1.8 g of powdered titanium dioxide to obtain a test agent used in this example. The prepared test drug was stored in the drug storage section of the chlorine dioxide generating unit shown in FIG. 9, and irradiated with visible light from the ^two light source sections (each 100 mm ² ). This test was performed in a 1 m ³ chamber, 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 one surface (one surface) of the light source was irradiated with visible light.

  In the example and the comparative example, the result of measuring the change over time of the chlorine dioxide concentration in the chamber is shown in FIG. In addition, FIG. 12 shows the ratio of the chlorine dioxide concentration in the chamber between the example and the comparative example at each time from the start of irradiation. In FIG. 12, when light is emitted from two light source parts (both sides), the amount of chlorine dioxide generated is twice that when light is emitted from only one light source part (one side). In order to show the above, the chlorine dioxide generation amount in the case of single-sided irradiation for taking the ratio of the chlorine dioxide generation amount uses a double value.

  As shown in FIG. 11 and FIG. 12, when visible light is irradiated from two light source parts (both sides), surprisingly, compared with the case where visible light is irradiated from only one light source (one side), It was shown that the amount of chlorine dioxide generated is more than doubled. Furthermore, 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 increases with the passage of time.

  The above results can be explained by FIG. In other words, the light intensity decreases exponentially as light passes through the medium. Therefore, irradiation from only one side makes it difficult for light to reach the inside or the back of the drug, and the light is efficiently transmitted to the entire drug. Irradiation is difficult. However, by irradiating the drug with light from two directions (or more than two directions), it becomes possible to supply the amount of light required for the reaction to the inside of the drug, and generate chlorine dioxide efficiently. It became possible to make it.

Example 5: Examination of the relative humidity of the medicine container Using the chlorine dioxide generating unit shown in FIG. 9 and the chlorine dioxide generator shown in FIG. 10, chlorine dioxide is generated by the relative humidity in the medicine container. Changes in the amount were examined.

  The same conditions as in Example 4 were used for measuring the drug stored in the drug storage unit, the visible light irradiation method, and the chlorine dioxide concentration. The relative humidity in 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 the blower fan. 14 and 15 show the relationship between the relative humidity in the medicine container and the chlorine dioxide concentration in the chamber. FIG. 14 shows the average value of the chlorine dioxide concentration measured several times during the light irradiation of 0.5 to 2 hours and its standard deviation, and FIG. 15 shows the change over time of the 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 can. In addition, when the relative humidity in the medicine container is less than 30%, water necessary for the reaction of generating chlorine dioxide from chlorite is insufficient, and when the relative humidity is higher than 80%, it is generated in condensed water. As chlorine dioxide dissolves, the amount of chlorine dioxide released as gas is thought to decrease.

  Moreover, 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 with the case of, even if the time from the start of irradiation elapses, the concentration of released chlorine dioxide can be kept high. Even when the relative humidity is 20%, the chlorine dioxide concentration at the beginning of irradiation is considered to be high because some amount of water is contained in the medicine itself before the start of irradiation.

Example 6: Examination of usefulness of intermittent irradiation Using the unit for generating chlorine dioxide shown in FIG. 9, the usefulness of intermittent irradiation of visible light in the present invention was examined.

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

(1) The light is continuously irradiated for 2 minutes from the start of irradiation, and after 2 minutes from the start of irradiation, the light is irradiated for 10 seconds (LED is turned on) and the light irradiation is stopped for 80 seconds (the LED is turned off). It was.
(2) Repeated the cycle of irradiating light for 2 minutes from the start of irradiation, irradiating light for 20 seconds (LED is turned on) and stopping light irradiation for 80 seconds (LED is turned off) after 2 minutes from the start of irradiation. It was.
(3) The light irradiation is continued for 2 minutes after the start of irradiation, and after 2 minutes from the start of irradiation, the light is irradiated for 30 seconds (LED is turned on) and the light irradiation is stopped for 80 seconds (the LED is turned off). 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, it was possible to generate chlorine dioxide having a desired concentration by intermittently irradiating visible light from the light source unit and adjusting the balance between the irradiation time and the stop time in the intermittent irradiation. .

  Further, in the present invention, by intermittently irradiating visible light from the light source part, it was possible to prevent a relatively high concentration of chlorine dioxide from being released at the beginning of irradiation. When visible light is continuously emitted from the light source unit (that is, when intermittent irradiation is not performed), for example, as shown in the graph of FIG. 6, the chlorine dioxide generation concentration becomes maximum at the beginning of irradiation, and then gradually decreases. That is, in the present invention, chlorine dioxide can be released more stably by intermittently irradiating visible light from the light source unit.

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

Example 7: Deactivation of suspended microorganisms using a chlorine dioxide generator (1)

  In order to prove that the chlorine dioxide generator incorporating the unit for generating chlorine dioxide of the present invention can be effectively used to inactivate suspended microorganisms in the space, the following experiment was conducted.

1. Experimental materials and equipment (test virus)
Escherichia coli phage phiX174 (NBRC 103405)
(Host fungus)
Escherichia coli (NBRC 13898)
(Gas generator)
Chlorine dioxide generator (laboratory equipment) incorporating the unit for generating chlorine dioxide of the present invention
1m ³ chamber (custom product)
14ml Tube (352059, FALCON)
AZE (INO-001, IWAKI)
AC FAN (MU1225S-11, ORIX)
Nebulizer (NE-C29, OMRON)
Hepa filter for exhaust (ultra-small special filter for exhaust, OSHIARI LABORATORY)
Impinger (Biosampler, 5 ml, SKC)
(Experimental equipment)
Shaking incubator (AT12R, THOMAS)
Chlorine dioxide gas sensor (ClO ₂ 1000ppb, INTERSCAN)
Chlorine dioxide gas sensor (Midas GAS Detector, ClO ₂ MIDAS-E-BR2, Honeywell)
Particle counter (KC-52, RION)
Air filter for particle removal (MAC-11FR-UL, Nippon Airtech)
Spectrophotometer (V-560, JASCO)
Thermostatic bath (MCO-175, SANYO)
Air pump (SPP-25GA, TECHNO TAKASUKI)
Thermo-hygrometer (PC-5000TRH, SATO)
Ion chromatograph (HIC-20ASP, SHIMADZU)
(Experimental material)
NB medium (234000, Nutrient Broth, Difco)
702 medium (polypeptone 10 g, yeast extract 2 g, magnesium sulfate heptahydrate 1 g, distilled water 1 L)
Ordinary agar medium (E-MP21, Eiken Chemical)
Agar (Bacto Agar 21410, BD)

2. Experimental method (adjustment of test virus solution)
The pre-cultured stock strain Escherichia coli was inoculated into 5 ml of NB + 0.5% NaCl liquid medium and cultured with shaking at 30 ° C. and 200 rpm for 6 hours. After incubation, Escherichia coli (about 1 × 10 ⁹ cells / ml) (100 μl) and phase phiX174 (about 1 × 10 ⁵ PFU / ml) in NB + 0.5% NaCl liquid medium (500 μl) were mixed and incubated at 37 ° C. for 5 minutes. 3 ml of NB + 0.5% NaCl medium (0.6% agar) was added to the mixture and mixed, and the mixture was overlaid on a normal agar medium and cultured at 37 ° C. for 18 hours. The top agar was recovered by adding 2 ml of NB + 0.5% NaCl liquid medium, and filtered through a 0.22 μm filter, and stored at −85 ° C. A part thereof was subjected to a plaque assay according to a conventional method to obtain a virus solution of about 1 × 10 ¹⁰ PFU / ml. A virus frozen at −85 ° C. before the test was thawed and diluted 10-fold with distilled water to obtain a test virus solution (spray solution; 1 × 10 ^{8 to 9} PFU / ml).

(experimental method)
An outline of the experiment in this example is shown in FIG.
1 m ³ established the chlorine dioxide generator of the present invention in the central portion of the chamber, on the device by the timer, by operating at a controlled off, the chlorine dioxide gas concentration in the chamber 0.05, 0.1, Or it adjusted so that it might become 0.3 ppmv. Using a nebulizer, phiX174 phage virus (about 1 × 10 ^{8 to 9} PFU / ml) was sprayed at a rate of 0.2 ml / min for 5 minutes in a chamber where the gas concentration was stable. In a chamber with a chlorine dioxide concentration of about 0.05 ppmv, after 0, 30, 60, 75, 90 minutes, in a chamber with a chlorine dioxide concentration of about 0.1 ppmv, 0, 15, 30, 45, 60 minutes. Later, in a chamber having a chlorine dioxide concentration of about 0.3 ppmv, after 0, 5, 10, 15, and 30 minutes, air containing virus was collected using an impinger. The collected virus was subjected to a plaque assay, and the number of viruses in 10 L of air was determined and evaluated. Similarly, a control in which the LED of the chlorine dioxide generator was always turned off was used as a control.

(Monitoring of chlorine dioxide gas concentration)
Chlorine dioxide gas concentration of 1 m ³ chamber was monitored by chlorine dioxide gas sensor. The concentration value of the chlorine dioxide gas sensor was corrected in comparison with the gas concentration value obtained by ion chromatography.

3. Results Figure 18 shows the change in virus titer in the air of the chamber with a chlorine dioxide concentration of about 0.05 ppmv, and Figure 19 shows the change in virus titer in the air of the chamber with a chlorine dioxide concentration of about 0.1 ppmv. FIG. 20 shows the change in virus titer in the air in the chamber where the chlorine dioxide concentration was about 0.3 ppmv. The experiment shown in FIG. 18 was performed under the conditions of temperature: 23.1 ± 0.2 ° C. and relative humidity: 57.2 ± 0.4%, and the experiment shown in FIG. The experiment shown in FIG. 20 was conducted at a temperature of 23.1 ± 0.3 ° C. and a relative humidity of 59.3 ± 0. Performed under 5% condition.

In the control experiment in which the LED of the chlorine dioxide generator of the present invention was always turned off, the virus titer was 1.5 × 10 ⁵ PFU / 10L in 75 minutes (FIG. 18), and 9.3 × 10 ^{4 in} 45 minutes. PFU / 10L (FIG. 19), 1.2 × 10 ⁶ PFU / 10L (FIG. 20) in 15 minutes.

On the other hand, when the LED of the chlorine dioxide generator is turned on and the chlorine dioxide gas concentration is set to 0.05 ppmv, the virus titer becomes 8.3 × 10 ² PFU / 10L after 75 minutes of exposure, and the control (1. 2 log ₁₀ or more (99% or more) with respect to 5 × 10 ⁵ PFU / 10 L) (FIG. 18).

When the chlorine dioxide gas concentration was 0.08 ppmv, the virus titer was 2.0 × 10 ² PFU / 10 L after an exposure time of 45 minutes, and ² log _{10 with} respect to the control (9.3 × 10 ⁴ PFU / 10 L). It decreased more (99% or more) (FIG. 19).

When the chlorine dioxide gas concentration is 0.27 ppm, the virus titer becomes 1.7 × 10 ³ PFU / 10L after 15 minutes of exposure, and 2 log ₁₀ or more with respect to the control (1.2 × 10 ⁶ PFU / 10L). (99% or more) decreased (FIG. 20).

  From the above results, using the chlorine dioxide generator incorporating the chlorine dioxide generating unit of the present invention, by supplying chlorine dioxide gas into the space at a safe concentration (0.3 ppm or less) for humans, It was proved that airborne microorganisms in the space can be inactivated in a short time. Furthermore, by supplying chlorine dioxide gas into the space at a concentration of about 0.3 ppm using a chlorine dioxide generator incorporating the unit for generating chlorine dioxide of the present invention, it can be achieved in a very short time (15 minutes or less). It was proved that airborne microorganisms in the space can be almost completely inactivated.

4). Discussion There is a report of the number of airborne influenza viruses in hospital emergency departments measured by Blachere et al. (Blachere, MF, et al. Measurement of airborne virus in a hospital epidemic. -440 (2009)). This document describes the results of measuring the number of influenza viruses in the air by aspirating indoor air at 3.5 L / min for 4 hours using the National Institute for Occupational Safety and Health 2-stage cycle aerosol sampler. It is described that the number of 16,278 virus particles was detected in the waiting room. From this result, the virus concentration contained in the space is calculated to be about 1.9 × 10 ² virus particles / 10 L. That is, in a space where there is a high possibility that many influenza viruses exist (for example, hospitals where many influenza virus patients visit), the concentration of influenza virus in the space is about 1.9 × 10 ² virus particles / 10 L. It is believed that there is.

The virus concentration used in this 0.05 ppm chlorine dioxide gas exposure experiment is about 7.5 × 10 ⁵ PFU / 10 L, which is about 3900 times higher than the hospital emergency department example. Nevertheless, it has been shown that the inactivation effect of the virus was sufficiently observed. Therefore, when the influenza virus concentration in the space is about 1.9 × 10 ² virus particles / 10 L, the virus is inactivated at a chlorine dioxide gas concentration of about 0.00001 ppm (0.05 ppm / 3900). Is considered possible.

Example 8: Deactivation of airborne microorganisms using a chlorine dioxide generator (2)

  In order to prove that the chlorine dioxide generator incorporating the chlorine dioxide generating unit of the present invention can inactivate suspended microorganisms in the space in a very short time (for example, 10 minutes or less), the following additional experiment was conducted. It was.

1. Experimental materials and experimental equipment The same materials as in Example 7 were used.

2. Experimental Method Test Virus solution preparation and chlorine dioxide gas concentration monitoring were performed using the same method as in Example 7.

(experimental method)
1 m ³ established the chlorine dioxide generator of the present invention in the central portion of the chamber, on the device by the timer, by operating at a controlled off, so that the chlorine dioxide gas concentration in the chamber is about 0.3ppmv Adjusted. Using a nebulizer, a phiX174 phage virus (about 1 × 10 ^{8 to 9} PFU / ml) was sprayed at a rate of 0.2 ml / min for 1 minute in a chamber with a stable gas concentration. At 0, 2, 4, and 6 minutes after virus spraying, air containing virus was collected using an impinger. The collected virus was subjected to a plaque assay, and the number of viruses in 10 L of air was determined and evaluated. Similarly, a control in which the LED of the chlorine dioxide generator was always turned OFF was used.

3. Results In the control experiment in which the LED of the chlorine dioxide generator of the present invention was always turned off, the virus titer in 10 L of air in the 1 m ³ chamber was 9.2 × 10 ⁴ PFU / 10 L in 2 minutes and 4 minutes. It was 8.5 × 10 ⁴ PFU / 10L and 6.3 × 10 ⁴ PFU / 10L in 6 minutes (FIG. 21).

On the other hand, when the LED of the chlorine dioxide generator of the present invention is turned on and the chlorine dioxide gas concentration is 0.28 ppmv, the virus titer in the space is 1.6 × 10 ⁴ PFU in 2 minutes of exposure time. / 10L, 2.8 × 10 ³ PFU / 10L with an exposure time of 4 minutes, and 9.1 × 10 ² PFU / 10L with an exposure time of 6 minutes, respectively 82.9% (2 minutes exposure), 96 Reduced by 8% (4 minutes exposure), 98.6% (6 minutes exposure) (Figure 21).

  From the above results, using the chlorine dioxide generator incorporating the chlorine dioxide generating unit of the present invention, by supplying chlorine dioxide gas into the space at a safe concentration (0.3 ppm or less) for humans, It was proved that suspended microorganisms in the space can be inactivated in an extremely short time of 10 minutes or less.

Example 9: Deactivation of suspended microorganisms using a chlorine dioxide generator (3)

  In order to prove that the chlorine dioxide generator incorporating the unit for generating chlorine dioxide of the present invention can be effectively used to inactivate various floating microorganisms, the following experiment was conducted.

1. Experimental materials and equipment (test virus)
Feline Calicivirus (FCV, F9, ATCC VR-782); used as an alternative to norovirus (host cells)
Crandell Reese felt kidney cells (CRFK, ATCC CCL-94)
(Gas generator)
Chlorine dioxide generator (laboratory equipment) incorporating the unit for generating chlorine dioxide of the present invention
100L stainless steel chamber (custom product)
96-well microplate (353072, FALCON)
96-well deep well plate (BM6030, BM Bio)
Reagent Researchers / Tip-Tub (022265806, eppendorf)
AC FAN (MU825S-13N, ORIX)
Nebulizer (NE-C29, OMRON)
Hepa filter for exhaust (ultra-small special filter for exhaust, OSHIARI LABORATORY)
Impinger (Biosampler, 5 ml, SKC)
Centriprep 50K ultrafiltration membrane (4310, Merck Millipore)
Amicon Ultra 50K Ultrafiltration Membrane (UFC505024, Merck Millipore)
(Experimental equipment)
Shaking incubator (AT12R, THOMAS)
Chlorine dioxide gas sensor (Midas GAS Detector, ClO ₂ MIDAS-E-BR2, Honeywell)
Data logger (GL220, GRAPHTEC)
OMRON Timer (H5CX, OMRON)
Particle counter (KC-52, RION)
CO ₂ incubator (MCO-175AICUVH, PANASONIC)
Air pump (SPP-25GA, TECHNO TAKASUKI)
Thermo-hygrometer (TR-72wf, T & D)
Ion chromatograph (HIC-20ASP, SHIMADZU)
Humidity adjuster (ADPAC-N1000-AH, ADTEC)
Clean air supply device (ADFRES-1000, ADTEC)
Temperature and humidity unit (TH-RS12, ADTEC)
Thermo-hygrometer (TR-72wf, T & D CORPORATION)
Flow meter (RK3300, KOFLOC)
Ion chromatography (ICS-3000, DIONEX)
Phase contrast microscope (CK30, OLYMPUS)
(Experimental material)
Dulbecco's Modified Eagle's Medium-high glucose (D-MEM, D5796, SIGMA)
Dulbecco's Phosphate Buffered Saline (D8537, SIGMA)
0.25% Trypsin Solution (35555-54, Nacalai quest)
Fetal Bovine Serum (FBS, 30-2020, ATCC)
EDTA Disodium Salt 2% Solution in PBS Saline (2820549, MP)
(Impinger virus recovery solution (neutralization solution))
5 mL of 0.1% FBS D-MEM (antibiotic added) containing 1 mM sodium thiosulfate solution ^* was used as a virus recovery solution for Impinger.
* 1 mM sodium thiosulfate solution has a concentration that can be neutralized without problems when 12.5 L of 0.3 ppmv chlorine dioxide gas is passed through.

2. Experimental method (adjustment of virus spray)
-80 ° C. Feline were cryopreserved calicivirus a ⁽¹⁰ 8.5 _TCID 50 / 50μL) what was diluted 10-fold with 0.1% FBS solution was virus spray ⁽¹⁰ 7.5 _TCID 50 / ^50μL) .

(experimental method)
Install the chlorine dioxide generator of the present invention in the center of a 100 L stainless steel chamber and operate it while controlling the on / off of the device with a timer so that the chlorine dioxide gas concentration in the chamber becomes 0.3 ppmv. Adjustment (Figure 22). Using a nebulizer, a feline calicivirus (10 ^7.5 TCID _50/50 μL) is sprayed at a rate of 0.2 ml / min for 1 minute in a chamber with a stable gas concentration, and then 0, 2.5, 5, 10 minutes. Later, the virus was recovered by Impinger. 5 mL of virus recovery solution was concentrated to about 50 μL by two types of ultrafiltration membranes (virus in 12.5 L of air). The titer was measured from this virus concentrate, and the virus infectivity in 10 L of air was determined and evaluated. As a control, an experiment similar to the above was performed in the chlorine dioxide generating unit in the chlorine dioxide generator without putting the drug in the drug storage unit.

(Chlorine dioxide gas concentration)
The chlorine dioxide gas concentration in the 100 L chamber was monitored by a chlorine dioxide gas sensor. The concentration value of the chlorine dioxide gas sensor was corrected in comparison with the gas concentration value obtained by ion chromatography.

3. Experimental results In a control experiment in which no drug was used in the apparatus, the virus titer after 10 minutes was 10 ^4.0 TCID ₅₀ / 10L air. On the other hand, when the experiment was conducted by putting the drug into the apparatus of the present invention, the chlorine dioxide gas concentration in the chamber was 0.25 ppmv (min; 0.22 ppmv, max; 0.32 ppmv) on average, and the virus after 10 minutes The titer was 10 ^0.6 TCID ₅₀ / 10L air, which was 2 log ₁₀ or more (99% or more) lower than the control (FIG. 23).

Example 10: Deactivation of airborne microorganisms using a chlorine dioxide generator (4)

  In order to prove that the chlorine dioxide generator incorporating the chlorine dioxide generating unit of the present invention can be used effectively to inactivate airborne bacteria, the following experiment was conducted.

1. Experimental materials and equipment (test microorganisms)
Staphylococcus epidermidis (NBRC 12993)
(Gas generator)
Chlorine dioxide generator (laboratory equipment) incorporating the unit for generating chlorine dioxide of the present invention
1m ³ chamber (custom product)
AZE (INO-001, IWAKI)
96-well deep well plate (BM6030, BM Bio)
Reagent Researchers / Tip-Tub (022265806, eppendorf)
AC FAN (MU1225S-11, ORIX)
Nebulizer (NE-C29, OMRON)
Hepa filter for exhaust (ultra-small special filter for exhaust, OSHIARI LABORATORY)
Impinger (Biosampler, 5 ml, SKC)
(Experimental equipment)
Chlorine dioxide gas sensor (Midas GAS Detector, ClO ₂ MIDAS-E-BR2, Honeywell)
Particle counter (KC-52, RION)
Air filter for particle removal (MAC-11FR-UL, Nippon Airtech)
Spectrophotometer (V-560, JASCO)
Thermostatic bath (MCO-175, SANYO)
Air pump (SPP-25GA, TECHNO TAKASUKI)
Thermo-hygrometer (PC-5000TRH, SATO)
Flow meter (RK3300, KOFLOC)
Ion chromatograph (HIC-20ASP, SHIMADZU)
(Experimental material)
SCD medium (393-00185, Nissui Pharmaceutical)
SCD agar medium (396-00175, Nissui Pharmaceutical)
Ordinary agar medium (E-MP21, Eiken Chemical)
Trypticase Soy Agar (236950, BD Biosciences)
0.1 mol / l sodium thiosulfate solution (191-03625, wako)
(Floating bacteria collection solution for impinger (neutralization solution))
5 mL of 1 mM sodium thiosulfate solution ^* -containing SCD medium was used as a suspension recovery solution for Impinger.
* 1 mM sodium thiosulfate solution has a concentration that can be neutralized without problems when 12.5 L of 0.05 ppmv chlorine dioxide gas is passed through.

2. Experimental method (adjustment of test bacterial solution)
The pre-cultured stock strain Staphylococcus epidermidis was inoculated on a normal agar medium and cultured at 30 ° C. A solution obtained by diluting the obtained bacterial cells with sterilized purified water was used as a test bacterial solution (spray solution; 1 × 10 ^{8 to 9} CFU / ml).

(experimental method)
The chlorine dioxide generator of the present invention is placed in the center of 1 m ³ chamber, on the device by a timer, not operate while controlling the off, the chlorine dioxide gas concentration in the chamber was adjusted to be 0.05ppmv (FIG. 24). Using a nebulizer, a bacterial suspension (approximately 1 × 10 ^{8 to 9} CFU / ml) is sprayed at a rate of 0.2 ml / min for 1 minute using a nebulizer in a chamber with a stable gas concentration, and 0, 30, 60, 90 After a minute, airborne bacteria were collected by an impinger. After collection, the number of viable bacteria at each time was measured and evaluated by a dilution plate method. As a control, an experiment similar to the above was performed with the LED of the chlorine dioxide generator of the present invention turned off.

(Chlorine dioxide gas concentration)
Chlorine dioxide gas concentration of 1 m ³ chamber was monitored by chlorine dioxide gas sensor. The concentration value of the chlorine dioxide gas sensor was corrected in comparison with the gas concentration value obtained by ion chromatography.

3. In the case of a control experiment in which the experiment was performed with the LED turned off in the experimental result apparatus, the viable cell count was 4.1 × 10 ³ CFU / 10L air in 90 minutes. On the other hand, when the experiment was performed with the LED of the apparatus of the present invention turned on, the chlorine dioxide gas concentration in the chamber was an average of 0.05 ppmv, and the viable cell count was 3.4 × 10 ² CFU / at an exposure time of 90 minutes. It became 10L air, and decreased by 1 log ₁₀ or more (90% or more) with respect to the control (FIG. 25).

DESCRIPTION OF SYMBOLS 10 Chlorine dioxide generation unit 11 Drug storage part 12 LED chip 13 Operation base 14 Drug 15 Tube 16 Opening part 20 Chlorine dioxide generation device 21 Chlorine dioxide generation unit 22 Device body 23 Air supply port 24 Fan 25 Air discharge port 30 Chlorine dioxide Generation unit 31 Gas generation port 32 Drug storage unit 33 Electronic substrate 34 LED chip 35 Exterior unit 36 Air introduction port 40 Chlorine dioxide generator 41 LED chip mounting substrate 42 Drug storage unit 43 Housing unit 44 Blower fan

Claims (14)

A method of inactivating suspended microorganisms in space,
(1): (A) preparing a solid drug containing a porous material supporting chlorite and (B) a metal catalyst or a metal oxide catalyst;
Here, the mass ratio of the chlorite and the metal catalyst or metal oxide catalyst in the solid drug is 1: 0.04 to 0.8;
(2): irradiating the solid drug with visible light; and
(3): supplying chlorine dioxide gas generated from the solid drug to a space where airborne microorganisms exist;
Method. The method of claim 1, comprising:
In the step (3), the chlorine dioxide gas generated from the solid drug is supplied to the space where the floating microorganisms exist, and the concentration of the chlorine dioxide gas in the space can be survived by the animal. Is the step of setting the concentration to become inactive, "
Method. The method of claim 2, comprising:
The animal can survive, but the concentration at which the airborne microorganisms are inactivated is 0.00001 ppm to 0.3 ppm.
Method. The method of claim 3, comprising:
In the step (3), when the chlorine dioxide gas concentration in the space is 0.1 ppm to 0.3 ppm, the time for supplying the chlorine dioxide gas into the space is 0.5 minute to 480 minutes.
Method. A method according to any one of claims 1-4,
The floating microorganism is a floating virus or a floating bacterium,
Method. A method according to any one of claims 1-5,
The wavelength of visible light irradiated in the step (2) is 360 nm to 450 nm.
Method. The method according to any one of claims 1 to 6, comprising:
The metal catalyst or metal oxide catalyst is selected from the group consisting of palladium, rubidium, nickel, titanium, and titanium dioxide;
Method. A method according to any one of claims 1-7,
The porous material is selected from the group consisting of sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, and perlite;
The chlorite is selected from the group consisting of sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, and barium chlorite;
Method. The method according to any one of claims 1 to 8, comprising:
The “porous material supporting chlorite” is obtained by impregnating porous material with chlorite and further drying.
Method. A method according to any one of claims 1 to 9, comprising
The porous material further carries an alkali agent;
Method. The method of claim 10, comprising:
The alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and lithium carbonate;
Method. 12. The method according to claim 10 or 11, comprising:
The molar ratio of the chlorite and the alkali agent is 1: 0.1 to 2.0.
Method. A method according to any one of claims 10 to 12, comprising
The “porous material supporting a chlorite and an alkali agent” is obtained by impregnating a porous material with a chlorite and an alkali agent simultaneously or sequentially and drying them.
Method. A method according to any one of claims 1 to 13, comprising
The water content of the porous material is 10% by weight or less,
Method.