KR102534711B1 - Method for inactivating airborne microorganisms in space - Google Patents

Abstract

[Problem] To provide a method for inactivating airborne microorganisms by supplying a necessary and sufficient amount of chlorine dioxide gas to a space.
[Solution] As a method of inactivating airborne microorganisms in a space, (1) preparing a solid agent containing (A) a chlorite-supported porous material and (B) a metal catalyst or a metal oxide catalyst, wherein: In the solid medicine, the mass ratio of the chlorite to the metal catalyst or metal oxide catalyst 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 airborne microorganisms exist.

Description

Method for inactivating airborne microorganisms in space

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

Chlorine dioxide gas is a safe gas for the living body of animals at low concentrations (for example, 0.3 ppm or less), but even at such low concentrations, it has an inactivating action against microorganisms such as bacteria, fungi and viruses, a deodorizing action, etc. It is known that there are Because of these characteristics, chlorine dioxide gas has attracted particular attention in applications such as deodorization, sterilization, virus removal, antifungal, antiseptic, etc. in environmental purification and transportation of food.

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 a respiratory virus or the like using a low-concentration chlorine dioxide gas has been proposed so far (for example, Patent Document 1). However, since chlorine dioxide gas can be harmful to the living body of animals at high concentrations and has a risk of explosion, development of a method for stably generating chlorine dioxide gas has been studied for practical use.

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

Therefore, a method of generating chlorine dioxide by irradiating ultraviolet rays to a gel composition composed of a chlorite and a water-absorbent resin (for example, Patent Document 2), or a stabilized chlorine dioxide prepared by impregnating a porous carrier with a chlorite and an alkali agent and drying it A method of generating chlorine dioxide by bringing the stabilized chlorine dioxide agent into contact with air has been proposed (for example, Patent Document 3).

WO/2007/061092 Japanese Unexamined Patent Publication No. 2005-224386 Japanese Unexamined Patent Publication No. 2011-173758

The inventors of the present invention have repeatedly studied a method for stably generating chlorine dioxide in order to put into practical use a method of using chlorine dioxide gas to inactivate airborne microorganisms in space. As a result, the methods described in Patent Document 2 and Patent Document 3 can control the generation of chlorine dioxide, but the efficiency of generating chlorine dioxide is poor, and it is difficult to stably generate a practical amount of chlorine dioxide. I found out.

Further, the inventors of the present invention, for example, as in the invention described in Patent Literature 2, investigated the cause of the poor generation efficiency of chlorine dioxide in a method for generating chlorine dioxide of a type in which ultraviolet rays are irradiated to chlorite in a solid or gel form. . Then, unexpectedly, when ultraviolet rays were irradiated to a drug containing solid chlorite, it was found that not only chlorine dioxide but also ozone was generated, and the amount of chlorine dioxide generated as a whole was reduced by the interference of this ozone with chlorine dioxide. (see also Example 1 and FIG. 3 herein).

Based on the above knowledge, the inventors of the present invention, in a method of using a composition containing solid chlorite as a source of chlorine dioxide, suppressed the generation of ozone while increasing the amount of chlorine dioxide generated as a whole, further review was repeated. As a result, by using light in the visible region (visible light) instead of ultraviolet light, which has conventionally been considered essential for generating chlorine dioxide from solid chlorite, the amount of ozone generated can be reduced, and the amount of chlorine dioxide generated as a whole. has been successfully increased to a practical level. In addition, in order to compensate for the decrease in reactivity due to the use of light in the visible region having lower energy than ultraviolet light, the amount of chlorine dioxide generated from chlorite can be further increased by mixing a metal catalyst or a metal oxide oxide. found out and came to complete the present invention.

That is, the method of the present invention, in one embodiment, is a method of inactivating airborne microorganisms in a space,

(1) preparing a solid agent containing (A) a porous material supported with chlorite and (B) a metal catalyst or metal oxide catalyst,

Here, in the solid drug, the mass ratio of the chlorite and the metal catalyst or metal oxide catalyst is 1: 0.04 to 0.8;

(2) irradiating the solid drug with visible light; and,

(3) It relates to a method comprising supplying chlorine dioxide gas generated from the solid medicine to a space where airborne microorganisms exist.

Further, in the method of the present invention, in one embodiment, the step (3) is "supplying chlorine dioxide gas generated from the solid agent to a space where airborne microorganisms exist, and the concentration of chlorine dioxide gas in the space is set to a concentration at which animals can survive but the airborne microorganisms are inactivated”.

In one embodiment, the method of the present invention is characterized in that the concentration at which the airborne microorganisms are inactivated is 0.00001 to 0.3 ppm, although the animals can survive.

In addition, in the method of the present invention, in one embodiment, in the step (3), when the chlorine dioxide gas concentration in the space is 0.1 to 0.3 ppm, the time for supplying the chlorine dioxide gas into the space, It is characterized in that 0.5 to 480 minutes.

In one embodiment, the method of the present invention is characterized in that the airborne microorganism is an airborne virus or airborne bacteria.

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

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

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

In one embodiment, the method of the present invention is characterized in that the "porous material supported with chlorite" is obtained by impregnating the porous material with chlorite and further drying it.

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

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

In one embodiment, the method of the present invention is characterized in that the molar ratio between the chlorite and the alkali agent is 1:0.1 to 2.0.

Further, in the method of the present invention, in one embodiment, the "porous material supported with chlorite and alkali agent" is obtained by simultaneously or sequentially impregnating the porous material with chlorite and alkali agent and drying it. do.

Further, the method of the present invention, in one embodiment, is characterized in that the moisture content of the porous material is 10% by weight or less.

In another embodiment, the method of the present invention is a method for inactivating airborne microorganisms in a space, comprising:

(1) preparing a unit for generating chlorine dioxide having the following configuration;

The unit includes a medicine storage unit and at least two light source units,

The light source unit is for generating light substantially consisting of a wavelength in the visible region,

In the drug storage unit, a drug containing solid chlorite is stored,

The drug storage unit is provided with one or a plurality of openings so that air can move inside and outside the drug storage unit,

Here, the drug present in the drug storage unit is irradiated with the light generated from the light source unit, thereby generating chlorine dioxide gas; and,

(2) supplying chlorine dioxide gas generated from the chlorine dioxide generating unit to a space where airborne microorganisms exist; Including, it relates to a method.

Further, in the method of the present invention, in one embodiment, the drug storage unit and the at least two light source units are integrally disposed, and the at least two light source units are applied to the drug stored in the drug storage unit. , it is characterized in that light is irradiated in at least two directions.

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

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

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

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

Further, in the method of the present invention, in one embodiment, the solid chlorite-containing agent contains (A) a chlorite-supported porous material, and (B) a metal catalyst or a metal oxide catalyst. Characterized in that it is a drug.

In one embodiment, the method of the present invention is characterized in that the "porous material supported with chlorite" is obtained by impregnating the porous material with an aqueous chlorite solution and further drying it.

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

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

In one embodiment, the method of the present invention is characterized in that the mass ratio of the chlorite to the metal catalyst or metal oxide catalyst in the drug in the drug storage unit is 1:0.04 to 0.8.

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

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

In one embodiment, the method of the present invention is characterized in that the molar ratio of the chlorite salt and the alkali agent in the chemical agent is 1:0.1 to 2.0.

Further, in the method of the present invention, in one embodiment, the "porous material supported with chlorite and alkali agent" is obtained by simultaneously or sequentially impregnating the porous material with chlorite and alkali agent and drying it. do.

In another embodiment, the method of the present invention is characterized in that it is carried out using a chlorine dioxide generating device including the chlorine dioxide generating unit described in any one of the above.

In one embodiment, the chlorine dioxide generating device used in the method of the present invention further includes a blowing unit for sending air to the medicine stored in the medicine storage part in the chlorine dioxide generating unit. characterized by

In addition, in the chlorine dioxide generator used in the method of the present invention, in one embodiment, the blowing unit is a fan for drawing air from the outside to the inside of the chlorine dioxide generator, or a fan of the chlorine dioxide generator. Characterized in that it is a fan for discharging air from the inside to the outside.

Further, 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 storage part is present on the side of the medicine storage part, and the air sent from the blowing part is , It is characterized in that the medicine is sent, at least in part, through an opening present in the side surface of the medicine storage unit.

Further, in the chlorine dioxide generator used in the method of the present invention, in one embodiment, the relative humidity in the medicine storage unit is maintained at 30 to 80% RH by air sent from the blowing unit. to be

Needless to say, any combination of one or more features of the present invention described above without technical contradiction from the viewpoint of those skilled in the art is also included in the scope of the present invention.

According to the method of the present invention, it is possible to stably generate a practical amount of chlorine dioxide. In addition, by adjusting the amount of light to be irradiated, the amount of chlorine dioxide generated can be easily adjusted. Due to these effects, it became possible to stably supply chlorine dioxide gas into the space at a concentration at which animals could survive but airborne microorganisms were deactivated.

Fig. 1 shows a longitudinal sectional view of a unit for generating chlorine dioxide, into which a medicament containing solid chlorite is inserted.
Fig. 2 shows a longitudinal sectional view of the chlorine dioxide generating device in which the chlorine dioxide generating unit of Fig. 1 is inserted.
Fig. 3 is a graph showing changes in measured values of chlorine dioxide concentration and ozone concentration in air when light is irradiated to a drug containing solid chlorite, when the wavelength of the irradiated light is changed.
FIG. 4 is a graph showing the average value of the measured values in the ultraviolet region and the average value of the measured values in the visible region among the measured values of the chlorine dioxide concentration and the ozone concentration in FIG. 3 .
5 is a graph showing changes in the amount of chlorine dioxide generated depending on the shape of a metal catalyst or metal oxide catalyst mixed with the drug when light is irradiated on the drug containing solid chlorite.
Fig. 6 shows the change in the amount of chlorine dioxide generated when the ratio of chlorite to titanium dioxide in a drug containing solid chlorite and a metal catalyst or metal oxide catalyst (titanium dioxide) is changed.
Fig. 7 shows the relationship between the content of titanium dioxide in a solvent containing solid chlorite and a metal catalyst or metal oxide catalyst (titanium dioxide) and the maximum value of the chlorine dioxide concentration generated by irradiation with visible light.
Fig. 8 shows the change in the amount of chlorine dioxide generated when a chemical containing a solid chlorite and a metal catalyst or metal oxide catalyst (titanium dioxide) is continuously irradiated with visible light for a long time.
9 shows a perspective view, a top view, and a side view of a unit for generating chlorine dioxide, which is an embodiment of the present invention.
Fig. 10 shows a schematic diagram of a chlorine dioxide generating device in which a chlorine dioxide generating unit is inserted, which is an embodiment of the present invention.
11 shows a case in which light is irradiated from only one light source unit (plane) and a case in which light is irradiated from two light source units (both sides) to the medicine in the medicine storage unit in the chlorine dioxide generation unit according to an embodiment of the present invention. Comparison of the amount of chlorine dioxide generated is shown.
Fig. 12 shows a case in which light is irradiated from only one light source unit (one side) to the medicine in the drug storage unit in the chlorine dioxide generating unit according to an embodiment of the present invention, and light is emitted from two light source units (both sides). A diagram in which the ratio of the amount of chlorine dioxide generated in the case of irradiation is plotted is shown. In addition, when light is irradiated from two light source units (both sides), compared to the case where light is irradiated from only one light source unit (one side), since it shows that the amount of chlorine dioxide generated is more than doubled, the amount of chlorine dioxide generated The doubled value is used for the amount of chlorine dioxide generated in the case of single-sided irradiation to obtain the ratio.
Fig. 13 shows that in the chlorine dioxide generation unit according to an embodiment of the present invention, when light is irradiated from two light source units (both sides), compared with the case where light is irradiated only from one light source unit (one side), the drug storage unit It is a drawing explaining that it is a drug in the middle and can efficiently reach the light.
Fig. 14 shows a change in the amount of chlorine dioxide generated when the relative humidity in the medicine storage section is changed in the chlorine dioxide generating unit according to an embodiment of the present invention. 14 shows data when light is irradiated only from one light source unit (one side).
Fig. 15 shows time-dependent changes in the amount of chlorine dioxide generated when the relative humidity in the medicine storage section is changed in the unit for generating chlorine dioxide according to an embodiment of the present invention. 15 shows data when light is irradiated from two light source units (both sides).
Fig. 16 shows time-dependent changes in the amount of chlorine dioxide generated when light is intermittently irradiated from two light source units (both sides) to the medicine in the medicine storage unit in the chlorine dioxide generating unit according to an embodiment of the present invention. do. In addition, "10 s/80 s" in the figure means that light is continuously irradiated 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 is stopped for 80 seconds (LED is turned OFF). ) indicates that the cycle is repeated. Similarly, in the drawing, "20s/80s" means that light is continuously irradiated for 2 minutes from the start of irradiation, light is irradiated for 20 seconds (LED is turned ON) after 2 minutes from the start of irradiation, and irradiation of light is stopped for 80 seconds (LED is turned ON). “30s/80s” means that light is continuously irradiated for 2 minutes from the start of irradiation, and after 2 minutes from the start of irradiation, light is irradiated for 30 seconds (LED is turned ON), and light is irradiated for 80 seconds. indicates that the cycle of stopping (LED off) is repeated.
17 shows a schematic diagram of an experiment to inactivate airborne microorganisms in a space using the method of the present invention.
Fig. 18 shows the change in virus titer in the air of the chamber at a chlorine dioxide concentration of about 0.05 ppmv.
Fig. 19 shows the change in virus titer in the air of the chamber at a chlorine dioxide concentration of about 0.1 ppmv.
Fig. 20 shows the change in virus titer in the air of the chamber at a chlorine dioxide concentration of about 0.3 ppmv.
Fig. 21 shows the change in virus titer in the air of the chamber at a chlorine dioxide concentration of about 0.3 ppmv.
22 shows a schematic diagram of the experiment of Example 9.
23 shows the results of the experiment of Example 9.
24 shows a schematic of the experiment of Example 10.
25 shows the results of the experiment of Example 10.

The method of the present invention, in one embodiment, is a method for inactivating airborne microorganisms in a space,

(1) preparing a solid agent containing (A) a porous material supported with chlorite and (B) a metal catalyst or metal oxide catalyst,

wherein, in the solid drug, the mass ratio of the chlorite to the metal catalyst or metal oxide catalyst 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 airborne microorganisms exist; Including, it provides a method.

The space to which the present invention can be applied is not particularly limited, and can be applied to any space that can take a closed state or an open state. For example, according to the present invention, since chlorine dioxide gas can be supplied at a concentration at which animals can survive but airborne microorganisms are inactivated, the present invention can be applied to a space where animals exist. More specifically, the present invention, living spaces (eg, residences, offices), medical institutions (eg, hospital waiting rooms, consultation rooms, treatment rooms, operating rooms, front rooms, hospitalization rooms), research institutions (eg, hospital rooms) , university research labs, front rooms), disaster medical facilities (e.g., disaster containers, tents), public facilities (e.g., stations, airports, schools), vehicles (e.g., private cars, buses, trams) , airplane).

The floating microorganisms in the method of the present invention broadly mean microorganisms that can float in the space,

Examples include airborne viruses, airborne bacteria, and airborne fungi. As floating viruses, viruses with envelopes or viruses without envelopes, such as varicella zoster virus, influenza virus (human, bird, swine, etc.), herpes simplex virus, adenovirus, enterovirus, rhinovirus, and human papilloma Viruses (Human Papilloma Virus), Pox Virus, Coxsackie Virus, Herpes Simplex Virus, Cytomegalo Virus, EB Virus, Adenovirus, Papilloma Virus, JC Virus, Parvovirus, Hepatitis B Virus, Hepatitis C Virus, Lassa Viruses, necocalicivirus, norovirus, sapovirus, coronavirus, SARS virus, rubella virus, mumps virus, measles virus, RS virus, polio virus, coxsackie virus, echo virus, marburg virus, ebola virus, yellow fever viruses, viruses of the field virus family, rabies virus, viruses of the reoviridae family, rotavirus, human immunodeficiency virus, human T lymphotropic virus, monkey immunodeficiency virus, STLV and the like. In addition, as airborne bacteria, Gram-positive bacteria or Gram-negative bacteria, for example, Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, Escherichia coli, streptococcus, gonorrhea, syphilis, meningitis, Mycobacterium tuberculosis, mycobacteria, Klebsiella (bacillus pneumococcal) ), Salmonella, Bacillus botulinus, Proteus, Pertussis bacillus, Serratia, Enterobacteriaceae, Citrobacter, Acinetobacter, Campylobacter, Enterobacter, Mycoplasma, Chlamydia, Clostridium, and the like. Moreover, as a floating fungus, Aspergillus, trichophyte, Maracetia bacterium, candida etc. are mentioned, for example.

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

The time for supplying the chlorine dioxide gas into the space using the method of the present invention is not particularly limited, but the supply time may be appropriately adjusted according to the chlorine dioxide gas concentration to be supplied. For example, when the chlorine dioxide gas concentration in space is 0.00001 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 to 0.1 ppm, the time for supplying the chlorine dioxide gas into the space is preferably 10 to 480 minutes, more preferably 15 to 90 minutes, and 15 to 90 minutes. It is more preferable to set it as 60 minutes. In addition, when the chlorine dioxide gas concentration in the space is 0.1 to 0.3 ppm, the time for supplying the chlorine dioxide gas into the space is preferably 0.5 to 480 minutes, more preferably 1 to 60 minutes, It is more preferable to set it as 2 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 alkali earth metal chlorite include calcium chlorite, magnesium chlorite and barium chlorite. Among these, sodium chlorite and potassium chlorite are preferred, and sodium chlorite is most preferred, from the viewpoint of easy availability. These chlorite may be used individually by 1 type, and even if it uses 2 or more types together, it does not matter.

As the porous material used in the method of the present invention, for example, sepiolite, paligosite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, etc. can be used. Those exhibiting alkalinity are preferred, palygosite and sepiolite being more preferred, and sepiolite being particularly preferred.

In the method of the present invention, a porous material supported with chlorite is used, but the method for supporting the porous material with chlorite is not particularly limited. For example, a "porous material carrying chlorite" can be obtained by impregnating a porous material with an aqueous solution of chlorite and drying it. It is preferable that the moisture content of the "porous material supporting chlorite" is 10% by weight or less, and more preferably 5% by weight or less.

The "porous material carrying chlorite" used in the method of the present invention may have any particle diameter, but in particular those having an average particle diameter of 1 to 3 mm can be suitably used.

The average particle diameter of the "porous substance supported by chlorite" in the method of the present invention is determined by, for example, measuring the particle diameter of the "porous substance supported by chlorite" using an optical microscope, and subjected to statistical processing. It can be calculated by performing and calculating the average value and standard deviation.

The concentration of chlorite in the "porous material supporting chlorite" used in the method of the present invention is effective if it is 1% by weight or more, but if it exceeds 25% by weight, it is a polar substance, so it is 1% by weight or more 25% by weight % or less is preferable, and it is more preferable that it is 5 weight% or more and 20 weight% or less.

As a metal catalyst or metal oxide catalyst used in the method of this invention, palladium, rubidium, nickel, titanium, and titanium dioxide are mentioned, for example. Among these, titanium dioxide is particularly suitably used. In addition, titanium dioxide is sometimes simply called 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 form or particulate form, and depending on the mixing ratio of the chlorite in the drug and the metal catalyst or metal oxide catalyst, those skilled in the art can suitably select the form can choose For example, when the proportion of the metal catalyst or metal oxide catalyst in the drug is relatively high, a particulate metal catalyst or metal oxide catalyst can be selected, and when the proportion of the metal catalyst or metal oxide catalyst in the drug is relatively low, a powdery catalyst can be selected. Metal catalysts or metal oxide catalysts may be selected, but are not limited thereto.

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

The mass ratio of chlorite to metal catalyst or metal oxide catalyst in the solid agent used in the method of the present invention may be chlorite:metal catalyst or metal oxide catalyst = 1:0.04 to 0.8, preferably 1:0.07. to 0.6, more preferably 1:0.07 to 0.5. In the drug, both when the content of the metal catalyst or metal oxide catalyst exceeds 1 times the content of chlorite, and when the content of the metal catalyst or metal oxide catalyst is less than 0.04 times the content of chlorite. However, the amount of chlorine dioxide generated when irradiated with visible light can be reduced.

The "porous substance supported by chlorite" used in the method of the present invention may further contain an alkali agent.

Examples of the alkali agent used in the preparation of the drug used in the method of the present invention include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, rubidium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate, but preferably Sodium hydroxide can be used. By additionally supporting an alkali agent on the "porous substance supported with chlorite", the pH of the agent used in the present invention can be adjusted, the stability of the agent itself is improved, and unnecessary storage such as when not irradiated with light is performed. The release of chlorine dioxide can be suppressed.

The amount of the alkali agent used in the preparation of the chemical used in the method of the present invention is appropriately 0.1 equivalent or more and 2.0 equivalent or less, preferably 0.1 equivalent or more and 1.0 equivalent or less, based on chlorite (mol). is 0.1 equivalent or more and 0.7 equivalent or less. If it is less than 0.1 equivalent, the supported chlorite may decompose even at room temperature, and if it exceeds 2.0 equivalent, stability is improved, but it is not preferable because chlorine dioxide is difficult to generate and the generated concentration is lowered.

In the preparation of the chemical used in the method of the present invention, the method of further supporting the alkali agent on the "porous material supported by the chlorite" is not particularly limited, but for example, the chlorite and the alkali agent are simultaneously or sequentially As such, it is good to use a method of impregnating a porous material and drying it. In addition, in this specification, there are cases where the target composition is obtained by subjecting a porous substance to "spray adsorption" and/or an alkali agent to be dried, but in this specification, the term "spray adsorption" refers to the term "impregnation" It shall be included in ".

In another embodiment, the method of the present invention is a method for inactivating airborne microorganisms in a space, comprising:

(1) preparing a unit for generating chlorine dioxide having the following configuration;

The unit includes a medicine storage unit and at least two light source units,

The light source unit is for generating light substantially consisting of a wavelength in the visible region,

In the drug storage unit, a drug containing solid chlorite is stored,

The drug storage unit is provided with one or a plurality of openings so that air can move inside and outside the drug storage unit,

Here, the drug present in the drug storage unit is irradiated with the light generated from the light source unit, thereby generating chlorine dioxide gas; and,

(2) supplying chlorine dioxide gas generated from the chlorine dioxide generating unit to a space where airborne microorganisms exist; Including, it provides a method.

In the chlorine dioxide generation unit used in the method of the present invention, at least two light source units (for example, 2, 3, 4, 5, 6 or more light source units) are provided, but the at least two light source units The positional relationship is not particularly limited as long as light can be irradiated from at least two directions (for example, 2, 3, 4, 5, 6 or more directions) to the drug that is the source of chlorine dioxide. Preferably, the at least two light source units are arranged in symmetrical positions around the drug that is the 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 including the visible region. Therefore, the wavelength of light generated from the light source used in the method of the present invention is not limited only to the wavelength of light in the visible region (360 to 830 nm), and the wavelength of light in the ultraviolet region (~360 nm) and the wavelength of light in the infrared region. Even light containing (830 nm -) may be used. However, when a drug containing solid chlorite is irradiated with light of a wavelength in the ultraviolet region, ozone is likely to be generated as a by-product, and light of a wavelength in the infrared region is weak in energy. Even when irradiated with chemicals, the amount of chlorine dioxide generated is small. Therefore, it is preferable that the light emitted from the light source used in the method of the present invention substantially consists of light having a wavelength in the visible region. The light generated from the light source used in the method of the present invention is preferably light with a wavelength of 360 to 450 nm, more preferably light with a wavelength of 380 to 450 nm or 360 to 430 nm, and light with a wavelength of 380 to 430 nm. is most preferable

Whether the wavelength of light emitted from the light source is substantially within a specific wavelength range can be confirmed by measuring the wavelength or energy of light generated from the light source using a known measuring device.

The light source used by the method of the present invention is not particularly limited as long as it generates light of a wavelength in the visible region, but examples include a lamp (incandescent lamp, LED lamp), a chip, a laser device, etc. that generate light in the visible region. , you can use a variety of From the viewpoint of directivity of light generated from the light source and also from the viewpoint of miniaturization of the device, it is preferable to use a chip-type light source. Since the light source in the form of a chip has a narrow directivity, the light is not diffused, so that the light can be efficiently irradiated to the object to be irradiated, and the efficiency of generating chlorine dioxide of the device can be improved. Further, from the viewpoint of limiting the wavelength of light generated from the light source and not including light in the ultraviolet or infrared region, it is preferable to use an LED that generates light in the visible region as the light source. Further, from the viewpoint of miniaturization of the device and the efficiency of generating chlorine dioxide, the light source used in the present invention is most preferably an LED chip that generates light in the visible region.

In addition, the light source used in the method of the present invention may be any light source capable of intermittently irradiating light. For example, the light source used in the method of the present invention may be a light source that repeats a cycle of irradiating light for a certain period of time and then stopping light irradiation for a certain period of time. The control method of the light source for intermittently irradiating light is not particularly limited, and can be implemented using a known method by those skilled in the art. That is, the step of irradiating the solid drug with visible light in the method of the present invention may be a 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 integrally disposed or may be separately disposed. In order to irradiate light efficiently, it is preferable to arrange integrally. Here, the light source unit and the drug storage unit may be integrally disposed or connected in a non-separable form, or may be integrally disposed or connected in a separable form. In the case where the light source unit and the drug storage unit are integrally disposed or connected in a separable fashion, the drug storage unit may be a replaceable cartridge.

The medicine container used in the method of the present invention is not limited in its material or structure as long as it has one or more openings so that air can move inside and outside. For example, by using a known light-transmitting material as the material of the drug storage unit (particularly, the surface of the drug storage unit to which light from the light source unit is directly irradiated), the light emitted from the light source unit is transmitted to the medicine inside the drug storage unit. can be investigated with Preferably, the material of the drug storage unit is made of a resin that substantially transmits light in the visible region, so that the light generated from the light source unit is not absorbed by the resin and irradiates the drug inside the drug storage unit. In the present specification, the resin that substantially transmits light of a wavelength in the visible region may be a resin that transmits, for example, 80% or more of the light of a wavelength in the visible region that is irradiated. Any resin that transmits 90% or more of the light of the wavelength may be used, and more preferably, it may be a resin that transmits 95% or more of the light of the wavelength of the visible region irradiated. Specifically, as a material for the surface of the drug storage unit to which light from the light source unit is directly irradiated, for example, acrylic, vinyl chloride, and PET materials can be used, but it is not particularly limited thereto.

Further, for example, the medicine storage unit can also be constituted by a mesh plate having meshes to the extent that stored objects do not overflow. According to this configuration, the air outside the medicine storage unit can move inside and outside the medicine storage unit, and the light generated in the light source unit is irradiated to the medicine inside the medicine storage unit through the mesh.

In addition, one or more openings of the drug container used in the method of the present invention may be covered with an air permeable sheet. In this specification, a "breathable sheet" means gas (e.g., air, gas, moisture, etc.) passes through, but does not substantially pass solid substances (e.g., powder-like objects, particulate objects). It means a sheet-like structure that does not The "breathable sheet" in the present invention may further have a property of not substantially passing liquid (eg, water droplets). The material of the air permeable sheet in the present invention is not limited, but, for example, a material made into a sheet form by bonding or entangling fibers by thermal/mechanical or chemical action, a microporous film (a material having many very small holes) of film) alone or overlapping multiple layers, non-porous materials that enable the movement of gas, air, or moisture (vapor), coating-type materials with strong water-repellent treatment applied to high-density fabrics, or these materials A material formed by combining can be exemplified. More specifically, as an air permeable sheet in the present invention, for example, nonwoven fabric (Elves (registered trademark, manufactured by Unitica Co.), Axta (registered trademark, manufactured by Torre Co.), etc.), Gore-Tex (registered trademark) Exepol (registered trademark, manufactured by Mitsubishi Jushi Co., Ltd.: a material that combines microporous polyolefin film and various nonwoven fabrics, etc., excellent in breathability, moisture permeability, and waterproofness), Entrant E (registered trademark, manufactured by Torres), etc. can Further, the air-permeable sheet in the present invention preferably has heat-sealing properties (thermal welding properties) in order to facilitate attachment to the medicine storage unit.

Regarding the shape and thickness of the air permeable sheet used in the drug storage unit, the air permeable sheet at the boundary between the inside and outside of the drug storage unit is "permeable to gas, air, and moisture, but passes through an object of a certain size." A person skilled in the art can select it appropriately as long as the purpose of "do not let it be done" can be achieved. For example, when a nonwoven fabric is used as an air permeable sheet, the basis weight is 15 to 120 g/m2 (preferably 40 to 100 g/m2, more preferably 50 to 80 g/m2), and the thickness is 0.1 to 1.0 mm (preferably 0.1 to 1.0 mm). Preferably 0.2 to 0.5 mm, more preferably 0.2 to 0.4 mm) can be used.

In one embodiment, the method of the present invention may be carried out using a chlorine dioxide generator equipped with the unit for generating chlorine dioxide of the present invention. The chlorine dioxide generator used in the method of the present invention may further include a blowing unit for sending air to the medicine stored in the medicine container of the chlorine dioxide generating unit. The blowing unit may be for drawing air from the outside of the device to the inside, or may be for discharging air from the inside of the device to the outside.

In the chlorine dioxide generator used in the method of the present invention, the blower for sending air to the medicine stored in the medicine container may be, for example, a fan or an air pump, but a fan is preferable. By providing such an air blowing unit, more air can be supplied to the medicine inside the medicine storage part. By supplying more air to the chemical, the frequency of contact between the chemical containing the solid chlorite and moisture (steam) in the air increases, so that chlorine dioxide is easily generated from the solid chlorite irradiated with light.

In the chlorine dioxide generator used in the method of the present invention, the relative humidity in the chemical storage section is set to 30 to 80%RH (preferably 40 to 70%RH, more preferably 40 to 70%RH, more preferably 40 to 60% RH). By adjusting the relative humidity in the medicine storage unit to the above range, the amount of chlorine dioxide generated can be increased.

In addition, in the chlorine dioxide generator used in the method of the present invention, as another method for supplying water vapor in the air into the medicine storage unit, a Peltier element (Peltier effect) that condenses and collects moisture in the air can also be used ( It can also work to increase humidity by using the defect of the Peltier element that intrusion of water vapor or condensation occurs).

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

In addition, since the chlorine dioxide generation unit used in the method of the present invention is small, the method of the present invention can be implemented by inserting it into a home appliance or the like that does not generate chlorine dioxide as its main purpose. For example, the present invention can be implemented by inserting the chlorine dioxide generating unit used in the method of the present invention into a home appliance or the like that does not generate chlorine dioxide as its main purpose, and supplying chlorine dioxide gas. For example, by inserting the chlorine dioxide generating unit used in the method of the present invention into air conditioning equipment such as heating equipment, cooling equipment, air purifiers, and humidifiers, the effect of the wind discharged from the air conditioning equipment causes the chlorine dioxide generating unit to While the generation of chlorine dioxide in the air conditioner is promoted, the chlorine dioxide can be efficiently diffused into the space by being carried by the wind discharged from the air conditioning equipment into the space.

Terms used in this specification are used to describe specific embodiments, and are not intended to limit the invention.

In addition, the term "includes" used in this specification intends that the described items (members, steps, elements, numbers, etc.) exist, except where clearly different understandings are required from the context. It does not exclude the existence of other matters (such as members, steps, elements or numbers).

Unless otherwise defined, all terms (including technical terms and scientific terms) used herein have the same meaning as is widely understood by one of ordinary skill in the art to which this invention belongs. The terms used herein are to be interpreted as having a meaning consistent with the meaning in this specification and in the related art, unless a different definition is specified, and is idealized, or in an overly formal sense. It does not have to be interpreted.

Embodiments of the present invention are sometimes described with reference to schematic diagrams, but in the case of schematic diagrams, they are sometimes exaggeratedly expressed in order to clarify the description.

In this specification, for example, when "1 to 10%" is expressed, those skilled in the art will understand that the expression is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10% individually. Understand what is specifically pointed out.

In this specification, all numerical values used to indicate component content or numerical ranges are interpreted as including the meaning of the term "about" unless otherwise specified. For example, "10 times" is understood to mean "about 10 times" unless otherwise specified.

Documents cited in this specification should be regarded as having all of these disclosures incorporated in this specification, and those skilled in the art, in accordance with the context of this specification, may refer to these prior art documents without departing from the spirit and scope of the present invention. It is understood by integrating the relevant disclosure content in the text as part of this specification.

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

Example

Example 1: Change in the amount of chlorine dioxide generated by the wavelength of irradiated light

In this Example, tests were conducted using the chlorine dioxide generator unit and chlorine dioxide generator described in FIGS. 1 and 2 .

Fig. 1 is a longitudinal cross-sectional view showing the internal structures of a chemical storage unit and a light source unit of a unit for generating chlorine dioxide used in this embodiment. As shown in FIG. 1, the unit 10 for generating chlorine dioxide is equipped with the chemical|medical agent storage part 11 and the light source part (LED chip 12 and operation board 13) which generate light of a visible region. The drug storage unit 11 contains a test drug 14 . The medicine container 11 has an opening 16 so that air can move inside and outside. The unit 10 for generating chlorine dioxide has a tube 15 for guiding air outside the device into the device.

The air introduced from the tube 15 is supplied to the inside of the medicine container 11 through the opening 16 . Water vapor contained in the supplied air is absorbed by the chlorite in the test agent 14. Light in the visible region generated from the light source unit passes through the bottom surface of the drug storage unit 11 and is irradiated to the test drug 14 present inside the drug storage unit 11 . Chlorite containing water vapor reacts with the irradiated light to generate chlorine dioxide. Titanium dioxide contained in the test agent 14 together with chlorite promotes a reaction in which chlorine dioxide is generated from chlorite by irradiating light in the visible region. Generated chlorine dioxide is discharged to the outside through the opening (16).

Fig. 2 is a longitudinal sectional view showing the overall structure of the chlorine dioxide generator used in this embodiment. As shown in Fig. 2, the chlorine dioxide generator 20 includes a chlorine dioxide generator unit 21 inside. The device main body 22 of the chlorine dioxide generator 20 includes an air supply port 23 for introducing air outside the device into the device, and an air outlet 25 for discharging air inside the device to the outside of the device. to provide In addition, the chlorine dioxide generator 20 includes a fan 24 inside in order to efficiently introduce air into the device.

By driving the fan 24, air is introduced from the air supply port 23 into the inside of the main body 22 of the device. The introduced air passes through the chlorine dioxide generation unit 21 installed inside the device and is discharged from the air discharge port 25. In the unit 21 for generating chlorine dioxide, since chlorine dioxide is generated by the same mechanism as the device described in FIG. 1, the air discharged from the air outlet 25 contains chlorine dioxide.

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

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

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

As shown in Fig. 3, it was found that when the wavelength of the light irradiated on the drug was shifted from the ultraviolet region to the visible region, the ozone concentration in the air was maximized in the ultraviolet region and decreased from the ultraviolet region to the visible region. . On the other hand, surprisingly, it was found that the concentration of chlorine dioxide in air increased from the ultraviolet region to the visible region. From this result, those skilled in the art can understand that the range of wavelengths suitably used in the present invention exceeds 430 nm, which is the upper limit of the measurement range of this embodiment, and, for example, at least a wavelength of about 450 nm can be used without problems. can understand that

Further, as shown in FIG. 4 , comparing average values of ozone concentration and chlorine dioxide concentration in air in the ultraviolet region and the visible region, the ozone concentration decreased by about 43% from the ultraviolet region to the visible region. In contrast, the chlorine dioxide concentration rose from the ultraviolet to the visible range by about 213%.

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

Example 2: Change in the amount of chlorine dioxide generated by the shape of the catalyst

In Sample 1 used in this Example, a drug was prepared in the same manner as in Example 1, except that particulate titanium dioxide (prepared by firing titanium) was used. In samples 2 and 3 used in this example, drugs were prepared in the same manner as in example 1.

The drugs (Samples 1 to 3) prepared by the above method were stored in the drug storage unit of the chlorine dioxide generator described in Example 1, respectively. For Samples 1 and 2, air was introduced into the apparatus at 1 L/min from the opening of the medicine storage unit, and 405 nm light was irradiated from the LED chip of the light source unit. In Sample 3, air was only introduced into the apparatus at 1 L/min from the opening of the medicine storage portion, but no light was irradiated. The concentration of chlorine dioxide contained in the air discharged from the apparatus until 11 hours after the start of the irradiation was measured. The measurement results for each of Samples 1 to 3 are shown in FIG. 5 .

As shown in FIG. 5, when particulate titanium dioxide is mixed in the drug (Sample 1), chlorine dioxide is generated more efficiently than when particulate titanium dioxide is mixed in the drug (Sample 2). knew what could be

Example 3: Examination of the content ratio of chlorite and titanium dioxide in drugs

70 g of 10 wt% sodium chlorite aqueous solution was spray-adsorbed on 100 g of sepiolite and dried, and then 20 g of 10 wt% sodium hydroxide aqueous solution was spray-adsorbed and dried. Here, powdery titanium dioxide was mixed in varying amounts to form a test agent used in this example. Irradiation of the test drug with visible light was performed with the same chlorine dioxide generator and irradiation method as in Example 1, and the measurement of the chlorine dioxide concentration was also performed 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 to titanium dioxide in the composition of the present invention is changed. Table 6 shows the relationship between the content of titanium dioxide (wt%) in the drug, the mass ratio of chlorite and titanium dioxide in the drug, and the concentration of chlorine dioxide (ppm) contained in the air 1 hour after the start of irradiation with visible light. 1. 7 shows the relationship between the content of titanium dioxide in the drug of the present invention and the maximum value of the chlorine dioxide concentration generated by irradiation with visible light.

As shown in Figs. 6, 7 and Table 1, the amount of chlorine dioxide generated when the test drug is irradiated with visible light increases as the mass ratio of titanium dioxide to chlorite in the drug increases from 0 to about 0.3. , a gradual decrease was shown when the mass ratio of titanium dioxide to chlorite exceeded about 0.3. It was also found that when the mass ratio of titanium dioxide to chlorite in the composition exceeded about 1.0, the amount of chlorine dioxide generated was lower than when titanium dioxide was not mixed.

Fig. 8 is a diagram showing the change in the amount of chlorine dioxide generated when the test drug in 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, as shown in the results shown in Figs. 6 and 7, the mixing ratio (mass ratio) of chlorite and titanium dioxide in the test agent was 1:0.04 to 1:0.04. When it is set to 0.8 (preferably 1:0.07 to 0.6, more preferably 1:0.07 to 0.5), it is possible to stably and continuously release high-concentration chlorine dioxide compared to when the mixing ratio is set to other ranges. It was confirmed that there is

Example 4: Examination of the sandwich structure of the light source unit

In the present invention, the effectiveness of the sandwich structure of the light source unit was tested. In this Example, an experiment was conducted using the chlorine dioxide generating unit shown in FIG. 9 and the chlorine dioxide generating device shown in FIG. 10 .

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

The air introduced from the air introduction part 36 is supplied to the inside of the medicine storage part 32 . Water vapor contained in the supplied air is absorbed by the test drug stored in the drug storage section 32 . Light in the visible region generated from the light source unit passes through the exterior portion 35 of the drug storage portion 32 and is irradiated to the drug stored inside the drug storage portion 32 . The test chemical containing water vapor reacts with the irradiated light to generate chlorine dioxide. 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 generator 40 of the present invention is an embodiment of the present invention, a chlorine dioxide generator unit (LED chip mounting substrate 41, and chemical storage unit 42) is provided inside. The chlorine dioxide generator further includes a blower fan 44 therein, and by driving the blower fan 44, air is supplied to the inside of the chlorine dioxide generator unit. By controlling the driving of the blowing fan 44, the relative humidity in the chemical storage unit in the chlorine dioxide generating unit can be adjusted.

By driving the blowing fan 44, air is supplied from the air inlet of the chlorine dioxide generating unit to the inside of the chemical storage unit. Water vapor contained in the supplied air is absorbed by the test drug stored in the drug storage unit. Light in the visible region generated from the light source unit passes through the exterior of the drug storage unit and is irradiated to the drug stored inside the drug storage unit. The test chemical containing water vapor reacts with the irradiated light to generate chlorine dioxide. Generated chlorine dioxide is discharged to the outside through the gas generating port.

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

In Examples and Comparative Examples, the results of measuring time-wise changes in the chlorine dioxide concentration in the chamber are shown in FIG. 11 . Moreover, the ratio of the chlorine dioxide concentration in the chamber in the Example and the comparative example in each time from the start of irradiation is shown in FIG. 12, in the case of irradiating light from two light source units (both sides), compared to the case of irradiating light only from one light source unit (single side), to show that the amount of chlorine dioxide generated is more than doubled. , The chlorine dioxide generation amount in the case of single-side irradiation for obtaining the ratio of the chlorine dioxide generation amount uses a doubled value.

As shown in Figs. 11 and 12, when visible light is irradiated from two light source units (both sides), the amount of chlorine dioxide generated is surprisingly more than doubled compared to when visible light is irradiated from only one light source (one side). It appeared to be Moreover, as shown in FIG. 12, it was also found that the value of the ratio of the amount of chlorine dioxide generated in Examples to the amount of chlorine dioxide generated in Comparative Examples further increased with the passage of time.

The above results can be explained by FIG. 13 . That is, since the light intensity decreases exponentially as the light passes through the medium, it is difficult for the light to reach the inside or the inside of the drug when irradiated from only one side, so it is important to efficiently irradiate the entire drug with light. It is difficult. However, by irradiating the drug with light from two directions (or two or more directions), it became possible to supply light in an amount necessary for the reaction to the inside of the drug, and it became possible to efficiently generate chlorine dioxide.

Example 5: Examination of Relative Humidity of Medicine Storage Unit

Using the chlorine dioxide generating unit shown in FIG. 9 and the chlorine dioxide generating device shown in FIG. 10 , changes in the amount of chlorine dioxide generated according to the relative humidity in the chemical storage unit were examined.

The same conditions as in Example 4 were used for the measurement of the medicine stored in the medicine storage unit, the visible light irradiation method, and the chlorine dioxide concentration. The relative humidity in the medicine storage unit was regulated by controlling the amount of air supplied to the medicine storage unit (ie, the amount of water vapor supplied to the medicine) by driving the blowing fan. 14 and 15 show the relationship between the relative humidity in the medicine storage unit and the chlorine dioxide concentration in the chamber. Fig. 14 shows the average value of the chlorine dioxide concentrations measured multiple times during light irradiation for 0.5 to 2 hours and their standard deviation, and Fig. 15 shows the time-lapse change of the chlorine dioxide concentration in the chamber.

As shown in Fig. 14, the amount of chlorine dioxide generated is increased by adjusting the relative humidity in the medicine storage unit to 30 to 80%RH (preferably 50 to 70%RH, more preferably 40 to 60%RH). Something that could be done appeared. In addition, when the relative humidity in the medicine storage unit is less than 30%, the moisture required for the reaction of generating chlorine dioxide from chlorite is insufficient, and when the relative humidity exceeds 80%, the chlorine dioxide generated in the condensed water is difficult to dissolve. Therefore, it is thought that the amount of chlorine dioxide released as a gas is reduced.

Further, as shown in FIG. 15, by adjusting the relative humidity in the medicine storage unit to 30 to 80%RH (preferably 40 to 70%RH, more preferably 40 to 60%RH), the relative humidity is 30% RH. Compared to the case of less than %, even if time elapses from the start of irradiation, the released chlorine dioxide concentration can be maintained high. In addition, even when the relative humidity is 20%, it is considered that the reason why the chlorine dioxide concentration in the initial stage of irradiation is high is that a certain amount of water is contained in the drug itself before the start of irradiation.

Example 6: Examination of usefulness of intermittent irradiation

Using the unit for generating chlorine dioxide described in FIG. 9 , the usefulness of intermittent irradiation of visible light in the present invention was examined.

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

(1) The cycle of continuously irradiating light for 2 minutes from the start of irradiation, irradiating light for 10 seconds (LED turned ON) after 2 minutes from the start of irradiation, and stopping irradiation of light for 80 seconds (LED OFF) was repeated.

(2) The cycle of continuously irradiating the light for 2 minutes from the start of irradiation, irradiating the light for 20 seconds (LED ON), and stopping the irradiation of light (LED OFF) for 80 seconds after 2 minutes from the start of irradiation was repeated.

(3) The cycle of continuously irradiating light for 2 minutes from the start of irradiation, irradiating light for 30 seconds (LED turned ON) after 2 minutes from the start of irradiation, and stopping irradiation of light for 80 seconds (LED OFF) was repeated.

The results of this test are shown in FIG. 16 . In addition, "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 set to 1.

As shown in Fig. 16, in the present invention, visible light was intermittently irradiated from the light source unit, and chlorine dioxide at a desired concentration could be generated by adjusting the balance between the irradiation time and the stop time in the intermittent irradiation.

Further, in the present invention, by intermittently irradiating visible light from the light source unit, it was possible to prevent relatively high-concentration chlorine dioxide from being released at the beginning of irradiation. In the case where visible light is continuously irradiated from the light source unit (i.e., when intermittent irradiation is not performed), the chlorine dioxide generation concentration is maximized at the beginning of irradiation and then gradually decreases, as shown in the graph of FIG. 6, for example. That is, in the present invention, chlorine dioxide can be released more stably by intermittently irradiating visible light from the light source unit.

In addition, as a matter of course, when visible light is intermittently irradiated from the light source unit, the consumption of a chemical containing solid chlorite, which is a source of chlorine dioxide, can be suppressed compared to the case where visible light is continuously irradiated from the light source unit. 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 airborne microorganisms using a chlorine dioxide generator (1)

In order to prove that the chlorine dioxide generator into which the chlorine dioxide generating unit of this invention was inserted can be effectively used for inactivating airborne microorganisms in space, the following experiment was conducted.

1. Experimental Materials and Experimental Equipment

(test virus)

Escherichia coli phage phiX174 (NBRC 103405)

(Host bacteria)

Escherichia coli (NBRC 13898)

(gazogene)

Chlorine dioxide generating device incorporating the chlorine dioxide generating unit of the present invention

(experimental instrument)

1㎥ chamber (special order)

14㎖ Tube (352059, FALCON)

Platinum Lee (INO-001, IWAKI)

AC FAN(MU1225S-11, ORIX)

Nebulizer (NE-C29, OMRON)

HEPA filter for exhaust (ultra-small special filter for exhaust, OSHITARI LABORATORY)

Impinger (Biosampler, 5㎖, SKC)

(experimental device)

Shaking Incubator (AT12R, THOMAS)

Chlorine dioxide gas sensor (ClO ₂ , 1000ppb, INTERSCAN)

Chlorine dioxide gas sensor (Midas GAS Detector, ClO ₂ , MIDAS-E-BR2, Honeywell)

Particle Counter (KC-52, RION)

Air filter for particle removal (MAC-11FR-UL, Nippon Air Tech)

Spectrophotometer (V-560, JASCO)

Thermostat (MCO-175, SANYO)

Air Pump (SPP-25GA, TECHNO TAKATSUKI)

Thermo-hygrometer (PC-5000TRH, SATO)

Ion chromatograph (HIC-20ASP, SHIMADZU)

(experimental material)

NB Badge (234000, Nutrient Broth, Difco)

702 medium (polypeptone 10g, yeast extract 2g, magnesium sulfate heptahydrate 1g, distilled water 1L)

Ordinary agar medium (E-MP21, Eiken Kagaku)

Agar (Bacto Agar 214010, BD)

2. Experimental method

(Adjustment of test virus solution)

The pre-cultured preserved strain Escherichia coli was inoculated into 5 ml of NB+0.5% NaCl liquid medium, and cultured with shaking at 30° C. and 200 rpm for 6 hours. 100 μl of cultured Escherichia coli (about 1×10 ⁹ cell/ml) and 500 μl of phage phiX174 (about 1×10 ⁵ PFU/ml) in NB+0.5% NaCl liquid medium were mixed and incubated at 37° C. for 5 minutes. 3 ml of NB+0.5% NaCl medium (0.6% agar) was added to the mixed solution, mixed, and then layered on normal agar medium, followed by incubation at 37°C for 18 hours. 2 ml of NB+0.5% NaCl liquid medium was added to the top agar to recover, and filtered through a 0.22 μm filter was dispensed and stored at -85°C. A portion thereof was subjected to plaque assay according to a conventional method to obtain a virus solution of about 1×10 ¹⁰ PFU/ml. After dissolving the virus frozen at -85°C before the test, a solution diluted 10 times with distilled water was used as a test virus solution (spray; 1×10 ^{8 to 9} PFU/ml).

(experimental method)

An outline of the experiment in this example is shown in FIG. 17 .

The chlorine dioxide generator of the present invention was installed in the center of a 1 m3 chamber, and the chlorine dioxide gas concentration in the chamber was adjusted to 0.05, 0.1, or 0.3 ppmv by operating the device while controlling on and off by a timer. The phiX174 phage virus (about 1×10 ^{8 to 9} PFU/ml) was sprayed at a rate of 0.2 ml/min for 5 minutes using a nebulizer in a chamber having a stable gas concentration. After 0, 30, 60, 75, and 90 minutes in a chamber with a chlorine dioxide concentration of about 0.05 ppmv, and after 0, 15, 30, 45, and 60 minutes in a chamber with a chlorine dioxide concentration of about 0.1 ppmv, In the chamber in which the chlorine dioxide concentration was about 0.3 ppmv, after 0, 5, 10, 15, and 30 minutes, the air containing the virus was recovered using an impinger. The recovered viruses were subjected to plaque assay, and the number of viruses in 10 L of air was determined and evaluated. Similarly, it was set as the control that the LED of the chlorine dioxide generator was always turned OFF.

(monitoring of 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 compared with the gas concentration value obtained by the ion chromatography method and corrected.

3. Results

Fig. 18 shows the change in virus titer in the air of the chamber where the chlorine dioxide concentration is about 0.05 ppmv, and Fig. 19 shows the change in the virus titer in the air in the chamber where the chlorine dioxide concentration is about 0.1 ppmv. Fig. 20 shows the change in virus titer in the air of the chamber at a concentration of about 0.3 ppmv. In addition, the experiment shown in FIG. 18 was carried out 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 carried out under conditions of temperature: 22.9±0.2° C. and relative humidity: 59.4±0.4%. The experiments conducted under the conditions of 0.7% and shown in FIG. 20 were conducted under the conditions of temperature: 23.1±0.3° C. and relative humidity: 59.3±0.5%.

In the case of a 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 at 75 minutes (FIG. 18) and 9.3×10 ⁴ PFU/10L at 45 minutes (FIG. 18). 19), and 1.2×10 ⁶ PFU/10L at 15 minutes (FIG. 20).

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 75 minutes of exposure time, and the control (1.5 × 10 ⁵ PFU /10L) was reduced by more than 2 log ₁₀ (more than 99%) (FIG. 18).

When the chlorine dioxide gas concentration is 0.08 ppmv, the virus titer becomes 2.0 × 10 ² PFU/10 L at 45 minutes of exposure time, and decreases by 2 log ₁₀ or more (99% or more) compared to the control (9.3 × 10 ⁴ PFU/10 L). was (FIG. 19).

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

From the above results, by using the chlorine dioxide generator in which the chlorine dioxide generator unit of the present invention is inserted, chlorine dioxide gas is supplied into the space at a concentration safe for humans (0.3 ppm or less), thereby eliminating airborne microorganisms in the space in a short time. It has been proven that inactivation is possible. In addition, by supplying chlorine dioxide gas into the space at a concentration of about 0.3 ppm using a chlorine dioxide generator in which the chlorine dioxide generator unit of the present invention is inserted, airborne microorganisms in the space can be eliminated in a very short time (15 minutes or less). It has been proven that it can be almost completely inactivated.

4. Consideration

There is a report on measuring the number of airborne influenza viruses in a hospital emergency department by Blachere et al. (Blachere, MF, et. al. Measurement of airborne influenza virus in a hospital emergency department. Clin. Infect. Dis. 48, 438-440 (2009) ). In this document, using a National Institute for Occupational Safety and Health 2-stage cyclone aerosol sampler, indoor air was sucked at 3.5 L/min for 4 hours, and the number of influenza viruses present in the air was measured. As a result, in the waiting room It is described that 16,278 virus particles were detected. When the virus concentration contained in the space is calculated from this result, it is about 1.9×10 ² The number of virus particles/10 L. That is, in a space where there is a high possibility that a large amount of influenza virus exists (for example, a hospital where many influenza virus patients visit), the influenza virus concentration in the space is considered to be about 1.9×10 ² number of virus particles/10 L. do.

The virus concentration used in this 0.05ppm chlorine dioxide gas exposure experiment was about 7.5×10 ⁵ PFU/10L, and compared to the example of the hospital first aid department, the virus inactivation effect was about 3900 times higher despite the high virus concentration conditions. It is shown that has appeared sufficiently. Therefore, when the influenza virus concentration in the space is about 1.9 × 102 number of virus particles/10 L, it is considered that the virus can be inactivated with a chlorine dioxide gas concentration of about 0.00001 ppm (0.05 ppm/3900).

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 generator unit of the present invention can inactivate airborne microorganisms in a space in a very short time (for example, 10 minutes or less), the following additional experiments were conducted.

1. Experimental Materials and Experimental Equipment

The same as in Example 7 was used.

2. Experimental method

Regarding the adjustment of the test virus solution and the monitoring of the chlorine dioxide gas concentration, the same method as in Example 7 was used.

(experimental method)

The chlorine dioxide generator of the present invention was installed in the center of a 1 m3 chamber, and the chlorine dioxide gas concentration in the chamber was adjusted to about 0.3 ppmv by operating the device while controlling on and off by a timer. The phiX174 phage virus (about 1×10 ^{8 to 9} PFU/ml) was sprayed at a rate of 0.2 ml/min for 1 minute using a nebulizer in a chamber having a stable gas concentration. After 0, 2, 4, and 6 minutes from spraying the virus, the air containing the virus was recovered using an impinger. The recovered viruses were subjected to plaque assay, and the number of viruses in 10 L of air was determined and evaluated. Similarly, it was set as the control that the LED of the chlorine dioxide generator was always turned OFF.

3. Results

In the case of 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 a 1 m3 chamber was 9.2 × 10 ⁴ PFU/10 L in 2 minutes and 8.5 × 10 ⁴ PFU/ in 4 minutes. It was 6.3×10 ⁴ PFU/10L at 10L and 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/10L at 2 minutes of exposure time and 4 minutes of exposure time. 2.8 × 10 ³ PFU/10L and 9.1 × 10 ² PFU/1OL at 6 min of exposure time, respectively, 82.9% (2 min exposure), 96.8% (4 min exposure), and 98.6% (6 min exposure) relative to the control. ) was reduced (FIG. 21).

From the above results, by using the chlorine dioxide generator in which the chlorine dioxide generator unit of the present invention is inserted, chlorine dioxide gas is supplied into the space at a concentration safe for humans (0.3 ppm or less), in a very short time of 10 minutes or less. It has been proven that airborne microorganisms in the space can be inactivated.

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

In order to prove that the chlorine dioxide generator into which the chlorine dioxide generator unit of the present invention was inserted can be effectively used for inactivating various airborne microorganisms, the following experiment was conducted.

1. Experimental Materials and Experimental Equipment

(test virus)

Feline Calicivirus (FCV, F9, ATCC VR-782); Use as a substitute for norovirus

(host cell)

Crandell Reese feline kidney cells (CRFK, ATCC CCL-94)

(gazogene)

Chlorine dioxide generating device incorporating the chlorine dioxide generating unit of the present invention

(experimental instrument)

100L stainless steel chamber (special order)

96-hole 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)

HEPA filter for exhaust (ultra-small special filter for exhaust, OSHITARI LABORATORY)

Impinger (Biosampler, 5㎖, SKC)

Centriprep 50K ultrafiltration membrane (4310, Merck Millipore)

Amicon Ultra 50K ultrafiltration membrane (UFC505024, Merck Millipore)

(experimental device)

Shaking Incubator (AT12R, THOMAS)

Chlorine dioxide gas sensor (Midas GAS Detector, ClO ₂ MIDAS-3-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 (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)

Fetal Bovine Serum (FBS, 30-2020, ATCC)

EDTA Disodium Salt 2% Solution in PBS Saline(2820549, MP)

(Virus recovery solution for impinger (neutralization solution))

5 mL of 0.1% FBS D-MEM (with antibiotic added) containing 1 mM sodium thiosulfate solution* was used as a virus recovery liquid for impingers.

* 1 mM sodium thiosulfate solution is a concentration that can be neutralized without problems when 0.3 ppmv chlorine dioxide gas is ventilated by 12.5 L.

2. Experimental method

(Adjustment of virus spray solution)

Feline calicivirus (10 ^8.5 TCID ₅₀ / 50 μL), which was cryopreserved at -80 ° C., was diluted 10-fold with a 0.1% FBS solution as a virus spray solution (10 ^7.5 TCID ₅₀ / 50 μL).

(experimental method)

The chlorine dioxide generator of the present invention was installed in the center of a 100 L stainless steel chamber, and operated while controlling the on and off of the device by a timer, so that the chlorine dioxide gas concentration in the chamber was adjusted to 0.3 ppmv (FIG. 22). . Necocalisi virus (10 ^7.5 TCID ₅₀ / 50 μL) is sprayed for 1 minute at a rate of 0.2 ml/min using a nebulizer in a chamber in which the gas concentration is stable, and after 0, 2.5, 5, and 10 minutes, the impinger virus was recovered. 5 mL of the recovered virus solution was concentrated to about 50 µL by two types of ultrafiltration membranes (virus in 12.5 L of air). A timer was measured from this virus concentrate, and the virus infectivity titer in 10 L of air was determined and evaluated. In addition, as a control, in the unit for generating chlorine dioxide in the chlorine dioxide generator, the above experiment was conducted without putting the chemical into the chemical storage unit.

(Chlorine dioxide gas concentration)

The chlorine dioxide gas concentration in the 100 L chamber was monitored by a chlorine dioxide gas sensor. The concentration value of the chlorine dioxide gas sensor was compared with the gas concentration value obtained by the ion chromatography method and corrected.

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 the experiment was conducted by putting a drug into the apparatus of the present invention, the average chlorine dioxide gas concentration in the chamber was 0.25 ppmv (min; 0.22 ppmv, max; 0.32 ppmv), and the virus titer after 10 minutes was 10 ^0.6 TCID ₅₀ / It became 10 L air, and it was reduced by 2 log ₁₀ or more (99% or more) relative to the control (FIG. 23).

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

In order to prove that the chlorine dioxide generator into which the chlorine dioxide generator unit of the present invention was inserted can be effectively used also for inactivating airborne bacteria, the following experiment was conducted.

1. Experimental Materials and Experimental Equipment

(test microorganism)

Staphylococcus epidermidis (NBRC 12993)

(gazogene)

Chlorine dioxide generating device incorporating the chlorine dioxide generating unit of the present invention

(experimental instrument)

1㎥ chamber (special order)

Platinum Lee (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)

HEPA filter for exhaust (ultra-small special filter for exhaust, OSHITARI LABORATORY)

Impinger (Biosampler, 5㎖, SKC)

(experimental device)

Chlorine dioxide gas sensor (Midas GAS Detector, ClO ₂ MIDAS-E-BR2, Honeywell)

Particle Counter (KC-52, RION)

Air filter for particle removal (MAC-11FR-UL, Nippon Air Tech)

Spectrophotometer (V-560, JASCO)

Thermostat (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 Badge (393-00185, Nihonsei Yaku)

SCD agar medium (396-00175, Nihon Seiyaku)

Ordinary agar medium (E-MP21, Eiken Kagaku)

Trypticase Soy Agar Medium (236950, BD Biosciences)

0.1 mol/l sodium thiosulfate solution (191-03625, wako)

(Liquid recovery liquid for impinger (neutralization liquid))

5 mL of the SCD medium containing 1 mM sodium thiosulfate solution* was used as a recovery liquid for the impinger.

* A 1 mM sodium thiosulfate solution is a concentration that can neutralize 0.05 ppmv chlorine dioxide gas without problems when 12.5 L is ventilated.

2. Experimental method

(Adjustment of test bacterial solution)

The pre-cultured conserved strain Staphylococcus epidermidis was phagocytosed on an ordinary agar medium and cultured at 30°C. The obtained cells were diluted with sterilized purified water and used as a test bacterial solution (spray solution; 1×10 ^{8 to 9} CFU/ml).

(experimental method)

The chlorine dioxide generator of the present invention was installed in the center of a 1 m3 chamber, and operated while controlling the on and off of the device by a timer, so that 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 is stable, the bacterial suspension (about 1×10 ^{8 to 9} CFU/ml) is sprayed for 1 minute at a rate of 0.2 ml/min, and after 0, 30, 60, and 90 minutes, the impinger Floating bacteria were recovered by. After recovery, the number of viable cells at each time was measured and evaluated by the dilution plate method. As a control, the above experiment was conducted with the LED of the chlorine dioxide generator of the present invention turned 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 compared with the gas concentration value obtained by the ion chromatography method and corrected.

3. Experimental results

In the case of a control experiment in which the experiment was conducted with the LED turned off in the apparatus, the number of viable cells was 4.1 × 10 ³ CFU/10 L air at 90 minutes. On the other hand, when the experiment was conducted with the LED of the apparatus of the present invention turned ON, the average concentration of chlorine dioxide gas in the chamber was 0.05 ppmv, and the number of viable cells was 3.4×10 ² CFU/10L air at 90 minutes of exposure time, which is was reduced by more than 1 log ₁₀ (more than 90%) (FIG. 25).

10 Unit for generating chlorine dioxide
11 drug storage unit
12 LED chips
13 operation base
14 drugs
15 tube
16 openings
20 Chlorine dioxide generator
21 Unit for generating chlorine dioxide
22 device body
23 Air supply port
24 fan
25 air outlet
30 units for generating chlorine dioxide
31 gas generator
32 drug storage unit
33 electronic board
34 LED chips
35 Exterior
36 Air inlet
40 Chlorine dioxide generator
41 LED chip mounting board
42 drug storage unit
43 housing part
44 blowing fan

Claims (14)

As a method of inactivating airborne microorganisms in space,
(1) preparing a solid agent containing (A) a porous material supported with chlorite and (B) a metal catalyst or metal oxide catalyst,
In the solid medicine, the mass ratio of the chlorite and the metal catalyst or metal oxide catalyst is 1:0.04 to 0.8;
(2) irradiating the solid drug with visible light; and
(3) A method comprising supplying chlorine dioxide gas generated from the solid medicine to a space where airborne microorganisms exist. According to claim 1,
In step (3), chlorine dioxide gas generated from the solid medicine is supplied to a space where airborne microorganisms exist, and the chlorine dioxide gas concentration in the space is set to a concentration at which animals can survive but airborne microorganisms are inactivated. Steps to do, how. According to claim 2,
The method of claim 1, wherein the animal can survive but the concentration at which airborne microorganisms are inactivated is 0.00001 to 0.3 ppm. According to claim 3,
In the step (3), when the chlorine dioxide gas concentration in the space is 0.1 to 0.3 ppm, the time for supplying the chlorine dioxide gas into the space is 0.5 to 480 minutes. According to any one of claims 1 to 4,
wherein the airborne microorganisms are airborne viruses or airborne bacteria. According to any one of claims 1 to 4,
The method in which the wavelength of visible light irradiated in the said step (2) is 360-450 nm. According to any one of claims 1 to 4,
wherein the metal catalyst or metal oxide catalyst is selected from the group consisting of palladium, rubidium, nickel, titanium, and titanium dioxide. According to any one of claims 1 to 4,
the porous material is selected from the group consisting of sepiolite, paligoscite, montmorillonite, silica gel, diatomaceous earth, zeolite, and perlite;
wherein the chlorite is selected from the group consisting of sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, and barium chlorite. According to any one of claims 1 to 4,
A method wherein the porous material carrying the chlorite is obtained by impregnating the porous material with chlorite and further drying it. According to any one of claims 1 to 4,
A method in which the porous material further supports an alkali agent. According to claim 10,
wherein the alkali agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and lithium carbonate. According to claim 10,
A method wherein the molar ratio of the chlorite and the alkali agent is 1:0.1 to 2.0. According to claim 10,
A method wherein the porous material carrying the chlorite and alkali agent is obtained by simultaneously or sequentially impregnating the porous material with the chlorite and alkali agent and drying the porous material. According to any one of claims 1 to 4,
The method of claim 1, wherein the moisture content of the porous material is 10% by weight or less.

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