JP2013067566A - Member having antiviral activity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a member having antiviral activity capable of inactivating attached virus even in the presence of a lipid or a protein regardless of presence/absence of an envelope.SOLUTION: This member 100 having antiviral activity, which is a member capable of inactivating attached virus, includes a substrate 1 wherein at least a part of the surface comprises an inorganic material, and gold fine particles 2 fixed to the inorganic material part of the substrate 1.

Description

  The present invention relates to a member having antiviral properties, and particularly relates to a member having antiviral properties capable of inactivating 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 urgently 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. In addition, noroviruses have problems such as no vaccine. 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 due to antibiotic administration are directly from patients, or Nosocomial infections that cause contact infections to patients and health care workers are becoming a major social problem through health care workers or the environment including equipment such as white robes, pajamas, and sheets, and equipment such as walls and air conditioners. ing. 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. Moreover, since the virus inactivating agent using iodine is water-soluble, even if it is applied to a fabric or a 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.

  Therefore, in order to solve the above-mentioned problems, the present invention provides a member having antiviral properties that can inactivate a virus that is attached regardless of the presence or absence of an envelope or in the presence of lipids or proteins.

  That is, the first invention is a member that can inactivate the attached virus, and includes a substrate having at least a part of the surface made of an inorganic material, and gold fine particles fixed to the inorganic material portion of the substrate. This is a member having antiviral properties.

  In addition, in this specification, the member which has antiviral property means the member which has virus inactivation property (a virus infectivity reduction or inactivation). Therefore, in addition to the sheet body intended to inactivate viruses, it is a concept including building materials such as wallpaper and tiles intended for decoration, for example. Moreover, in this specification, antiviral property and virus inactivating property are used synonymously.

  Furthermore, a second invention is the member having antiviral properties according to the first invention, wherein the substrate is made of a fiber structure.

  Further, the third invention is a filter using the antiviral member of the first or second invention.

  ADVANTAGE OF THE INVENTION According to this invention, the member which has the antiviral property which can inactivate the virus adhering to the sheet | seat surface etc. can be provided, for example also in presence of proteins, such as a droplet and blood.

It is a schematic diagram of the cross section of the member which has antiviral property of 1st Embodiment. It is a schematic diagram of the cross section of the member which has antiviral property of 2nd Embodiment.

  Hereinafter, the first embodiment of the present invention will be described in detail with reference to FIG.

  FIG. 1 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. The antiviral member 100 of the present embodiment is composed of a base body 1 having at least a part of the surface made of an inorganic material, and antiviral gold particles 2 fixed to the inorganic material portion of the base body 1. Yes.

  The mechanism of virus inactivation is not necessarily clear at present, but transition metal or noble metal fine particles have a very high oxidation catalytic ability when supported on inorganic oxides. It is assumed that the surface is damaged and inactivated.

  The material of the substrate 1 of the first embodiment is not particularly limited as long as at least the portion to which the gold fine particles 2 adhere is an inorganic material, but it is more preferable that an oxide is formed on the surface. . Such materials include those in which an inorganic layer is formed on the surface of synthetic resin, natural resin, etc. by plating, sputtering, etc., tiles, glass, ceramics, fine ceramics, metals, inorganic oxides, and alloys and composites thereof. Is used. When the antiviral member 100 of the present invention is used as a filter, the use environment is not limited, but particularly when used at high temperatures, an inorganic layer is formed on a heat-resistant resin having heat resistance in addition to inorganic materials. What was used 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 engineering plastics such as polyamide, polyacetal, polycarbonate polyphenylene ether, polybutylene terephthalate, glass fiber reinforced polyethylene terephthalate, carbon fiber, ultrahigh molecular weight polyethylene, polysulfone, polyethersulfone, polyphenylene sulfide. Examples include super engineering plastics such as polyarylate, polyamide imide, polyether imide, polyether ether ketone, polyimide, fluororesins such as ETFE and PTFE, and heat-resistant thermosetting resins such as polyphenol, melamine resin, and epoxy resin. .

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

  More 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 glass. , Bulletproof glass, glass fiber, dichroic, gold stone (brown stone, sand gold stone, purple gold stone), glass ceramics, low melting point glass, metallic glass, saphiret, and the like.

  More specific ceramic compositions include elemental, oxide, hydroxide, carbide, carbonate, nitride, halide, and phosphate, or composites thereof. 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, new Ceramics such as carbon and new glass, high strength ceramics, functional ceramics, superconducting ceramics, nonlinear optical ceramics, antibacterial ceramics, biodegradable ceramics, and bioceramics can be used.

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

  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.

  Although the materials used for the substrate 1 have been described in detail above, those having a positive surface potential of the substrate 1 are particularly preferable. 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 substrate 1 is positive, the virus is electrically attracted to the substrate 1, and as a result This is because the virus is easily adsorbed on the surface of the antiviral member 100, and the antiviral effect of the antiviral gold fine particles 2 can be efficiently expressed.

  As the form of the substrate 1 of the first embodiment, various shapes and sizes suitable for the purpose of use, such as plate, film, fiber, cloth, mesh, honeycomb, punching sheet, etc. There are no particular restrictions, such as filters for various electrical products such as air purifiers, hot air heaters, dryers, vacuum cleaners, electric fans, air conditioners, ventilation fans, vehicle filters, and artificial respiration. Applicable to medical filters such as dexterous and artificial nose. In addition, medical members such as masks, caps, shoe covers, medical drapes (medical wraps, medical sheets), insize drapes, surgical tapes, gauze, ventilator masks, ventilator parts, hospitals, etc. Interior materials for buildings, interior materials for 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, it can be used for 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. Improvement can also be achieved.

  Furthermore, as a form of the substrate 1 of the first embodiment, other members such as a film or a sheet may be laminated. For example, waterproofing can be imparted to the virus inactivated sheet by laminating waterproof films and sheets. High-performance protective clothing and medical gloves that can prevent the transmission of viruses and blood by stitching the member with the anti-viral property having the waterproof property, 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, the virus inactivating mask can be obtained by sticking the antiviral member 100 of the first embodiment to 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 1 is made of polyester, polyethylene, polyamide, polyvinyl chloride, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl acetate, polyimide, polyamideimide, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, or the like. Sheets made of polymers 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, etc. You may comprise from a metal into a film form.

  The antiviral member 100 using a film or sheet as the substrate 1 can be used in various fields.

  The virus that can be inactivated in the antiviral member 100 of the present embodiment is not particularly limited, and various viruses can be inactivated regardless of the type of genome or the presence or absence of an envelope. 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 gold fine particles 2 having antiviral properties according to the first embodiment of the present invention can be freely determined by the user depending on the use conditions, but the particle size is preferably 1 nm or more and less than 1 μm, preferably 1 nm or more and 50 nm or less. Those having a particle size smaller than 1 nm are very unstable as substances and cannot exist. On the other hand, when the particle size is 1 μm or more, it is difficult to fix the gold fine particles 2 to the substrate with a small amount of binder, and when the gold fine particles 2 are fixed with a large amount of binder, the surface of the gold fine particles 2 is covered. This is because antiviral properties are reduced. In addition, when the particle size is larger than 50 nm, the gold fine particles 2 become stable, so that the redox action is difficult to occur. It is more preferable.

  Further, the gold fine particles 2 of the first embodiment of the present invention are alloy fine particles of one or more metals such as silver, copper, iron, aluminum, zinc, platinum, palladium, nickel, bismuth, manganese and gold. Alternatively, mixed fine particles of one or more of these metal fine particles and gold fine particles may be used.

  The method for fixing the gold fine particles 2 to the surface of the substrate 1 is not particularly limited, but specific examples include a coprecipitation method, a precipitation method, a sol-gel method, an impregnation method, and a drop neutralization precipitation method. , Reducing agent addition method, pH controlled neutralization precipitation method, carboxylate metal salt addition method, dipping in an aqueous solution containing gold ions, or applying an aqueous solution containing gold ions to adsorb gold ions, 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. In the case of a resin that is subjected to reduction treatment or has high heat resistance, a method such as a method of supporting gold fine particles by heating in the air can be cited. These methods are more suitable depending on the type of the carrier. It can be selectively used.

  In addition, in the member 100 having antiviral properties of the first embodiment of the present invention, in addition to the gold fine particles 2, a function arbitrarily used for imparting a desired function to the member 100 having antiviral properties. The active material may be fixed to the surface of the substrate 1. Examples of the functional material include other antiviral agents, antibacterial agents, antifungal agents, antiallergen agents, and catalysts. These functional materials may be fixed and bonded to the substrate 1 or the gold fine particles 2 through a general binder, or may be chemically bonded to a silane monomer or an oligomer thereof, for example. You may make it fix to the base | substrate 1. FIG. In addition to the silane monomer and oligomers described later, other reinforcing agents (hard coat agents) may be used regardless of whether functional materials other than these gold fine particles 2 are fixed to the substrate 1. .

  Next, the method for producing the antiviral member 100 according to the first embodiment of the present invention will be described by taking a method using a colloidal solution of gold fine particles 2 as an example.

The colloidal solution of the gold fine particles 2 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 colloidal solution of the gold fine particles 2 thus produced is applied to the substrate by spraying or the like and dried at 100 ° C. in a nitrogen atmosphere. Further, the surface of the gold fine particles 2 in the colloidal solution may be coated with a protective agent such as a surfactant.

  The fixing amount of the gold fine particles 2 is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass with respect to the substrate 1. The reason for this is that if the amount is more than 20% by mass, the gold fine particles 2 aggregate and the antiviral properties are reduced.

  In the first embodiment, the form in which the gold fine particles 2 are fixed to the surface of the substrate 1 is not particularly limited, and can be appropriately selected by those skilled in the art. For example, the gold fine particles 2 may be scattered on the surface of the substrate 1. Alternatively, the gold fine particles 2 may be fixed in the form of a gold 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.

(Second Embodiment)
Then, the virus inactivation sheet 200 of 2nd Embodiment of this invention is explained in full detail using 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. 2 is an enlarged schematic view of a part of the cross section of the antiviral member 200 of the second embodiment of the present invention. The antiviral member 200 of the present embodiment is configured by adhering antiviral gold fine particles 2 to an inorganic material portion of a substrate 1 whose surface is at least partially made of an inorganic material. The difference from the first embodiment is that 2 is in a substantially polyhedron state having a bonding interface peripheral edge and is in close contact with and bonded to the inorganic material portion of the substrate 1.

  It is known that the gold fine particles have a substantially polyhedral shape such as an icosahedron when the particle diameter is at the nano level. Here, the bonding interface peripheral portion used in the present embodiment indicates both the corner portion and the edge portion of the gold fine particle 2. The corner portion indicates a corner generated at a joint portion of three or more surfaces of the gold fine particles 2, and the edge portion indicates an edge generated at a joint portion between the two surfaces of the gold fine particles 2.

  In the antiviral member 200 of the second embodiment, as an example, the gold microparticles 2 are joined by utilizing the difference in zeta potential between the base 1 and the gold microparticles 2 having at least part of the surface made of an inorganic material. Yes. Further, it is considered that the activity is lost because the gold fine particles 2 are agglomerated with a reducing agent or the like, but in the second embodiment, by bonding the gold fine particles 2 to the inorganic material portion of the substrate 1, It is possible to prevent aggregation of the gold fine particles 2.

  As the gold fine particles 2 bonded to the substrate 1, one having a particle diameter of 1 nm to 50 nm can be used. This is because when the particle size is larger than 50 nm, the gold fine particles 2 become stable, so that the redox action is difficult to occur, and those having a particle size smaller than 1 nm become very unstable and cannot exist. .

  Examples of a method for supporting the gold fine particles 2 having such a particle size on the substrate 1 include a coprecipitation method, a precipitation method, a sol-gel method, a drop neutralization precipitation method, a reducing agent addition method, a pH control neutralization precipitation method, Examples thereof include a carboxylic acid metal salt addition method, an adsorption reduction method, a dipping method in a colloidal gold solution, and a coating method of a colloidal gold solution, and these methods can be appropriately used depending on the type of carrier.

  Next, a method for fixing the gold fine particles 2 to the surface of the substrate 1 will be described taking the precipitation method as an example.

  First, an aqueous solution in which a gold compound is dissolved is heated to 20 to 90 ° C., preferably 50 to 70 ° C. and stirred, and adjusted with an alkaline solution to have a pH of 3 to 10, preferably a pH of 5 to 8, and then The sheet body 1 is impregnated with the adjusted liquid and thoroughly washed with ion-exchanged water. Furthermore, 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 loading amount of the gold fine particles 2 is preferably 0.3 to 20% by mass, and more preferably 0.5 to 10% by mass with respect to the substrate 1. The reason for this is that when the amount is more than 20% by mass, the gold fine particles 2 are aggregated to reduce the antiviral property.

  The antiviral member 200 of the present embodiment may further carry fine oxide particles such as manganese and cobalt on the surface of the base 1 having at least a part of the surface made of an inorganic material. 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 present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

(Creation of virus inactivation sheet)
Example 1
A stainless mesh (manufactured by NBC Meshtec Co., Ltd., 500 mesh) was immersed in vinyltriethoxysilane diluted to 0.5% by mass with methanol and dried. Subsequently, an aqueous colloidal gold solution (manufactured by Shinko Chemical Industries, Ltd., 30 nm) was applied onto the treated stainless steel mesh by spraying. When the amount of gold supported at this time was measured by ICP emission spectroscopic analysis, it was 1.30% by mass relative to the weight of the member.

(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. A titania nonwoven fabric (Aqua Solution (registered trademark) manufactured by Ube Industries, Ltd.) (10 cm × 10 cm) (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 an antiviral member having gold fine particles supported on its surface. When this member was observed with an electron microscope, the average particle size of the gold fine particles was 4.4 nm. Further, the amount of gold supported was measured by ICP emission spectroscopic analysis and found to be 0.40% by mass relative to the weight of the member.

(Example 3)
An alumina sol (Nissan Chemical Industry Co., Ltd., Alumina Sol 100) was applied to the surface of an alumina fiber cloth (manufactured by Nichibi Co., Ltd., 4018-D) with a solid content diluted to 10% by mass with ion-exchanged water, and 900 ° C. The alumina sol coated on the surface of the alumina fiber cloth was crystallized to γ-alumina. Next, an antiviral member carrying gold fine particles under the same conditions as in Example 2 was obtained. When the surface of the obtained member was observed with a super-resolution field emission scanning electron microscope, gold having an average particle diameter of 3.8 nm was supported. The amount of gold supported was measured by ICP emission spectroscopic analysis and found to be 0.38% by mass relative to the weight of the member.

Example 4
The aluminum plate (JISH1050 material) was immersed in a 5% by mass sodium hydroxide aqueous solution heated to 50 ° C. for 30 seconds, then washed with running water, and the excess alkali was immersed in a 3% by mass nitric acid aqueous solution to be removed. Next, it is immersed in a 20 ° C. aqueous solution containing 200 g / l sodium carbonate and 10 g / l 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, and HAuCl ₄ was adsorbed on the γ-alumina coating. Next, the γ-alumina film-formed aluminum plate on which HAuCl ₄ was adsorbed was immersed in an aqueous solution containing 3% by mass of sodium borohydride to obtain an antiviral member carrying gold fine particles. When the surface of the obtained member was observed with a super-resolution field emission scanning electron microscope, gold having an average particle diameter of 5.8 nm was supported. Further, the amount of gold supported was measured by ICP emission spectroscopic analysis and found to be 0.58% by mass relative to the weight of the member.

(Example 5)
By immersing an industrial pure titanium plate (manufactured by Kobe Steel, Ltd., KS40S) in a 20 ° C. aqueous solution containing 200 g / l of sodium carbonate and applying a DC voltage of 170 V to the counter electrode using a carbon electrode, A white oxide film made of anatase type mixed crystal was formed. Next, a commercially available colloidal gold solution (Tanaka Kikinzoku Kogyo Co., Ltd., Au colloidal solution SC) is applied to a titanium plate on which an oxide film is formed by spraying, and heated and dried at 120 ° C. for 30 minutes, thereby providing antiviral properties. A member having was obtained. When the surface of the obtained member was observed with a super-resolution field emission scanning electron microscope, gold having an average particle diameter of 40.0 nm was supported. Further, the amount of gold supported was measured by ICP emission spectroscopic analysis and found to be 0.83% by mass relative to the weight of the member.

(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.

(Antiviral evaluation method of the virus inactivation sheet of the present invention)
The virus inactivation property of the virus inactivation sheet was measured 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.

Each sample 16 cm ² (2 cm × 2 cm, 4 layers) of Examples 1 and 2 and Comparative Examples 1 and 2 was put into a sterilized vial, 0.1 ml of 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, it diluted with the MEM diluent until each reaction sample became 10 ^<-2 > ^{-10 < -4} > (10 time serial dilution). 100 μl of the 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 effect was observed in the fiber structure carrying the gold fine particles of the present invention. The effect is an extremely high action of 99.99% inactivation rate in 60 minutes in all examples, and by using the antiviral member of the present invention, the risk of virus infection was reduced. We were able to provide an environment.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Gold fine particle 100, 200 Antiviral member

Claims (3)

A member that can inactivate the attached virus,
A substrate having at least part of its surface made of an inorganic material;
Gold fine particles fixed to the inorganic material portion of the substrate;
A member having antiviral properties, comprising:   2. The antiviral member according to claim 1, wherein the substrate is made of a fiber structure.   A filter using the antiviral member according to claim 1 or 2.

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