JP2013067577A - Antiviral agent and member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antiviral agent and a member using the same capable of inactivating attached virus even in the presence of a lipid or a protein regardless of presence/absence of an envelope.SOLUTION: This antiviral agent 10 comprises inorganic fine particles 2 wherein at least each surface thereof comprises an inorganic material, and gold fine particles 1 fixed to the surface of the inorganic fine particles 2.

Description

  The present invention relates to a virus inactivating sheet, and more particularly to a virus inactivating sheet that can inactivate various attached viruses regardless of the presence or absence of an envelope or in the presence of lipids or proteins.

  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 healthcare workers through workers, or the environment including equipment such as white coats, pajamas and sheets, and equipment such as walls and air conditioners have become a major social problem. Yes. Therefore, there is a strong demand for the development of a member having antiviral properties capable of exhibiting bactericidal and antiviral effects that is effective against various viruses and bacteria.

  As a means for solving these problems, there is a virus inactivating sheet using a composite containing an inorganic porous crystal carrying an antibacterial metal ion such as silver ion or copper ion inside a resin (Patent Document 1). . Moreover, what is called the virus inactivating agent which melt | dissolved the iodine-cyclodextrin inclusion product is also reported (patent document 2, 3, 4).

JP 2006-291031 A JP 2006-328039 A JP 2007-39395 A JP 2007-39396 A

  However, the method of containing an inorganic porous crystal inside the resin can be applied to a fibrous fabric, but cannot be applied to a film or sheet that does not use fibers, and to an inorganic material. In addition, since the virus inactivating agent using iodine is water-soluble, even if it is applied to a fabric or sheet by impregnation or the like, the components are easily dissolved when wet.

  Here, viruses can be classified into viruses that do not have an envelope, such as norovirus, and viruses that have an envelope, such as influenza virus. May not. In addition, when an inactivated sheet is affixed to a mask, or used for surgical protective clothing, pillow covers, etc., it is an article that is used in contact with the mouth or nose of an infected person. In some cases, lipids and proteins contained in body fluids such as saliva and the like are attached. Therefore, it is preferable that the virus can be inactivated even in an environment where lipids and proteins are present, but such verification is not made in the above-mentioned document.

  In order to solve the above problems, the present invention provides an antiviral agent that can inactivate a virus that is attached regardless of the presence or absence of an envelope or in the presence of a lipid or protein, and a member using the same. is there.

  That is, the first invention is an antiviral agent characterized by comprising inorganic fine particles having at least a surface made of an inorganic material and gold fine particles fixed to the inorganic material portion of the inorganic fine particles. Here, the inorganic fine particle of the present application is a concept including not only fine particles made of an inorganic material as a whole, but also fine particles made of an inorganic material on the entire surface, and fine particles made of an inorganic material on a part of the surface.

  The second invention is the antiviral agent according to the first invention, wherein the gold fine particles are bonded to an inorganic material portion of the inorganic fine particles and have a bonded interface peripheral edge.

  Furthermore, the third invention is a member having antiviral properties, characterized by comprising a base material and the antiviral agent of the first or second invention fixed to the surface of the base material.

  Still further, a fourth invention is the antiviral member according to the third invention, wherein the base material is made of a fiber structure.

  The fifth invention is a filter using the antiviral member of the third or fourth invention.

  According to the present invention, for example, an antiviral agent capable of inactivating a virus attached to the surface of an antiviral agent or the like even in the presence of a protein such as droplets or blood, and an antiviral member using the antiviral agent are provided. can do.

It is a schematic diagram of the antiviral agent of this invention. It is the schematic diagram which expanded a part of antiviral agent of this invention. It is a schematic diagram of the cross section of 1st Embodiment of the member which has antiviral property of this invention. It is a schematic diagram of the cross section of 2nd Embodiment of the member which has antiviral property of this invention. It is a schematic diagram of the cross section of 3rd Embodiment of the member which has antiviral property of this invention.

  Hereinafter, the antiviral agent of this invention is explained in full detail using FIG. 1, FIG. Further, in the figure, the gold fine particles are indicated by ◯ for easy understanding, but this also includes the concept of a polygon having the peripheral edge portion of the bonding interface in FIG.

  FIG. 1 is a schematic diagram of an antiviral agent 10 according to the first embodiment of the present invention. The antiviral agent 10 of the first embodiment is composed of inorganic fine particles 2 having at least a surface made of an inorganic material, and gold fine particles 1 having antiviral properties, which are fixed to the inorganic material portion.

  The mechanism of virus inactivation is not necessarily clear at present, but it has a very high oxidation catalytic ability by supporting transition metal or noble metal fine particles on inorganic oxide, so the surface of the contacted virus cell membrane Is estimated to be damaged and inactivated.

  As the inorganic fine particles 2 having at least a surface made of an inorganic material, for example, titania, zirconia, alumina, ceria (cerium oxide), silica, activated carbon, diatomaceous earth, and the like are preferably used, and chromium, manganese, iron, cobalt, nickel Also included are metal oxides made of copper, tin, and the like. Further, an organic fine particle made of a synthetic resin or a natural resin may be used in which an inorganic oxide or metal oxide film is formed on the surface by sputtering or plating.

  In addition, the particle size of the inorganic fine particles 2 is preferably 10 nm or more and less than 500 μm. In particular, when used as an aerosol, considering the effect of inhalation on human lungs, use of particles having a particle size of 4 μm or more is preferable because a safer antiviral agent can be provided. Furthermore, when fixing the antiviral agent 10 of this invention to a woven or knitted fabric, a sheet | seat, a film, etc., when adhesiveness with a base material is considered, it is preferable that it is 10 nm or more and less than 1 micrometer. If the particle size is less than 10 nm, it is difficult to fix the gold fine particles 1, which is not preferable.

  Methods for fixing the anti-viral gold fine particles 1 to the inorganic fine particles 2 include coprecipitation method, precipitation method, sol-gel method, impregnation method, drop neutralization precipitation method, reducing agent addition method, pH control neutralization. Examples thereof include a precipitation method and a carboxylic acid metal salt addition method, and these methods can be appropriately used depending on the kind of the inorganic fine particles 2.

  Although the gold fine particles 1 of the antiviral agent 10 of the first embodiment can be freely determined by the user depending on the use conditions, the particle size is preferably 500 nm or less, and more preferably 100 nm or less. This is because if the particle diameter is larger than 500 nm, the gold fine particles 1 are difficult to be stably fixed to the inorganic fine particles 2. In addition, gold fine particles of 100 nm or less are preferable because the redox action is liable to occur, and the antiviral effect is further exhibited. However, those having a particle size smaller than 1 nm are very unstable as substances and cannot exist.

  The supported amount of the gold fine particles 1 is preferably 50% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less with respect to the inorganic fine particles 2. The reason for this is that if the amount of gold fine particles 1 to be adhered is too large, the particles will aggregate, and thus the antiviral effect cannot be efficiently expressed. If the amount is less than 0.1% by mass, sufficient antiviral effect is obtained. This is because is not expressed.

  The gold fine particles 1 of the antiviral agent 10 of the first embodiment are alloy fine particles with one or more metals such as silver, copper, iron, aluminum, zinc, platinum, palladium, nickel, bismuth and manganese. Alternatively, mixed fine particles of one or more of these metal fine particles and gold fine particles may be used. This is because these oxide fine particles suppress the adhesion of harmful substances to the gold fine particles 1, and thus the antiviral effect can be stably maintained over a long period of time.

  Further, the material used for the inorganic fine particles 2 is preferably a material in which the surface potential of the inorganic fine particles 2 is positive. This is because the surface potential of the virus is negative regardless of the type of genome, the presence or absence of the envelope, etc. Therefore, if the surface potential of the inorganic fine particles 2 is positive, the virus is electrically attracted to the inorganic fine particles 2, As a result, the virus is easily adsorbed on the surface of the antiviral agent 10, and the antiviral effect by the gold microparticles 2 having antiviral properties can be expressed more efficiently.

  Next, the method for producing the antiviral agent 10 according to the first embodiment of the present invention will be described by taking a method using a colloidal solution of gold fine particles 1 as an example.

The colloidal solution of the gold fine particles 1 is manufactured by a known method such as adding a reducing agent such as sodium citrate into an aqueous gold compound solution such as HAuCl ₄ .4H ₂ O. As the dispersion medium, water, acetone, methanol, ethanol or the like is preferably used. The inorganic fine particles 2 are added to the colloidal aqueous solution of the gold fine particles 1 produced in this way and stirred, and then dried at 100 ° C. in a nitrogen atmosphere. Further, the surface of the gold fine particles 1 in the colloidal solution may be coated with a protective agent such as a surfactant.

  Next, a second embodiment of the antiviral agent 10 of the present invention will be described in detail with reference to FIG.

  FIG. 2 is an enlarged schematic view of a part of the antiviral agent 10 of the present invention. The antiviral agent 10 of the second embodiment is configured by adhering the gold fine particles 1 to the inorganic material portion of the inorganic fine particles 2, but the gold fine particles 1 are not spherical but have a substantially polyhedral state having a joint interface peripheral portion. The point which adhere | attaches closely and is a point different from 1st Embodiment.

In general, it is known that when the gold particle diameter is set to the nano level, the shape of the gold fine particles is substantially polyhedral, such as an icosahedron. Here, the bonding interface peripheral portion used in the second embodiment indicates both the corner portion A and the edge portion B of the gold fine particles 1. The corner portion A indicates a corner generated at a joint portion of three or more surfaces of the gold fine particles 1, and the edge portion B indicates an edge generated at a joint portion between the two surfaces of the gold fine particles 1.

  The mechanism of virus inactivation when the gold fine particles 1 have a peripheral edge of the bonding interface is not necessarily clear at present. However, when chemically stable gold is made into nanoparticles, it is not coordinated as shown in FIG. Since the ratio of the corner part A and the edge part B, which are saturated sites, increases and has a very high oxidation catalytic ability, it is assumed that the cell membrane surface of the contacted virus is damaged and inactivated. .

In the antiviral agent 10 of the second embodiment of the present invention, the gold fine particles 1 are supported on the inorganic fine particles 2 by utilizing the difference in zeta potential between the inorganic fine particles 2 and the gold fine particles 1 as an example. In addition, if the gold fine particles 1 are formed into particles with a reducing agent without using the inorganic fine particles 2, it is considered that the activity is lost because of aggregation, but in the antiviral agent 10 of the second embodiment, at least the gold fine particles 1 By bonding the surface to the surface of the inorganic fine particles 2 made of an inorganic material, the aggregation of the gold fine particles 1 can be prevented.

  As the gold fine particles 1 bonded to the inorganic material portion of the inorganic fine particles 2, those having a particle size of 10 nm or less can be suitably used. The reason for this is that when the particle size is larger than 10 nm, the length of the bonding interface is shortened, and it becomes difficult to form a polyhedral structure as shown in FIG. 2. This is because the ratio of the interface peripheral portion becomes sufficiently large.

  The method for adjusting the antiviral agent 10 according to the second embodiment of the present invention will be specifically described below using the precipitation method as an example. As a specific method of the precipitation method, first, the aqueous solution in which the gold compound is dissolved is heated to 20 to 90 ° C., preferably 50 to 70 ° C., and the pH is adjusted to 3 to 10, preferably 5 to 8 with stirring. After adjusting with an alkali solution so that it may become, after adding the inorganic fine particle 2, it heat-drys at 100-200 degreeC.

Examples of the gold compound aqueous solution used 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, are like NaAuBr _4, the concentration of the gold compound is preferably a ^{1 × 10 -2 ~1 × 10 -5} mol / L.

  The supported amount of the gold fine particles 1 is preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass with respect to the inorganic fine particles 2. The reason for this is that when 20% by mass or more is supported, the gold fine particles 1 aggregate and the antiviral properties are reduced.

  Moreover, the virus that can be inactivated in the antiviral agent 10 of all the embodiments of the present invention is not particularly limited, and various viruses can be inactivated regardless of the type of genome, the presence or absence of an envelope, and the like. it can. 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, hepatitis B / 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 agent 10 of all the embodiments of the present invention can be used in various modes. For example, the antiviral agent 10 of the present invention is preferably a powder from the viewpoint of handling, but is not limited thereto, and may be a powder or a granule depending on the purpose of use. Furthermore, it is used even if it is formed into a tablet by press forming. In the case of powder, the antiviral agent 10 is attached to clothes, hands, etc. by spraying with an inert gas in an aerosol container, filling the powder of the antiviral agent 10 and spraying. It is done. Furthermore, you may use the said antiviral agent 10 in the state disperse | distributed to dispersion media, such as water. Here, when the antiviral agent 10 of the present invention is dispersed in a dispersion medium, the gold fine particles 1 as the active ingredient are contained in an amount of 0.1% by mass or more in the dispersion, thereby providing more sufficient antiviral properties. It is preferable in obtaining. Although not particularly limited in the present invention, those skilled in the art can appropriately set it. However, it is preferable that the content of the gold fine particles 1 in the dispersion is, for example, 60% by mass or less from the viewpoint of the stability and handleability of the dispersion. . It is also conceivable that the effect can be further improved by using in combination with known antiviral agents such as ethanol and hypochlorous acid. Furthermore, you may mix and use with another antiviral agent, an antibacterial agent, an antifungal agent, an antiallergen agent, a catalyst, an antireflection material, a material with a heat shielding characteristic, etc.

  Then, the member which has the antiviral property which fixed the antiviral agent 10 of this invention to the base material is explained in full detail using FIGS.

  FIG. 3 is an enlarged schematic view of a part of the cross section of the antiviral member 100 of the first embodiment of the present invention. In the antiviral member 100 of the present embodiment, the antiviral agent 10 having the antiviral gold fine particles 1 fixed thereon is supported on at least the surface of the inorganic fine particles 2 made of an inorganic material.

  Regarding the base material 3 of the antiviral member 100 of the first embodiment, a woven or knitted fabric or nonwoven fabric made of a synthetic resin or a natural resin, a film, a sheet, a tile, glass, ceramic, fine ceramic, metal, inorganic, etc. Oxides, and materials composed of alloys and composites thereof can also be used. When the antiviral member 100 according to the first embodiment of the present invention is used as a filter, the use environment is not limited, but particularly when used at high temperatures, in addition to inorganic materials, heat resistance has heat resistance. What formed the inorganic layer in resin is used suitably.

  Specific synthetic resins and natural resins include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, EVA resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polymethyl acrylate resin, Polyvinyl acetate 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 (polytetrafluoroethylene), 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.

  Specific heat-resistant resins include polyamide, polyacetal, polycarbonate polyphenylene ether, polybutylene terephthalate, glass fiber reinforced polyethylene terephthalate, ultra-high molecular weight polyethylene, etc. Polyamide, polyetherimide, polyetheretherketone, polyimide, super engineering plastics such as fluororesins such as ETFE and PTFE, and heat-resistant thermosetting resins such as polyphenols, melamine resins, and epoxy resins.

  Furthermore, concrete tiles include concrete, glass, plastic, etc., as well as pottery, stoneware, porcelain.

  Furthermore, specific glass includes 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 and borosilicate Examples thereof include glass, bulletproof glass, glass fiber, dichroic, gold stone (brown stone / sand gold stone / purple gold stone), glass ceramics, low-melting glass, metallic glass, and saphiret.

  In addition, specific ceramic compositions include elemental, oxide, hydroxide, carbide, carbonate, nitride, halide, and phosphate, or composites thereof. Used in the case of fine ceramics, barium titanate, lead zirconate titanate, ferrite, alumina, forsterite, zirconia, zircon, mullite, steatite, cordierite, aluminum nitride, silicon nitride, silicon carbide, It is possible to use ceramics such as new carbon and new glass, high strength ceramics, functional ceramics, superconducting ceramics, nonlinear optical ceramics, antibacterial ceramics, biodegradable ceramics, and bioceramics.

  Furthermore, specific metals include refractory metals such as tungsten, molybdenum, tantalum, niobium, TZM, and W-Re, noble metals such as silver and ruthenium, and alloys thereof, titanium, nickel, zirconium, chromium, inconel, Special metals such as Hastelloy, aluminum and alloys thereof, copper and alloys thereof and alloys thereof, stainless steel, zinc and alloys thereof, magnesium and alloys thereof, and various plating and vacuum deposition, CVD methods, An inorganic material processed by a sputtering method or the like is used. Further, an oxide thin film is preferably formed on the surface of the material, and an oxide thin film is formed chemically by a known method, or an oxide thin film is formed by a known electrochemical method such as anodic oxidation. Is preferable.

  Further, as specific inorganic oxides, titania, zirconia, alumina, ceria (cerium oxide), zeolite, apatite, silica, activated carbon, diatomaceous earth and the like are preferably used. Furthermore, the inorganic oxide of this embodiment includes metal oxides made of chromium, manganese, iron, cobalt, nickel, copper, tin, and the like.

  As a form of the base material 3 used in the antiviral member 100 of the first embodiment, a plate shape, a film shape, a fiber shape, a cloth shape, a mesh shape, a honeycomb shape, a punching sheet, or the like is used. Various shapes and sizes suitable for the purpose can be applied and are not particularly limited. For various electric products such as air cleaners, hot air heaters, dryers, vacuum cleaners, electric fans, air conditioners, and exhaust fans. It can be applied to filters, medical filters, respirators, artificial noses, and other medical filters. In addition, medical members such as masks, caps, shoe covers, medical drapes (medical wraps, medical sheets), in-size drapes, surgical tape, gauze, respirator masks, ventilator parts, hospitals, etc. Interior materials for buildings, interior materials such as trains and cars, vehicle seats, chair and sofa covers, virus handling equipment, antifouling sheets for doors and floor boards, nets for screen doors, nets for poultry houses, nets for mosquito houses, etc. In addition to food storage bags, food wrap films, keyboard covers, touch panels, touch panel covers, blinds, desk mats, interior materials, wallpaper, curtains, clothing, bedding, multi-purpose sheets that can be cut, etc. Can be improved.

  Furthermore, as a form of the base material 3 of the antiviral member 100 of the first embodiment, another member, for example, a film or a sheet may be laminated. As an example, waterproofing can be imparted to a virus inactivated sheet by laminating waterproof films and sheets. High-performance protective clothing and medical gloves that can prevent the passage of viruses and blood by stitching the sheet using the waterproof member 100 having antiviral properties, and sheets for hospitals and nursing care Etc. can be configured.

  Further, as the film or sheet to be laminated, those having moisture permeability that shields water and allows air (humidity) to pass therethrough are preferably used so that the user can spend comfortably. Specifically, a commercially available product may be selected and used according to the purpose of use.

  Furthermore, an adhesive or the like can be laminated on at least one main surface of the antiviral member 100 of the first embodiment so that the user can easily adhere to a mask, wall or floor arbitrarily. . Specifically, a virus inactivation mask can be obtained by pasting on the surface of a hand-held mask.

  Further, regardless of the structure having air permeability, air may not be transmitted, in other words, an air shielding property may be provided. Specifically, the substrate 3 is made of polyester, polyethylene, polyamide, polyvinyl chloride, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl acetate, polyimide, polyamideimide, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer. Such as resin, polycarbonate resin sheet / film, vinyl chloride sheet, fluororesin sheet, polyethylene sheet, silicone resin sheet, nylon sheet, ABS sheet, urethane sheet, titanium, aluminum, stainless steel, magnesium, brass You may comprise in film form from metals, such as.

  In addition, in the member 100 having antiviral properties of the first embodiment of the present invention, in addition to the antiviral agent 10, it is optionally used to impart a desired function to the member 100 having antiviral properties. The functional material may be fixed to the surface of the base material 3. Examples of the functional material include other antiviral agents, antibacterial agents, antifungal agents, antiallergen agents, and catalysts. These functional materials may be bonded and fixed to the base material 3 via, for example, a general binder, or may be based on a chemical bond with a silane monomer or an oligomer thereof described later. It may be fixed to the material 3. Moreover, regardless of whether functional materials other than these antiviral agents 10 are fixed to the base material 3, in addition to the silane monomer and oligomers described later, other reinforcing agents (hard coat agents) are used. Also good.

  Furthermore, the antiviral member 100 of the first embodiment of the present invention may further be bonded to the base material 3 with fine oxide particles such as manganese and cobalt. This is because these oxide fine particles suppress the adhesion of harmful substances to the gold fine particles 2, and thus the antiviral effect can be stably maintained over a long period of time.

  Next, the manufacturing method of the virus inactivation sheet 100 of 1st Embodiment of this invention is demonstrated concretely.

  As a specific method for producing the antiviral member 100 of the first embodiment of the present invention, the antiviral agent 10 is suspended in a known dispersion medium such as ethanol, and the resulting slurry is dip by a sol-gel method. After the antiviral agent 10 is applied to the surface of the substrate 3 by coating, spin coating, hydrothermal synthesis, or the like, it is baked at 150 ° C. or higher. Therefore, it is desirable that the material of the base material 3 has heat resistance. Moreover, these methods can be properly used depending on the type of the substrate.

  In 1st Embodiment, it does not specifically limit about the form by which the antiviral agent 10 is fixed to the base material 3 surface, A person skilled in the art can select suitably. For example, the antiviral agent 10 may be scattered on the surface of the base material 3. Further, the antiviral agent 10 may be fixed in the form of an aggregate of inorganic fine particles 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.

  In the antiviral member 100 of the first embodiment, the fixed amount of the gold fine particles 1 is preferably 50% by mass or less, more preferably 0.1-5% by mass with respect to the base material 3. More preferred. This is because if the loading amount is too large, the agglomeration causes agglomeration, so that it cannot act efficiently. On the other hand, if the loading amount is too small, the effect cannot be exhibited.

(Second Embodiment)
Next, the antiviral member 200 of the second embodiment of the present invention will be described in detail with reference to FIG. In addition, about the structure which is common in 1st Embodiment, the same code | symbol is attached | subjected and the description is abbreviate | omitted suitably.

  FIG. 4 is an enlarged schematic view of a part of the cross section of the antiviral member 200 according to the second embodiment of the present invention. The member 200 having antiviral properties of the present embodiment includes a base material 3 and an antiviral agent 10 in which gold fine particles 1 are fixed to the surface of inorganic fine particles 2, and the antiviral agent 10 is formed on the surface of the base material 3. It is firmly fixed by the chemical bond 5 through the silane monomer 4 having an unsaturated bond part or the oligomer 4 which is a silane monomer polymer.

  As a specific silane monomer 4 used in the antiviral member 200 of the second embodiment of the present invention, a silane represented by a general formula of X—Si (OR) n (n is an integer of 1 to 3). Monomer. 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 produce 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, the antiviral member 200 of the second embodiment firmly fixes the antiviral agent 10 to the surface of the base material 3 by the chemical bond 5 through the silane monomer 4 having such excellent reactivity. .

  As an example of the silane monomer 4 represented by the above general formula, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ- Aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacrylo Xylpropylmethyldiethoxysilane, 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-mercaptopropylmethyldimethoxysila 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, special aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltri Methoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, hexyltrimethoxysilane, decyltrimethoxysilane, hydrolyzable group-containing siloxane, fluoroalkyl group-containing oligomer, methylhydrogensiloxane And 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 member 200 having antiviral properties of the second embodiment, the antiviral agent 10 is based on a state in which at least a part of its surface is exposed by the silane monomer having an unsaturated bond or the oligomer 4 thereof. It is firmly fixed to the material 3. Therefore, the probability that the virus or bacteria attached to the surface of the antiviral member 200 is in contact with the antiviral agent 10 is higher than that in the case where it is fixed to the base material 3 using a binder such as a general resin. Therefore, the virus can be inactivated efficiently even with a small amount.

  Further, since the antiviral agent 10 is firmly fixed to the sheet main body 1 by the chemical bond 5 with the silane monomer having an unsaturated bond or its oligomer 4, it is possible that the anti-viral agent 10 is removed from the sheet main body 1 by a general resin or the like. It is suppressed more than the case where it is coated and fixed with a component such as a binder. Therefore, the antiviral member 200 of the second embodiment can maintain the virus inactivating action for a longer time. In addition, by selecting the silane monomer to be used, the antiviral agent 10 may be fixed by condensation reaction, amide bond, hydrogen bond, ionic bond, van der Waals force, physical adsorption or the like instead of the chemical bond 5. .

  Thus, since the antiviral agent 10 is fixed on the surface of the base material 3 as a three-dimensional aggregate, many fine irregularities are formed on the surface of the base 3, and the irregularities on the base 3 are formed by the irregularities. Adhesion of dust and the like is suppressed, and the antiviral property of the antiviral member 200 can be maintained for a longer time.

  Next, the production of the antiviral member 200 of the second embodiment will be specifically described. However, the present invention is not limited to only these examples.

  First, the silane monomer 4 having an unsaturated bond is bonded to the surface of the inorganic fine particles 2 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 2 and the silane monomer 4 having an unsaturated bond can be formed by an ordinary method. For example, the silane monomer 4 is added to the dispersion and then heated under reflux. A method of forming a thin film composed of the silane monomer 4 by bonding the silane monomer 4 to the surface of the inorganic fine particle 2 by a dehydration condensation reaction, or after adding the silane monomer 4 to the dispersion liquid in which the inorganic fine particle 2 is dispersed, A method of separating and heating at 100 ° C. to 180 ° C. to bond the silane monomer 4 to the surface of the antiviral agent 10 by a dehydration condensation reaction, and then pulverizing and crushing to re-disperse.

  Here, after adding the silane monomer 4 to the dispersion liquid obtained by refluxing or pulverizing, or by adding the silane monomer 4 and pulverizing to fine particles, solid-liquid separation is performed from 100 ° C. When the silane monomer 4 is bonded to the surface of the inorganic fine particles 2 by heating at 180 ° C. by a dehydration condensation reaction, the amount of the silane monomer 4 depends on the average particle diameter and material of the inorganic fine particles 2, but the mass of the inorganic fine particles 2. If it is 3 mass% to 30 mass%, the bonding strength between the inorganic fine particles 2 and between the inorganic fine particles 2 and the base material 3 forming the antiviral member 200 of the second embodiment is a practical problem. Absent.

  The slurry of inorganic fine particles 2 produced as described above is applied to the surface of the substrate 2 by dipping, spraying, roll coater, bar coater, spin coating, gravure printing, offset printing, screen printing, ink jet. Apply by printing 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 base material 3 and the surface of the inorganic fine particles 2 facing the surface of the base material 3 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 4 is chemically bonded (formation of chemical bond 5). In addition, after the chemical bonding 5 between the silane monomers 4 on the surface of the inorganic fine particles 2, the method for producing the antiviral agent 10 described above is applied to the inorganic fine particles 2 fixed on the surface of the substrate 3 via the silane monomers 4. The gold fine particles 1 are fixed by the same method.

(Third embodiment)
Next, the antiviral member 300 of the third embodiment of the present invention will be described in detail with reference to FIG. In addition, about the structure which is common in 1st, 2nd embodiment, the same code | symbol is attached | subjected and the description is abbreviate | omitted suitably.

  FIG. 5 shows a schematic cross-sectional view of an antiviral member 300 according to the third embodiment of the present invention. The antiviral member 300 of the third embodiment includes a coupling agent 6 bonded in a condensation reaction with a hydroxyl group on the surface of the substrate 3 in addition to the configuration of the second embodiment. For example, when the surface of the substrate 3 is an inorganic material, the silanol group of the coupling agent 6 is bonded to the hydroxyl group on the surface of the inorganic substrate by a condensation reaction, and further, the surface of the coupling agent 6 and the antiviral agent 10 is bonded. Since the silane monomer having a fixed unsaturated bond or the oligomer 4 thereof and the silane monomer 4 bonded to the surface of the antiviral agent 10 can be covalently bonded to each other, the antiviral agent 10 is more firmly formed than the above-described embodiment. The difference is that it can be fixed.

  The material of the base material 3 of the third embodiment is the same as that of the first and second embodiments. In particular, when the surface of the base material 3 is a metal, an oxide film is usually formed on the surface. Therefore, the antiviral agent 10 can be more firmly fixed to the surface of the base material 3 by the covalent bond by the dehydration condensation reaction with the coupling agent 6. At that time, in order to use the oxide film, it is necessary to remove the oil and dirt adhering by a known method in advance in order to fix the antiviral agent 10 stably and uniformly. preferable.

  Next, the method for manufacturing the antiviral member 300 according to the third embodiment of the present invention will be described more specifically.

  First, the oil and dirt on the surface are washed, the coupling agent 6 is applied to the surface of the base material 3 where the hydroxyl groups are exposed, and dehydration condensation is performed to form the coupling layer 60. The coupling layer 60 is configured by arranging and fixing the coupling agent 6 on the surface of the substrate 3. As the coupling agent 6 constituting the coupling layer 60 of the third 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 slurry in which the antiviral agent 10 having the silane monomer 4 immobilized on the surface is dispersed is applied to the surface of the base material 3 on which the coupling layer 60 is formed, and the solvent is removed by heating and drying. Subsequently, the silane coupling agent in the silane coupling layer 60 and the silane monomer 4 on the surface of the antiviral agent 10 is 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. 6 is produced by so-called co-irradiation graft polymerization, in which the antiviral agent 10 is bonded simultaneously with graft polymerization.

  Specific coating methods for the dispersion liquid of the coupling agent 6 and the antiviral agent 10 include spin coating, dip coating, spray coating, cast coating, bar coating, , Micro gravure coating method, gravure coating method or partial coating method, screen printing method, pad printing method, offset printing method, dry offset printing method, flexographic printing method, inkjet printing method Various methods, such as these, are used, and it will not specifically limit if the application | coating suitable for the purpose can be performed.

  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 agent)
Example 1
100 mg of γ-alumina powder was added to a 1 mg / 10 ml colloidal gold aqueous solution (particle size: 10 nm), and then heated and dried with stirring. Then, gold fine particle carrying γ-alumina was obtained by sieving with a 60 mesh sieve.

(Example 2)
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 an aqueous NaOH solution. 5 g of γ-alumina powder as inorganic fine particles was added to the aqueous solution and stirred for 1 hour. Thereafter, the mixture was separated into solid and liquid, dried under reduced pressure, dried and pulverized at 200 ° C. for 4 hours under a nitrogen atmosphere to obtain a gold fine particle-fixed antiviral agent. As a result of observing the obtained antiviral agent with an electron microscope, the average particle size of the gold fine particles was 4.0 nm.

(Creation of antiviral components)
(Example 3)
An alumina plate was prepared by dispersing 10% by mass silica fine particles in ethanol. It was applied and baked at 180 ° C. and fixed. Thereafter, a 1% by mass Au colloid aqueous solution (particle size: 10 nm) was applied by spraying. Then, it baked at 300 degreeC.

Example 4
Zirconium oxide particles in which methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., K6M-503), which is a silane monomer having an unsaturated bond portion, is dehydrated and condensed by an ordinary method and covalently bonded to the surface as inorganic fine particles ( 100 g of NIPPON Denko KK, 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 concentration was 1% by mass.

Subsequently, an inorganic fine particle fixed sheet was obtained by impregnating and drying 70 g / m ² of a polyethylene terephthalate non-woven fabric (manufactured by Asahi Kasei Fibers Co., Ltd., Elutus) in the coating solution.

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 an aqueous NaOH solution. The inorganic fine particle fixed sheet (10 cm × 10 cm) was added to the aqueous solution as a sheet body 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 a member having antiviral properties in which inorganic fine particles having gold fine particles bonded to the surface were fixed. As a result of observing this sample with an electron microscope, the average particle size of the gold fine particles was 4.4 nm.

(Example 5)
As inorganic fine particles, methacryloxypropyltrimethoxysilane (K6M-503, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane monomer having an unsaturated bond portion, is dehydrated and condensed by a conventional method (Akiraaki) Chemical Industry Co., Ltd., Tymicron), a colloidal gold aqueous solution (manufactured by Shinko Chemical Co., Ltd., 30 nm) was added so that gold was 1% by mass with respect to the alumina particles, and the coating solution was stirred. Obtained.

Subsequently, a 70 g / m ² polyethylene terephthalate nonwoven fabric (Asahi Kasei Fibers Co., Ltd., Ertas) was impregnated in the coating solution, and dried at 100 ° C. for 4 hours in a nitrogen atmosphere to obtain a member having antiviral properties.

(Example 6)
In Example 5, an alumina woven fabric (manufactured by Nichibi Co., Ltd.) of 80 g / m ² was used instead of the polyethylene terephthalate nonwoven fabric.

(Example 7)
Commercially available zirconia fine particles (Nippon Denko Co., Ltd., PCS) are 10.0% by mass with respect to methanol, and 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) as fine particles is used as fine particles. On the other hand, it was prepared with hydrochloric acid so that the pH was 4.0 by adding 5.0% by mass, and then pulverized and dispersed to an average particle size of 16 nm by a bead mill. Thereafter, solid-liquid separation was performed with a freeze dryer, and heating was performed at 120 ° C. to chemically bond the silane monomer to the surface of the zirconia fine particles by a dehydration condensation reaction to form a coating.

  Add silane monomer-coated zirconia fine particles prepared by the above method to 3% by mass in methanol, and add 30% tetramethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-04) as a binder component to the silane monomer-coated zirconia fine particles. The dispersion was dispersed by 0.0% by mass and pulverized and dispersed again to an average particle size of 16 nm by a bead mill.

  After the surface was washed with an alkaline detergent, washed with ion-exchanged water, immersed in methanol, and then dried with a dryer, the alumina fabric (manufactured by Nichibi Co., Ltd.) was washed under the same conditions, and then 3-methacryloxypropyltrimethoxy. A methanol solution containing 1.0% by mass of silane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) is applied by spraying and dried at 120 ° C. for 10 minutes to dehydrate and condense the silane coupling agent on the surface of the alumina fabric. The reaction was combined. Next, a silane monomer-coated zirconia dispersion containing a binder is applied by spraying, dried at 100 ° C. for 5 minutes, and then irradiated with 5 Mrad of an electron beam with 200 kV accelerated electrons, thereby fixing the zirconia fine particles. A member having was obtained.

  Thereafter, an alumina woven fabric having zirconia fine particles fixed on the surface was joined with gold fine particles on the surface of the zirconia fine particles in the same manner as in Example 4. As a result of observing this sample with an electron microscope, the average particle diameter of the gold fine particles was 5.0 nm.

(Comparative Example 1)
A comparative example 1 was prepared under the same conditions as in Example 1 except that the gold fine particles used in Example 1 were not supported.

(Comparative Example 2)
A comparative example 2 was prepared under the same conditions as in Example 2 except that the gold fine particles used in Example 2 were not supported.

(Comparative Example 3)
A comparative example 3 was prepared under the same conditions as in Example 3 except that the gold fine particles used in Example 3 were not supported.

(Comparative Example 4)
A comparative example 4 was prepared under the same conditions as in Example 4 except that the gold fine particles used in Example 4 were not supported.

(Comparative Example 5)
A comparative example 5 was prepared under the same conditions as in Example 7 except that the gold fine particles used in Example 7 were not supported.

(Antiviral evaluation method of antiviral agent and antiviral member of the present invention)
Measurement of virus inactivation of the virus inactivation sheet was carried out using influenza virus (influenza A / Kitakyushu / 159/93 (H3N2)) and cat kidney passage cells (CrFK strain) cultured using MDCK cells. Feline calicivirus (F9 strain) was used.

  For Examples 1 and 2 and Comparative Examples 1 and 2 in which the sample was powder, antiviral properties were measured by the following method. Specifically, samples were prepared by diluting each sample with PBS so that the suspension concentration was 1.0% by mass and 10.0% by mass, respectively. 100 μl of the virus solution was added to 100 μl of each sample having two concentrations, and the mixture was reacted at room temperature for 10 minutes or 60 minutes with stirring using a microtube rotator. As a control, 100 μl of the virus solution was added to 100 μl of PBS, and the mixture was stirred for 10 minutes or 60 minutes using a microtube rotator in the same manner as each sample. After stirring for a predetermined time, 1800 μl of 20 mg / ml bouillon protein was added to stop the reaction between the virus and the compound in each sample. Thereafter, the solid content was precipitated by a microcentrifuge, and the supernatant was collected to obtain a sample solution.

When the sample was a non-woven fabric or a woven fabric, a sample of 16 cm ² (2 cm × 2 cm, 4 layers) was placed in a sterilized vial, 0.1 ml of the virus solution was dropped and allowed to act at room temperature for 60 minutes. After acting for 60 minutes, 1900 μl of 20 mg / ml bouillon protein solution containing a surfactant was added, and the virus was washed out by pipetting. Then, what was diluted with the MEM diluent until each reaction sample became 10 ⁻² to 10 ⁻⁵ was used as a sample solution (10-fold serial dilution).

Subsequently, 100 μl of each sample solution was inoculated on MDCK cells cultured in a petri dish. After standing for 90 minutes to adsorb the virus to the cells, 0.7% agar medium was overlaid and cultured for 48 hours at 34 ° C in a 5% CO ₂ incubator, followed by formalin fixation and methylene blue staining. The number of plaques was counted, and the virus infectivity titer (PFU / 0.1 ml, Log 10); (PFU: plaque-forming units) was calculated. The results are shown in Table 1.

  From the above results, a high virus inactivating action was observed in the antiviral agent by the inorganic fine particles carrying the gold fine particles of the present invention and various members (structures) to which the antiviral agent was fixed. As for the effect, a very high effect of an inactivation rate of 99.99% or more in 60 minutes was observed in all examples. Therefore, by using the antiviral agent of the present invention and the antiviral member, it is possible to provide an environment in which the risk of infection with a virus is reduced.

DESCRIPTION OF SYMBOLS 1 Gold fine particle 2 Inorganic fine particle 3 Base material 4 Silane monomer and its oligomer 5 Chemical bond part
6 Coupling agent 10 Antiviral agent 60 Coupling layer 100, 200, 300 Antiviral member

Claims (5)

Inorganic fine particles having at least a surface made of an inorganic material;
Gold fine particles fixed to the surface of the inorganic fine particles;
An antiviral agent comprising:   The antiviral agent according to claim 1, wherein the gold fine particles are bonded to the surface of the inorganic fine particles and have a bonding interface peripheral edge. A substrate;
The antiviral agent according to claim 1 or 2 fixed to the surface of the substrate;
A member having antiviral properties, comprising:   4. The antiviral member according to claim 3, wherein the base material comprises a fiber structure.   A filter using the antiviral member according to claim 3 or 4.

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