JP6725153B2 - How to inactivate suspended microorganisms in space - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for deactivating airborne microorganisms in a space using a low concentration of chlorine dioxide gas.

Chlorine dioxide gas is a gas that is safe for living organisms of animals at low concentrations (for example, 0.3 ppm or less), but even at such low concentrations, it has an inactivating effect on microorganisms such as bacteria, fungi, and viruses. It is known to have a deodorizing effect and the like. Due to such characteristics, chlorine dioxide gas has been particularly attracting attention in applications such as deodorization, sterilization, virus removal, mold prevention and antiseptic during environmental purification and food transportation.

As described above, chlorine dioxide gas is safe for the living body of animals at low concentrations and can be used for various purposes. For example, a method of inactivating respiratory viruses and the like using low-concentration chlorine dioxide gas has been proposed so far (for example, Patent Document 1). However, chlorine dioxide gas can be harmful to the living body of animals at high concentrations and there is also a risk of explosion, so development of a method for stably generating chlorine dioxide gas has been considered for practical use. ..

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

Therefore, a method of irradiating a gel composition composed of a chlorite salt and a water-absorbent resin with ultraviolet rays to generate chlorine dioxide (for example, Patent Document 2), or a porous carrier containing a chlorite salt and an alkaline agent A method of generating chlorine dioxide by contacting the stabilized chlorine dioxide agent with air using a stabilized chlorine dioxide agent that has been impregnated and dried has been proposed (for example, Patent Document 3).

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

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

Further, the inventors of the present invention, for example, in the invention described in Patent Document 2, cause a poor generation efficiency of chlorine dioxide in a chlorine dioxide generation method of a type in which solid or gel chlorite is irradiated with ultraviolet rays. 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. It was found that the amount of chlorine dioxide was reduced (see also Example 1 herein and Figure 3).

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 source of chlorine dioxide. In order to make it possible, further examination was repeated. As a result, the amount of ozone generated is reduced by using light in the visible range (visible light) instead of ultraviolet light, which has been considered to be essential for generating chlorine dioxide from solid chlorite. It was possible to increase the amount of chlorine dioxide generated to a practical level as a whole. Furthermore, the amount of chlorine dioxide generated from chlorite is increased by mixing a metal catalyst or a metal oxide oxide in order to compensate for the decrease in reactivity due to the use of light in the visible region, which has lower energy than ultraviolet light. The present invention has been completed and the present invention has been completed.

That is, the method of the present invention is, in one embodiment, a method of inactivating floating microorganisms in the space,
(1): a step of preparing a solid medicine containing (A) a chlorite-supported porous substance and (B) a metal catalyst or a metal oxide catalyst,
Here, the mass ratio of the chlorite to the metal catalyst or the 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 medicine to a space where floating microorganisms are present;

Further, in one embodiment of the method of the present invention, the step (3) comprises: "supplying chlorine dioxide gas generated from the solid chemical to a space in which floating microorganisms are present, and chlorine dioxide gas in the space; The step is such that the concentration is a concentration at which the animal can survive but the airborne microorganisms are inactivated”.

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

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

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

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.

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

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

In addition, the method of the present invention is, in one embodiment, that the "chlorite-supported porous substance" is obtained by impregnating a porous substance with chlorite and further drying. Characterize.

In addition, the method of the present invention is, in one embodiment, characterized in that the porous substance further carries an alkaline agent.

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

Further, the method of the present invention is characterized in that, in one embodiment, a molar ratio of the chlorite and the alkaline agent is 1:0.1 to 2.0.

In addition, the method of the present invention is, in one embodiment, the above-mentioned "porous material carrying a chlorite and an alkaline agent", wherein the chlorite and the alkaline agent are simultaneously or sequentially added to the porous material. It is characterized by being obtained by impregnation and drying.

In one embodiment, the method of the present invention is characterized in that the porous substance has a water content of 10% by weight or less.

In another embodiment, the method of the present invention is a method for inactivating airborne microorganisms in a space,
(1): a step of preparing a chlorine dioxide generating unit 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 substantially in the visible region,
The drug storage unit stores a drug containing solid chlorite,
The medicine container is provided with one or a plurality of openings so that air can move inside and outside the medicine container,
Here, chlorine dioxide gas is generated by irradiating the medicine existing inside the medicine container with the light generated from the light source portion; 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. It is characterized in that the medicine is irradiated with light from at least two directions.

Further, in one embodiment of the method of the present invention, the wavelength of the light to be irradiated is 360 nm to 450 nm.

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

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

Further, the method of the present invention is characterized in that, in one embodiment, the light source unit is a light source unit capable of intermittently emitting light.

In one embodiment of the method of the present invention, the solid chlorite-containing agent comprises (A) a chlorite-carrying porous substance, and (B) a metal catalyst or a metal oxide. It is a drug containing a physical catalyst.

Further, the method of the present invention is, in one embodiment, that the “porous substance supporting chlorite” is obtained by impregnating a porous substance with an aqueous chlorite solution and further drying. Is characterized by.

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

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

Further, 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 the metal oxide catalyst is 1:0.04 to 0. It is characterized by being 0.8.

In addition, the method of the present invention is, in one embodiment, characterized in that the porous substance further carries an alkaline agent.

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

Further, the method of the present invention is characterized in that, in one embodiment, a molar ratio of the chlorite to the alkaline agent in the agent is 1:0.1 to 2.0.

In addition, the method of the present invention is, in one embodiment, the above-mentioned "porous material carrying a chlorite and an alkaline agent", wherein the chlorite and the alkaline agent are simultaneously or sequentially added to the porous material. It is characterized by being obtained by impregnation and drying.

In addition, the method of the present invention is characterized in that, in another embodiment, it is carried out by using a chlorine dioxide generation apparatus including the chlorine dioxide generation unit described in any of the above.

Further, the chlorine dioxide generating device used in the method of the present invention further comprises, in one embodiment, a blower for blowing air to the medicine stored in the medicine storing section in the chlorine dioxide generating unit. It is characterized by

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

Also, in the chlorine dioxide generator used in 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 blown from the blower. The air is delivered to the medicine at least partially through an opening existing on a side surface of the medicine container.

Further, in the chlorine dioxide generator used in the method of the present invention, in one embodiment, the relative humidity in the medicine container is kept at 30 to 80% RH by the air sent from the air blower. Characterize.

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

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

FIG. 1 shows a vertical cross-sectional view of a chlorine dioxide generating unit incorporating a drug containing solid chlorite. FIG. 2 shows a vertical cross-sectional view of a chlorine dioxide generation device incorporating the chlorine dioxide generation unit of FIG. FIG. 3 is a graph showing changes in the measured values of chlorine dioxide concentration and ozone concentration in the air when the wavelength of the irradiation light is changed, when the medicine containing solid chlorite is irradiated with light. Is. FIG. 4 is a graph showing an average value of measured values in the ultraviolet region and an average value of measured values in the visible region among the measured values of the chlorine dioxide concentration and the ozone concentration in FIG. 3. FIG. 5 is a graph showing changes in the amount of chlorine dioxide generated depending on the shape of the metal catalyst or metal oxide catalyst mixed with the drug when the drug containing solid chlorite is irradiated with light. FIG. 6 shows the chlorine dioxide generation amount when the ratio of chlorite and titanium dioxide in a solid chlorite and a drug containing a metal catalyst or a metal oxide catalyst (titanium dioxide) is changed. Show changes. FIG. 7 shows the content of titanium dioxide in a drug containing solid chlorite and a metal catalyst or a metal oxide catalyst (titanium dioxide) and the maximum value of the chlorine dioxide concentration generated by visible light irradiation. Shows the relationship. FIG. 8 shows a change in the amount of chlorine dioxide generated when a drug containing a solid chlorite and a metal catalyst or a metal oxide catalyst (titanium dioxide) is continuously irradiated with visible light for a long time. FIG. 9 shows a perspective view, a top view, and a side view of a chlorine dioxide generation unit that is an embodiment of the present invention. FIG. 10 is a schematic view of a chlorine dioxide generation device incorporating a chlorine dioxide generation unit, which is an embodiment of the present invention. FIG. 11 is a diagram showing a chlorine dioxide generating unit according to an embodiment of the present invention in which a drug in a drug storage unit is irradiated with light from only one light source unit (one side) and two light source units (both sides). ) Shows the comparison of chlorine dioxide generation amount with the case of irradiating light. FIG. 12 is a diagram showing a chlorine dioxide generating unit according to an embodiment of the present invention in which a drug in a drug container is irradiated with light from only one light source unit (one side) and two light source units (both sides). ) Shows a plot of the ratio of chlorine dioxide generation to the case of irradiation with light. It should be noted that when light is emitted from two light source units (both sides), the amount of chlorine dioxide generated is more than double that in the case where light is emitted from only one light source unit (one side). For the purpose of illustration, a double value is used as the chlorine dioxide generation amount in the case of single-sided irradiation for obtaining the ratio of chlorine dioxide generation amounts. FIG. 13 shows a case where light is emitted from two light source units (both sides) in the chlorine dioxide generating unit according to one embodiment of the present invention, and light is emitted from only one light source unit (one side). It is a figure explaining that light can be efficiently delivered to the medicine in the medicine container by comparison. FIG. 14 shows a change in the chlorine dioxide generation amount when the relative humidity in the chemical container is changed in the chlorine dioxide generation unit according to the embodiment of the present invention. Note that FIG. 14 shows data when light is emitted from only one light source unit (one surface). FIG. 15 shows the change over time in the chlorine dioxide generation amount when the relative humidity in the chemical container is changed in the chlorine dioxide generation unit according to one embodiment of the present invention. Note that FIG. 15 shows data when light is emitted from two light source units (both sides). FIG. 16 shows the amount of chlorine dioxide generated in the chlorine dioxide generating unit according to one embodiment of the present invention when light is intermittently irradiated from two light source units (both sides) to the drug in the drug storage unit. Shows the change over time. In the figure, “10 s/80 s” means that light irradiation is continued for 2 minutes from the start of irradiation, light is irradiated for 10 seconds (LED is turned on) after 2 minutes from the start of irradiation, and irradiation of light for 80 seconds is stopped ( Indicates that the cycle of turning off the LED) has been repeated. Similarly, in the figure, "20s/80s" means that light irradiation is continued for 2 minutes after the start of irradiation, light is irradiated for 20 seconds (LED is turned on) after 2 minutes after the start of irradiation, and irradiation of light for 80 seconds is stopped. It shows that the cycle of turning off (LED is turned off) is repeated, and "30s/80s" continues to irradiate light for 2 minutes after the start of irradiation, and irradiates light for 30 seconds after 2 minutes after the start of irradiation (turns on LED) Then, the cycle of stopping the irradiation of light for 80 seconds (turning off the LED) is repeated. FIG. 17 shows a schematic diagram of an experiment for inactivating airborne microorganisms in the space using the method of the present invention. FIG. 18 shows the change in virus titer in the air in the chamber when the chlorine dioxide concentration was about 0.05 ppmv. FIG. 19 shows the change in virus titer in the air in the chamber when the chlorine dioxide concentration was about 0.1 ppmv. FIG. 20 shows the change in virus titer in the air in the chamber when the chlorine dioxide concentration was about 0.3 ppmv. FIG. 21 shows the change in virus titer in the air in the chamber when the chlorine dioxide concentration was 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.

The method of the present invention is, in one embodiment, a method for inactivating floating microorganisms in a space,
(1): a step of preparing a solid medicine containing (A) a chlorite-supported porous substance and (B) a metal catalyst or a metal oxide catalyst,
Here, the mass ratio of the chlorite to the metal catalyst or the 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 step of supplying chlorine dioxide gas generated from the solid medicine to a space where floating 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 an animal can survive but suspended microorganisms are inactivated, and thus the present invention can be applied to a space where an animal exists. More specifically, the present invention can be applied to a living space (for example, a residence, an office), a medical institution (for example, a waiting room of a hospital, an examination room, a treatment room, an operating room, an anterior room, an inpatient room), a research institution (for example, , University laboratories, anterooms, disaster medical facilities (eg disaster containers, tents), public facilities (eg stations, airports, schools), vehicles (eg private cars, buses, trains, planes) Can be applied in.

The floating microorganisms in the method of the present invention broadly mean microorganisms that can float in the space,
For example, airborne viruses, airborne bacteria, and airborne fungi can be mentioned. As floating viruses, viruses with envelopes or viruses without envelopes such as varicella-zoster virus, influenza virus (human, bird, pig, etc.), herpes simplex virus, adenovirus, enterovirus, rhinovirus, human papillomavirus (human Papillary virus), 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 lymphophile virus, simian immunodeficiency virus, STLV and the like. Further, as the floating bacteria, Gram-positive bacteria or Gram-negative bacteria, for example, Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, Escherichia coli, Streptococcus, Neisseria gonorrhoeae, Syphilis, Meningococcus, Mycobacterium tuberculosis, Mycobacteria, Klebsiella (Klebsiella pneumoniae), Salmonella, Botulinum, Proteus, B. pertussis, Serratia, Vibrio parahaemolyticus, Citrobacter, Acinetobacter, Campylobacter, Enterobacter, Mycoplasma, Chlamydia, Clostridia, and the like. Further, examples of the airborne fungi include Aspergillus, Trichophyton, Malassezia, Candida and the like.

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

The time for supplying the chlorine dioxide gas into the space by using the method of the present invention is not particularly limited, but the time for supplying may be appropriately adjusted depending on the concentration of the chlorine dioxide gas to be supplied. For example, when the chlorine dioxide gas concentration in the space is 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 The time is more preferably 60 minutes, further preferably 2 minutes to 15 minutes.

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

The 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 in order to not decompose chlorite, when suspended in water. Those exhibiting alkalinity are preferable, palygorskite and sepiolite are more preferable, and sepiolite is particularly preferable.

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

The "chlorite-supported porous substance" used in the method of the present invention may have any particle size, but an average particle size of 1 mm to 3 mm is particularly preferred. Can be used for

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

The concentration of chlorite in the “porous substance supporting chlorite” used in the method of the present invention is effective at 1% by weight or more, but if it exceeds 25% by weight, it becomes a deleterious substance. Therefore, it is preferably 1% by weight or more and 25% by weight or less, and more preferably 5% by weight or more and 20% by weight or less.

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

In addition, in the present specification, as an approximate standard of the size of “powder” or “granular”, for example, “powder” means a solid substance having an average particle diameter of 0.01 mm to 1 mm, and The term “granular” refers to a solid material having an average particle size 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. ˜0.8, preferably 1:0.07 to 0.6, more preferably 1:0.07 to 0.5. In the drug, when the content of the metal catalyst or the metal oxide catalyst is more than 1 time the content of the chlorite salt, and the content of the metal catalyst or the metal oxide catalyst is 0% of the content of the chlorite salt. In any case of less than 0.04 times, the amount of chlorine dioxide generated upon irradiation with visible light can be reduced.

The “porous substance carrying chlorite” used in the method of the present invention may further carry an alkaline 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 or lithium carbonate. However, sodium hydroxide can be preferably used. By further supporting an alkaline agent on the "chlorite-supported porous material", the pH of the drug used in the present invention can be adjusted, the stability of the drug itself is enhanced, and light irradiation is performed. It is possible to suppress the wasteful emission of chlorine dioxide when it is not stored.

The amount of the alkaline agent used in the preparation of the drug used in the method of the present invention is appropriately 0.1 equivalent or more and 2.0 equivalents or less, preferably 0.1 equivalent to chlorite (mol). The amount is not less than 1.0 and not more than 1.0, and more preferably not less than 0.1 and not more than 0.7. 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 generation concentration is lowered, which is preferable. Absent.

In the preparation of the drug used in the method of the present invention, the method of further supporting an alkaline agent on the "porous substance supporting chlorite" is not particularly limited, for example, a chlorite and an alkaline agent, A method in which the porous material is impregnated and dried simultaneously or sequentially may be used. In the present specification, the composition of interest may be obtained by "spraying and adsorbing" the aqueous chlorite solution and/or the alkaline agent onto the porous material and drying, but in the present specification, The term "spray adsorption" shall be included in the term "impregnation".

In another embodiment, the method of the present invention is a method for inactivating airborne microorganisms in a space,
(1): a step of preparing a chlorine dioxide generating unit 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 substantially in the visible region,
The drug storage unit stores a drug containing solid chlorite,
The medicine container is provided with one or a plurality of openings so that air can move inside and outside the medicine container,
Here, chlorine dioxide gas is generated by irradiating the medicine existing inside the medicine container with the light generated from the light source portion; and
(2): a step of supplying chlorine dioxide gas generated from the chlorine dioxide generating unit to a space in which suspended microorganisms are present.

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

As the light source used in the 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 in 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), and the wavelength of light in the ultraviolet region (to 360 nm) and infrared region The light may include the wavelength of the light (830 nm to). However, when a drug containing solid chlorite is irradiated with light having a wavelength in the ultraviolet region, ozone is likely to be generated as a by-product, and since light having a wavelength in the infrared region has low energy, solid chlorite is The amount of chlorine dioxide generated is small even when a drug containing salt is irradiated. Therefore, the light generated from the light source used in the method of the present invention preferably consists essentially of light of a wavelength in the visible region. The light emitted 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 further preferably 380 nm to 430 nm. Most preferably, the light has a wavelength of

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

The light source used in the method of the present invention is not particularly limited as long as it emits light having a wavelength in the visible range. For example, a lamp (incandescent lamp, LED lamp), a chip, a laser device that emits light in the visible range. Etc., various things can be used. From the viewpoint of the directivity of the light generated from the light source and the viewpoint of downsizing of the device, it is preferable to use the light source in the form of a chip. Since the light source in the form of a chip has a narrow directivity, it is possible to efficiently irradiate the object to be irradiated with light without the light being diffused, and it is possible to improve the chlorine dioxide generation efficiency of the device. Further, from the viewpoint of limiting the wavelength of light emitted from the light source so that light in the ultraviolet region or infrared region is not included, it is preferable to use an LED that emits light in the visible region as the light source. Particularly, from the viewpoint of downsizing of the device and the efficiency of chlorine dioxide generation, the light source used in the present invention is most preferably an LED chip that generates light in the visible region.

Further, the light source used in the method of the present invention may be a light source capable of emitting light intermittently. 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 period of time and then stopping irradiation of the light for a certain period of time. The method of controlling the light source for intermittently irradiating the light is not particularly limited, and a method known to those skilled in the art can be used. That is, in the method of the present invention, the step of irradiating the solid drug with visible light may be the step of intermittently irradiating the solid drug with visible light.

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

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

In addition, for example, the medicine container may be formed of a mesh plate having a mesh that does not allow the stored items to fall. With such a configuration, the air outside the medicine container can move inside and outside the medicine container, and the light generated from the light source unit passes through the mesh to the medicine inside the medicine container. It is irradiated.

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

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

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

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

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

Further, in the chlorine dioxide generator used in the method of the present invention, as another method for supplying the water vapor in the air into the chemical container, a Peltier element (Peltier element) for condensing and collecting water in the air is used. (Effect) can also be used (the disadvantage of the Peltier element that causes the intrusion of water vapor and dew condensation can be reversely used to increase the humidity).

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

Moreover, since the chlorine dioxide generating unit used in the method of the present invention is small, the method of the present invention can be carried out by incorporating it into a home electric appliance or the like whose main purpose is not to generate chlorine dioxide. For example, the present invention can be carried out by incorporating the chlorine dioxide generating unit used in the method of the present invention into a home electric appliance or the like whose main purpose is not to generate chlorine dioxide and supplying chlorine dioxide gas. For example, by incorporating the 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 purifier, a humidifier, etc., the chlorine dioxide generating unit can be produced by the effect of the wind emitted from the air conditioning facility. The generation of chlorine dioxide in the air conditioner is promoted, and chlorine dioxide can be efficiently diffused into the space by being placed on the air discharged from the air conditioning equipment into the space.

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

Further, the term “comprising” used in the present specification is intended to mean that the described items (members, steps, elements or numbers) exist unless there is a clear difference in context. It does not exclude the existence of other matters (members, steps, elements, numbers, etc.).

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein should be construed as having meanings consistent with the meanings in the present specification and the related technical field, and idealized or excessively formalized, unless a different definition is explicitly stated. It should not be construed in a conventional sense.

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

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

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

References cited herein should be considered to be incorporated herein by reference in their entireties, and one of ordinary skill in the art, in accordance with the context of the present specification, should understand the spirit of the invention. And without departing from the scope, the relevant disclosures in those prior art documents are understood to be incorporated as part of this specification.

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

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

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

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

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

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 a mechanism similar to that of the device shown in FIG. 1, so the air discharged from the air discharge port 25 contains chlorine dioxide.

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

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

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

As shown in Fig. 3, when the wavelength of the light irradiating the drug is moved from the ultraviolet region to the visible region, the ozone concentration in the air becomes maximum in the ultraviolet region and decreases from the ultraviolet region to the visible region. It has been shown. On the other hand, it was surprisingly shown that the 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 any problem even at a wavelength of at least about 450 nm, which exceeds the upper limit of 430 nm of the measurement range of the present embodiment. Understand that.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The same conditions as in Example 4 were used for the drug stored in the drug storage portion, the visible light irradiation method, and the chlorine dioxide concentration measurement. 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 a blower fan. The relationship between the relative humidity in the drug container and the chlorine dioxide concentration in the chamber is shown in FIGS. 14 and 15. FIG. 14 shows a value obtained by averaging chlorine dioxide concentrations measured multiple times during light irradiation for 0.5 hours to 2 hours and its standard deviation, and FIG. 15 shows a temporal change of chlorine dioxide concentration in the chamber. Show.

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

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

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

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

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

As shown in FIG. 16, in the present invention, visible light was intermittently irradiated from the light source unit, and by adjusting the balance between the irradiation time and the stop time in the intermittent irradiation, it was possible to generate chlorine dioxide having a desired concentration. ..

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

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

Example 7: Inactivation of floating microorganisms using a chlorine dioxide generator (1)

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

1. Experimental materials and equipment (test virus)
Escherichia coli page phiX174 (NBRC 103405)
(Host bacterium)
Escherichia coli (NBRC 13898)
(Gas generator)
Chlorine dioxide generator incorporating the chlorine dioxide generating unit of the present invention (laboratory equipment)
1m ³ chamber (custom product)
14 ml Tube (352059, FALCON)
Eze (INO-001, IWAKI)
AC FAN (MU1225S-11, ORIX)
Nebulizer (NE-C29, OMRON)
Exhaust hepa filter (Ultra small special exhaust filter, OSHIARI LABORATORY)
Impinger (Biosampler, 5ml, SKC)
(Experimental equipment)
Shaking incubator (AT12R, THOMAS)
Chlorine dioxide gas sensor (ClO ₂ 1000 ppb, 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, Japan Airtech)
Spectrophotometer (V-560, JASCO)
Constant temperature bath (MCO-175, SANYO)
Air pump (SPP-25GA, TECHNO TAKATSUKI)
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 214010, BD)

2. Experimental method (preparation of test virus solution)
The precultured stock strain Escherichia coli was inoculated into 5 ml of NB+0.5% NaCl liquid medium, and shake-cultured at 30° C. and 200 rpm for 6 hours. After culturing, 100 μl of Escherichia coli (about 1×10 ⁹ cells/ml) and 500 μl of phase phiX174 (about 1×10 ⁵ PFU/ml) in NB+0.5% NaCl liquid medium were mixed and incubated at 37° C. for 5 minutes. To the mixture, 3 ml of NB+0.5% NaCl medium (0.6% agar) was added and mixed, and after overlaying on a regular agar medium, the mixture was cultured at 37° C. for 18 hours. 2 ml of NB+0.5% NaCl liquid medium was added to the top agar to collect, filtered with a 0.22 μm filter, dispensed, and stored at −85° C. A plaque assay was carried out on a portion of the mixture according to a conventional method to obtain a virus solution of about 1×10 ¹⁰ PFU/ml. Before the test, the virus frozen at −85° C. was thawed, and then diluted 10 times with distilled water to obtain a test virus solution (spray solution; 1×10 ^{8 to 9} PFU/ml).

(experimental method)
The outline of the experiment in this example is shown in FIG.
By installing the chlorine dioxide generator of the present invention in the center of the 1 m ³ chamber and operating it while controlling the on/off of the device by a timer, the chlorine dioxide gas concentration in the chamber is 0.05, 0.1, Alternatively, it was adjusted to 0.3 ppmv. 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 5 minutes in a chamber with a stable gas concentration. After 0, 30, 60, 75, 90 minutes in a chamber with a chlorine dioxide concentration of about 0.05 ppmv, 0, 15, 30, 45, 60 minutes in a chamber with a chlorine dioxide concentration of about 0.1 ppmv. Later, in a chamber having a chlorine dioxide concentration of about 0.3 ppmv, virus-containing air was recovered using an impinger after 0, 5, 10, 15, 30 minutes. The recovered virus was subjected to plaque assay, and the number of virus in 10 L of air was obtained and evaluated. Similarly, the control was such that the LED of the chlorine dioxide generator was always off.

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

3. Results Figure 18 shows the change in virus titer in the air in the chamber with chlorine dioxide concentration of about 0.05 ppmv, and Figure 19 in the air in the chamber with 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. 19 was performed at a temperature: 22.9. The experiment shown in FIG. 20 was conducted under the conditions of ±0.2° C. and relative humidity: 59.4±0.7%, and the experiment shown in FIG. It was carried out under conditions of 0.5%.

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. It was PFU/10L (FIG. 19) and 1.2×10 ⁶ PFU/10L (FIG. 20) at 15 minutes.

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

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

When the chlorine dioxide gas concentration was 0.27 ppm, the virus titer was 1.7×10 ³ PFU/10 L at an exposure time of 15 minutes, which was 2 log ₁₀ or more with respect to the control (1.2×10 ⁶ PFU/10 L). (99% or more) (Fig. 20).

From the above results, by 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 concentration safe for humans (0.3 ppm or less), It was proved that airborne microorganisms in space could be inactivated in a short time. Furthermore, by using the chlorine dioxide generator incorporating the unit for generating chlorine dioxide of the present invention to supply chlorine dioxide gas into the space at a concentration of about 0.3 ppm, it is possible to carry out in an extremely short time (15 minutes or less). It has been proved that airborne microorganisms in space can be almost completely inactivated.

4. Discussion Blachere et al. have reported that the number of floating influenza viruses in a hospital emergency department was measured (Blachere, MF, et. al. -440 (2009)). In this document, the results of measuring the number of influenza viruses present in the air at 3.5 L/min for 4 hours using a National Institute for Occupational Safety and Health 2-stage cyclone aerosol sampler , It was described that the number of 16,278 virus particles was detected in the waiting room. From this result, the concentration of virus contained in the space was calculated to be about 1.9×10 ² virus particles/10 L. That is, in a space where a large number of influenza viruses are likely to exist (for example, a hospital where many influenza virus patients come to the hospital), the influenza virus concentration 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 was about 7.5×10 ⁵ PFU/10 L, which was about 3900 times more concentrated than the above example of the hospital emergency department. Despite this, it has been shown that a sufficient virus inactivating effect was 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: Inactivation 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 airborne microorganisms in an extremely short time (for example, 10 minutes or less), the following additional experiment is conducted. It was

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

2. Experimental Method The same method as in Example 7 was used to adjust the test virus solution and monitor the chlorine dioxide gas concentration.

(experimental method)
By installing the chlorine dioxide generator of the present invention in the center of a 1 m ³ chamber and operating it while controlling the on/off of the device by a timer, the chlorine dioxide gas concentration in the chamber becomes about 0.3 ppmv. I adjusted. 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 1 minute in a chamber with a stable gas concentration. The virus-containing air was collected using an impinger at 0, 2, 4, and 6 minutes after the virus was sprayed. The recovered virus was subjected to plaque assay, and the number of virus in 10 L of air was obtained and evaluated. Similarly, the one in which the LED of the chlorine dioxide generator was always off was used as a control.

3. Results In a 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 in 4 minutes. It was 8.5×10 ⁴ PFU/10L and 6.3×10 ⁴ PFU/10L at 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 after the exposure time of 2 minutes. /10 L, 2.8×10 ³ PFU/10 L with an exposure time of 4 minutes, and 9.1×10 ² PFU/10 L with an exposure time of 6 minutes, which are 82.9% (2 minutes exposure) and 96, respectively, relative to the control. It was decreased by 8% (4 minutes exposure) and 98.6% (6 minutes exposure) (FIG. 21).

From the above results, by 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 concentration safe for humans (0.3 ppm or less), It was proved that the airborne microorganisms in the space can be inactivated in an extremely short time of 10 minutes or less.

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

The following experiments were conducted in order to prove that the chlorine dioxide generator incorporating the chlorine dioxide generating unit of the present invention can be effectively used to inactivate various suspended microorganisms.

1. Experimental materials and equipment (test virus)
Feline Calivirus (FCV, F9, ATCC VR-782); Used as a substitute for Norovirus (host cell)
Crandell Reese feltine kidney cells (CRFK, ATCC CCL-94)
(Gas generator)
Chlorine dioxide generator incorporating the chlorine dioxide generating unit of the present invention (laboratory equipment)
100L stainless steel chamber (special order)
96-well microplate (353072, FALCON)
96-well deep well plate (BM6030, BM Bio)
Reagent Reservoirs/Tip-Tub (022265806, eppendorf)
AC FAN (MU825S-13N, ORIX)
Nebulizer (NE-C29, OMRON)
Exhaust hepa filter (Ultra small special exhaust filter, OSHIARI LABORATORY)
Impinger (Biosampler, 5ml, 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 TAKATSUKI)
Thermo-hygrometer (TR-72wf, T&D)
Ion chromatograph (HIC-20ASP, SHIMADZU)
Humidity controller (ADPAC-N1000-AH, ADTEC)
Clean air supply device (ADFRESH-1000, ADTEC)
Temperature and humidity unit (TH-RS12, ADTEC)
Thermo-hygrometer (TR-72wf, T&D CORPORATION)
Flowmeter (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 tesque)
Feet Bovine Serum (FBS, 30-2020, ATCC)
EDTA Disodium Salt 2% Solution in PBS Saline (2820549, MP)
(Virus recovery liquid for impinger (neutralization liquid))
5 mL of 0.1% FBS D-MEM (containing an antibiotic) containing 1 mM sodium thiosulfate solution ^* was used as a virus recovery solution for impinger.
*1 mM sodium thiosulfate solution is a concentration that can neutralize without problems when 12.5 L of chlorine dioxide gas of 0.3 ppmv is passed.

2. Experimental method (preparation of virus spray)
Feline calicivirus (10 ^8.5 TCID ₅₀ /50 μL) that had been frozen and stored at −80° C. was diluted 10 times with 0.1% FBS solution to obtain a virus spray solution (10 ^7.5 TCID ₅₀ /50 μL). ..

(experimental method)
The chlorine dioxide generator of the present invention is installed in the center of a 100-liter stainless steel chamber and is operated while controlling the on/off of the device by a timer so that the chlorine dioxide gas concentration in the chamber becomes 0.3 ppmv. It was adjusted (Figure 22). Feline calicivirus (10 ^7.5 TCID ₅₀ /50 μL) was sprayed at a rate of 0.2 ml/min for 1 minute using a nebulizer in a chamber with a stable gas concentration, and then 0, 2.5, 5, 10 minutes. The virus was later 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, in the chlorine dioxide generating unit in the chlorine dioxide generating device, an experiment similar to the above was conducted without putting the medicine in the medicine storing section.

(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 by comparing it with the gas concentration value obtained by the ion chromatography method.

3. Experimental Results In the case of a control experiment in which no drug was used in the apparatus, the virus titer after 10 minutes was 10 ^4.0 TCID ₅₀ /10 L air. On the other hand, when an experiment was carried out with a drug in the device 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: Inactivation of suspended microorganisms using a chlorine dioxide generator (4)

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

1. Experimental materials and equipment (test microorganisms)
Staphylococcus epidermidis (NBRC 12993)
(Gas generator)
Chlorine dioxide generator incorporating the chlorine dioxide generating unit of the present invention (laboratory equipment)
1m ³ chamber (custom product)
Eze (INO-001, IWAKI)
96-well deep well plate (BM6030, BM Bio)
Reagent Reservoirs/Tip-Tub (022265806, eppendorf)
AC FAN (MU1225S-11, ORIX)
Nebulizer (NE-C29, OMRON)
Exhaust hepa filter (Ultra small special exhaust filter, OSHIARI LABORATORY)
Impinger (Biosampler, 5ml, 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, Japan Airtech)
Spectrophotometer (V-560, JASCO)
Constant temperature bath (MCO-175, SANYO)
Air pump (SPP-25GA, TECHNO TAKATSUKI)
Thermo-hygrometer (PC-5000TRH, SATO)
Flowmeter (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 medium (236950, BD Biosciences)
0.1 mol/l sodium thiosulfate solution (191-03625, wako)
(Floating bacteria recovery liquid for impinger (neutralization liquid))
5 mL of a 1 mM sodium thiosulfate solution ^* -containing SCD medium was used as a suspension-bacteria recovery liquid for impinger.
*1 mM sodium thiosulfate solution is a concentration that can neutralize without problems when 12.5 L of 0.05 ppm chlorine dioxide gas is passed.

2. Experimental method (adjustment of test bacterial solution)
The precultured stock strain Staphylococcus epidermidis was inoculated on a regular agar medium and cultured at 30°C. The obtained bacterial cells were diluted with sterile purified water to obtain a test bacterial solution (spray solution; 1×10 ^{8 to 9} CFU/ml).

(experimental method)
The chlorine dioxide generator of the present invention was installed in the center of a 1 m ³ chamber and operated while controlling the on/off of the device by a timer, and the chlorine dioxide gas concentration in the chamber was adjusted to 0.05 ppmv. (FIG. 24). Using a nebulizer in a chamber in which the gas concentration was stable, a bacterial suspension (about 1×10 ^{8 to 9} CFU/ml) was sprayed at a rate of 0.2 ml/min for 1 minute, and 0, 30, 60, 90 was sprayed. After the minutes, floating bacteria were collected by an impinger. After collection, the number of viable bacteria at each time was measured and evaluated by the dilution plate method. As a control, the same experiment as above was conducted with the LED of the chlorine dioxide generator of the present invention kept off.

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

3. Experimental Results In the control experiment in which the LED was turned off in the apparatus, the viable cell count was 4.1×10 ³ CFU/10L air in 90 minutes. On the other hand, when an experiment was conducted with the LED of the device of the present invention turned on, the chlorine dioxide gas concentration in the chamber was 0.05 ppmv on average, and the viable cell count was 3.4×10 ² CFU/ with an exposure time of 90 minutes. It was 10 L air, which was 1 log ₁₀ or more (90% or more) lower than the control (FIG. 25 ).

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

Claims (13)

A method for inactivating airborne microorganisms in a space,
(1): a step of preparing a solid medicine containing (A) a chlorite-supported porous substance and (B) a metal catalyst or a metal oxide catalyst,
Here, the mass ratio of the chlorite to the metal catalyst or the 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 floating microorganisms are present,
Method. The method of claim 1, wherein
The step (3) is a step of "supplying chlorine dioxide gas generated from the solid drug to a space where floating microorganisms are present, and setting the chlorine dioxide gas concentration in the space to 0.00001 ppm to 0.3 ppm" Is,
Method. The method of claim 2 , wherein
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 minutes to 480 minutes,
Method. The method according to any one of claims 1 to 5 , wherein
The floating microorganism is a floating virus or a floating bacterium,
Method. The method according to any one of claims 1-4,
The wavelength of the visible light irradiated in the step (2) is 360 nm to 450 nm,
Method. The method according to any one of claims 1 to 5
The metal catalyst or metal oxide catalyst is selected from the group consisting of palladium, rubidium, nickel, titanium, and titanium dioxide,
Method. The method according to any one of claims 1 to 6
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 7
The "chlorite-supported porous substance" is obtained by impregnating a porous substance with chlorite and further drying.
Method. The method according to any one of claims 1 to 9 ,
The porous material further carries an alkaline agent,
Method. The method of claim 9 , wherein
The alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and lithium carbonate,
Method. The method according to claim 9 or 10 , wherein
The molar ratio of the chlorite to the alkaline agent is 1:0.1 to 2.0,
Method. The method according to any one of claims 9 to 11 ,
The above-mentioned "porous substance supporting chlorite and an alkaline agent" is obtained by impregnating a porous substance with a chlorite and an alkaline agent simultaneously or sequentially and drying.
Method. The method according to any one of claims 1 to 12 ,
The water content of the porous material is 10 wt% or less,
Method.