JP2013078573A - Floating virus removal unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a floating virus removal unit capable of promptly inactivating viruses caught which are irrespective of the presence of an envelope and highly maintaining antiviral properties.SOLUTION: The virus removal unit which removes viruses containing a gas includes: at least a first electrode, a second electrode and a dielectric provided, and a plasma generation part for generating plasma by applying a voltage between the first electrode and the second electrode to generate electric discharge; and a virus inactivating part containing particles having antiviral properties arranged in a space existing plasma generated by the plasma generation part.

Description

  The present invention relates to a floating virus removal unit that inactivates microorganisms such as various bacteria and viruses floating in the space by combining plasma with an antiviral filter carrying nanoparticles having antiviral properties. is there.

  In recent years, deaths due to viral infections such as SARS (Severe Acute Respiratory Syndrome), Norovirus and avian influenza have been reported. Furthermore, due to traffic development and virus mutations, we faced a “pandemic (infection explosion)” crisis that spreads virus infection all over the world, and in 2009 there was a lot of damage caused by viruses such as foot-and-mouth disease. Urgent measures are needed.

  In order to cope with such a situation, development of antiviral agents using vaccines is urgently needed. However, in the case of vaccines, infection can be prevented only by specific viruses due to its specificity. Furthermore, noroviruses have problems such as lack of vaccines.

  In hospitals and clinics, MRSA (methicillin-resistant Staphylococcus aureus) brought into the hospital by carriers or infected individuals, and strains that have been mutated from Staphylococcus aureus to MRSA by administration of antibiotics directly from patients or medical Nosocomial infections that cause contact infections to patients and health care workers have become a major social problem through the environment including workers, used items such as lab coats, pajamas, sheets, and equipment such as walls and air conditioners. Yes. Accordingly, there is a strong demand for an antiviral member that can exhibit antibacterial and antiviral effects that are effective against various viruses and bacteria, and an environment that prevents infection.

  Here, viruses can be classified into viruses encapsulated in a membrane called lipid-containing envelope and viruses without an envelope. Since the envelope consists mostly of lipids, it can be easily destroyed when treated with disinfectants such as ethanol, organic solvents, and soap. For this reason, viruses with envelopes are generally easy to inactivate (decrease or inactivate viruses) with these disinfectants. In contrast, viruses without an envelope are said to be highly resistant to the above-mentioned disinfectants. Also, sodium hypochlorite, which is effective for these, can be used as a disinfectant, but cannot be applied to members. In the present specification, virus inactivation and antiviral properties refer to the same action.

  As means for solving these problems, an enzyme filter (Patent Document 1) that inactivates captured microorganisms and viruses by an enzyme carried on the filter has been developed. In addition, as an air purifier for removing microorganisms and harmful substances using active species generated by plasma, a ferroelectric filter is placed between the electrodes, and plasma generated by applying voltage is generated. An air purifier (Patent Document 2), an air purifier (Patent Document 3) that removes harmful substances by performing streamer discharge from a needle-shaped discharge electrode toward a counter electrode, and ionization caused by atmospheric discharge There is an air cleaner that releases positive ions and negative ions generated by a phenomenon (Patent Document 4).

JP2008-212824 Japanese Patent No. 3632579 Patent 4200757 Patent No. 3680121

  However, in the filter as shown in Patent Document 1, since the dead bodies of microorganisms and viruses remain when used for a long time, the antiviral performance can be lowered. Moreover, in the air purification apparatus of patent document 2, in order to generate a plasma stably, a special ferroelectric filter must be used, and in the air cleaners of patent documents 3 and 4, the activity generated by the plasma is required. Since the seeds are released into the air, the effect is diminished.

  Further, it is known that ozone, nitrogen oxides, and the like are generated during discharge in air. Ozone and nitrogen oxides are harmful. In an air cleaner, it is important not only to inactivate viruses but also not to generate them.

  Therefore, the present invention quickly inactivates the virus collected regardless of the presence or absence of the envelope, can maintain high antiviral properties, and suppresses the generation of harmful gases such as ozone and nitrogen oxides. A floating virus removal unit is provided.

  That is, the first invention is a virus removal unit that removes viruses contained in gas, and includes at least a first electrode, a second electrode, and a dielectric, and the first electrode and the second electrode. A virus including a plasma generating unit that generates a plasma by generating a discharge by applying a voltage between and a particle having antiviral properties disposed in a space where the plasma generated by the plasma generating unit exists A virus removal unit comprising an inactivation unit.

  According to a second aspect of the present invention, in the virus removal unit according to the first aspect of the present invention, the virus inactivating portion further includes an inorganic substance portion that contacts the antiviral particles.

  The third invention further includes a gas supply unit that supplies a gas to be processed for removing viruses, and the plasma generation unit includes the first electrode, the second electrode, the dielectric, and the virus. The inactivation part is arranged side by side in the flow direction of the gas to be processed supplied from the gas supply part, each has gas permeability in the gas flow direction, and the virus inactivation part has the gas flow direction. The first or the second is characterized in that it is air permeable and is disposed in at least one of the discharge space of the discharge and the downstream position in the gas flow direction with respect to the discharge space. 2. The virus removal unit according to the invention of 2.

  The fourth aspect of the present invention further includes a gas supply unit that supplies a gas to be processed for removing viruses, and the plasma generation unit includes the first electrode, the second electrode, the dielectric, and the virus. The inactivation part is arranged side by side in a direction orthogonal to the flow direction of the gas to be processed supplied from the gas supply part.

  According to a fifth aspect of the present invention, the virus inactivating part further includes a base material for fixing the antiviral particles, and the base material has at least a portion to which the antiviral particles are fixed as an inorganic material. The virus removal unit according to any one of the first to fourth inventions, wherein:

In a sixth aspect of the invention, the virus inactivating part is
Inorganic particles formed of an inorganic material and having antiviral properties fixed on the surface thereof;
The virus removal unit according to any one of the first to fourth inventions, further comprising a base material on which the inorganic particles are fixed.

  According to a seventh aspect of the invention, the virus inactivating part is formed by filling the composite particles in which the antiviral particles are fixed on the surface of the inorganic particles. The virus removal unit according to any one of the above.

  In an eighth aspect of the invention, the virus inactivating portion is formed on at least one of the surfaces of the first electrode, the second electrode, and the dielectric. The virus removal unit according to any one of the above.

  The ninth invention is the floating virus removal unit according to any one of the first to eighth inventions, wherein the plasma is generated by at least one of creeping discharge and silent discharge.

  According to a tenth invention, any one of the first to ninth inventions, wherein the antiviral particles are made of at least one of gold, platinum, palladium, cerium, and oxides thereof. The floating virus removal unit according to any one of the above.

  According to the present invention, it is possible to quickly inactivate viruses collected regardless of the presence or absence of an envelope, to maintain high antiviral properties, and to suppress the generation of harmful gases such as ozone and nitrogen oxides. A floating virus removal unit can be provided.

It is a cross-sectional schematic diagram of the floating virus removal unit of embodiment. It is a cross-sectional schematic diagram of the antiviral filter which concerns on embodiment. It is sectional drawing of the antiviral filter which concerns on other embodiment. It is sectional drawing of the antiviral filter which concerns on other embodiment. It is sectional drawing of the antiviral filter which concerns on other embodiment. It is sectional drawing of the antiviral filter which concerns on other embodiment. It is a schematic diagram which shows the structure of the floating virus removal unit which concerns on other embodiment. It is a schematic diagram which shows the structure of the floating virus removal unit which concerns on other embodiment. It is a schematic diagram which shows the structure of the floating virus removal unit which concerns on other embodiment. It is a schematic diagram which shows the structure of the floating virus removal unit which concerns on other embodiment. It is a schematic diagram which shows the structure of the floating virus removal unit which concerns on other embodiment. It is a schematic diagram which shows the structure of the floating virus removal unit which concerns on other embodiment. It is a schematic diagram which shows the structure of the floating virus removal unit which concerns on other embodiment. It is a graph which shows the result of antiviral performance evaluation of an Example and a comparative example. It is a graph which shows the relationship between the frequency of the power supply in Example 5, and the ozone concentration which generate | occur | produced. It is a graph which shows the relationship between the frequency of the power supply in Example 6, and the ozone concentration which generate | occur | produced. It is a graph which shows the relationship between the frequency of the power supply in Example 7, and the ozone concentration which generate | occur | produced.

  Hereinafter, embodiments of the floating virus removal unit of the present invention will be described with reference to the drawings.

(First embodiment)
A first embodiment will be described. FIG. 1 is a schematic diagram of a cross section of the floating virus removal unit 200 of the present embodiment. The floating virus removal unit 200 includes an antiviral filter 100 as a virus inactivation unit, an application electrode 11, a ground electrode 12, a dielectric 13, and a power source 14. The application electrode 11, the ground electrode 12, the dielectric 13, and the power source 14 function as a plasma generation unit that generates plasma. As will be described in detail later, the floating virus removal unit 200 of this embodiment first captures and inactivates viruses contained in a gas such as a gas circulated through the floating virus removal unit 200 by the antiviral filter 100. . And the virus inactivated in the antiviral filter 100 can be decomposed and removed by the plasma generated by the plasma generator. One of the application electrode 11 and the ground electrode 12 is the first electrode, and the other is the second electrode. In another embodiment, when a plurality of application electrodes 11 and a plurality of ground electrodes 12 are combined, each of the plurality of electrodes of any one type is the first electrode and each of the plurality of electrodes of the other type is This is the second electrode.

  As shown in FIG. 1, the floating virus removal unit 200 has a configuration in which the application electrode 11, the antiviral filter 100, the dielectric 13, and the ground electrode 12 are in close contact and stacked in this order from the left side of the drawing. In order to generate plasma, the dielectric 13 and the ground electrode 12 need to be stacked in close contact, but the application electrode 11, the antiviral filter 100, and the dielectric 13 may be stacked in close contact with each other. However, it may be arranged with a gap.

  Note that the positions of the antiviral filter 100 and the dielectric 13 may be interchanged (that is, the dielectric 13 may be in close contact with the application electrode 11). In this case, the application electrode 11 and the dielectric 13 are in close contact. The dielectric 13, the antiviral filter 100, and the ground electrode 12 may be stacked in close contact with each other, or may be disposed with a gap therebetween. That is, as long as the dielectric 13 is in close contact with one electrode and stacked, the other components may be in close contact with each other or may be arranged with a gap therebetween. Further, the dielectric 13 may be disposed adjacent to both the application electrode 11 and the ground electrode 12 (two dielectrics).

  Hereinafter, each structure of the floating virus removal unit 200 of this embodiment is demonstrated. Note that the floating virus removal unit 200 can remove any virus that floats in the gas. However, in the following description, the floating virus removal unit 200 will be described as removing a virus floating in the gas.

  First, the configuration of the antiviral filter 100 will be described. FIG. 2 is a schematic cross-sectional view of the antiviral filter 100. The antiviral filter 100 of the present embodiment includes a filter portion 1 that is a base material and antiviral particles 2 fixed on the surface of the filter portion 1. The antiviral filter 100 has a function of capturing the virus contained in the flowing gas and inactivating the captured virus.

  And as above-mentioned, the antiviral filter 100 of this embodiment needs to decompose and remove the inactivated virus with the plasma which the plasma generation part produced | generated. Therefore, the antiviral filter 100 needs to be disposed at least in a range where plasma exists. Specifically, as shown in FIG. 1, it is preferably disposed between the applied voltage 11 and the dielectric 13. In addition, since the application electrode 11, the ground electrode 12, and the dielectric 13 of this embodiment have a gas-permeable structure as will be described later, the application electrode 11 and the ground are not only between the application electrode 11 and the dielectric 13. Some plasma is also present outside the electrode 12. Therefore, the antiviral filter 100 is located outside the ground electrode 12 and the application electrode 11 (a space between the application electrode 11 and the ground electrode 12) at a position where the virus inactivated by the presence of plasma is removed. It may be arranged outside). In addition, when arrange | positioning the antiviral filter 100 outside, it is preferable to arrange | position in the downstream of the flow of the gas distribute | circulated in the floating virus removal unit 200. FIG. For example, when gas flows from the application electrode side to the ground electrode side, the antiviral filter 100 is outside the ground electrode 12 on the downstream side in the gas flow direction with respect to the discharge space, and in a range where plasma exists. Should be placed in

  Each configuration of the antiviral filter 100 will be described. First, the filter unit 1 has a filter function for capturing viruses in the gas. The filter unit 1 has air permeability so that gas can pass, and has a structure capable of capturing viruses in the gas. Specifically, it has a fiber shape, a cloth shape, a mesh shape, and a structure such as a woven fabric, a net, a nonwoven fabric, a honeycomb shape, a lattice shape, a saddle shape, a punching process, or a porous shape or an expanded mesh shape.

  In the filter unit 1, it is preferable that at least a part to which the antiviral particle 2 is fixed (a part where the antiviral particle 2 comes into contact) is formed of an inorganic material. The exact mechanism of this is unknown, but when metal particles are used as antiviral particles, they have a very high oxidation catalytic ability when the metal particles are fixed to an inorganic material. It is presumed that the surface of the contacted virus is damaged and a very high virus inactivating effect is obtained. In addition, since at least the part to which the antiviral particle 2 is fixed may be an inorganic material, the entire filter part 1 may be formed of an inorganic material, or only on the surface layer part where the antiviral particle 2 is fixed. Inorganic materials may be present. In consideration of plasma resistance, the filter portion 1 is preferably an inorganic material. This is because the filter unit 1 is disposed in a region where plasma is present, and thus has a plasma resistance, so that the virus capturing function and the antiviral function of the filter unit 1 can be maintained for a long period of time. Note that the plasma resistance is durability in a plasma atmosphere and is not easily eroded by plasma.

  Furthermore, it is preferable that the filter part 1 is formed with the material which has heat resistance. This is because the antiviral filter 100 is disposed in a space where plasma is generated, and thus the ambient temperature may be high.

  As a material constituting the filter unit 1, ceramics, metal, alloy, inorganic oxide, or a composite thereof can be used.

  As ceramics, ceramics, concrete, glass and the like can be used. Specific compositions of ceramics include elemental, oxide, hydroxide, carbide, carbonate, nitride, halide, and phosphate, or composites thereof. . Also, barium titanate, lead zirconate titanate, ferrite, alumina, forsterite, zirconia, zircon, mullite, steatite, cordierite, aluminum nitride, silicon nitride, silicon carbide, new carbon, new glass, etc. Fine ceramics such as strength ceramics, functional ceramics, superconducting ceramics, nonlinear optical ceramics, antibacterial ceramics, biodegradable ceramics, and bioceramics may be used. As glass, soda lime glass, potash glass, crystal glass, quartz glass, chalcogen glass, organic glass, uranium glass, acrylic glass, water glass, polarizing glass, tempered glass, laminated glass, heat resistant glass / borosilicate glass, bulletproof glass, Examples thereof include glass fiber, dichroic, gold stone (brown gold stone / sand gold stone / purple gold stone), glass ceramics, low melting point glass, metallic glass, and saphiret.

  Metals include refractory metals such as tungsten, molybdenum, tantalum, niobium, TZM and W-Re, precious metals such as silver and ruthenium and their alloys, and special metals such as titanium, nickel, zirconium, chromium, inconel and hastelloy , Aluminum and its alloys, Copper and its alloys, Iron alloys such as iron and stainless steel, Zinc and its alloys, Magnesium and its alloys, Hafnium, Tungsten, Bismuth, Antimony, Manganese, Cobalt, Tin, etc. Is mentioned.

  Examples of the inorganic oxide include titania, zirconia, alumina, ceria (cerium oxide), zeolite, apatite, silica, activated carbon, and diatomaceous earth.

  Moreover, what is necessary is just to provide the inorganic material layer mentioned above in the surface part of a base material, when setting it as the structure which an inorganic material exists only in the surface part which fixes the antiviral particle 2 of the filter part 1. FIG. As the base material, the inorganic material as described above may be used, or an organic material such as a resin may be used.

  Resins that can be used as base materials include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, EVA resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polymethyl acrylate resin, polyacetic acid Vinyl resin, polyamide resin, polyimide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, polyarylate resin, polysulfone resin, polyvinylidene fluoride resin, Vectran (registered trademark), PTFE (poly tetrafluoroethylene), etc. Thermoplastic resin, polylactic acid resin, polyhydroxybutyrate resin, modified starch resin, polycaprolacto resin, polybutylene succinate resin, polybutylene adipate terephthalate tree , Biodegradable resins such as polybutylene succinate terephthalate resin and polyethylene succinate resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, silicon resin, acrylic urethane resin And thermosetting resins such as urethane resins, silicone resins, polystyrene elastomers, polyethylene elastomers, polypropylene elastomers, polyurethane elastomers and other elastomers, and lacquer.

  In addition, as described above, since the antiviral filter 100 preferably has heat resistance, it is preferable to use a resin having heat resistance when using a resin for the base material. Examples of heat-resistant resins include polyamide, polyacetal, polycarbonate polyphenylene ether, polybutylene terephthalate, glass fiber reinforced polyethylene terephthalate, ultra-high molecular weight polyethylene, polysulfone, polyethersulfone, polyphenylene sulfide polyarylate, polyamideimide, poly Examples thereof include super engineering plastics such as etherimide, polyetheretherketone, polyimide, fluorine resin such as ETFE and PTFE, and heat-resistant thermosetting resins such as polyphenol, melamine resin, and epoxy resin.

  In the case where the inorganic material layer is formed only on the surface portion, the inorganic material layer can be formed by various plating methods, vacuum deposition methods, CVD methods, sputtering methods, and the like.

  When a metal oxide is used as the inorganic material, an oxide film is chemically formed on the surface of the metal by a known method, or oxidized on the surface of the metal by a known electrochemical method such as anodization. What formed the film may be used.

  Next, the structure of the antiviral particle 2 will be described. The antiviral particle 2 is a fine particle formed of a material having antiviral properties. The virus attached to the filter unit 1 is inactivated by the antiviral action of the antiviral particle 2.

  As the antiviral particle 2, gold, silver, copper, iron, aluminum, zinc, platinum, palladium, nickel, bismuth, cerium, or an oxide thereof can be used. Among these, it is preferable to use gold, platinum, palladium, cerium, or an oxide thereof. A combination of the above metals or oxides thereof may be used. Further, the gold, platinum, palladium, cerium or oxide thereof may be fine particles of an alloy with one or more of silver, copper, iron, aluminum, zinc, nickel, bismuth, manganese and the like. Also, a mixture in which at least one fine particle of gold, platinum, palladium, cerium or its oxide is mixed with at least one fine particle selected from silver, copper, iron, aluminum, zinc, nickel, bismuth, manganese, etc. Particles may be used.

  The antiviral particle 2 preferably has a particle size of 1 nm to 50 nm. This is because when the particle size is larger than 50 nm, the antiviral particle 2 becomes stable, the oxidation-reduction action hardly occurs, and the action of inactivating the virus by damaging the cell membrane surface of the contacted virus becomes low. If the particle size is smaller than 1 nm, the substance becomes very unstable and it is difficult to securely fix it on the filter unit 1.

  The form in which the antiviral particles 2 are fixed to the surface of the filter part (member main body) 1 is not particularly limited, and can be appropriately selected by those skilled in the art. For example, the antiviral nanoparticles 2 may be scattered on the surface of the member main body 1. Further, the antiviral nanoparticles 2 may be fixed in the form of a fine particle aggregate arranged in a planar or three-dimensional manner. That is, it can be fixed in the shape of dots, islands, thin films or the like. The antiviral particles 2 are preferably fixed to such an extent that the air permeability of the filter unit 1 is maintained.

  The method for fixing the antiviral particle 2 to the surface of the filter unit 1 is not particularly limited. For example, when the antiviral particle 2 is gold (Au), a coprecipitation method, a precipitation method, A sol-gel method, an impregnation method, a dropping neutralization precipitation method, a reducing agent addition method, a pH control neutralization precipitation method, a carboxylic acid metal salt addition method, and the like can be used. When the antiviral particle 2 is palladium, the filter unit 1 is immersed in an aqueous solution containing palladium ions or an aqueous solution containing palladium ions is applied to the filter unit 1 to adsorb the palladium ions to the filter unit 1. Then, immerse in an aqueous solution containing a reducing agent such as hydrazine, formaldehyde, tartaric acid, citric acid, glucose, tin chloride, sodium borohydride, sodium phosphite, sodium hypophosphite, or in a hydrogen reducing atmosphere. For example, if the resin is subjected to a reduction treatment or is a resin having high heat resistance, it is heated in the air to carry metal palladium. In addition, when the antiviral particle 2 is cerium oxide, there is a method of impregnating a filter part into a methanol dispersion solution containing cerium oxide and drying by heating at 50 to 150 ° C. These methods can be properly used depending on the type of carrier.

  The amount of antiviral particles 2 fixed to the filter part 1 is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less with respect to the filter part 1. It is. This is because when the content is more than 20% by mass, the antiviral particles 2 are aggregated to weaken the antiviral effect. When it is less than 0.1% by mass, the virus inactivating effect is small. If it is 0.5 mass% or more and 10 mass% or less, while aggregation of the antiviral particle 2 is prevented more, the virus inactivation effect is acquired more.

  Here, a method for manufacturing the antiviral filter 100 will be described. As an example of the production method, a production method using a colloid solution of antiviral particles 2 will be described.

First, when gold is used as the antiviral particle 2, a gold colloid solution is generated. The colloidal gold solution is produced by adding a reducing agent such as sodium citrate into an aqueous gold compound solution such as HAuCl ₄ · 4H ₂ O. When palladium is used as the antiviral particle 2, a palladium colloid aqueous solution is generated. Specifically, a surfactant such as stearyltrimethylammonium chloride, sodium dodecylbenzenesulfonate or polyethylene glycol mono-p-norylphenyl ether is added to an aqueous solution containing palladium chloride, and the aqueous sodium borohydride solution is vigorously stirred. While dropping, Pd sol (palladium colloidal solution) is produced. When platinum is used as the antiviral particle 2, a platinum colloid solution is generated. Specifically, a platinum colloid solution is produced by adding a protective material such as sodium polyacrylate to a platinum compound aqueous solution such as hexachloroplatinic acid aqueous solution and stirring, and then adding ethanol and refluxing in a nitrogen atmosphere. can do. As the colloidal dispersion medium, water, acetone, methanol, ethanol, or the like can be used.

  The colloidal solution of the antiviral particles 2 produced in this way is applied to the filter unit 1 by spraying and dried at 100 ° C. in a nitrogen atmosphere, so that the antiviral particles 2 are fixed to the filter unit 1. The antiviral filter 100 can be generated. The antiviral particles 2 in the colloidal solution may be coated on the surface with a protective agent such as a surfactant.

  Next, as another manufacturing method of the antiviral filter 100, a method of manufacturing the antiviral filter 100 by fixing the antiviral particles 2 to the filter portion 1 by precipitation precipitation will be described.

  First, an aqueous solution containing a gold compound, a palladium compound, or a platinum compound is heated to 20 to 90 ° C., preferably 50 to 70 ° C., and stirred, and the alkaline solution is adjusted to pH 3 to 10, preferably pH 5 to 8. Adjust. Then, the filter unit 1 is impregnated with the adjusted solution. After impregnating the filter unit 1 in the solution, the solution is thoroughly washed with ion exchange water. And the filter part 1 which wash | cleaned is heat-dried at 100-200 degreeC.

Examples of the gold compound contained in the gold compound aqueous solution include HAuCl ₄ · 4H ₂ O, NH ₄ AuCl ₄ , KauCl ₄ · nH ₂ O, Kau (CN) ₄ , Na ₂ AuCl ₄ , and KauBr _4. · 2H ₂ O and, like NaAuBr _4. The concentration of these gold compound aqueous solutions is preferably 1 × 10 ⁻² to 1 × 10 ⁻⁵ mol / L.

The palladium compound is not particularly limited as long as it is a compound that dissolves in water. Palladium chloride, palladium nitrate, palladium sulfate, palladium hydroxide, tetrachloropalladium (II) salt, tetraamminepalladium (II) salt, dichloroethylenediamine palladium (II), tetranitropalladium (II) acid salt, tetracyanopalladium (II) acid salt, tetrabromopalladium (IV) acid salt, and the like. The concentration of the palladium compound aqueous solution is from a saturated concentration to 1 × 10 ^−5. The mol / L is preferable.

As the platinum compound, a compound that dissolves in water, such as dinitrodiamine platinum, hexahydroxo platinum, hexaammine platinum hydrochloride, hexachloroplatinate, which is a platinum salt, can be used. The concentration of the platinum compound aqueous solution is preferably a saturated concentration to 1 × 10 ⁻⁵ mol / L.

  The above is the configuration and manufacturing method of the antiviral filter 100.

  The antiviral filter 100 of this embodiment can inactivate various viruses regardless of the kind of genome, the presence or absence of an envelope, and the like. For example, rhinovirus, poliovirus, foot-and-mouth disease virus, rotavirus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, A, B, C influenza virus, parainfluenza virus, mumps virus (mumps) ), Measles virus, human metapneumovirus, RS virus, Nipah virus, Hendra virus, yellow fever virus, dengue virus, Japanese encephalitis virus, West Nile virus, type B, hepatitis C virus, eastern and western equine encephalitis virus, Onyon Nyon virus, rubella virus, Lassa virus, Junin virus, Machupo virus, Guanarito virus, Sabia virus, Crimea Congo hemorrhagic fever virus, snail fever, hantavirus, shi Nombre virus, rabies virus, Ebola virus, Marburg virus, bat lyssa virus, human T cell leukemia virus, human immunodeficiency virus, human coronavirus, SARS coronavirus, human porvovirus, polyomavirus, human papillomavirus, adenovirus Herpes virus, chickenpox, zonal rash virus, EB virus, cytomegalovirus, smallpox virus, monkeypox virus, cowpox virus, molasipox virus, parapox virus, and the like.

  The antiviral filter 100 can also sterilize various bacteria without regard to the presence or absence of Gram staining or the type of genome. For example, proteobacteria, aquifex, chlamydia, bacteroides, chlorobium, fibrobacter, spirochete, cyanobacteria, chloroflexus, dinococcus-thermus, thermotoga, actinomycetes, and fermicutes can be mentioned.

  Next, the configuration of the plasma generator will be described. The plasma generation unit can generate plasma between the application electrode 11 and the dielectric 13 by applying a predetermined voltage to the application electrode 11 by the power supply 14. Like the antiviral filter 100, the application electrode 11, the ground electrode 12, and the dielectric 13 preferably have a breathable structure. Specifically, it is not particularly limited as long as it has air permeability, and examples thereof include a mesh structure and a structure in which a large number of holes are formed by punching processing such as punching processing on a plate-like member. Note that the application electrode 11, the ground electrode 12, and the dielectric 13 do not have to have the same structure as long as the structure has air permeability. Each configuration will be described below.

  First, the application electrode 11 is an electrode to which a voltage is applied by the power source 14. The application electrode 11 may be formed of a material that functions as an electrode. For example, metals such as Cu, Ag, Au, Ni, Cr, Fe, Al, Ti, W, Ta, Mo, and Co, alloys thereof, or oxides thereof may be used.

  The ground electrode 12 is an electrode connected to the ground wiring 12a and grounded. The ground electrode 12 may function as an electrode similarly to the applied electrode, and may be a metal such as Cu, Ag, Au, Ni, Cr, Fe, Al, Ti, W, Ta, Mo, Co, or an alloy thereof, or their What is necessary is just to form with an oxide.

The dielectric 13 only needs to have a property of becoming an insulator. The dielectric 13 can be formed of an inorganic material or a polymer material, but it is preferable to use an inorganic material in consideration of plasma resistance and heat resistance. As the inorganic _{material, ZrO 2, γ-Al 2} O 3, α-Al 2 O 3, θ-Al 2 O 3, η-Al 2 O 3, amorphous Al ₂ O _3, alumina nitride, mullite, steer Light, forsterite, cordierite, magnesium titanate, barium titanate, SiC, Si ₃ N ₄ , Si-SiC, mica, glass and the like can be mentioned. Examples of the polymer material include polyimide, liquid crystal polymer, PTFE, ETFE, PVF (polyvinyl fluoride), PVDF (polyvinylidene difluoride), polyetherimide, and polyamideimide. In the case where the antiviral filter 100 is formed of an insulator having a performance as a dielectric and is disposed between the application electrode 11 and the ground electrode 12 and functions as a dielectric, the antiviral filter 100 is used. May have a function as a dielectric.

  The power source 14 applies a voltage to the application electrode 11. The power source 14 may be an AC high voltage, a pulse high voltage, a DC high voltage, a DC bias with AC or a pulse superimposed, or a high voltage power source such as a microwave. A predetermined potential may be applied to the application electrode 11 and the ground electrode 12 so that plasma is generated in the plasma generation space between the application electrode 11 and the dielectric 13 by the power source 14. The voltage applied by the power supply 14 varies depending on the amount (concentration) of suspended viruses in the gas to be processed, but is usually 1 to 20 kV, preferably 2 to 10 kV. The type of discharge generated by the electric power supplied from the power supply 14 for generating plasma is not particularly limited as long as the plasma can be generated. For example, silent discharge, creeping discharge, corona discharge, pulse discharge, etc. I just need it. Further, two or more kinds of these discharges may be combined to generate plasma.

  When the power source 14 is a power source whose voltage changes periodically, such as alternating current (including pulses), the output frequency of the power source is preferably a high frequency. Specifically, the type of antiviral metal used However, it is preferably 1 kHz or more, more preferably 1 kHz or more and 20 kHz or less, and more preferably 1 kHz or more and 10 kHz or less. When the frequency is lower than 1 kHz, the amount of intermediate products and ozone generated increases, and when the frequency is higher than 20 kHz, the virus inactivation effect decreases.

  The above is the configuration of the plasma generator.

  Next, the removal process of the virus in gas by the floating virus removal unit 200 demonstrated above is demonstrated. First, the power supply 14 applies the voltage as described above to the application electrode 11 to generate a discharge between the application electrode 11 and the dielectric 13 to generate plasma. In this state, the gas to be processed is circulated through the floating virus removal unit 200. For example, in FIG. 1, gas is circulated from the application electrode 11 to the ground electrode 12.

  Then, first, when a virus is contained in the gas, the virus is supplemented to the antiviral filter 100 by the function of the filter unit 1. And the antiviral particle 2 fixed to the antiviral filter 100 inactivates the captured virus.

  Although the mechanism by which the antiviral particle 2 inactivates the virus is not necessarily clear as described above, when the antiviral particle 2 is a metal fine particle (or transition metal), the metal fine particle is preferably an inorganic material, preferably It is presumed that by supporting the inorganic oxide on the inorganic oxide, the metal particles have a very high oxidation catalytic ability, and the surface of the contacted virus is damaged and inactivated. In addition, when the antiviral particle 2 has a high oxidation catalytic ability such as a metal oxide, it is presumed that the surface of the virus in contact with the antiviral particle 2 is damaged and inactivated.

  Then, the inactivated virus remaining on the surface of the antiviral filter 100 is decomposed and removed from the antiviral filter 100 by the plasma generated by the plasma generator. In other words, the antiviral properties of the antiviral particles 2 can inactivate airborne viruses and microorganisms, but the surface of the antiviral particles 2 can also be activated by the action of active species generated by the combined use of plasma. Inactivated viruses attached to can be degraded. If the inactivated virus remains attached to the surface of the antiviral particle 2, the virus inactivating action of the antiviral particle 2 is reduced. However, as described above, the virus is removed and cleaned by the plasma, so that the antiviral particles 2 are exposed again, and the virus inactivating action is restored in a short time. Therefore, as long as plasma is generated, the area in which the antiviral particles 2 and the virus can come into contact with each other is kept large, so that a strong virus inactivating effect can be obtained even in a short time. On the other hand, when there is no plasma, since there is no cleaning effect, the virus inactivating effect is reduced at the portion where the antiviral particles 2 and the virus are in contact with each other. Therefore, a powerful virus inactivating effect can be obtained in a short time due to the synergistic effect of the filter 100 and the plasma. Moreover, the virus inactivating function is maintained over a long period of time due to the cleaning effect.

  Note that the plasma generated by the plasma generation unit can decompose and remove sterilized bacteria when the antiviral particles 2 also have a sterilizing action. Therefore, even if the killed bacteria adhere to the antiviral filter 100, even if the virus inactivating action is reduced, the bacteria are decomposed and removed by the plasma, so that the virus inactivating action is maintained.

  According to the present embodiment described above, the virus can be inactivated by the antiviral filter 100, and the virus inactivated by the plasma is removed, whereby the virus inactivating action of the antiviral filter 100 is high. Can be maintained. Therefore, the floating virus removal unit 200 that can maintain the virus inactivating action for a long time can be provided.

  That is, in this embodiment, after collecting the virus and microorganisms which are floating by circulating the gas contaminated by the virus and microorganisms to this unit, the antiviral properties and plasma of the antiviral nanoparticles are used. They can be inactivated. In addition, the action of active species generated by the combined use of plasma decomposes inactivated viruses and microorganisms adhering to the surface of antiviral nanoparticles in a short time, so the surface of antiviral nanoparticles is cleaned. Is done. For this reason, more viruses can come into contact with the surface of the antiviral particles in a short period of time, so a floating virus removal unit that provides a powerful virus inactivation effect (antiviral properties) by synergistic effects with plasma. Can be provided.

  In addition, since the surface of the antiviral particles is cleaned by plasma, the antiviral properties can be maintained even if the virus removal treatment is performed for a long time.

  Further, in the present embodiment, it has been described that only the antiviral particle 2 is fixed to the antiviral filter 100, but the present invention is not limited to this. In order to impart a desired function to the antiviral filter 100, a functional material having a function other than the antiviral particles 2 may be fixed. Examples of the functional material include other antiviral agents, antibacterial agents, antifungal agents, antiallergen agents, and catalysts. These functional materials can be bonded and fixed to the filter unit 1 and the antiviral particle 2 through a binder, for example. As a binder, a functional material can be fixed to the filter part 1 or the antiviral particle 2 fixed to the filter part 1 using a chemical bond such as a general resin, a silane monomer, or an oligomer thereof. Further, in order to strengthen the fixation of the functional material, a reinforcing material such as a hard coat agent may be further added. In addition to chemical bonding, a known fixing method such as van der Waals force or physical adsorption may be used.

  In the present embodiment, the anti-viral filter 100 is described as a virus inactivating unit, but the present invention is not limited to this. The antiviral particles 2 may be fixed to the application electrode 11, the ground electrode 12, and the dielectric 13. However, in this case, the antiviral particle 2 needs to be fixed in a range where plasma exists.

(Second Embodiment)
Next, a second embodiment will be described. The second embodiment is a modification of the antiviral filter 100 described in the first embodiment.

  FIG. 3 is a cross-sectional view of the antiviral filter 100 according to the present embodiment. In addition, about the structure which is common in 1st Embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted. The antiviral filter 100 of the present embodiment includes a filter portion 1 ′ and composite antiviral particles 30.

  First, the composite antiviral particle 30 is obtained by supporting the antiviral particle 2 described in the first embodiment on the surface of the inorganic fine particle 3. The composite antiviral particle 30 is fixed to the surface of the filter portion 1 '.

  The antiviral particle 2 is the same as that described in the first embodiment.

  The inorganic fine particles 3 have a function corresponding to the inorganic material layer in the filter unit 1 in the first embodiment. That is, as described above, when metal particles are used as the antiviral particles 2, a very high virus inactivating effect is obtained when the metal particles are fixed to an inorganic material. Accordingly, by supporting the metal antiviral particles 2 on the inorganic fine particles 3 formed of an inorganic material, the antiviral particles 2 can similarly exert a high virus inactivating action. In consideration of plasma resistance, the filter portion 1 is preferably an inorganic material.

  As the inorganic fine particles 3, ceramics, metals, alloys, and inorganic oxides mentioned as the material of the filter unit 1 in the first embodiment can be used. Alternatively, a surface of fine particles made of resin or the like formed with a film of an inorganic material such as an inorganic oxide or a metal oxide by sputtering or plating may be used.

  Further, the particle size of the inorganic fine particles 3 can be appropriately set according to the particle size of the antiviral particles 2, but is preferably 100 nm or less in consideration of the bond strength to the filter portion 1 ′, and further 20 nm. More preferably, it is as follows.

  Methods for supporting the antiviral particles 2 having antiviral properties on the inorganic fine particles 3 include coprecipitation method, precipitation method, sol-gel method, impregnation method, drop neutralization precipitation method, reducing agent addition method, pH control. Examples thereof include a neutralization precipitation method and a carboxylic acid metal salt addition method, and these methods can be appropriately used depending on the type of the carrier.

  Next, the filter unit 1 ′ is a base material for fixing the composite antiviral particles 30 and has a function of capturing a virus, as in the first embodiment. The filter unit 1 ′ may have the same configuration as that of the first embodiment. However, in the present embodiment, the antiviral particles 2 are fixed to the inorganic fine particles 3, and thus may not be an inorganic material. This is because, as described above, when the antiviral particle 2 is a metal particle, it is fixed to the inorganic fine particle 3, so even if the filter portion 1 ′ is not an inorganic material, a very high virus inactivating effect. Is obtained. Therefore, in this embodiment, as the filter portion 1 ′, a general filter such as a mesh shape, a woven shape, or a non-woven fabric using a polymer material such as a synthetic resin or a natural resin is used as a surface such as a sputter of an inorganic material. It can also be used as it is without processing.

  The manufacturing method of the antiviral filter 100 of this embodiment is the same as that of 1st Embodiment. That is, the composite antiviral particles 30 may be applied to the surface of the filter portion 1 ′ by dip coating, spin coating, hydrothermal synthesis, or the like by a sol-gel method, and then fired at 150 ° C. or higher. Therefore, it is desirable that the material of the filter portion 1 ′ has heat resistance.

  In the second embodiment, the form in which the composite antiviral particle 30 is fixed to the surface of the filter portion 1 ′ is not particularly limited, and can be appropriately selected by those skilled in the art. For example, the composite antiviral particles 30 may be scattered on the surface of the filter portion 1 ′. The composite antiviral particle 30 may be fixed in the form of an inorganic fine particle aggregate arranged in a planar or three-dimensional manner. That is, it can be fixed in a shape such as a dot shape, an island shape, or a thin film shape.

  Since the configuration of the floating virus removal unit 200 other than the antiviral filter 100 is the same as that of the first embodiment, the description thereof is omitted.

  According to the present embodiment described above, the virus can be similarly inactivated by the antiviral filter 100 even when the antiviral particles 2 are fixed to the inorganic fine particles 3 to form the composite antiviral particles 30. At the same time, it is possible to provide the floating virus removal unit 200 capable of removing the virus inactivated by the plasma and maintaining the virus inactivation action for a long period of time.

(Third embodiment)
Next, a third embodiment will be described. The third embodiment is a modification of the antiviral filter 100. FIG. 4 is a cross-sectional view of the antiviral filter 100 of the present embodiment. In addition, about the structure which is common in embodiment mentioned above, the same code | symbol is attached | subjected and description is abbreviate | omitted. In the antiviral filter 100 of the present embodiment, the inorganic particles 4 carrying the antiviral particles 2 are placed in the plasma generation space between the application electrode 11 and the dielectric 13 of the floating virus removal unit 200 shown in FIG. It is filled and configured. That is, the gap between the inorganic particles 4 functions as a filter, and the virus in the gas passing through the gap between the inorganic particles 4 is inactivated by the antiviral particles 2 on the surface of the inorganic particles 4. Therefore, the point which the antiviral particle 2 is not fixed to base materials, such as the filter part 1, differs from embodiment mentioned above.

  As the inorganic particles 4, the same material as the inorganic fine particles 3 of the second embodiment can be used. However, the size of the inorganic particles 4 is preferably larger than that of the inorganic fine particles 3 so as to form a gap through which gas can pass when filled. Specifically, the average particle diameter of the inorganic particles 4 is preferably 100 μm or more and 5000 μm or less, more preferably 100 or more and 1000 μm or less. Further, the inorganic particles may be composed of only one kind of material, or two or more kinds of inorganic particles may be mixed.

The supported amount of the antiviral particles 2 is 0.5 to 40% by mass, preferably 0.5 to 20% by mass, and more preferably 0.5 to 10% by mass with respect to the inorganic particles 4. The reason is that when 40% by mass or more is supported, the antiviral particles 2 are aggregated and the antiviral effect is weakened. The antiviral particle 2 is not preferable because the sufficient antiviral effect cannot be obtained at 0.5% by mass or less, and the description thereof is omitted because it is the same as in the first embodiment.

  Although the manufacturing method of the antiviral filter 100 of this embodiment will not be specifically limited if the inorganic particle 4 and the antiviral particle 2 can be compounded, For example, the inorganic particle 4 and the antiviral particle 2 are mixed with a mortar etc. By combining them, composite particles in which the antiviral particles 2 are embedded in the inorganic particles 4 can be formed. In addition, for example, a high-speed air impact method in which the inorganic particles 4 and the antiviral particles 2 are mechanically bonded by colliding the inorganic particles 4 and the antiviral particles 2, or the inorganic particles 4 and the antiviral particles are combined. It can also be formed by a mechanochemical method such as a surface fusion method in which the inorganic particles 4 and the antiviral particles 2 are bonded by energy generated by applying a strong pressure to 2.

  As an apparatus that can carry out these manufacturing methods, in addition to a general-purpose ball mill, Kawata's super mixer can be exemplified for a rotary blade type, and a shaker type can be exemplified by a paint shaker of Asada Iron Works Co., Ltd. Examples thereof include a hybridization system (registered trademark) manufactured by Nara Machinery Co., Ltd., Mechanofusion (registered trademark) manufactured by Hosokawa Micron Corporation, and a medium fluidized dryer, but are not particularly limited to these apparatuses.

  In the compounding process in these apparatuses, the composition is added to the above-described compound apparatus so that the ratio of the antiviral particles 2 to the inorganic particles 4 is 0.5% by mass or more and less than 40% by mass. Further, in the complexing treatment by the above-described apparatus, complex particles of the antiviral agent having a smooth surface can be formed by adjusting the stirring time and the like. That is, in the composite treatment, after the antiviral particles 2 are embedded in the inorganic particles 4, the composite fine particles collide with each other, so that the antiviral particles 2 are embedded deeper in the inorganic particles 4. A smooth surface in which the conductive particles 2 do not protrude from the surface of the inorganic particles 4 is formed.

  In addition to the method described above, as in the second embodiment, the coprecipitation method, the precipitation method, the sol-gel method, the impregnation method, and the dropping method can be used as a method for supporting the antiviral particles 2 on the inorganic particles 4. Methods such as a sum precipitation method, a reducing agent addition method, a pH-controlled neutralization precipitation method, and a carboxylic acid metal salt addition method may be used, and these methods can be appropriately used depending on the type of the carrier.

  When used in the third embodiment, the plasma discharge space is filled with a breathable sheet or film in which many openings smaller than the inorganic particles 4 are formed so that the inorganic particles 4 are not scattered. It may be covered or filled in a plasma discharge space by filling a container or the like in which a large number of openings smaller than the inorganic particles 4 are formed on the gas ventilation surface so as to have gas permeability in the gas ventilation direction. May be. Alternatively, if a sheet or film having an opening smaller than that of the inorganic particles 4 is formed into a bag shape and filled with the inorganic particles, it is located downstream of the plasma discharge space in the gas flow direction and adjacent to the discharge space. May be installed.

  According to the above embodiment, as the antiviral filter 100, instead of fixing the antiviral particles 2 to the base filter, a large number of composite particles having the antiviral particles 2 fixed on the surface of the inorganic particles are filled. Even if the antiviral filter 100 is configured, the floating virus removal unit 200 can be provided in the same manner. In particular, the effect that the anti-viral properties are sustained due to the large particle size and the difficulty of scattering.

(Fourth embodiment)
Next, a fourth embodiment will be described. FIG. 5 is a cross-sectional view of the antiviral filter 100 of the present embodiment. In addition, about the structure which is common in embodiment mentioned above, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  The antiviral filter 100 of the present embodiment includes a filter portion 1 and composite antiviral particles 30 that carry the antiviral particles 2 on the surface of the inorganic fine particles 3. The composite antiviral particle 30 is firmly fixed to the surface of the filter portion 1 by the chemical bond 6 via the silane compound 5 which is an oligomer which is a silane monomer having an unsaturated bond portion or a silane monomer polymer. Yes.

  Examples of the silane monomer that is the silane compound 5 include silane monomers represented by a general formula of X—Si (OR) n (n is an integer of 1 to 3). X is a functional group that reacts with an organic substance, such as a vinyl group, an epoxy group, a styryl group, a methacrylo group, an acryloxy group, an isocyanate group, a polysulfide group, an amino group, a mercapto group, or a chloro group. OR is an alkoxy group such as a hydrolyzable methoxy group or ethoxy group, and the three functional groups related to the silane monomer may be the same or different. These alkoxy groups composed of methoxy groups and ethoxy groups are hydrolyzed to form silanol groups. It is known that functional groups having silanol groups, vinyl groups, epoxy groups, styryl groups, methacrylo groups, acryloxy groups, isocyanate groups, and unsaturated bonds have high reactivity. That is, in the antiviral filter 100 of the fourth embodiment, the composite antiviral particle 30 is firmly fixed to the surface of the member body 1 by the chemical bond 6 through such a reactive silane monomer.

  Examples of the silane monomer represented by the above general formula include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-amino. Propyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloki Cypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, special aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxy Silane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, hexyltrimethoxysilane, decyltrimethoxysilane, hydrolyzable group-containing siloxane, fluoroalkyl group-containing oligomer, methylhydrogensiloxane, Examples thereof include silicone quaternary ammonium salts.

  Examples of the silane oligomer include KC-89S, KR-500, X-40-9225, KR-217, KR-9218, KR-213, and KR-510 manufactured by Shin-Etsu Chemical Co., Ltd., which are commercially available. These silane oligomers may be used alone or in combination of two or more, and may be used in combination with one or more of the aforementioned silane monomers.

  As described above, in the antiviral filter 100 of the present embodiment, the composite antiviral particle 30 is firmly attached to the filter unit 1 with at least a part of the surface thereof exposed by the silane compound 5 having an unsaturated bond. It is fixed to. Therefore, according to the antiviral filter 100 of the present embodiment, the antiviral particles 2 are exposed to the surface while the antiviral particles 2 are firmly fixed by the filter portion 1 through the inorganic fine particles 3. The virus inactivating function similar to that of the above-described embodiment can be maintained. On the other hand, in the case of a general resin, the antiviral particles 2 can be firmly fixed, but the area exposed to the outside of the antiviral particles 2 because the antiviral particles 2 are covered with the resin. Greatly reduces the virus inactivation function.

  Depending on the type of silane monomer used, the composite antiviral fine particles 30 are fixed not by chemical bonds 6 but by condensation reaction, amide bonds, hydrogen bonds, ionic bonds, van der Waals force, physical adsorption, or the like.

  Thus, since the composite antiviral particles 30 are fixed on the surface of the filter unit 1 as a three-dimensional aggregate, many fine irregularities are formed on the surface of the filter unit 1, and the filter unit 1 is formed by the irregularities. The attachment of dust and the like to the surface is suppressed, and the virus inactivating action of the antiviral filter 100 can be maintained for a longer time.

  Next, an example of the manufacturing method of the antiviral filter 100 of this embodiment is demonstrated concretely. First, a silane monomer, which is a silane compound 5 having an unsaturated bond, is bonded to the surface of the inorganic fine particles 3 by dehydration condensation, and then dispersed in a dispersion medium such as water, methanol, ethanol, MEK, acetone, xylene, or toluene. . The chemical bond between the inorganic fine particles 3 and the silane monomer having an unsaturated bond can be formed by an ordinary method. For example, the inorganic fine particles are added to the dispersion and then heated under reflux while adding the silane monomer. A method of forming a thin film composed of a silane monomer by bonding a silane monomer to the surface of 3 by a dehydration condensation reaction, or adding a silane monomer to a dispersion in which inorganic fine particles 3 are dispersed, followed by solid-liquid separation and starting from 100 ° C. A method of heating at 180 ° C. to bind the silane monomer to the surface of the composite antiviral fine particle 30 by a dehydration condensation reaction, and then pulverizing and pulverizing and redispersing may be mentioned.

  Here, after adding a silane monomer to a dispersion obtained by microparticulation under reflux or by pulverization, or after adding silane monomer to microparticles by pulverization, solid-liquid separation is performed, and the temperature is 100 ° C. to 180 ° C. When the silane monomer is bonded to the surface of the inorganic fine particle 3 by a dehydration condensation reaction by heating at a temperature of 3, the amount of the silane monomer is 3 with respect to the mass of the inorganic fine particle 3, although it depends on the average particle size and material of the inorganic fine particle 3. If it is mass% to 30 mass%, the bonding strength between the inorganic fine particles 3 and between the inorganic fine particles 3 and the member main body 1 forming the antiviral filter 100 of the present invention is not a problem in practice.

  The slurry produced as described above is applied to the surface of the filter unit 1 by dipping, spraying, roll coater, bar coater, spin coating, gravure printing, offset printing, screen printing, ink jet printing, etc. Apply by the method. At this time, if necessary, the solvent is removed by heat drying or the like. Subsequently, the functional group on the surface of the filter unit 1 and the surface of the inorganic fine particles 3 facing the surface of the filter unit 1 are obtained by graft polymerization by reheating or by graft polymerization by irradiation with radiation such as infrared rays, ultraviolet rays, electron beams, and γ rays. The bonded silane monomer is chemically bonded (formation of chemical bond 6). At the same time, an oligomer is formed by chemically bonding 6 silane monomers on the surface of the inorganic fine particles 3.

  Thereafter, in the same manner as in the first embodiment, the metal nanoparticles can be supported on the inorganic fine particles 3 bonded to the surface of the main body 1 via a silane monomer. The loading amount of the metal nanoparticles 2 is preferably 0.5 to 20% by mass, and more preferably 0.5 to 10% by mass with respect to the member main body 1. The reason for this is that when 20% by mass or more is supported, the metal nanoparticles 2 aggregate and the antiviral effect is weakened.

  In the antiviral filter 100 of the fourth embodiment, oxide fine particles such as manganese and cobalt may be further bonded to the surface of the inorganic fine particles 3 made of an inorganic substance. This is because these oxide fine particles suppress the adhesion of harmful substances to the metal nanoparticles 2, and thus the area that can be contacted with the virus can be secured, so that the effect of quickly inactivating the virus can be maintained. . In particular, organic substances can be removed by plasma, but inorganic substances cannot be removed. Therefore, the presence of these oxide fine particles is effective in suppressing adhesion of harmful inorganic substances that cannot be removed by plasma.

  According to the fourth embodiment described above, even when the antiviral filter 100 in which the inorganic fine particles 3 according to the present embodiment are fixed with a silane compound is used, floating virus removal that maintains the function of quickly inactivating viruses is maintained. A unit 200 can be provided. In particular, in the present embodiment, fine irregularities are formed on the surface of the antiviral filter 100, and the adhesion of dust is suppressed. Therefore, the floating virus removal unit 200 with higher durability can be realized.

(Fifth embodiment)
Next, a fifth embodiment will be described. FIG. 6 is a cross-sectional view of the antiviral filter 100 of the present embodiment. In addition, about the structure which is common in embodiment mentioned above, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  In addition to the configuration of the fourth embodiment, the antiviral filter 100 of the present embodiment includes a coupling agent 7 bonded by a condensation reaction with a hydroxyl group on the surface of the filter unit 1. For example, when the surface of the filter unit 1 is an inorganic material such as a metal or an inorganic oxide, the silanol group of the coupling agent 7 is bonded to the hydroxyl group on the surface of the inorganic substrate by a condensation reaction, and the coupling agent 7 and the composite anti-oxidant are combined. The silane compound 5 having an unsaturated bond or its oligomer fixed on the surface of the virus agent 30 and the silane monomer (silane compound 5) bonded to the surface of the composite antiviral agent 30 can be covalently bonded to each other. .

  As a material of the filter part 1 of 5th Embodiment, it is the same as that of 1st-4th Embodiment. However, especially when the surface of the filter part 1 is a metal, the surface is usually formed with the oxide film. The composite antiviral particle 30 can be firmly fixed to the surface of the member main body 1 by the covalent bond by the dehydration condensation reaction with the coupling agent 7.

  However, in order to use the natural oxide film present on the surface of the metal and the alloy thereof, it is possible to remove oil and dirt adhering by an ordinary known method in advance stably and uniformly. This is preferable for immobilizing the complex antiviral agent 30.

  Then, the manufacturing method of the antiviral filter 100 of 5th Embodiment of this invention is demonstrated more concretely.

  First, the coupling agent 7 is applied to the surface of the filter portion 1 made of an inorganic material whose hydroxyl groups are exposed by washing, and dehydration condensation is performed (coupling layer 70). The coupling layer 70 is configured by arranging and fixing the coupling agent 7 on the surface of the filter unit 1. As the coupling agent 7 constituting the coupling layer 70 of the fifth embodiment, a silane coupling having a vinyl group, an epoxy group, a styryl group, a methacrylo group, an acryloxy group, an isocyanate group, a thiol group, or the like. The agent is mainly used.

  Next, the solution in which the composite antiviral particles 30 to which the silane compound 5 is fixed is dispersed is applied to the surface of the filter unit 1 to which the coupling agent 7 is covalently bonded, and the solvent is removed by heating and drying. As a result, the silane compound 5 on the surface of the composite antiviral particle 30 and the silane coupling agent 7 on the surface of the filter portion 1 made of inorganic material are graft-polymerized and simultaneously bonded to the composite antiviral particle 30. Manufactured by graft polymerization.

  Specific coating methods for the dispersion of the coupling agent 7 and the composite antiviral particles 30 include spin coating, dip coating, spray coating, cast coating, bar coating, and the like. Screen printing method, pad printing method, offset printing method, dry offset printing method, flexographic printing method, ink jet printing method, micro gravure coating method, gravure coating method or partial application method Various methods such as a printing method are used, and there is no particular limitation as long as a coating suitable for the purpose can be achieved.

  According to the present embodiment described above, the antiviral filter 100 fixed by bonding of the silane coupling layer 70 in which the inorganic fine particles 3 are applied to the surface of the filter portion 1 and the silane compound on the surface of the inorganic fine particles 3 is used. However, the floating virus removal unit 200 that maintains the function of quickly inactivating viruses can be provided. In particular, in the case of the antiviral filter 100 of the present embodiment, the inorganic fine particles 3 bonded to the filter unit 1 are firmly held by the filter unit 1 by the silane compound 5, so that an effect of suppressing peeling or the like can be obtained.

(Sixth embodiment)
Next, a sixth embodiment will be described. This embodiment is a modification of the floating virus removal unit described in the first embodiment. FIG. 7 is a schematic diagram showing the configuration of the floating virus removal unit 300 of the present embodiment. In FIG. 7, the floating virus removal unit 300 is shown in an exploded perspective view for easy understanding of the laminated state of the electrodes (11 and 12) and the antiviral filter 100.

  The specific configuration of the floating virus removal unit 300 according to the present embodiment is a voltage configured by alternately installing the application electrode 11 and the ground electrode 12 in which the dielectric 13 is fixed to the surface on the application electrode 11 side. A low-temperature plasma reaction layer 8 that generates plasma by application and an antiviral filter 100 disposed between both electrodes are provided. In addition, a power source 14 that can apply a high voltage between the application electrode 11 and the ground electrode 12 is connected to the application electrode 11. A set of the application electrode 11, the antiviral filter 100, the dielectric 13 and the ground electrode 12 corresponds to the floating virus removal unit 200 described in the first embodiment.

  For example, as shown in FIG. 7, gas is flowed from one end side to the floating virus removal unit 300 in the direction of arrow a and discharged from the other end side (arrow b), so that the gas has a plurality of antiviral properties. It will pass through the filter 100. Therefore, according to the floating virus removal unit 300 of the present embodiment, the virus can be removed more reliably. In addition, since each antiviral filter 100 is disposed in the plasma reaction layer 8 formed of an electrode and a dielectric, the inactivated virus is removed from the antiviral filter 100 and has a virus inactivating function. Since it is regenerated, it can quickly act to inactivate viruses.

(Seventh embodiment)
Next, a seventh embodiment will be described. FIG. 8 is a diagram schematically showing a part of a cross section of the floating virus removal unit 400 which is an example of the present embodiment. The floating virus removal unit 400 of this embodiment generates plasma by silent discharge.

  The floating virus removal unit 400 has an antiviral property between the electrodes in the low temperature plasma reaction layer in which the application electrode 11, the ground electrode 12, and the dielectric 13 that generate voltage by applying a voltage using the high voltage power source 14 are installed. A filter 100 is installed. In the present embodiment, the electrodes (11 and 12) and the dielectric 13 may not have air permeability. These electrodes, dielectric 13 and antiviral filter 100 are stacked in close contact with each other. In FIG. 8, the dielectrics 13 are stacked in close contact with both the application electrode 11 and the ground electrode 12, but only one of the dielectrics 13 may be provided.

  Further, the antiviral filter 100 may or may not be in close contact with the dielectric 13. The antiviral filter 100 needs to be breathable when it is in close contact with both dielectrics, but the antiviral filter 100 may not be breathable when it is not in close contact with at least one of the dielectrics 13. In the case of the floating virus removal unit 400 of the present embodiment, the floating virus is removed by flowing gas from the direction of arrow a in FIG. 8 and discharging the gas from the other end side in the direction of arrow b. The floating virus removal unit 400 has a multi-layer structure, so that a large amount of floating viruses can be efficiently removed, and the viruses can be efficiently removed according to usage conditions such as the amount of floating viruses and the flow rate. The antiviral filter 100 may be either a single layer or a plurality of layers, and can be arbitrarily set.

(Eighth embodiment)
Next, an eighth embodiment will be described. This embodiment is a modification of the floating virus removal unit. FIG. 9 is a schematic diagram showing the configuration of the floating virus removal unit 500 of the present embodiment. FIG. 10 is a cross-sectional view of the floating virus removal unit 500 shown in FIG. FIG. 9 is an exploded perspective view in which the floating virus removal unit 500 is disassembled in order to easily show the structure. The floating virus removal unit 500 is characterized in that the application electrode 11 is installed on one side of a plate- or sheet-like dielectric 13 and the ground electrode 12 is installed on the opposite side, and discharge is performed on both sides of the dielectric 13.

  The floating virus removal unit 500 of this embodiment is a comb-shaped electrode in which the application electrode 11 and the ground electrode 12 are each composed of a number of electrodes extending in a predetermined direction. Then, gas is circulated between the comb teeth of the comb-shaped electrode, and the virus in the gas is inactivated by the antiviral particles 2 on the antiviral filter 100. Then, creeping discharge is generated between the comb-shaped electrodes 11 and 12 and the dielectric 13, and the antiviral particles 2 can be cleaned by the plasma generated thereby. In order for the antiviral filter 100 and the plasma presence region 9 to overlap, it is preferable that the thicknesses of the application electrode 11 and the ground electrode 12 are thin.

  According to this embodiment, since the antiviral filter is provided so as to be in contact with both electrodes, the virus removal effect is great and a large amount of gas can be processed.

(Ninth embodiment)
Next, a ninth embodiment will be described. This embodiment is a modification of the floating virus removal unit. FIG. 11 is a schematic diagram showing the configuration of the floating virus removal unit 600 of the present embodiment. The floating virus removal unit 600 of this embodiment is a stack of a plurality of floating virus removal units 500 of the eighth embodiment. Since a plurality of floating virus removal units 500 are stacked, the virus removal effect is great and a large amount of gas can be processed.

(10th Embodiment)
Next, a tenth embodiment will be described. This embodiment is a modification of the floating virus removal unit. FIG. 12 is a diagram showing the configuration of the floating virus removal unit 700 of this embodiment.

  The floating virus removal unit 700 has a cylindrical structure in which a cylindrical application electrode 11, a ground electrode 12, and an antiviral filter 100 are laminated radially outward in an annual ring shape. A low-voltage plasma reaction layer 8 in which a dielectric 13 is installed on each of an inner diameter portion of an application electrode 11 that generates a plasma by applying a voltage using a high-voltage power supply 14 and an outer diameter portion of a ground electrode 12, An antiviral filter 100 is installed. In the figure, both the application electrode 11 and the ground electrode 12 are laminated in close contact with the dielectric 13, but only one dielectric 13 may be provided. The antiviral filter 100 is configured to have air permeability, and in the floating virus removal unit 700 of the present embodiment, gas can flow through the antiviral filter 100 portion. Therefore, in the case of this floating virus removal unit 700, the gas is inactivated from one end of the circular shape and discharged from the other end surface through the antiviral filter 100, thereby inactivating the virus in the gas. I do. The plasma reaction layer 8 of the floating virus removal unit 700 has an annual ring-like multilayer structure, and a large amount of floating viruses can be efficiently decomposed as in the case of the multilayer structure of the floating virus removal unit 300 or 600. Depending on the usage conditions such as the amount of suspended virus and flow rate, the number of cylindrical annual rings of the antiviral filter 100 installed in the plasma reaction layer 8 is one or more so that the suspended virus can be efficiently decomposed. But it can be set arbitrarily.

  A virus removal unit may be configured by combining a plurality of annual ring-shaped floating virus removal units 700 of this embodiment. FIG. 13 is a schematic diagram showing the configuration of the floating virus removal unit 800. This floating virus removal unit 800 is configured by arranging four floating virus removal units 700 in two rows. According to such a configuration, a larger amount of airborne viruses can be efficiently decomposed. The way of combining the floating virus removal unit 800 is not limited to that shown in FIG. 13 and can be appropriately arranged according to the shape of the place where the floating virus removal unit 800 is installed. For example, a plurality of floating virus removal units 800 may be arranged so that the floating virus removal unit 800 may be arranged in a line vertically or horizontally, and the cross section of the floating virus removal unit 800 may be a polygon, such as a rectangle, a trapezoid, or a triangle, or a circle. May be.

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

(Creation of antiviral metal particle-carrying filter)
Example 1
As inorganic fine particles, zirconium oxide particles in which methacryloxypropyltrimethoxysilane (KBS-503, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane monomer having an unsaturated bond, is dehydrated and condensed by an ordinary method and covalently bonded to the surface ( 100 g of NIPPON Denko Corporation (PCS) was pre-dispersed in 900 g of ethanol, and then pulverized and dispersed with a bead mill to obtain a particle dispersion. The average particle size of the obtained particle dispersion was 105 nm. In addition, the average particle diameter as used in this specification means a volume average particle diameter. The obtained particle dispersion was adjusted by adding ethanol so that the solid content concentration was 1% by mass.

Subsequently, an alumina fiber woven fabric (manufactured by Nichibi Co., Ltd., 80 g / m ² ) was impregnated into the coating solution and dried to obtain an inorganic fine particle fixed sheet.

0.5 mmol of HAuCl ₄ · 4H ₂ O was dissolved in 100 ml of water (5 mmol / l), heated to 70 ° C. and adjusted to pH 4.8 with NaOH aqueous solution. The inorganic fine particle fixed sheet (10 cm × 10 cm) as a sheet body was added to the aqueous solution and stirred for 1 hour. Thereafter, it was washed with distilled water and dried at 100 ° C. for 4 hours in a nitrogen atmosphere to obtain an antiviral metal particle-carrying filter on which inorganic fine particles carrying gold nanoparticles on the surface as antiviral particles were fixed. When the surface of the obtained filter was observed with a super-resolution field emission scanning electron microscope, gold with an average particle diameter of 4.4 nm was supported.

(Example 2)
A punched aluminum plate (JISH1050 material) with a large number of holes of 1.0 mmφ was immersed in a 5% by mass sodium hydroxide aqueous solution heated to 50 ° C. for 30 seconds, then washed in running water to remove excess alkali. It was removed by dipping in a mass% aqueous nitric acid solution. Next, it is immersed in a 20 ° C. aqueous solution containing 200 g / l of sodium carbonate and 10 g / l of sodium fluoride, and a γ-alumina coating is formed on the aluminum plate surface by applying a DC voltage of 150 V using a carbon electrode as the counter electrode. Formed. Thereafter, the γ-alumina-coated aluminum plate was immersed in an aqueous solution of 10 mmol / l HAuCl ₄ · 4H ₂ O to adsorb HAuCl ₄ to the γ-alumina coating. Next, γ-alumina film-formed aluminum plate adsorbed with HAuCl ₄ was immersed in an aqueous solution containing 3% by mass of sodium borohydride to fix inorganic fine particles carrying gold nanoparticles on the surface as antiviral particles. An antiviral metal particle-carrying filter was obtained. When the surface of the obtained filter was observed with a super-resolution field emission scanning electron microscope, gold having an average particle diameter of 5.8 nm was supported.

(Example 3)
By immersing a 200 mesh screen woven with 38 μm titanium wire (manufactured by Toho Tech Co., Ltd.) in a 20 ° C. aqueous solution containing 200 g / l of sodium carbonate, and applying a DC voltage of 170 V using a carbon electrode as the counter electrode, A white oxide film made of a mixed crystal of rutile type and anatase type was formed. Next, a commercially available gold colloidal solution (Au colloidal solution SC, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) is applied to a titanium mesh on which an oxide film is formed by spraying, and is heated and dried at 120 ° C. for 30 minutes, thereby being antiviral. An antiviral metal particle-carrying filter in which inorganic fine particles carrying gold nanoparticles on the surface as particles was fixed was obtained. When the surface of the obtained filter was observed with a super-resolution field emission scanning electron microscope, gold with an average particle diameter of 40.0 nm was supported.

Example 4
After 0.7 g of zirconia powder and 1.4 mg of palladium acetate powder were mixed in a mortar, they were added to 70 g of methanol. Furthermore, 14 μL of hydrochloric acid was added thereto, and the mixture was stirred with a homogenizer at 20,000 rpm for 5 minutes to prepare a palladium supporting solution. An alumina woven fabric was immersed in this solution, and the dried alumina woven fabric was pre-dried at 70 ° C. for 20 minutes. Thereafter, the pre-dried alumina fabric was heat-treated at 210 ° C. for 4 hours in an oxygen atmosphere to obtain an antiviral particle-carrying filter in which inorganic fine particles carrying palladium oxide particles on the surface were fixed as antiviral particles. It was. When the surface of the obtained filter was observed with a super-resolution field emission scanning electron microscope, palladium oxide having an average particle diameter of 32.0 nm was supported.

(Production of plasma irradiation device to antiviral particle-carrying filter)
The antiviral particle-carrying filter was inserted into a test space (10 cm × 10 cm × 1 mm) sandwiched between the application electrode and the counter electrode. The application electrode and the ground electrode (counter electrode) are covered with mica on the test space side. The floating virus removal unit shown in FIG. 1 was used as an apparatus for irradiating plasma to the antiviral particle-carrying filter by applying an AC power source to the application electrode and grounding the counter electrode and applying a voltage.

(Antiviral performance evaluation method)
The antiviral performance of the floating virus removal unit was evaluated using influenza virus (influenza A / Kitakyushu / 159/93 (H3N2)) cultured using MDCK cells.

The central part (4 cm × 4 cm) of the antiviral metal particle-carrying filter was cut out to obtain a test piece. 0.1 ml of virus solution was added dropwise and air-dried for 60 minutes. Thereafter, the test piece to which the virus solution was attached was returned to the original position of the antiviral metal particle-carrying filter and installed in the floating virus removal unit. Plasma was generated with a discharge output of 1 W and a frequency of 50 Hz. After plasma irradiation, the test piece was taken out, and the virus adhering to the test piece was washed out with a 20 mg / ml bouillon protein solution containing a surfactant. Thereafter, each washing solution was serially diluted 10-fold with MEM, and 100 μl of the diluted solution was inoculated on MDCK cells cultured in a petri dish. Number of plaques formed after allowing to stand for 60 minutes to adsorb the virus to cells, overlaying 0.7% agar medium, culturing in 34 ° C, 5% CO ₂ incubator for 48 hours, fixing with formalin and staining with methylene blue Were counted, and the virus infectivity titer (PFU / 0.1 ml, Log 10); (PFU: plaque-forming units) was calculated.

(Comparative Example 1)
Although it was the same as Example 1, the case where plasma was not irradiated was made into the comparative example 1. That is, this is a comparative example for evaluating only the virus inactivating action by the antiviral particles.

(Comparative Example 2)
The antiviral metal particle-carrying filter used in Example 1 was prepared under the same conditions as in Example 1 except that no gold nanoparticles were supported (that is, no antiviral particles), and plasma was generated. Irradiation was conducted to Comparative Example 2.

(Comparative Example 3)
As in Comparative Example 2, Comparative Example 3 is a case where gold nanoparticles are not supported on the metal nanoparticle-supported filter (in a state where no antiviral particles are present) and no plasma is irradiated.

(Comparative Example 4)
Although it is the same as that of Example 4, the case where plasma was not irradiated was made into the comparative example 4. That is, this is a comparative example for evaluating only the virus inactivating action by the antiviral particles.

  Table 1 shows the conditions of Examples 1 to 3 and Comparative Examples 1 to 3. The control is a value when the virus solution is added without a filter (test piece) and the plasma is not irradiated.

  Table 2 shows the results of antiviral performance evaluation of Examples 1 to 3 and Comparative Examples 1 to 3.

  From the results of the above tests, the gold nanoparticle-supported filter (Comparative Example 1) and the plasma (Comparative Example 2) were respectively used by using the antiviral metal particles of the present invention with plasma (Examples 1 to 3). A higher virus inactivating effect was observed compared to when used alone. The same applies when palladium oxide, which is a metal oxide, is used for the antiviral particles (comparison between Example 4 and Comparative Example 4). The difference in infectivity between Comparative Example 2 and Comparative Example 3 is 3.0, but this difference is the difference in the presence or absence of plasma irradiation. If 3.0 is subtracted from the infectivity value 6.2 of Comparative Example 1 by the difference in the presence or absence of the plasma irradiation, the result is 3.2. This value is an expected value of the infectious value due to the combined use of gold nanoparticles and plasma, but the actual infectious value of Example 1 is 1.3 or less (below the detection limit). The effect is that the virus on the surface of the antiviral nanoparticle is cleaned by the plasma, and the area where the antiviral nanoparticle and the virus can be contacted always maintains the initial state, so the number of viruses that can be contacted increases. It is considered that more viruses can be inactivated in a short time (60 minutes).

(Example 5)
(Creation of antiviral particle-supporting filter)
As inorganic fine particles, 100 g of zirconium oxide particles (manufactured by Nippon Electric Works Co., Ltd., PCS) was pre-dispersed in 900 g of ethanol, and then pulverized and dispersed with a bead mill to obtain a particle dispersion. The average particle size of the obtained particle dispersion was 105 nm. In addition, the average particle diameter as used in this specification means a volume average particle diameter. The obtained particle dispersion was adjusted by adding ethanol so that the solid content concentration was 3% by mass.

Subsequently, an alumina fiber woven fabric (manufactured by Nichibi Co., Ltd., 265 g / m ² ) was impregnated into the coating solution and dried to obtain an inorganic fine particle fixed sheet.

The aqueous HAuCl ₄ solution was diluted to 3000 ppm with water, heated to 60 ° C., and adjusted to pH 7 with an aqueous NaOH solution. The inorganic fine particle fixing sheet was immersed in the aqueous solution for 30 minutes and then washed with distilled water. Thereafter, it was immersed in an aqueous manganese acetate solution (2500 ppm) at room temperature for 30 minutes and washed again with distilled water. Thereafter, the mixture was heated in the atmosphere at 300 ° C. for 2 hours to obtain an antiviral particle-carrying filter in which inorganic fine particles carrying gold nanoparticles on the surface were fixed. When the surface of the obtained filter was observed with a super-resolution field emission scanning electron microscope, gold with an average particle diameter of 4.4 nm was supported.

(Antiviral performance evaluation method)
The antiviral performance of the floating virus removal unit was evaluated using influenza virus (influenza A / Kitakyushu / 159/93 (H3N2)) cultured using MDCK cells.

An antiviral particle-carrying filter (10 cm × 10 cm) was used as a test piece. 0.4 ml of virus solution was dropped, and the test piece to which the virus solution was attached was placed in the floating virus removal unit of FIG. A voltage was applied to generate plasma. At this time, the discharge output was 1.0 W, and the frequency of the AC voltage to be applied was 0.05 to 10 kHz. After plasma irradiation, the test piece was taken out, and the virus adhering to the test piece was washed out with a 20 mg / ml bouillon protein solution containing a surfactant. Thereafter, each washing solution was serially diluted 10-fold with MEM, and 100 μl of the diluted solution was inoculated on MDCK cells cultured in a petri dish. Number of plaques formed after allowing to stand for 60 minutes to adsorb the virus to cells, overlaying 0.7% agar medium, culturing in 34 ° C, 5% CO ₂ incubator for 48 hours, fixing with formalin and staining with methylene blue Were counted, and the virus infectivity titer (PFU / 0.1 ml, Log 10); (PFU: plaque-forming units) was calculated.

(Example 6)
Although it is the same as that of Example 5, the thing which carry | supported the platinum nanoparticle instead of the gold nanoparticle which is an antiviral particle on the antiviral particle carrying | support filter was made into the Example. An antiviral particle-carrying filter with platinum nanoparticles fixed thereon was prepared as follows.
The above-mentioned alumina fiber fabric was immersed in a 2% aqueous solution prepared by diluting an alumina sol aqueous solution (Nissan Chemical Industry) and dried, and fired at 1200 ° C. for 2 hours in the atmosphere. Next, the dinitrodiamine platinum solution was sprayed on the fabric. At this time, the solution concentration was adjusted so that platinum was 1.5% by mass with respect to the fabric weight. After spraying, predrying at 110 ° C., followed by baking at 450 ° C. for 4 hours to obtain an antiviral particle-carrying filter having platinum particles fixed thereon. When the surface of the obtained filter was observed with a super-resolution field emission scanning electron microscope, platinum having an average particle diameter of 3.1 nm was supported.

(Example 7)
Example 7 is the same as in Example 5, except that the antiviral particle-carrying filter is not gold particles but cerium oxide particles are not carried on the zirconium oxide particles as inorganic fine particles but directly fixed to the alumina fiber fabric. . The antiviral nanoparticle-carrying filter fixed with cerium oxide was produced as follows.

  A methanol solution containing 5% by mass of cerium oxide was dispersed with a ball mill for 24 hours. An alumina fiber woven fabric was immersed in the solution and dried to obtain an antiviral particle-carrying filter on which cerium oxide particles were fixed. When the surface of the obtained filter was observed with a super-resolution field emission scanning electron microscope, cerium oxide having an average particle diameter of 45.0 nm was supported.

(Comparative Example 5)
Although it is the same as that of Example 5, the case where plasma was not irradiated was made into the comparative example 5. That is, this is a comparative example for evaluating only the virus inactivating action by the antiviral particles.

(Comparative Example 6)
Although it is the same as that of Example 6, the case where plasma was not irradiated was made into the comparative example 6.

(Comparative Example 7)
Although it is the same as that of Example 7, the case where plasma was not irradiated was made into the comparative example 7.

  Table 3 shows the conditions of Examples 5 to 7 and Comparative Examples 5 to 7. The control is a value when the virus solution is added without a filter (test piece) and the plasma is not irradiated.

  FIG. 14 shows the results of antiviral performance evaluation of Examples 5 to 7 and Comparative Examples 5 to 7. From these results, it was confirmed that by using plasma together with the antiviral nanoparticle of the present invention, a higher virus inactivating effect was observed compared to when the antiviral particle-carrying filter was used alone. Furthermore, even when the frequency was set to 0.05 kHz or higher, virus inactivating action was observed, and it was confirmed that the effect increased when the frequency was set to 0.5 kHz or higher.

  Next, in the test of antiviral performance evaluation in Example 5, the plasma discharge output is 1.0 W, the frequency of the applied AC voltage is 0.05, 1, 3, 5, 6, 7, 10 kHz, and the ozone at that time The generation concentration of was measured. The result is shown in FIG.

  Although there is no difference between 1kHz and 3kHz, it can be said that ozone concentration tends to decrease when the frequency is increased. In particular, when the frequency exceeds 5 kHz, the ozone generation concentration decreases rapidly.

  Subsequently, in the antiviral performance evaluation test in Example 6, the discharge output of plasma was 1.0 W, and the frequency of the applied AC voltage was 0.05, 0.5, 0.75, 1, 1.5, 2, 3, 5, 10 kHz. The ozone generation concentration at that time was measured. The result is shown in FIG.

  When the frequency is increased, the ozone generation concentration tends to decrease, and when the frequency exceeds 1 kHz, ozone is hardly generated.

  Subsequently, in the antiviral performance evaluation test in Example 7, the plasma discharge output was 1.0 W, and the frequency of the applied AC voltage was 0.05, 1, 2, 3, 4, 5, 6, 10 kHz. The generation concentration of ozone was measured. The result is shown in FIG.

  It can be said that the ozone generation concentration tends to decrease when the frequency is increased.

  The higher the frequency, the lower the ozone generation concentration. From this result, it was confirmed that the ozone generation concentration was decreasing when the frequency exceeded 1 kHz. Above 1kHz, the antiviral effect is good. Up to 10 kHz, virus inactivation was observed, and the ozone generation concentration was confirmed to be low.

DESCRIPTION OF SYMBOLS 100 Antiviral filter 200 Airborne virus removal unit 300 Airborne virus removal unit of other embodiment 400 Airborne virus removal unit of other embodiment 500 Airborne virus removal unit of other embodiment 600 Airborne virus removal unit of other embodiment 700 Floating Virus Removal Unit of Other Embodiments 1 Antiviral filter body 2 Antiviral nanoparticle 3 Inorganic fine particle 4 Inorganic particle 5 Silane monomer or oligomer 6 Chemical bond 7 Silane coupling agent 8 Discharge space 11 Applied electrode 12 Ground electrode 13 Dielectric 14 Power supply 30 Composite antiviral fine particle 70 Coupling layer

Claims (10)

A virus removal unit for removing viruses contained in gas,
A plasma generator that includes at least a first electrode, a second electrode, and a dielectric, and generates a plasma by applying a voltage between the first electrode and the second electrode to generate a discharge; ,
A virus inactivating part including particles having antiviral properties, disposed in a space where the plasma generated by the plasma generating part exists;
A virus removal unit comprising:   The virus removal unit according to claim 1, wherein the virus inactivation part further includes an inorganic substance part that contacts the antiviral particles. A gas supply unit that supplies a gas to be processed to remove viruses;
In the plasma generation unit, the first electrode, the second electrode, the dielectric, and the virus inactivation unit are arranged side by side in the flow direction of the gas to be processed supplied from the gas supply unit. , Each has gas permeability in the gas flow direction,
The virus inactivating part has air permeability in the gas flow direction, and is located in at least one of the discharge space of the discharge and the downstream position in the gas flow direction with respect to the discharge space. The virus removal unit according to claim 1 or 2, wherein the virus removal unit is arranged. A gas supply unit that supplies a gas to be processed to remove viruses;
The plasma generating unit is a direction in which the first electrode, the second electrode, the dielectric, and the virus inactivating unit are orthogonal to the flow direction of the gas to be processed supplied from the gas supply unit. The virus removal unit according to claim 1, wherein the virus removal unit is arranged side by side. The virus inactivating part further comprises a base material for fixing the antiviral particles,
The virus removing unit according to any one of claims 1 to 4, wherein at least a portion of the base material on which the particles having antiviral properties are fixed is an inorganic material. The virus inactivating part is
Inorganic particles formed of an inorganic material and having antiviral properties fixed on the surface thereof;
The virus removal unit according to any one of claims 1 to 4, further comprising a base material on which the inorganic particles are fixed.   The said virus inactivation part is what was filled with the composite particle by which the particle | grains which have the said antiviral property were fixed to the surface of the inorganic particle, The any one of Claim 1 to 4 characterized by the above-mentioned. Virus removal unit.   The said virus inactivation part is formed in the surface of at least any one of the said 1st electrode, the said 2nd electrode, and the said dielectric material, The description of any one of Claim 1 to 7 characterized by the above-mentioned. Virus removal unit.   The floating virus removal unit according to any one of claims 1 to 8, wherein the plasma is generated by at least one of creeping discharge and silent discharge.   The airborne virus according to any one of claims 1 to 9, wherein the antiviral particle is made of at least one of gold, platinum, palladium, cerium, and oxides thereof. Removal unit.

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