Antibacterial and antiviral glass composition

Abstract

To provide an antibacterial / antiviral glass composition for antibacterial / antiviral action.SOLUTION: An antibacterial / antiviral glass composition including vanadium oxide and phosphorus oxide, and further including at least either of silver oxide and copper oxide, and the antibacterial / antiviral glass composition the vanadium oxide, the phosphorus oxide, the silver oxide and the copper oxide contained therein are, by mol% in terms of oxides, are expressed as follows: 25≤[V2O5]≤35, 15≤[P2O5]≤30, 1≤[Ag2O]+[CuO]≤50.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] This invention relates to an antibacterial and antiviral glass composition that can inactivate viruses or kill bacteria, thereby suppressing and preventing their spread. [Background technology]

[0002] Traditionally, resin compositions and paint compositions have been developed that contain materials to exhibit antibacterial or antiviral properties, for the purpose of suppressing bacterial growth and inhibiting viruses in parts of building materials and home appliances that are frequently touched by people.

[0003] For example, Patent Document 1 discloses an antibacterial resin composition that incorporates antibacterial silver zeolite, in which a fluororesin film is formed on the surface of zeolite supporting antibacterial metal ions mainly composed of silver ions.

[0004] Furthermore, Patent Document 2 discloses a polyester resin sheet obtained by molding a resin composition containing a polyester resin (a) made of specific components, a polyester resin (b) made of specific components, a lubricant, and an antibacterial and antifungal agent such as an inorganic silver-based agent.

[0005] Furthermore, Patent Document 3 discloses an antibacterial and antiviral coating that can form an antibacterial and antiviral coating film with excellent water resistance, which is an acrylic-melamine coating in which a quaternary ammonium salt and a polycarboxylic acid having a hydrocarbon group with 6 or more carbon atoms and a carboxyl group with 2 or more carbon atoms are blended. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 10-045410 [Patent Document 2] Japanese Patent Publication No. 2007-031586 [Patent Document 3] International Publication No. 2015 / 046372 [Overview of the project] [Problems that the invention aims to solve]

[0007] In the resin compositions of Patent Documents 1 and 2, antibacterial properties are obtained by adding a general-purpose antibacterial agent to the resin composition. However, since the antibacterial agent is essentially an impurity, while increasing the amount of antibacterial agent improves the antibacterial function, it also leads to a problem of degrading the physical properties of the resin composition. Therefore, the amount of antibacterial agent added to the resin composition was kept low within the range in which antibacterial properties are exhibited. In other words, in the resin compositions of Patent Documents 1 and 2, the amount of antibacterial agent added was adjusted near the lower limit of the range in which antibacterial properties are exhibited in order to more stably exhibit antibacterial properties. Furthermore, in Patent Document 3, the challenge was to achieve both antiviral properties and material properties while keeping costs down.

[0008] Therefore, the present invention aims to provide an antibacterial and antiviral glass composition with antibacterial and antiviral properties. [Means for solving the problem]

[0009] An example of an embodiment of this product for solving the above problem is as follows: It contains vanadium oxide and phosphorus oxide, and further contains one or more of silver oxide and copper oxide, wherein the vanadium oxide, phosphorus oxide, silver oxide and copper oxide are present in the following molar percentages in terms of oxides: 25 ≤ [V2O5] ≤ 35, 15 ≤ [P2O5] ≤ 30, 1≦[Ag2O]+[CuO]≦50 An antibacterial and antiviral glass composition characterized by the following:

[0010] Furthermore, the antibacterial and antiviral glass composition further contains iron oxide or barium oxide, and the vanadium oxide, silver oxide, copper oxide, iron oxide and barium oxide are present in the following oxide equivalent molar percentages: 5 ≤ [Fe2O3] ≤ 15, [Ag2O] + [CuO] + 3[Fe2O3] ≤ 2[V2O5] or 5 ≤ [BaO] ≤ 30, [Ag2O] + [CuO] + [BaO] ≤ 2[V2O5] The antibacterial and antiviral glass composition characterized by the above is given as a preferable example.

[0011] Further, in the antibacterial and antiviral glass composition, it further contains at least one of tungsten oxide and zinc oxide, and the vanadium oxide, silver oxide, copper oxide, tungsten oxide and zinc oxide are in mol% in terms of the following oxides: [WO3] ≤ 15, [ZnO] ≤ 10, [Ag2O] + [CuO] + [ZnO] ≤ 2[V2O5] The antibacterial and antiviral glass composition characterized by the above is given as a preferable example.

[0012] Furthermore, an example of another embodiment of the present invention is as follows. A composition characterized by containing the antibacterial and antiviral glass composition and at least one component selected from polymers and monomers. [Advantages of the Invention]

[0013] According to the present invention, an antibacterial and antiviral glass composition capable of storing silver etc. with excellent antibacterial and antiviral effects at a high density can be provided. Further, by using the antibacterial and antiviral glass composition together with a material such as a polymer, the antibacterial and antiviral effects of the antibacterial and antiviral glass composition can be quickly exerted while maintaining the material properties, and it can be continued for a long time. [Brief Description of the Drawings]

[0014] [Figure 1] An example of the result of typical differential thermal analysis (DTA) of glass is shown. [Figure 2]Schematic diagrams of an aluminum alloy plate having a glass-fired coating (Figure 2A) and an aluminum alloy plate having a layer formed from a composition containing a glass composition and a polymer (Figure 2B) are shown in the examples and comparative examples. [Figure 3] The glass firing temperature profiles (Figure 3A), polypropylene heating temperature profiles (Figure 3B), and acrylic heating temperature profiles (Figure 3C) for the examples and comparative examples are shown. [Modes for carrying out the invention]

[0015] Embodiments of the present invention will be described below with reference to the drawings and other figures. The following description provides specific examples of the content of the present invention, and the present invention is not limited to these descriptions. Various changes and modifications are possible by those skilled in the art within the scope of the technical ideas disclosed herein. In addition, in all the figures used to illustrate the present invention, components having the same function are denoted by the same reference numerals, and repeated descriptions may be omitted.

[0016] In this specification, the symbol "~" is used to mean that the numbers before and after it are included as the lower and upper limits. In numerical ranges described stepwise in this specification, the upper or lower limit described in one numerical range may be replaced by the upper or lower limit described in another stepwise range. The upper or lower limit of numerical ranges described in this specification may be replaced by the values ​​shown in the examples.

[0017] When selecting materials from the group of materials exemplified below, you may select materials individually, in combination, or, to the extent that it does not contradict what is disclosed herein, you may also select materials other than those exemplified below, to the extent that it does not contradict what is disclosed herein.

[0018] The antibacterial and antiviral glass composition according to this embodiment contains vanadium oxide, phosphorus oxide, and further contains one or more of silver oxide and copper oxide, wherein the vanadium oxide, phosphorus oxide, silver oxide and copper oxide are present in the following molar percentages in terms of oxides: 25 ≤ [V2O5] ≤ 35, 15 ≤ [P2O5] ≤ 30, 1 ≤ [Ag2O] + [CuO] ≤ 50 characterized by the following.

[0019] The glass composition generally has characteristic temperatures such as the transition point T + , , 2+ ,

[0020] , the yield point M g , and the softening point T s . Strictly speaking, the transition point T g , the yield point M g , and the softening point T s are defined by the viscosity of the glass composition. T g is 10 13.3 poise, M g is 10 11.0 poise, and T s is the temperature corresponding to 10 7.65 poise. The lower these characteristic temperatures are, the better the softening fluidity at low temperatures, and glass coating and bonding at low temperatures become possible. In actual glass coating and bonding, a viscosity of about 10 4 to 10 6 poise is required, and it is carried out at a temperature about 30 to 50 °C higher than T s , resulting in strong characteristics against external forces. However, on the other hand, generally, the lower the characteristic temperatures of these glasses, the more likely they are to have inferior chemical stability such as water resistance and salt water resistance. Also, among the characteristic temperatures of the glass, the closer the softening point T s and the crystallization temperature T cry are, the greater the crystallization tendency, and it becomes easier to crystallize during heat firing. When the glass crystallizes, the softening fluidity deteriorates, and it becomes difficult to obtain good adhesion and denseness.

[0020] The antibacterial and antiviral glass composition (lead-free low melting point glass composition) contains vanadium oxide and phosphorus oxide as main components, and further contains silver oxide or copper oxide for antibacterial and antiviral effects. The structure of this glass composition has a layered structure composed of VO5 pyramids, and PO4 tetrahedrons and Ag + ions or Cu 2+It is believed that ions are present. The contained phosphorus oxide (P2O5) is a vitrification component for vitrifying vanadium oxide (V2O5). In the glass composition of the present invention, silver oxide is Ag + In ionic form, or copper oxide Cu 2+ By introducing ions into the glass structure, we discovered antibacterial and antiviral properties in a V2O5-P2O5 lead-free low-melting-point glass composition.

[0021] In general SiO2-Na2O-based glass compositions and SiO2-B2O3-based glass compositions, Ag + It is well known that it can contain and possess antibacterial and antiviral properties. However, if the amount of Ag exceeds a certain amount, + The presence of [unclear] caused the problem of metallic silver precipitation. However, the glass composition of the present invention contains a large amount of Ag + Ions and Cu 2+ It can contain ions and is extremely useful from the standpoint of antibacterial and antiviral effects.

[0022] Furthermore, the lead-free low-melting-point glass composition of the present invention may also contain iron oxide (Fe2O3) and potassium oxide (K2O). These are thought to exist between the layers of the layered structure. Fe2O3 is effective in improving the water resistance and saltwater resistance of the V2O5-P2O5 lead-free low-melting-point glass composition, while K2O is effective in increasing thermal expansion for thermal expansion matching with the substrate. However, if the content is too high, Fe2O3 may lead to a deterioration of softening fluidity due to an increased tendency to crystallize, and K2O may lead to a deterioration of water resistance and saltwater resistance, for example, the leaching of barium oxide if barium oxide is included. When the glass composition contains potassium oxide, it is preferable that the molar percentage in terms of oxide is 5 ≤ ​​[K2O] ≤ 20.

[0023] Furthermore, the lead-free low-melting-point glass composition of the present invention may further contain barium oxide (BaO). Barium oxide is added particularly when iron oxide is not present and serves as a vitrification component for vitrifying vanadium oxide (V2O5). In terms of oxide molars, it is preferable that 5 ≤ [BaO] ≤ 30, and particularly 15 ≤ [BaO] ≤ 30.

[0024] From the above viewpoint, the vanadium oxide, phosphorus oxide, silver oxide, and copper oxide contained in the glass composition are in the following mol% in terms of oxides: 25 ≤ [V2O5] ≤ 35, 15 ≤ [P2O5] ≤ 30, 1≦[Ag2O]+[CuO]≦50 That is the case.

[0025] Furthermore, in one embodiment of the glass composition, the glass composition further comprises iron oxide or barium oxide, wherein the vanadium oxide, silver oxide, copper oxide, iron oxide, and barium oxide are present in the following oxide equivalent molar percentages: 5 ≤ [Fe2O3] ≤ 15, [Ag2O]+[CuO]+3[Fe2O3]≦2[V2O5] is or 5 ≤ [BaO] ≤ 30, [Ag2O]+[CuO]+[BaO]≦2[V2O5] It is preferable that this is the case. In this embodiment, one preferred embodiment is one in which the product contains iron oxide and substantially does not contain barium oxide, or contains barium oxide and substantially does not contain iron oxide.

[0026] Furthermore, in one embodiment of the glass composition, it further contains one or more of tungsten oxide and zinc oxide, and the vanadium oxide, silver oxide, copper oxide, tungsten oxide and zinc oxide are present in the following oxide equivalent molars: [WO3] ≤ 15, [ZnO] ≤ 10, [Ag2O]+[CuO]+[ZnO]≦2[V2O5] It is preferable that this is the case. In this embodiment, one preferred embodiment is one in which the product contains iron oxide and substantially does not contain barium oxide, or contains barium oxide and substantially does not contain iron oxide.

[0027] Furthermore, in one embodiment of the glass composition, the glass composition contains iron oxide, and further contains one or more of tungsten oxide and zinc oxide, wherein the vanadium oxide, silver oxide, copper oxide, iron oxide, tungsten oxide, and zinc oxide are present in the following oxide equivalent molar percentages. [WO3] ≤ 15, [ZnO] ≤ 10, [Ag2O]+[CuO]+3[Fe2O3]+[ZnO]≦2[V2O5] is or, The aforementioned barium oxide is included, and further includes one or more of tungsten oxide and zinc oxide, wherein the vanadium oxide, silver oxide, copper oxide, barium oxide, tungsten oxide, and zinc oxide are present in the following oxide equivalent molar percentages: [WO3] ≤ 15, [ZnO] ≤ 10, [Ag2O]+[CuO]+[BaO]+[ZnO]≦2[V2O5] It is preferable that this is the case. In this embodiment, one preferred embodiment is one in which the product contains iron oxide and substantially does not contain barium oxide, or contains barium oxide and substantially does not contain iron oxide.

[0028] In this disclosure, "substantially free of a certain component" means that the component is present in an oxide-based mole percentage of 0.01 mol% or less, and preferably 0.001 mol% or less.

[0029] The glass composition is preferably in the form of a plate or film, and is a powder with an average particle size (D50) of 3 to 50 μm. If it is in the form of a plate, the thickness is preferably 0.1 to 30 mm, and more preferably 1.8 to 5 mm. If it is in the form of a film, the thickness is preferably 10 to 100 μm, and more preferably 50 to 100 μm. Within these ranges, it is possible to fully perform the functions of glass and maintain its effects over a long period of time.

[0030] There are no particular restrictions on the method for producing the aforementioned glass composition, and it can be produced by referring to conventionally known methods for producing lead-free low-melting-point glass using vanadium oxide (V2O5) and phosphorus oxide (P2O5). For example, oxides containing each element as raw material, such as V2O5, P2O5, Ag2O, AlPO4, Fe2O3, BaO, K2CO3, KVO3, CuO, WO3, and ZnO, can be blended and mixed according to the desired composition of the glass composition, placed in a container such as a platinum crucible, heated at 850 to 1300°C for 0.5 to 3.0 hours, and the molten material in the container is stirred as appropriate to produce the glass composition in the form of cullet, plates, etc. When obtaining the glass composition as powder (particles), the glass composition in the form of cullet, plates, etc. can then be granulated by crushing or other methods to produce a powdered glass composition. The powdered glass composition is also referred to as glass particles or glass powder.

[0031] The composition of this embodiment is characterized by comprising an antibacterial and antiviral glass composition and at least one component selected from polymers and monomers. Because the glass composition has antibacterial and antiviral properties, the composition can also exhibit antibacterial and antiviral properties. In the composition, one preferred embodiment is that the antibacterial and antiviral glass composition is in the form of a powder, and it is preferable that the antibacterial and antiviral glass composition is in the form of a powder with an average particle size (D50) of 3 to 50 μm, as this increases the specific surface area, thereby producing an antiviral effect and maintaining the effect for a long period of time.

[0032] There are no particular restrictions on the polymer used in the above composition, and polymers such as resins and rubbers can be used. Examples of polymers include polyvinyl alcohol, polyvinyl acetal (butyral resin, etc.), celluloses, acrylic urethane resins, acrylic resins, urethane resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, polyethylene terephthalate, polyester resins, polystyrene, polyamide resins, polycarbonate resins, and ABS resins.

[0033] There are no particular restrictions on the monomer; for example, monomers that can be polymerized to form the aforementioned polymers can be used. Furthermore, macromonomers (high molecular weight monomers with polymerizable functional groups) may also be used as monomers.

[0034] In this embodiment, the composition preferably contains 5% to 50% by volume of the glass composition, more preferably 5% to 30% by volume, and particularly preferably 5% to 25% by volume. Furthermore, in this embodiment, the composition preferably contains 50% to 95% by volume of at least one component selected from the polymer and monomer, more preferably 70% to 95% by volume, and more preferably 75% to 95% by volume. Within this range, the antibacterial and antiviral effects can be sufficiently exhibited, which is preferable.

[0035] The composition of this embodiment may contain other components. Examples of other components include various additives. Examples of additives include plasticizers, stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, pigments, dyes, and waxes (e.g., natural waxes such as plant-based, animal-based, or mineral-based waxes). Additives may be included individually or in combination of two or more types.

[0036] There are no particular limitations on the method for producing the above composition. For example, a composition containing the polymer and the glass composition can be obtained by mixing the polymer and the glass particles and then drying them. When mixing the polymer and the glass composition, it is preferable to use a solvent or dispersion medium capable of dissolving or dispersing the polymer. Either an organic solvent or an aqueous solvent may be used as the solvent or dispersion medium. For example, a solution can be prepared by dissolving the polymer in a solvent, the solution can be mixed with the glass particles (glass composition), and the solvent can be removed by drying or other means to obtain the glass composition. Alternatively, a composition containing the monomer and the glass composition can be obtained by mixing the monomer and the glass composition. Furthermore, a composition containing the polymer and the glass composition can be obtained by polymerizing the monomer in a composition containing the monomer and the glass composition.

[0037] The uses of the composition of this embodiment will now be described. When the composition includes a polymer and a glass composition, it can be used for various purposes as an antibacterial and antiviral molded article. Examples of molded articles include plates, sheets, fibers, woven fabrics, nonwoven fabrics, etc. When the composition includes a monomer and a glass composition, the composition may also be a paint. The molded article may be a single-layer molded article or a multi-layer molded article. In the case of a multi-layer molded article, at least one layer is formed from the composition. In the case of a multi-layer molded article, it is preferable that at least a part of the part that comes into contact with air or the part that comes into contact with people, etc., is formed from the composition. The paint may be a single-component paint or a multi-component paint that is used by mixing multiple agents. When the sheet is a single-layer structure, the thickness is preferably in the range of 20 to 500 μm, and more preferably in the range of 30 to 100 μm. When the sheet is a multi-layer structure, it is preferable that the thickness of each layer is 20 μm or more from the viewpoint of producing a uniform sheet. The molded article may have three or more layers of nonwoven fabric. As fibers, it is envisioned that the composition be formed into fibers, mixed with polymer fibers, etc., or attached to the surface of any fiber, and it can be used in any thickness. As woven fabric, it can be applied to objects such as clothing as appropriate. In a molded article having three or more layers of nonwoven fabric, the inner layer may have a nonwoven fabric formed from the composition of this embodiment. Since nonwoven fabrics are normally permeable to air, antibacterial and antiviral effects can be exerted even when the nonwoven fabric formed from the composition is located in the inner layer. For layers other than the inner layer, known nonwoven fabrics can be used, and for example, masks can be manufactured. Furthermore, the molded article may be subjected to mesh treatment using the composition. As for the shape of the mesh, specific shapes such as grids, dots, and polygons can be given, but are not limited to these. The nonwoven fabric obtained from the above composition can be laminated with other nonwoven fabrics or other substrates as needed, and / or subjected to various processing such as embossing or pleating, and then suitably used for various applications such as filters for filtering gases or liquids.Examples of uses for compositions containing the aforementioned polymer and glass composition include: clothing (medical clothing) (masks, lab coats, protective clothing, gloves, etc.); bedding (medical bedding) (futon / pillowcases, curtains, patient amenities, etc.); handrails, doorknobs, touch buttons for elevators and automatic doors, escalator belts, medical equipment terminals, etc. in hospitals; air conditioning filters in hospitals; tents for temporary medical sites; mosquito nets for home care; floor wax; handrails, straps, and touch buttons for trains, buses, aircraft, ships, elevators, taxis, etc. These include door knobs, floors, walls, ceilings, sheets, air conditioning filters, etc.; building materials (floors, walls, doors, ceilings), furniture (tables, desks, chairs, curtains, etc.), air conditioning filters for schools, libraries, companies, supermarkets, detached houses, apartment buildings, etc.; shopping cart grips, shopping basket handles; medical equipment; vehicles; elevators; escalators (belts); home appliances; odor-resistant underwear; socks for preventing athlete's foot; odor-resistant sportswear; odor-resistant shoe insoles; and bathroom (sanitary) products (kitchens, toilets, baths, washbasins, etc.). The composition of this embodiment can be used as a component constituting all or part of these uses. [Examples]

[0038] The embodiments will be described below with reference to examples, but this disclosure is not limited to these examples.

[0039] [Example 1] In this example, the influence and effects of the glass composition of the glass composition on the glass properties, as well as the effects of the composition, were investigated. Tables 1 to 6 show the glass composition and properties of the glass compositions of the examples and comparative examples (V2O5-P2O5-based lead-free low-melting-point glass composition and V2O5-TeO2-based lead-free low-melting-point glass composition).

[0040] (Preparation of lead-free low-melting-point glass compositions) Lead-free low-melting-point glass compositions having the compositions listed in Tables 1-6 were prepared by the following method. The glass raw materials in Table 1 were powders of V2O5, P2O5, Ag2O, AlPO4, Fe2O3, BaO, K2CO3, KVO3, CuO, WO3, and ZnO. The glasses in Table 4 were comparative examples using conventional vanadium glass, zinc-based glass, and silica-based glass. Each glass raw material was mixed in predetermined amounts according to the proportions listed in Table 1 or Table 4, so that the total glass raw material amounted to approximately 200g, and then placed in a platinum crucible. The platinum crucible was heated in an electric furnace in air at a heating rate of approximately 10°C / min to approximately 900°C and held for 1-2 hours. During this holding period, the molten material in the platinum crucible was stirred with an alumina rod at 20-30 minute intervals to ensure uniform glass formation. After holding, the platinum crucible was removed from the electric furnace, and the molten material inside the crucible was poured onto a thick stainless steel plate to obtain glass cullet of a lead-free, low-melting-point glass composition.

[0041] (Evaluation of the vitrification state) The glass cullet of the obtained lead-free low-melting-point glass composition was observed visually and under an optical microscope to evaluate the vitrification state by checking for surface devitrification, crystallization, phase separation, and the presence or absence of undissolved material. In cases where the state was unclear, the glass cullet was crushed and the presence or absence of sharp diffraction peaks was checked by powder X-ray diffraction to evaluate the vitrification state. If none of the following were observed in the obtained glass cullet: surface devitrification, crystallization, phase separation, or undissolved material, or if no sharp diffraction peaks were observed in powder X-ray diffraction, it was judged to be a uniform vitrification state and evaluated as good (○). On the other hand, if any of the following were observed in the obtained glass cullet: surface devitrification, crystallization, phase separation, or undissolved material, or if sharp diffraction peaks were observed in powder X-ray diffraction, it was judged to be a poor (×) vitrification state.

[0042] (Preparation of glass particles) The glass cullet obtained in the above (preparation of lead-free low-melting-point glass composition) was pulverized using a pulverizer and a jet mill to obtain glass particles (glass powder) with an average particle size (D50) of approximately 20 μm.

[0043] (Measurement of glass property temperature) The characteristic temperatures (transition point, yield point, softening point, etc.) of the glass particles (lead-free low-melting-point glass composition) were measured by differential thermal analysis (DTA). The glass powder (glass particles) was placed in an aluminum DTA cell and heated from room temperature to 550°C at a heating rate of 5°C / min in air to obtain a DTA curve. Figure 1 shows an example of a typical differential thermal analysis (DTA) result for glass. As shown in Figure 1, when glass powder (glass particles) is heated, the transition point T g Endothermic heating begins from [location], and the bending point M corresponds to the first endothermic peak. g It reaches this point. Then, the amount of endothermic heat decreases temporarily, and then increases again. The temperature corresponding to the second endothermic peak is the softening point T. s Therefore, if heated further, the crystallization temperature T cry The amount of heat generated increases sharply from this point, reaching the heat generation peak. This heat generation peak is due to the crystallization of the glass, and the temperature at which heat generation begins is called the crystallization temperature T. cry The temperature at which the exothermic peak shows its maximum value is the crystallization peak temperature T. cry-p This is what it is called. Typically, the characteristic temperatures for each are determined by the tangent method.

[0044] (Evaluation of glass softening fluidity) The softening and flowability of the glass particles (lead-free low-melting-point glass composition) was evaluated by a button flow test. As an evaluation sample, a compacted body with a diameter of 10 mm and a thickness of 5 mm was obtained using the glass powder (glass particles). This compacted body was placed on an aluminum plate and heated at a rate of 10°C / min in air until the glass softened point T s The softening and flowing state was observed after heating to a temperature approximately 30-40°C higher and holding for 30 minutes. A "○" was given if good softening and flowing was obtained, and a "×" was given if good softening and flowing was not obtained due to surface devitrification, crystallization, phase separation, etc.

[0045] (chemical stability) Samples were prepared by mixing α-terpineol and glass powder on a 50mm x 50mm x 1mm aluminum plate and firing it at 170°C for 30 minutes and 390°C for 30 minutes. The glass-fired aluminum plates were immersed in water or 3.5 wt% salt water and left for at least one day. Samples were marked with ○ if no glass components other than silver leached into the solution, and × if other components were detected.

[0046] (comprehensive evaluation) The overall evaluation of the glass was that it was not crystallized, and in the chemical stability test, there was no leaching of anything other than silver, and the amount of silver leached was below the required amount (5 × 10⁻¹⁰). -7 g / cm 3 Items that were confirmed to meet or exceed the specified value were marked with ○, and items that did not meet the required value in any category were marked with ×.

[0047] (Firing onto the surface of an alloy substrate (production of a film-like glass composition)) 25 g of the aforementioned glass particles (lead-free low-melting-point glass composition) were added to a solvent (5 g) and kneaded in a sieve for about 30 minutes to prepare a paste. The paste was applied to an aluminum alloy plate as described below, dried, and fired, and the coverage of the coating was evaluated by observing it. α-terpineol (α-T) was used as the solvent.

[0048] Each paste was applied to a 50 × 50 × 2 mm aluminum alloy plate with a thickness of 0.1 mm over a 50 × 50 mm area, as shown in Figure 2A. A6501 aluminum alloy plate was used. The aluminum alloy plate with the paste applied was dried in air at 150-170°C for 30 minutes. After drying, it was further heated in air at a heating rate of 10°C / min, as shown in the glass firing temperature profile in Figure 3A, held at a temperature approximately 30-40°C above the softening point of glass for 30 minutes, and then furnace-cooled to form a glass firing coating (film-like glass composition) on the aluminum alloy plate, obtaining the sample.

[0049] (Mixing with polymers (resin materials) (production of glass compositions and compositions containing polymers)) 25 g of the aforementioned glass particles (lead-free low-melting-point glass composition) were added to a solution (15 g of polypropylene, 18 g of solvent) in which a resin binder (powdered polypropylene) was dissolved in a solvent, and the mixture was kneaded in a sieve for about 30 minutes to prepare a paste. The paste was applied to an aluminum alloy plate as described below, dried, and evaluated by observing the coverage of the coating film. The volume ratio of glass varies depending on the glass component used, but the glass particles and polypropylene were used in amounts such that the dried composition contained 5-20% by volume of glass particles and 80-95% by volume of polypropylene. α-Terpineol (α-T) was used as the solvent.

[0050] As shown in Figure 2B, the paste was applied to a 50 × 50 × 2 mm aluminum alloy plate with a thickness of 0.1 mm over a 50 × 50 mm area. A6501 aluminum alloy plate was used. Furthermore, as shown in the polypropylene heating temperature profile in Figure 3B, the plate was heated in air at a heating rate of 10°C / min, held at 200°C for 1 hour, and then furnace-cooled to form a layer on the alloy plate consisting of a glass composition and a polymer (polypropylene), thereby obtaining the sample.

[0051] (Mixing with monomers (preparation of glass composition and composition (paint) containing monomers) and curing (production of glass composition and composition containing polymer)) The aforementioned glass particles (lead-free low-melting-point glass composition) and acrylic powder were added to α-terpineol and kneaded in a lithograph for about 30 minutes to prepare a paste. The paste was applied to an aluminum alloy plate as described below, dried, and evaluated by observing the coverage of the coating film. The glass particles and acrylic powder were used in amounts such that, in the paste state (a mixture of glass particles, an acrylic-containing composition precursor, and a solvent), the amount of glass particles was 5-20% by volume and the amount of acrylic powder was 80-95% by volume when the solvent was removed. Similarly, in the coating film (a composition containing glass particles and acrylic resin), the amount of glass particles and acrylic powder was 5-20% by volume and 80-95% by volume.

[0052] As shown in Figure 2B, the paste was applied to a 50 × 50 × 2 mm aluminum alloy plate with a thickness of 0.1 mm over a 50 × 50 mm area. A6501 aluminum alloy plate was used. Furthermore, as shown in the acrylic heating temperature profile in Figure 3C, the plate was heated in air at a heating rate of 10°C / min, held at 80°C for 3 hours, and then furnace-cooled. This formed a layer on the alloy plate consisting of a glass composition and a polymer (acrylic), thus obtaining the sample.

[0053] Next, antiviral tests were conducted using the prepared samples. The antiviral tests were performed in accordance with ISO 21702 (Measurement of antiviral activity of plastics and other non-porous surfaces). The results of this test, which used enveloped SARS-CoV-2 and influenza A viruses, are summarized in Tables 7-12. These results take into account the antiviral properties of the material and cytotoxicity to the human body. The test items in Tables 7-12 were measured as follows.

[0054] (Immediate effect) Antiviral activity value (R): This value represents the difference (R = Ut - At) between the logarithm of the viral infectivity titer (Ut) of an untreated test specimen (no drug added) after 2 hours and the viral infectivity titer (At) of a treated test specimen (with antiviral agent added) after 2 hours. An R value of 2 or higher is considered acceptable.

[0055] As shown in Tables 7-12, the test specimens of Examples A-1 to A-31 and B-1 showed good results against both SARS-CoV-2 and influenza A virus. In contrast, the antiviral activity values ​​(R) of the test specimens of Comparative Examples B-2 to B-5 did not reach the acceptable level. Furthermore, a test to confirm antibacterial activity was conducted according to JIS-Z2911. It was confirmed that bacteria were reduced in all of the test specimens in the examples.

[0056] (Persistence) Each sample was immersed in pure water for 744 hours, and the duration of silver ion elution into the water was evaluated. A sample was considered acceptable if the amount of Ag ions eluted at 744 hours could be maintained for 10 years. A linear approximation was used to evaluate the results as follows, with samples meeting the requirements marked with ○ and those not meeting the requirements marked with ×. Amount of Ag ions eluted in 744 hours / Total amount of Ag ions contained in the glass < 0.0085 (= 744 / (24 × 365 × 10))

[0057] (Non-cytotoxic) Materials that do not contain elements that are harmful to the human body (e.g., Ni, Te, Hg, Co) were marked with a circle (○), while materials that do contain such elements were marked with a cross (×).

[0058] [Table 1]

[0059] [Table 2]

[0060] [Table 3]

[0061] [Table 4]

[0062] [Table 5]

[0063] [Table 6]

[0064] [Table 7]

[0065] [Table 8]

[0066] [Table 9]

[0067] [Table 10]

[0068] [Table 11]

[0069] [Table 12]

[0070] Glass compositions, and compositions containing glass compositions and polymers, have been shown to have antibacterial and antiviral properties, and to be particularly effective against coronaviruses and influenza viruses. Needless to say, these effects can be extended to all viruses and bacteria in which silver ions and copper ions are effective.

[0071] The present invention is not limited to the above embodiments and examples, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention, and includes various modifications. For example, the above embodiments and examples are described in detail to make the present invention easier to understand, and are not necessarily limited to those having all the described configurations. Furthermore, it is possible to replace parts of the configuration of one embodiment and example with the configuration of another embodiment and example, and it is also possible to add the configuration of another embodiment and example to the configuration of one embodiment and example. In addition, it is possible to add, delete, or replace parts of the configuration of each embodiment and example with other configurations.

Claims

1. It contains vanadium oxide, phosphorus oxide, and further contains one or more of silver oxide and copper oxide, and the vanadium oxide, phosphorus oxide, silver oxide and copper oxide are present in the following oxide equivalent molar percentages: 25≦[V ２ O ５ ]≦35、 15≦[P ２ O ５ ]≦30、 1≦[Ag] ２ O] + [CuO] ≦ 50 A glass composition for antibacterial and antiviral purposes, characterized by the following:

2. In the antibacterial and antiviral glass composition according to claim 1, Furthermore, it contains iron oxide or barium oxide, and the vanadium oxide, silver oxide, copper oxide, iron oxide and barium oxide are present in the following oxide equivalent mol%: 5≦[Fe ２ O ３ ]≦15、 [Ag ２ O]+[CuO]+3[Fe ２ O ３ ]≦2[V ２ O ５ ] is or 5≦[BaO]≦30, [Ag] ２ O]+[CuO]+[BaO]≦2[V ２ O ５ ] A glass composition for antibacterial and antiviral purposes, characterized by the following:

3. In the antibacterial and antiviral glass composition according to claim 1, Furthermore, it contains one or more of tungsten oxide and zinc oxide, and the vanadium oxide, silver oxide, copper oxide, tungsten oxide and zinc oxide are present in the following molar percentages in terms of oxides: [[WO] ３ ]≦15、 [ZnO] ≤ 10, [A' ２ O]+[ ２ O ５ ] A glass composition for antibacterial and antiviral purposes, characterized by the following:

4. In the antibacterial and antiviral glass composition according to claim 2, The aforementioned iron oxide is included, and further includes one or more of tungsten oxide and zinc oxide, wherein the vanadium oxide, silver oxide, copper oxide, iron oxide, tungsten oxide, and zinc oxide are present in the following oxide equivalent molar percentages: [[WO] ３ ]≦15、 [ZnO] ≤ 10, [Ag ２ O]+[CuO]+3[Fe ２ O ３ ]+[ZnO]≦2[V ２ O ５ ] is or, The aforementioned barium oxide is included, and further includes one or more of tungsten oxide and zinc oxide, wherein the vanadium oxide, silver oxide, copper oxide, barium oxide, tungsten oxide, and zinc oxide are present in the following oxide equivalent mole percent: [[WO] ３ ]≦15、 [ZnO] ≤ 10, [A' ２ O]+[ ２ O ５ ] A glass composition for antibacterial and antiviral purposes, characterized by the following:

5. In the antibacterial and antiviral glass composition according to claim 2, A substance containing the aforementioned iron oxide and substantially free of the aforementioned barium oxide, or An antibacterial and antiviral glass composition characterized by containing the barium oxide and substantially not containing the iron oxide.

6. In the antibacterial and antiviral glass composition according to claim 4, A substance containing the aforementioned iron oxide and substantially free of the aforementioned barium oxide, or An antibacterial and antiviral glass composition characterized by containing the barium oxide and substantially not containing the iron oxide.

7. In the antibacterial and antiviral glass composition according to claim 1, An antibacterial and antiviral glass composition characterized by being a powder with a plate-like or film-like shape and an average particle size (D50) of 3 to 50 μm.

8. An antibacterial and antiviral glass composition according to any one of claims 1 to 7, and a composition characterized by comprising at least one component selected from polymers and monomers.

9. In the composition according to claim 8, The aforementioned antibacterial and antiviral glass composition is characterized in that it is a powder with an average particle size (D50) of 3 to 50 μm.

10. In the composition according to claim 8, A composition characterized in that the content of the antibacterial and antiviral glass composition in the composition is 5% by volume or more and 50% by volume or less.

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