Antibacterial and / or antiviral borohydride-containing sheet and composition, and antibacterial and / or antiviral member
A borohydride-containing sheet with a two-dimensional network structure, combined with additional materials, provides effective antibacterial and antiviral solutions for both viruses and bacteria, ensuring safety and efficacy under visible light conditions.
Patent Information
- Application Number
- JP2021124983
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2021-07-30
- Publication Date
- 2025-09-29
- Estimated Expiration
- 2041-07-30
AI Technical Summary
Existing technologies lack effective materials for inactivating both viruses and bacteria, particularly under visible light conditions, and there is a need for improved antibacterial and antiviral compositions and members that can be safely used at room temperature and pressure.
A borohydride-containing sheet with a two-dimensional network structure, composed of (BH)n, which includes a two-dimensional network of boron and hydrogen atoms, combined with materials like metals, metal oxides, semiconductors, and organic compounds capable of generating electron-hole pairs upon photoexcitation, forming antibacterial and antiviral compositions and members.
The borohydride-containing sheet effectively inactivates both enveloped and non-enveloped viruses, as well as gram-positive and gram-negative bacteria, with high transparency and safety at room temperature, enhancing antibacterial and antiviral properties under visible light exposure.
Smart Images

Figure 0007745195000001 
Figure 0007745195000002 
Figure 0007745195000003
Abstract
Description
[Technical Field]
[0001] The present invention relates to an antibacterial and antiviral borohydride-containing sheet, and also to an antibacterial and antiviral composition and antibacterial and antiviral member containing the antibacterial and antiviral borohydride-containing sheet. [Background technology]
[0002] The current pandemic of the novel coronavirus disease (COVID-19) has increased the need for infection prevention measures, creating a demand for the development of products that can inactivate viruses and bacteria. For example, Patent Document 1 proposes an antibacterial and antiviral composition that includes a resin, an antibacterial and antiviral agent composed of monovalent copper compound microparticles coated with a dispersant, and a hydrophilic compound that is dispersed in the resin and is incompatible with the resin (Patent Document 1). Furthermore, Non-Patent Document 1 discloses a technology that uses MgB2 as an antibacterial agent. It has also been reported that photoexcitable semiconductors and organic compounds exhibit antibacterial and antiviral effects through photocatalytic action under excitation light irradiation (Non-Patent Documents 2 and 3).
[0003] Although not for antibacterial or antiviral applications, the present inventors have recently proposed a technology for extracting hydrogen from boron-containing sheets by heat treatment at relatively low temperatures of 200°C or less (Non-Patent Document 4, Patent Document 2). They also reported that the reduction function of boron-containing sheets allows metal particles to be deposited on the surface of the boron-containing sheets (Non-Patent Document 5, Patent Document 3). [Prior art documents] [Patent documents]
[0004] [Patent Document 1] International Publication No. 2019 / 045110 [Patent Document 2] International Publication No. 2018 / 074518 [Patent Document 3] International Publication No. 2020 / 179779
Non-licensed literature
[0005]
Non-licensed literature 1
Non-licensed Document 2
Non-licensed Document 4
Non-licensed Document 5
[0006] The present invention has been made in view of the above-mentioned background, and aims to provide an antibacterial / antiviral borohydride-containing sheet that can inactivate viruses and bacteria, and an antibacterial / antiviral composition and antibacterial / antiviral member that contain this antibacterial / antiviral borohydride-containing sheet. [Means for solving the problem]
[0007] As a result of extensive research, the present inventors have found that the problems of the present invention can be solved by the following aspects, and have thus completed the present invention. [1]: (BH) n An antibacterial and antiviral borohydride-containing sheet having a two-dimensional network consisting of (n≧4, where n is an integer). [2]: An antibacterial and antiviral composition containing the antibacterial and antiviral borohydride-containing sheet according to [1]. [3]: The antibacterial and antiviral composition according to [2], characterized in that it contains an antibacterial and antiviral material made of at least one of a metal and a metal oxide. [4]: The antibacterial and antiviral composition according to [2] or [3], characterized in that it contains at least one of a semiconductor and an organic compound capable of generating electron-hole pairs upon photoexcitation. [5]: The antibacterial and antiviral composition according to any one of [2] to [4], characterized in that it contains a resin. [6]: The antibacterial and antiviral composition according to any one of [2] to [5], characterized in that it contains a solvent. [7]: An antibacterial and antiviral member comprising a member and the antibacterial and antiviral composition according to any one of [2] to [6] fixed to at least the surface of the member. [8]: The antibacterial and antiviral member according to [7], characterized in that the transmittance of the antibacterial and antiviral composition fixed to the member is 80% or more in the visible light range. [Effects of the Invention]
[0008] The present invention has the excellent effect of providing an antibacterial / antiviral borohydride-containing sheet that can inactivate viruses and bacteria, as well as an antibacterial / antiviral composition and antibacterial / antiviral member that contain this antibacterial / antiviral borohydride-containing sheet. [Brief explanation of the drawings]
[0009] [Figure 1] 1 is a schematic diagram of the local structure of a two-dimensional network consisting of (BH)n (n≧4, where n is an integer) of a boron-containing sheet according to this embodiment. [Figure 2] 1 is a schematic diagram showing the local structure of a two-dimensional network consisting of (BH)n (n≧4, where n is an integer) of a borohydride-containing sheet according to this embodiment. [Figure 3] 1 is a schematic diagram showing the local structure of a two-dimensional network consisting of (BH)n (n≧4, where n is an integer) of a borohydride-containing sheet according to this embodiment. [Figure 4] 1 is a transmission electron microscope photograph of the product of Example 1. [Figure 5] Graph showing the results of EELS measurement of the product of Example 1. [Figure 6] Graph showing the results of FT-IR measurement of the product of Example 1. [Figure 7] SEM image of the sample surface where a boron-containing sheet is coated on a glass substrate. [Figure 8] SEM image of a cracked area in a sample where a boron-hydride-containing sheet was coated on a glass substrate. [Figure 9]An enlarged SEM image of the cracked area in Figure 8. [Figure 10] SEM image (secondary electron image) of the fracture surface of a sample in which a boron-containing sheet is coated on a glass substrate. [Figure 11] Backscattered electron image of the same field of view as in Figure 10. [Figure 12] SEM image focusing on the crack in Figure 10. [Figure 13] Transmittance spectrum of borohydride-containing sheet-coated film. [Figure 14] FIG. 1 is a graph showing the time-dependent change in the antiviral activity of the antibacterial and antiviral composition of Example 1 against the enveloped bacteriophage φ6. [Figure 15] FIG. 1 is a graph showing the time-dependent change in the antiviral activity of the antibacterial and antiviral composition of Example 2 against the non-enveloped bacteriophage Qβ. [Figure 16] FIG. 1 is a graph showing the change over time in the antibacterial activity of the antibacterial and antiviral composition of Example 3 against Escherichia coli, a gram-negative bacterium. [Figure 17] FIG. 1 is a graph showing the change over time in the antibacterial activity of the antibacterial and antiviral composition of Example 4 against Staphylococcus aureus, a gram-positive bacterium. [Figure 18] FIG. 1 shows the results of a splash test in a glove box for the antibacterial and antiviral composition of Example 5. DETAILED DESCRIPTION OF THE INVENTION
[0010] An example of an embodiment to which the present invention is applied will be described below. Note that other embodiments are also included within the scope of the present invention as long as they are consistent with the spirit of the present invention. Furthermore, the size and proportions of each component in the following drawings are for the convenience of explanation and are not intended to be limiting.
[0011] [Antibacterial and antiviral borohydride-containing sheet] The antibacterial and antiviral borohydride-containing sheet of this embodiment (hereinafter simply referred to as the antibacterial and antiviral borohydride-containing sheet or the present borohydride-containing sheet) comprises (BH) n(n≧4, where n is an integer. Hereinafter, simply (BH) n It is a sheet-like material with a two-dimensional network consisting of (BH). n The two-dimensional network consisting of the above is formed by a molar ratio of boron atoms (B) and hydrogen atoms (H) of 1:1 (see Non-Patent Document 1).
[0012] "Antibacterial" refers to the use of a material that acts on bacteria to inhibit bacterial growth, while "antiviral" refers to the use of a material that acts on viruses to reduce their infectivity. This antibacterial and antiviral borohydride-containing sheet can be used as an antibacterial and / or antiviral agent.
[0013] Antibacterial and antiviral borohydride-containing sheets (BH) n It is sufficient to have a two-dimensional network consisting of (BH) n Compounds with a two-dimensional network structure as the main skeleton (e.g., (BH) n These include compounds in which a dopant is introduced into a part of a two-dimensional network consisting of the above, compounds whose ends are capped with oxides, hydroxides, nitrides, carbides, sulfides, etc., and / or compounds in which organic groups are bonded to the ends. Here, the main skeleton refers to a substance in which the proportion of boron-containing sheets in the compound is 80% or more.
[0014] Examples of the dopant include at least one element selected from the group consisting of elements such as carbon, nitrogen, oxygen, fluorine, phosphorus, sulfur, chlorine, arsenic, selenium, bromine, antimony, tellurium, and iodine; metal elements such as titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc, cadmium, indium, tin, yttrium, niobium, molybdenum, tungsten, tantalum, and lead; and noble metal elements such as ruthenium, rhodium, palladium, silver, gold, iridium, and platinum.
[0015] Figures 1 to 3 show (BH) nThe following is a schematic diagram of the local structure of a two-dimensional network consisting of the boron atoms. As shown in Figure 1, in the two-dimensional network, boron atoms are arranged in a hexagonal honeycomb pattern (a mesh formed by interconnected hexagons formed by the boron atoms), and two adjacent boron atoms have sites where they bond to the same hydrogen atom. The boron atoms form a honeycomb-like (honeycomb) sheet-like hexagonal lattice structure, and one hydrogen atom is bonded to two adjacent boron atoms in the hexagonal lattice structure above and below the sheet in a bridge-like manner, as shown in Figures 2 and 3. Furthermore, two hydrogen atoms are arranged facing each other above and below the sheet-like hexagonal lattice structure. Note that the arrangement of hydrogen atoms in borohydride does not necessarily have long-range order. Furthermore, the bonds between atoms may be tilted in the Z direction in Figures 2 and 3, or the sheet itself may be curved. Furthermore, not all hydrogen atoms necessarily bond to bridges.
[0016] The boron hydride-containing sheet is a thin film material and may consist of a single layer or multiple layers. In the antibacterial and antiviral boron hydride-containing sheet, the total number of boron atoms (B) and hydrogen atoms (H) forming the mesh-like surface structure is 1,000 or more.
[0017] The bond distance d1 (see FIG. 1) between two adjacent boron atoms (B) is, for example, 0.155 nm to 0.190 nm. When viewed from the Z direction, the bond distance d2 (see FIG. 2) between two adjacent boron atoms (B) separated by one hydrogen atom (H) is, for example, 0.155 nm to 0.190 nm. The bond distance d3 (see FIG. 2) between adjacent boron atoms (B) and hydrogen atoms (H) is, for example, 0.12 nm to 0.15 nm.
[0018] The thickness of the boron-containing sheet is, for example, 0.2 nm to 10 nm. The length of the boron-containing sheet in at least one direction (for example, the length in the X or Y direction in FIG. 1) is preferably 100 nm or more. By making the length in at least one direction 100 nm or more, the sheet can be more effectively used for antibacterial and antiviral purposes. The size (area) of the boron-containing sheet is not particularly limited, and it can be formed to any size.
[0019] This boron-containing sheet is a substance with a crystalline structure. Furthermore, this boron-containing sheet has strong bonding forces between the boron atoms (B) that form the hexagonal rings, and between the boron atoms (B) and the hydrogen atoms (H). Therefore, even if this boron-containing sheet forms a crystal (aggregate) consisting of multiple layers during production, it can be easily cleaved along the crystal planes, similar to graphite, and separated (recovered) as a single two-dimensional sheet.
[0020] This antibacterial and antiviral borohydride-containing sheet can provide a new material that exhibits antiviral activity (can inactivate) both enveloped and non-enveloped viruses. This antibacterial and antiviral borohydride-containing sheet can also provide a new material that exhibits antibacterial activity (can inactivate) both gram-positive and gram-negative bacteria. This borohydride-containing sheet also contains (BH), a compound consisting of hydrogen and boron. n The main skeleton of this sheet is a two-dimensional network composed of hydroxybenzoates, making it extremely lightweight. It is also safe because it can be used at room temperature and pressure. However, this does not preclude its use under conditions other than room temperature and pressure. Furthermore, this antibacterial and antiviral boron-containing sheet has excellent transparency, making it suitable for use as an antibacterial and antiviral coating agent, as described below.
[0021] (Method for manufacturing the present borohydride-containing sheet) The method for producing this boron-containing sheet is not particularly limited. For example, it can be produced by the following method. Specifically, first, a metal diboride with an MB2 structure and an ion-exchange resin in which the metal ions constituting the metal diboride and ion-exchangeable ions are coordinated are mixed in a polar organic solvent. The M is at least one selected from the group consisting of Al, Mg, Ta, Zr, Re, Cr, Ti, and V. This mixing process can be carried out in an inert atmosphere of an inert gas such as nitrogen (N2) or argon (Ar).
[0022] Metal diborides with MB2 structure have a hexagonal ring structure. Examples include aluminum diboride (AlB2), magnesium diboride (MgB2), tantalum diboride (TaB2), zirconium diboride (ZrB2), rhenium diboride (ReB2), chromium diboride (CrB2), titanium diboride (TiB2), and vanadium diboride (VB2). Magnesium diboride is preferred because it can be easily ion-exchanged with an ion-exchange resin in a polar organic solvent.
[0023] The ion exchange resin in which ion-exchangeable ions are coordinated with metal ions constituting the metal diboride is not particularly limited. Examples of such ion exchange resins include a styrene polymer having a functional group (hereinafter referred to as "functional group α") in which ion-exchangeable ions are coordinated with metal ions constituting the metal diboride, a divinylbenzene polymer having the functional group α, and a copolymer of styrene having the functional group α and divinylbenzene having the functional group α. Examples of the functional group α include a sulfo group and a carboxy group. Among these, a sulfo group is preferred because it can easily perform ion exchange with the metal ions constituting the metal diboride in a polar organic solvent.
[0024] An acid may be further added in the mixing step. Examples of the acid include acetic acid, carbonic acid, tartaric acid, malic acid, maleic acid, propionic acid, formic acid, succinic acid, citric acid, oxalic acid, lactic acid, hydrochloric acid, sulfuric acid, and phosphoric acid. By adding an acid, the time required for ion exchange between the metal ions constituting the metal diboride and the ion exchange resin in a polar solvent can be easily and significantly shortened.
[0025] The polar organic solvent is not particularly limited, and examples thereof include acetonitrile, N,N-dimethylformamide, and methanol.
[0026] When an acid is used in the mixing step, the acid is removed as necessary. The method for removing the acid is not particularly limited, but examples thereof include heating, drying under reduced pressure, and precipitation recovery.
[0027] The mixed solution is then filtered. For example, natural filtration, vacuum filtration, pressure filtration, centrifugal filtration, etc. may be used. The solution containing the product recovered by separating it from the precipitate by filtration is dried naturally or by drying under reduced pressure, heating, etc., to obtain (BH). n A borohydride-containing sheet having a two-dimensional network consisting of:
[0028] This antibacterial and antiviral borohydride-containing sheet can itself be used as an antibacterial and / or antiviral agent. For example, the powder can be placed in areas where droplets containing bacteria or viruses may adhere. When used in conjunction with existing antibacterial sheets or coating technologies, it can also be used as a powder to fill gaps and other areas that cannot be coated properly with conventional technologies. Furthermore, by placing this antibacterial and antiviral borohydride-containing sheet in powder form inside an air purifier, it is possible to blow clean air that has been sterilized and decontaminated. This antibacterial and antiviral borohydride-containing sheet in powder form can also be added directly to the washing machine tub.
[0029] This antibacterial and antiviral borohydride-containing sheet absorbs ultraviolet light, which generates electron-hole pairs within the sheet itself. Therefore, the antibacterial and antiviral functions of this antibacterial and antiviral borohydride-containing sheet can be enhanced by exposing it to ultraviolet light.
[0030] This antibacterial and antiviral borohydride-containing sheet can be kneaded into or mixed with existing disinfectants, wet wipes, films, fibers, rubber, detergents, etc. For example, by kneading this antibacterial and antiviral borohydride-containing sheet into decorative films for automobiles, etc., it can be used as a decorative film containing this antibacterial and antiviral borohydride-containing sheet. Furthermore, by kneading this antibacterial and antiviral borohydride-containing sheet into the hard coat layer of a smartphone, a hard coat layer containing this antibacterial and antiviral borohydride-containing sheet can be provided. Furthermore, by kneading this antibacterial and antiviral borohydride-containing sheet into floor waxes, coatings for walls, furniture, or cooking utensils, waxes and coatings containing this antibacterial and antiviral borohydride-containing sheet can be provided.
[0031] The antibacterial and antiviral borohydride-containing sheet may also be incorporated into creams, ointments, gels, waxes, etc. for medical and cosmetic use, as well as into hand soaps, hand washes, and various detergents.
[0032] [Antibacterial and antiviral compositions] The antibacterial and antiviral composition according to this embodiment (hereinafter also referred to as the present composition) contains the present antibacterial and antiviral borohydride-containing sheet. The present composition has antibacterial and antiviral effects and may contain the present antibacterial and antiviral borohydride-containing sheet, and may be a composition with any material.
[0033] The composition can further contain an antibacterial / antiviral material composed of at least one of a metal and a metal oxide. The inclusion of an antibacterial / antiviral material composed of at least one of a metal and a metal oxide can further enhance the antibacterial / antiviral properties. Examples of such metals and metal oxides include silver (Ag), silver oxide (AgO), copper (Cu), copper oxide (CuO, CuO), zinc (Zn), zinc oxide (ZnO), nickel (Ni), nickel oxide (NiO), cobalt (Co), and cobalt oxide (CoO, CoO, CoO).
[0034] The composition may also contain at least one of a semiconductor and an organic compound that can generate electron-hole pairs upon photoexcitation. The inclusion of such a semiconductor and organic compound can enhance the antibacterial and antiviral properties upon exposure to light. Examples of excitation light include ultraviolet light and visible light.
[0035] Semiconductors capable of generating electron-hole pairs under ultraviolet light include titanium oxide, zinc oxide, strontium titanate, tin oxide, tantalum oxide, and cerium oxide. Adding such semiconductors to the present composition exhibits a photocatalytic effect under ultraviolet light irradiation, thereby enhancing antibacterial and antiviral performance. Examples of semiconductors capable of generating electron-hole pairs under visible light include oxides such as tungsten oxide, bismuth oxide, iron oxide, nickel oxide, cobalt oxide, bismuth vanadate, and calcium iron ferrite; nitrides such as tantalum nitride; sulfides such as cadmium sulfide, zinc sulfide, indium sulfide, tin sulfide, and lead sulfide; selenides, tellurides, and phosphides. Adding such semiconductors to the present composition exhibits a photocatalytic effect under visible light irradiation, thereby more effectively enhancing antibacterial and antiviral performance.
[0036] As organic compounds capable of generating electron-hole pairs upon photoexcitation, cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)ruthenium(II) (hereinafter also referred to as "N3"), cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)ruthenium(II) bis-TBA salt (hereinafter also referred to as "N719"), cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)ruthenium(II) tetra-TBA salt (hereinafter also referred to as "N712"), tri(thiocyanato)-(4, Examples include ruthenium-based sensitizing dyes such as tris-tetrabutylammonium salt of 4',4''-tricarboxy-2,2':6',2''-terpyridine)ruthenium (hereinafter also referred to as "N749"), mono-tetrabutylammonium salt of cis-di(thiocyanato)-(2,2'-bipyridyl-4,4'-dicarboxylic acid)(4,4'-bis(5'-hexylthio-5-(2,2'-bithienyl))bipyridyl)ruthenium(II) (hereinafter also referred to as "black dye"), and C106; and iridium-based sensitizing dyes such as tris(2-pyridylphenyl)iridium(III). Furthermore, various organic sensitizing dyes such as coumarin-based, polyene-based, cyanine-based, hemicyanine-based, thiophene-based, indoline-based, xanthene-based, carbazole-based, perylene-based, porphyrin-based, phthalocyanine-based, merocyanine-based, catechol-based, azo-based, azine-based, and squarylium-based dyes are also suitable. Donor-acceptor composite sensitizing dyes that combine these sensitizing dyes may also be used. The dyes may be used alone or in combination of two or more. The dye preferably includes at least one of N3, N719, N712, and C106.
[0037] (Liquid antibacterial and antiviral composition) The present composition can be made into a solution, dispersion, or slurry by adding a solvent. The solvent can be an aqueous solvent or an organic solvent, or a mixture of these. The solvent can be used alone or in combination of two or more. Specific examples of the solvent include the aforementioned acetonitrile, methanol, and N,N-dimethylformamide, as well as various other solvents. For example, alcohol-based solvents such as water, ethanol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol, nitrile-based solvents such as acetonitrile, isobutyronitrile, and propylonitrile, ester-based solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate, aromatic hydrocarbon-based solvents such as toluene and xylene, aliphatic hydrocarbon-based solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol Examples of the glycol ether solvents include dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and esters thereof. As the esters, acetates are mainly selected, for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.
[0038] The composition may contain a dispersant. The dispersant may be a high molecular weight compound or a low molecular weight compound. A surfactant is suitable as the dispersant. A hydrophilizing agent or a hydrophobizing agent may also be used. In addition, various additives such as ultraviolet absorbers, antistatic agents, and flame retardants may be added as appropriate. Organic or inorganic fillers such as thermally conductive fillers may also be added.
[0039] Furthermore, this composition can be blended with antibacterial and / or antiviral components other than this borohydride-containing sheet. There is no universal antibacterial or antiviral agent that meets the requirement of not harming human health and is effective against all bacteria and viruses; instead, there are antibacterial and antiviral agents that are effective against each type of bacteria and virus. This borohydride-containing sheet exhibits antibacterial effects against both gram-negative and gram-positive bacteria, as well as antiviral effects against enveloped and non-enveloped viruses, making it an excellent antibacterial and antiviral agent. Furthermore, by combining it with other antibacterial and / or antiviral components, it is possible to increase the number of targets for antibacterial and / or antiviral effects.
[0040] The liquid or slurry composition can be suitably used, for example, as a hand sanitizer, an antibacterial and antiviral spray or disinfectant for doorknobs, or as an antibacterial and antiviral spray or disinfectant for spraying or coating on clothing, carpets, flooring, etc.
[0041] (Antibacterial and antiviral coating composition) This composition can be used as an antibacterial and antiviral composition in the form of a coating film. To form a coating film, a binder resin can be added as appropriate. The coating film can be obtained, for example, by applying the above-mentioned liquid antibacterial and antiviral composition.
[0042] The binder resin is not particularly limited, and examples thereof include acrylic resin, urethane resin, polyester resin, polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, ethylene-(meth)acrylic acid copolymer resin, ethylene-methyl(meth)acrylate copolymer resin, ethylene-ethyl(meth)acrylate copolymer resin, ethylene-vinyl alcohol copolymer resin, polyamide resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyester(meth)acrylate resin, epoxy(meth)acrylate resin, urethane(meth)acrylate resin, polyether(meth)acrylate resin, diallyl phthalate resin, nitrocellulose resin, rosin-modified malic acid resin, and the like. Examples of such resins include acrylic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, vinyl chloride, vinylidene chloride, polyamide resins, vinyl chloride-vinyl acetate copolymers, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, ethylene-vinyl alcohol resins, styrene-maleic acid resins, casein, alkyd resins, polyester (meth)acrylate resins, epoxy (meth)acrylate resins, urethane (meth)acrylate resins, polyether (meth)acrylate resins, diallyl phthalate resins, and silicone resins.
[0043] The antibacterial and antiviral composition may contain a monomer to form a binder resin during the desired production process of the composition, or a crosslinking agent may be used to form a crosslinked structure in the composition.
[0044] The antibacterial and antiviral coating composition can be used in a wide range of applications due to the high transparency of the borohydride-containing sheet. For example, it can be used as a coating film on the surface of various containers (plastic, ceramic, metal, etc.). It can also be used as an antibacterial sheet for lunch boxes, etc. It can also be used as a coating film for building materials such as flooring and wall materials.
[0045] (Antibacterial and antiviral fiber) The antibacterial and antiviral fiber of this embodiment has an antibacterial and antiviral composition fixed to the fiber. Fixation here includes adhesion, bonding, adhesion, impregnation, and other aspects. Known methods can be used for the fixing method. For example, by fixing the antibacterial and antiviral composition or the antibacterial and antiviral boron-containing sheet to a mask, a mask with antibacterial and antiviral effects can be provided. The antibacterial and antiviral composition or the antibacterial and antiviral boron-containing sheet can also be suitably applied to air conditioning equipment such as air purifiers and heating and cooling equipment, and filters for electrical appliances such as vacuum cleaners. In addition to fibers, the composition is also suitable for fixing to porous bodies and the like.
[0046] (Antibacterial and antiviral materials) The antibacterial and antiviral member of this embodiment comprises a member and an antibacterial and antiviral composition fixed to at least the surface of the member. Examples of the antibacterial and antiviral member include antibacterial and antiviral fibers fixed with the antibacterial and antiviral composition. Other examples include various containers such as Tupperware to which the antibacterial and antiviral composition is fixed. [Example]
[0047] Example 1 Based on Non-Patent Document 1, (BH) n We synthesized a borohydride-containing sheet with a two-dimensional network consisting of the above. Specifically, 500 mg of magnesium diboride (Sigma-Aldrich) and 30 mL of cation exchange resin (Organo) were stirred in acetonitrile at room temperature for 3 days. The solution was filtered through a 0.2 μm pore filter, and the filtrate was dried under reduced pressure at 80°C to obtain a yellow product (antibacterial and antiviral borohydride-containing sheet).
[0048] A transmission electron microscope photograph of the product obtained in Example 1 is shown in Figure 4. As shown in the figure, it was confirmed to be a sheet-like substance. Furthermore, the results of electron energy loss spectroscopy (EELS) of this product are shown in Figure 5, and peaks separated at 193 eV and 202 eV were confirmed. The former is attributed to a transition from the 1s orbital to the π* orbital of boron, and the latter is attributed to a transition from the 1s orbital to the σ* orbital, indicating that boron is a network consisting of two-dimensional sp2 hybrid orbitals. Figure 6 shows the infrared spectroscopy spectrum (FT-IR) of the product. As shown in the figure, there is a peak at 2500 cm -1 and 1400cm -1 BH and BHB vibrations were observed in the samples, respectively, confirming that the boron-hydride-containing sheets have a two-dimensional network.
[0049] An antibacterial and antiviral composition according to this example was obtained by dispersing 50 mg of the borohydride-containing sheet obtained in Example 1 in 2.5 mL of acetonitrile. 0.1 mL of the powder dispersion of the obtained antibacterial and antiviral composition was then dropped onto a 25 mm x 25 mm piece of glass so that 2 mg of the borohydride-containing sheet would adhere to the glass, and the glass was then dried at room temperature in nitrogen, thereby coating the borohydride-containing sheet onto the glass.
[0050] Figure 7 shows a scanning electron microscope (SEM) image of the surface of a sample in which the boron-containing sheet was coated on a glass substrate. As shown in the figure, the boron-containing sheet was uniformly coated on the substrate surface. Figure 8 shows the results of an observation of a region in the sample in which the boron-containing sheet was coated on a glass substrate, where a crack had appeared when the film dried and shrunk. Figure 9 shows the results of an enlarged observation of this cracked region. As a result, it was observed that a layered structure was stacked from the surface toward the depth. This also suggests that the boron-containing sheet has a two-dimensional network. Figure 10 shows a scanning electron microscope image (secondary electron image) of the fracture surface of a sample in which the boron-containing sheet was coated and fixed onto a glass substrate, and Figure 11 shows a backscattered electron image of the same field of view. In the backscattered electron image, lighter elements appear darker, but it was possible to observe that the boron-containing sheet, which consists of light elements, was uniformly coated on the silica glass substrate with a film thickness of approximately 1.5 μm. Figure 12 shows an image obtained by focusing on the cracks in the film cross section, and a sheet-like structure was observed inside. This also suggests that the boron-containing sheet has a two-dimensional network.
[0051] The transmittance spectrum of a sample in which the boron-containing sheet was coated on a glass substrate is shown in Figure 13. An uncoated glass plate was used as a reference. The boron-containing sheet coating film exhibited high transparency, with a transmittance of 80% or more in the visible light range of 500 nm to 800 nm, after subtracting the transmittance of the glass substrate.
[0052] Antiviral evaluation was performed with reference to JIS R 1756 and ISO 21702.
[0053] Figure 14 shows the results of an investigation into the antiviral activity of the antibacterial and antiviral composition of Example 1 against bacteriophage φ6. For comparison, the figure also shows the results of a similar measurement performed on a glass slide. From the figure, it was confirmed that the antibacterial and antiviral composition of Example 1 exhibits antiviral activity against enveloped bacteriophages.
[0054] Example 2 A sample was prepared in the same manner as in Example 1, except that bacteriophage φ6 was replaced with bacteriophage Qβ, and the antiviral effect of bacteriophage Qβ was evaluated.
[0055] Figure 15 shows the results of an investigation into the antiviral activity of the antibacterial and antiviral composition of Example 2 against bacteriophage Qβ. For comparison, the figure also shows the results of a similar measurement performed on a glass slide. As shown in the figure, it was confirmed that the antibacterial and antiviral composition of Example 2 exhibits antiviral activity against non-enveloped bacteriophages.
[0056] Example 3 Samples were prepared in the same manner as in Example 1, except that bacteriophage φ6 was replaced with E. coli, and the antibacterial activity against E. coli was evaluated in accordance with JIS Z 2801. Figure 16 shows the results of examining the antibacterial activity of the antibacterial and antiviral composition of Example 3 against E. coli. For comparison, the same figure also shows the results of a similar measurement performed on a glass slide. As shown in the figure, it was confirmed that the composition exhibited antibacterial activity against E. coli. This suggests that the composition has antibacterial activity against gram-negative bacteria.
[0057] Example 4 Samples were prepared in the same manner as in Example 1, except that bacteriophage φ6 was replaced with Staphylococcus aureus, and the antibacterial activity against Staphylococcus aureus was evaluated in accordance with JIS Z 2801. Figure 17 shows the results of examining the antibacterial activity of the antibacterial and antiviral composition of Example 4 against Staphylococcus aureus. For comparison, the same figure also shows the results of a similar measurement performed on a glass slide. As shown in the figure, it was confirmed that the composition exhibited antibacterial activity against Staphylococcus aureus. This suggests that the composition has antibacterial activity against gram-positive bacteria.
[0058] Example 5 A glass sheet coated with 2 mg of borohydride was placed in a glove box adjusted to a humidity of approximately 10%. 9One mL of pfu / mL bacteriophage Qβ was sprayed onto a glass surface coated with a borohydride-containing sheet by agitating the air with a fan inside the glove box. The glass sample was then removed from the glove box and placed in an environment similar to ISO 21702, at 25°C and approximately 90% humidity, and the infectivity titer of bacteriophage Qβ was measured over time. As shown in Figure 18, the antibacterial and antiviral composition demonstrated antiviral activity against non-enveloped bacteriophages, even in an environment simulating viral droplets.
Claims
1. (BH) n (n≧4, where n is an integer)
2. An antibacterial and / or antiviral composition comprising the borohydride-containing sheet according to claim 1.
3. 3. The composition according to claim 2, further comprising an antibacterial and / or antiviral material comprising at least one of a metal and a metal oxide.
4. 4. The composition according to claim 2, comprising at least one of a semiconductor and an organic compound capable of generating electron-hole pairs upon photoexcitation.
5. 5. The composition according to claim 2, further comprising a resin.
6. 6. The composition according to claim 2, further comprising a solvent.
7. The components and An antibacterial and / or antiviral member comprising the composition according to any one of claims 2 to 6 fixed to at least the surface of the member.
8. 8. The member according to claim 7, wherein the composition fixed to the member has a transmittance of 80% or more in the visible light region.
Citation Information
Patent Citations
Antibacterial deodorant and its manufacturing method
JP2005253547A
Antibacterial deodorant and its manufacturing method
JP2009082572A
Hydrogen generation method, hydrogen generation system, and fuel cell system
JP2019218251A
Sheet containing two-dimensional borohydride and production method for sheet containing two-dimensional boron compound
WO2018074518A1
Antibacterial / antiviral composition
WO2019045110A1