WO2022138456A1 - ウイルス不活化液状剤およびウイルス不活化物品 - Google Patents

ウイルス不活化液状剤およびウイルス不活化物品 Download PDF

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Publication number
WO2022138456A1
WO2022138456A1 PCT/JP2021/046578 JP2021046578W WO2022138456A1 WO 2022138456 A1 WO2022138456 A1 WO 2022138456A1 JP 2021046578 W JP2021046578 W JP 2021046578W WO 2022138456 A1 WO2022138456 A1 WO 2022138456A1
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Prior art keywords
virus
particles
mxene
layer
liquid agent
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PCT/JP2021/046578
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English (en)
French (fr)
Japanese (ja)
Inventor
佑介 小河
武志 部田
一太朗 岡村
リー コーブ，ジェラルド
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2022571383A priority Critical patent/JP7632484B2/ja
Priority to CN202180085839.8A priority patent/CN116615100B/zh
Publication of WO2022138456A1 publication Critical patent/WO2022138456A1/ja
Priority to US18/337,547 priority patent/US20240215586A1/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • This disclosure relates to virus inactivated liquid agents and virus inactivated articles.
  • Patent Document 1 silver is used as an active ingredient of an antibacterial agent, and an antibacterial layer containing the antibacterial agent and a binder (the water contact angle of a single binder is 20 ° or less) is arranged on a substrate.
  • Antibacterial sheets are disclosed.
  • Patent Document 1 describes that as an antibacterial agent, an antibacterial agent that exerts a bactericidal effect against pathogenic bacteria such as Staphylococcus aureus and Escherichia coli is preferably used.
  • the virus inactivating liquid agent is known to contain alcohol such as ethanol and 2-propanol as an active ingredient.
  • the WHO World Health Organization
  • the WHO recommends a prescription as a hand sanitizer with an alcohol concentration of 80% by volume ethanol or 75% by volume 2-propanol.
  • the effect of virus inactivation can be obtained even with a prescription having an alcohol concentration lower than this.
  • the virus inactivating effect can be obtained by prescribing the concentration of ethanol or 2-propanol to 30% by volume with respect to SARS-CoV-2 (so-called "new coronavirus"). It has been reported.
  • MXene has been attracting attention as a new material.
  • MXene is a kind of so-called two-dimensional material, and is a layered material having the form of one or a plurality of layers as described later.
  • MXene has the form of particles of such layered material, which may include powders, flakes, nanosheets, and the like.
  • Patent Document 2 discloses an antimicrobial agent containing MXene and an antibacterial membrane in which such an antibacterial agent is coated on a substrate of polyvinylidene fluoride (PVDF). Patent Document 2 describes that such an antibacterial agent has an antibacterial effect against each bacterium of Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis).
  • PVDF polyvinylidene fluoride
  • bacteria are unicellular organisms, have micron-order sizes, and are capable of self-propagation.
  • viruses are composed of nucleic acids (genes) and capsids, and optionally envelopes, have a size on the order of nanometers, are unable to self-proliferate, and parasitize cells (hosts) to multiply.
  • bacteria and viruses are quite different, at least in terms of structure, size and growth mechanism. Even if a substance exhibits an antibacterial effect, it cannot be determined by itself whether or not the substance exhibits a virus inactivating effect.
  • Patent Documents 1 and 2 make no mention of viruses.
  • the antibacterial property can be evaluated according to JIS Z 2801 as described in Patent Document 1, for example.
  • the virus inactivating ability can be evaluated by the TCID 50 method, for example, as described in Non-Patent Document 1, although there is no specific standard.
  • the purpose of the present disclosure is to provide a novel virus inactivating liquid agent and a virus inactivating article.
  • MXene has a virus inactivating ability, and have completed the present disclosure.
  • a virus inactivating liquid agent comprising a liquid medium and particles of a layered material comprising one or more layers.
  • the layer has the following formula: M m X n (In the formula, M is at least one group 3, 4, 5, 6, 7 metal, and X is a carbon atom, a nitrogen atom or a combination thereof, n is 1 or more and 4 or less, m is greater than n and less than or equal to 5)
  • T is at least one selected from the group consisting of hydroxyl groups, fluorine atoms, chlorine atoms and oxygen atoms).
  • the MmXn may be Ti 3 C 2 .
  • the average thickness of the particles may be 10 nm or less.
  • the liquid medium may contain at least one of water and alcohol.
  • the virus inactivating liquid agent further comprises at least one additive selected from the group consisting of dispersants, binders, antioxidants, viscosity modifiers and fragrances. obtain.
  • the content of the particles in the virus inactivating liquid agent may be 0.5 mg / mL or more and 100 mg / mL or less.
  • the pH of the liquid medium may be 2.7 or more and 7.0 or less.
  • the Li content in the particles may be 20 mass ppm or less.
  • the total content of chlorine and bromine in the particles may be 1500 mass ppm or less.
  • the particles may carry at least one of a metal and a metal oxide.
  • the particles may carry titanium oxide.
  • the virus inactivated layer comprises a virus inactivated layer disposed on the substrate, and the virus inactivated layer contains particles of a layered material containing one or more layers.
  • the layer has the following formula: M m X n (In the formula, M is at least one group 3, 4, 5, 6, 7 metal, and X is a carbon atom, a nitrogen atom or a combination thereof, n is 1 or more and 4 or less, m is greater than n and less than or equal to 5)
  • M is at least one group 3, 4, 5, 6, 7 metal
  • X is a carbon atom, a nitrogen atom or a combination thereof, n is 1 or more and 4 or less, m is greater than n and less than or equal to 5
  • T is at least one selected from the group consisting of hydroxyl groups, fluorine atoms, chlorine atoms and oxygen atoms.
  • the substrate may be selected from the group consisting of filters, masks, face shields, bandages, gloves, gowns, touch panels, displays, films and seals. ..
  • the MmXn may be Ti 3 C 2 .
  • the average thickness of the particles may be 10 nm or less.
  • the virus inactivated article may further comprise at least one additive selected from the group consisting of dispersants, binders, antioxidants, viscosity modifiers and fragrances. ..
  • the Li content in the particles may be 20 mass ppm or less.
  • the total content of chlorine and bromine in the particles may be 1500 mass ppm or less.
  • the particles may carry at least one of a metal and a metal oxide.
  • the particles may carry titanium oxide.
  • the virus inactivating liquid agent and the virus inactivating layer of the virus inactivating article contain particles of a predetermined layered material (also referred to as "MXene” herein), whereby the virus. Can be inactivated. Therefore, according to the present disclosure, a novel virus inactivating liquid agent and a virus inactivating article are provided.
  • FIG. 6 is a schematic schematic cross-sectional view showing MXene, a layered material that can be used in one embodiment of the present disclosure, where (a) shows a single layer MXene and (b) is a multi-layer (exemplarily two-layer) MXene. show. It is a figure explaining the virus inactivated article in one Embodiment of this disclosure, (a) shows the schematic schematic cross-sectional view of the virus inactivated article, (b) is the virus inactivated layer in the virus inactivated article. A schematic perspective view of the layered material is shown.
  • Example 2 is an SEM photograph showing that partial oxidation is proceeding in the heat treatment (oxidation treatment) of Example 2, (a) is an SEM photograph of solid content (particles) before treatment, and (b) is treatment. It is an SEM photograph of the later solid content (particle).
  • Embodiment 1 Virus inactivating liquid agent
  • the virus inactivating liquid agent in one embodiment of the present disclosure will be described in detail, but the present disclosure is not limited to such an embodiment.
  • the virus inactivating liquid agent of the present embodiment contains a liquid medium and particles of a predetermined layered material.
  • the predetermined layered material that can be used in this embodiment is MXene and is defined as follows: A layered material comprising one or more layers, wherein the layer has the following formula: M m X n (In the formula, M is at least one group 3, 4, 5, 6, 7 metal, so-called early transition metals such as Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and It may contain at least one selected from the group consisting of Mn.
  • the layer body represented by may have a crystal lattice in which each X is located in an octahedral array of M) and the surface of the layer body (more specifically, facing each other of the layer body).
  • a layered material containing a modification or termination T (T is at least one selected from the group consisting of hydroxyl groups, fluorine atoms, chlorine atoms and oxygen atoms) present on at least one of the two surfaces.
  • n can be 1, 2, 3 or 4, but is not limited to this.
  • M is preferably at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and Mn, and from Ti, V, Cr and Mo. More preferably, it is at least one selected from the group.
  • M can be titanium or vanadium and X can be a carbon atom or a nitrogen atom.
  • the MAX phase is Ti 3 AlC 2 and MXene is Ti 3 C 2 T s (in other words, M is Ti, X is C, n is 2 and m is 3). Is). That is, the above equation: Mm Xn is Ti 3 C 2 .
  • MXene particles are synthesized by selectively etching (removing and optionally layering) A atoms (and optionally a part of M atoms) from the MAX phase. be able to.
  • the MAX phase is as follows: M m AX n (In the formula, M, X, n and m are as described above, A is at least one group 12th, 13th, 14th, 15th and 16th element, usually a group A element, representatively.
  • Is a group IIIA and a group IVA may include at least one selected from the group consisting of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, S and Cd.
  • a layer composed of A atoms is located between two layers represented by and represented by Mm Xn (each X may have a crystal lattice located in an octahedral array of M ). It has a crystal structure.
  • Mm Xn Mm Xn
  • a atom layer a layer of A atoms
  • the A atom layer (and possibly part of the M atom) is removed by selectively etching (removing and possibly layering) the A atom (and possibly part of the M atom) from the MAX phase.
  • the surface of the exposed MmXn layer is modified with hydroxyl groups, fluorine atoms, chlorine atoms, oxygen atoms, etc. present in the etching solution (usually, but not limited to, an aqueous solution of fluoroacid is used). , Terminate such a surface.
  • the above etching is performed using an acid such as HF, HCl, HBr, HI, sulfuric acid, phosphoric acid, and nitric acid using a fluorine-based resin container.
  • an acid such as HF, HCl, HBr, HI, sulfuric acid, phosphoric acid, and nitric acid using a fluorine-based resin container.
  • it can be carried out using an etching solution containing F ⁇ , and may be, for example, a method using a mixed solution of lithium fluoride and hydrochloric acid, a method using hydrofluoric acid, or the like.
  • any suitable metal for example, Li
  • the intercalation treatment may be performed separately after the etching treatment or may be performed in combination with the etching treatment.
  • any suitable post-treatment may facilitate the layer separation of MXene (delamination, separation of multilayer MXene into single layer MXene).
  • a mechanical shaker, a vortex mixer, a homogenizer, an ultrasonic bath, or the like can be used to perform delamination processing for a predetermined time.
  • the supernatant and the precipitate are separated by a centrifuge, and the recovered supernatant can be obtained as a dispersion of single-layered MXene particles.
  • the shearing force is too large and the MXene can be destroyed.
  • MXene particles having a two-dimensional shape preferably single-layer MXene particles having a larger aspect ratio
  • a hand is used. It is preferable to apply an appropriate shearing force by shaking or an automatic shaker.
  • the MXene particles may contain a relatively small amount of residual A atom, for example, 10% by mass or less with respect to the original A atom.
  • the residual amount of A atom can be preferably 8% by mass or less, more preferably 6% by mass or less.
  • the residual amount of A atom exceeds 10% by mass, there may be no problem depending on the use and usage conditions of virus inactivation.
  • the MXene particles 10 thus synthesized are particles of a layered material containing one or more MXene layers 7a, 7b (as an example of the MXene particles 10, FIG. 1 (a), as schematically shown in FIG. ) Shows one layer of MXene particles 10a, and FIG. 1B shows two layers of MXene particles 10b, but is not limited to these examples). More specifically, the MXene layers 7a and 7b are formed on the surfaces of the layer bodies ( MmXn layer) 1a and 1b represented by MmXn and the layer bodies 1a and 1b (more specifically, in each layer). It has modifications or terminations T 3a, 5a, 3b, 5b that are present on at least one of the two surfaces facing each other.
  • the MXene layers 7a and 7b are also expressed as "MM X n T s ", and s is an arbitrary number.
  • the MXene particles 10 include a plurality of MXene layers even if the MXene layers are individually separated and exist in one layer (a single-layer structure shown in FIG. 1A, so-called single-layer MXene particles 10a). May be a laminated body (multilayer structure shown in FIG. 1B, so-called multi-layer MXene particles 10b) in which the particles are laminated apart from each other, or a mixture thereof.
  • the MXene particles 10 can be particles (which may also be referred to as powder or flakes) as an aggregate composed of single-layer MXene particles 10a and / or multilayer MXene particles 10b.
  • multi-layer MXene particles two adjacent MXene layers (eg, 7a and 7b) may not necessarily be completely separated or may be partially in contact.
  • the MXene particles 10 have as many single-layer MXene particles as possible (the content ratio of the single-layer MXene particles is high) as compared with the multilayer MXene particles.
  • the thickness of each layer (corresponding to the above MXene layers 7a and 7b) in the MXene particles is, for example, 0.8 nm or more and 5 nm or less, particularly 0.8 nm or more and 3 nm or less (corresponding to the above-mentioned MXene layers 7a and 7b).
  • the maximum dimension in a plane parallel to the layer (two-dimensional sheet surface) is, for example, 0.1 ⁇ m or more and 200 ⁇ m or less, particularly 1 ⁇ m or more and 40 ⁇ m or less.
  • the interlayer distance is, for example, 0.8 nm or more and 10 nm or less, particularly, for each laminated body. It is 0.8 nm or more and 5 nm or less, more particularly about 1 nm, and the maximum dimension in a plane (two-dimensional sheet surface) perpendicular to the stacking direction is, for example, 0.1 ⁇ m or more and 100 ⁇ m or less, particularly 1 ⁇ m or more and 20 ⁇ m or less.
  • the total number of layers in the MXene particles may be 1 or 2 or more, but is, for example, 1 or more and 100,000 or less, particularly 1,000 or more and 20,000 or less, and the thickness in the stacking direction is, for example, 0.1 ⁇ m or more. It is 200 ⁇ m or less, particularly 1 ⁇ m or more and 40 ⁇ m or less.
  • the MXene particles When the MXene particles are laminated (multilayer MXene) particles, it is preferable that the MXene particles have a small number of layers.
  • the term "small number of layers” means, for example, that the number of stacked MXene particles is 6 or less.
  • the thickness of the multilayer MXene particles having a small number of layers in the stacking direction is preferably 10 nm or less. In the present specification, this "multilayer MXene with a small number of layers" (multilayer MXene in a narrow sense) is also referred to as "small layer MXene".
  • the MXene particles are preferably particles (which may also be referred to as nanosheets), most of which are composed of single-layer MXene and / or small-layer MXene.
  • the single layer MXene and the small layer MXene may be collectively referred to as "single layer / small layer MXene”.
  • the average thickness of MXene particles is preferably 10 nm or less.
  • the average value of this thickness is more preferably 7 nm or less, and even more preferably 5 nm or less.
  • the lower limit of the thickness of the MXene particles can be 1.0 nm. Therefore, the average value of the thickness of MXene particles can be 1 nm or more.
  • the proportion of particles (single-layer MXene particles and / or small-layer MXene particles) having a thickness of 10 nm or less in the stacking direction in the entire MXene particles is preferably 90% by volume or more, more preferably. Is 95% by volume or more.
  • these dimensions described above are number average dimensions (for example, at least 40 number averages) or X-rays based on photographs of a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an interatomic force microscope (AFM). It is obtained as the distance in the real space calculated from the position on the inverted lattice space of the (002) plane measured by the diffraction (XRD) method.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • AFM interatomic force microscope
  • the liquid medium may be an aqueous medium.
  • the aqueous medium is typically water, and in some cases, contains other liquid substances in a relatively small amount (for example, 30% by mass or less, preferably 20% by mass or less based on the whole aqueous medium) in addition to water. May be good.
  • the liquid medium can be understood as a dispersion medium capable of dispersing MXene particles. Solutes such as ions may be dissolved in the liquid medium.
  • the liquid medium may contain at least one of water and alcohol.
  • the liquid medium is preferably water or a mixture of water and alcohol.
  • the alcohol is not particularly limited, but may be, for example, methanol, ethanol, propanol (1-propanol, 2-propanol) or the like.
  • an alcohol methanol, ethanol, propanol, etc.
  • the content of alcohol in the liquid medium as a whole is not particularly limited and is virus-free. It can be appropriately selected depending on the mode of use of the activating liquid agent and the like.
  • the liquid medium is preferably water, or a mixture of water and a relatively small amount of alcohol, more preferably water. preferable.
  • Water is nonflammable and does not have the flammable / flammable risk of alcohol.
  • the flash point can be within the normal temperature range and ignition, although it depends on the type and concentration of alcohol. There is a risk of ignition if there is a source.
  • the virus inactivating liquid agent of the present embodiment may further contain other components.
  • the virus inactivating liquid may further contain at least one additive selected from the group consisting of dispersants, binders, antioxidants, viscosity modifiers and fragrances.
  • Dispersants can be added to enhance the dispersibility of MXene particles in the liquid medium.
  • the binder is formed by applying a virus inactivating liquid agent to an object and drying it (at least partially removing the liquid medium), and then the MXene particles and the object (base material in the case of Embodiment 2 described later). It can be added to increase the adhesion strength between the spaces or to increase the strength of the virus inactivating layer itself, which can be formed from the virus inactivating liquid.
  • Antioxidants can be added where it is desired to prevent the oxidation of MXene particles, more specifically the oxidation of the metal (M) constituting the MXene layer.
  • the viscosity modifier can be added to adjust the viscosity of the virus inactivated liquid. More specific examples of additives include polyurethane (PU), polyvinyl alcohol (PVA), polyethylenedioxythiophene (PEDOT), sodium alginate (SA), polyamide resin (eg nylon), epoxy resin, acrylic. Examples thereof include resins, sodium hexametaphosphate, polyallylamine and the like.
  • Such other components may be added / mixed at any suitable time in the process of manufacturing the virus inactivated liquid.
  • other components can be added to a mixture (typically a slurry) containing the synthesized MXene particles in a liquid medium, or to the synthesized MXene particles (typically clay or powder). Can be added with a liquid medium.
  • the virus inactivating liquid agent of the present embodiment contains MXene particles having a virus inactivating ability as an active ingredient. It is a finding uniquely obtained by the present inventors that MXene particles have a virus inactivating ability.
  • MXene particles have a modified or terminated T (T is at least one selected from the group consisting of hydroxyl groups, fluorine atoms, chlorine atoms and oxygen atoms) on the surface of the layer body represented by MmXn . However, there are sites that are charged (negative or positive) due to this configuration.
  • MXene particles can be negatively charged at the plane (two-dimensional sheet surface) portion parallel to the layer and positive at the ends of the layer of MXene particles. Can be charged.
  • viruses can also have a charge (eg, a positive charge) and are adsorbed by Coulomb force to the opposite charged (eg, negative) sites present in MXene particles. Since the MXene particles are conductive, when the virus is adsorbed on the site of the MXene particles, the virus is electrically neutralized, resulting in immediate inactivation of the virus.
  • MXene particles inactivate a virus is fundamentally different from the mechanism by which MXene particles exhibit an antibacterial effect (suppress the growth of bacteria).
  • Bacteria have a size similar to or larger than MXene particles. Therefore, the bacterium is surrounded by a plurality of MXene particles (rather than being adsorbed by the MXene particles like a virus). In such a state, the effect of a specific site of MXene particles on bacteria is very small (compared to the effect on viruses).
  • bacteria have a cell wall and a cell membrane, they are not unable to grow immediately by being surrounded by a plurality of MXene particles, but are gradually suppressed from growing by inhibiting life-sustaining activities such as nutrient intake. ..
  • the MXene particles are preferably single-layer / small-layer MXene particles, and the average thickness of the MXene particles is preferably 10 nm or less.
  • the virus is not particularly limited.
  • the virus can be composed of nucleic acids (genes) and capsids, and optionally envelopes, and can generally have a size on the order of nanometers, eg, tens to hundreds of nm.
  • enveloped viruses viruses with envelopes
  • examples of enveloped viruses include SARS-CoV-2 (so-called "new corona virus"), influenza virus, herpes virus, ruin virus, hepatitis B virus, hepatitis C virus, AIDS virus, etc.
  • non-enveloped viruses include norovirus, rotavirus, poliovirus, adenovirus and the like. In the evaluation test of virus inactivating ability, feline calicivirus can be used as a substitute virus for norovirus.
  • virus inactivation means that the infectivity of the virus is lost, and may also be expressed as "antivirus”. Specifically, when the virus infectivity is evaluated by the TCID 50 method, if the virus infectivity is below the detection limit, it may be considered that "virus inactivation” has been achieved. It can be understood that the ability to inactivate a virus (the ability to inactivate a virus) is higher as the duration of action required for the virus infectivity to fall below the detection limit is shorter.
  • the "liquid agent” means a drug having a liquid form as a whole.
  • the liquid agent may be a dispersion (or suspension) in which MXene particles are dispersed (or suspended) in a liquid medium, and depending on the usage mode of the virus inactivating liquid agent, for example, a sprayable slurry or a dispenser. It may be a possible gel or the like.
  • the virus inactivating liquid agent of the present embodiment has a high virus inactivating ability, and can inactivate a virus in, for example, 1 minute or a short action time.
  • the virus inactivating liquid agent of the present embodiment contains MXene particles as an active ingredient, MXene particles even if the liquid medium is volatilized by being exposed to air after applying the virus inactivating liquid agent to the object. Remains on the surface of the object and can exert the effect of virus inactivation continuously for a long period of time, for example, even after 24 hours.
  • a conventional general alcohol-based disinfectant if the alcohol volatilizes, the effect of virus inactivation cannot be obtained.
  • the virus inactivating liquid agent of the present embodiment shows a sufficient virus inactivating effect even if the content of MXene particles as an active ingredient is small.
  • the content of MXene particles in the virus inactivating liquid agent can be, for example, 0.5 mg / mL or more, preferably 1 mg / mL or more, and more preferably 5 mg / mL or more.
  • the upper limit of the content of MXene particles in the virus inactivating liquid agent can be appropriately selected depending on the usage mode of the virus inactivating liquid agent and the like, but when a dilute virus inactivating liquid agent is desired, the above content is used. For example, it can be 100 mg / mL or less, 50 mg / mL or less if necessary, and 10 mg / mL or less if further required.
  • the pH of the liquid medium can be appropriately selected depending on the characteristics and applications desired for the virus inactivating liquid agent, and is, for example, 2.7 or more and 7.0 or less. obtain.
  • MXene particles can be stably dispersed in a liquid medium, and aggregation and / or sedimentation of MXene particles can be prevented or reduced.
  • Dispersion stability is the use of a virus inactivating liquid (applying to an object) and / or the desired virus inactivating effect of the virus inactivating liquid (or virus inactivation formed with it). It is important to obtain evenly over the entire layer.
  • the pH of the liquid medium is preferably 2.7 or more and 6.0 or less.
  • the pH of the liquid medium is preferably 3.0 or more and 5.0 or less.
  • the effect of virus inactivation can be continuously exerted for a longer period of time.
  • the present disclosure is not bound by any theory, it is considered that the oxidation of MXene particles is stabilized in the pH range of 3.0 or more and 5.0 or less, whereby the above-mentioned effects can be obtained.
  • MXene particles can undergo hydrolysis from the ends of the MXene layer and can form oxides of the metals (M) that make up the MXene layer (eg, Ti 3 C 2 T s ).
  • MXene particles represented by, TiO 2 can be produced, and CH 4 and / or amorphous carbon can be produced as a by-product). That is, the MXene particles are chemically decomposed in the portion where the oxidation has occurred without maintaining the MmXn of the layer body, and are coated with the oxide of the metal ( M ) (hereinafter,). Such partial oxidation is also simply referred to as "partial oxidation"). Even if some partial oxidation occurs in the MXene particles, not all of the charged sites of the MXene particles are lost, so that the effect of virus inactivation is not significantly inactivated.
  • partial oxidation of MXene particles may occur to some extent, but the oxidation is stabilized (in other words, apparently, the oxidation does not proceed substantially). It is possible to prevent the effect of virus inactivation from being completely inactivated, and it can be exerted continuously for a longer period of time at a level sufficient for virus inactivation. Further, it is considered that the fact that the decomposition of MXene particles does not apparently proceed due to the stabilization of oxidation as described above also contributes to the acquisition of high dispersion stability.
  • the pH of the liquid medium can be adjusted by the type and concentration of ions dissolved in the liquid medium. Not limited to this embodiment, but for example, depending on the treatment conditions for etching and / or intercalation (eg, acid and / or base type and charge concentration), a virus-inactivating liquid agent subsequently obtained (for example). Typically, the pH of the liquid medium in the slurry after delamination) can be adjusted. As described above, the intercalation treatment may be performed separately after the etching treatment or may be performed in combination with the etching treatment. Further, for example, when the synthesized MXene particles (typically clay or powder obtained by separating as solids after washing with water) are mixed with the liquid medium, the pH of the liquid medium may be adjusted in advance. can.
  • a virus-inactivating liquid agent subsequently obtained (for example).
  • the pH of the liquid medium in the slurry after delamination can be adjusted.
  • the intercalation treatment may be performed separately after the etching treatment or may be performed in combination with the
  • the Li content in MXene particles is preferably 20% by mass or less. It is known that Li can affect a living body when it is present in a relatively large amount, but the virus-inactivating liquid agent according to this embodiment has a Li content of 20% by mass or less in MXene particles. Therefore, it may have high biocompatibility.
  • the lower limit of the Li content in the MXene particles is not particularly limited and may be zero.
  • the content of Li in MXene particles can be suppressed to 20% by mass or less.
  • the Li content in the MXene particles can be, for example, 1 mass ppm or more.
  • the virus inactivated liquid agent in which the Li content is suppressed can be produced, for example, by the following first production method or second production method.
  • the first method for producing a virus-inactivated liquid agent is (A) Preparing a precursor composed of the MAX phase, (B1) Using an etching solution, an etching process for removing at least a part of A atoms from the precursor is performed. (C) Performing a Li intercalation treatment including a step of mixing and stirring the etched product obtained by the etching treatment and the Li-containing compound. (D) A delamination treatment including a step of centrifuging the Li intercalation-treated product obtained by the Li intercalation treatment, discarding the supernatant liquid, and then washing the remaining precipitate with water is performed.
  • Performing an acid treatment which comprises a step of mixing and stirring the delamination-treated product obtained by the delamination treatment and an acid solution.
  • the acid-treated product obtained by acid treatment is washed with water to obtain MXene particles, and
  • the obtained MXene particles are mixed with a liquid medium to obtain a virus-inactivated liquid agent. Including that.
  • a virus inactivating liquid agent having a Li content of 0.0020% by mass (20% by mass) or less in MXene particles can be produced.
  • the second method for producing a virus-inactivated liquid agent is (A) Preparing a precursor composed of the MAX phase, (B2) Etching at least a part of A atoms from the precursor using an etching solution containing a Li-containing compound, and performing Li intercalation treatment. (D) The step of centrifuging the treated product obtained by the etching and Li intercalation treatment (etching + Li intercalation), discarding the supernatant liquid, and then washing the remaining precipitate with water is included. Performing lamination processing, (E) Performing an acid treatment, which comprises a step of mixing and stirring the delamination-treated product obtained by the delamination treatment and an acid solution.
  • the acid-treated product obtained by acid treatment is washed with water to obtain MXene particles, and (g) the obtained MXene particles are mixed with a liquid medium to obtain a virus-inactivated liquid agent. Including that.
  • a virus inactivating liquid agent having a Li content of 0.0020% by mass (20% by mass) or less in MXene particles can be produced.
  • a precursor composed of the MAX phase is prepared.
  • the MAX phase is as described above.
  • the precursor may contain trace impurities inevitably mixed in addition to the MAX phase.
  • an etching process is performed in which at least a part of A atoms is removed from the precursor using an etching solution.
  • the etching treatment conditions are not particularly limited, and known conditions can be adopted.
  • Etching can be carried out using an etching solution containing F ⁇ , for example, a method using fluorine, a method using a mixed solution of lithium fluoride and hydrochloric acid, and an etching solution further containing phosphoric acid or the like.
  • the method that was used is mentioned. Examples of these methods include a method using a mixed solution with pure water as a solvent.
  • Examples of the etched product obtained by the above etching treatment include a slurry.
  • Step (c) A Li intercalation treatment including a step of mixing and stirring the etched product obtained by the etching treatment and the Li-containing compound is performed.
  • Li-containing compound examples include metal compounds containing Li ions.
  • the metal compound containing Li ion an ionic compound in which Li ion and cation are bonded can be used. Examples thereof include iodide, phosphates, sulfides including sulfates, nitrates, acetates and carboxylates of Li ions.
  • the content of the Li-containing compound in the intercalation treatment formulation is preferably 0.001% by mass or more.
  • the content is more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more.
  • the content of the Li-containing compound is preferably 10% by mass or less, more preferably 1% by mass or less.
  • step (c) for example, the slurry obtained by the etching treatment in the above step (b1) is washed by repeating centrifugation-removal of the supernatant liquid-adding pure water to the remaining precipitate-recentrifugation.
  • the Moisture Medium Clay of MXene may be subjected to an intercalation treatment as an etching treated product.
  • the specific method of the intercalation treatment is not particularly limited, and examples thereof include mixing a Li-containing compound with the above-mentioned MXene water medium clay and stirring at room temperature.
  • the etching treatment of the precursor and the Li intercalation treatment are performed together.
  • ⁇ Process (b2) In the second production method, at least a part of A atom (and a part of M atom in some cases) is etched (removed and optionally layer-separated) from the precursor using an etching solution containing a Li-containing compound. , Li etching processing is performed.
  • step (b2) Li ions are inserted between the layers of the MmXn layer during etching (removal and optionally layer separation) of at least some A atoms (and possibly some M atoms) from the MAX phase. Li intercalation processing is performed.
  • the content of the Li-containing compound in the etching solution is preferably 0.001% by mass or more.
  • the content is more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more.
  • the content of the Li-containing compound in the etching solution is preferably 10% by mass or less, more preferably 1% by mass or less.
  • the etching solution in the step (b2) may contain a Li-containing compound, and other configurations of the etching solution are not particularly limited, and known conditions can be adopted.
  • it can be carried out using an etching solution further containing F ⁇ , for example, a method using hydrofluoric acid, a method using a mixed solution of lithium fluoride and hydrochloric acid, and further.
  • Examples thereof include a method using an etching solution containing phosphoric acid and the like. Examples of these methods include a method using a mixed solution with pure water as a solvent.
  • Examples of the etched product obtained by the above etching treatment include a slurry.
  • Step (d) Centrifuge the Li intercalation-treated product obtained by the Li intercalation treatment in the first manufacturing method, or the (etching + Li intercalation) treated product obtained by the etching and Li intercalation treatment in the second manufacturing method.
  • a delamination treatment is performed, which comprises the step of separating, discarding the supernatant and then washing the remaining precipitate with water.
  • the conditions for the delamination process are not particularly limited and can be performed by a known method. For example, the method shown below may be used.
  • the supernatant may be centrifuged, the supernatant after centrifugation may be discarded, and a single-layer / small-layer MXene-containing clay before acid treatment may be obtained as a delamination-treated product.
  • a step of mixing and stirring a delamination-treated product (single-layer / small-layer MXene-containing supernatant liquid or single-layer / small-layer MXene-containing clay) obtained by the delamination treatment and an acid solution is included.
  • Perform acid treatment The acid used for the acid treatment is not limited, and for example, an inorganic acid such as a mineral acid and / or an organic acid can be used.
  • the acid is preferably only an inorganic acid or a mixed acid of an inorganic acid and an organic acid.
  • the acid is more preferably only an inorganic acid.
  • the inorganic acid for example, one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid and the like can be used. It is preferably one or more of hydrochloric acid and sulfuric acid.
  • the organic acid include acetic acid, citric acid, oxalic acid, benzoic acid, and sorbic acid.
  • the concentration of the acid solution to be mixed with the delamination-treated product may be adjusted according to the amount and concentration of the delamination-treated product to be treated.
  • the delamination-treated product and the acid solution are mixed and stirred.
  • the stirring method include stirring using a handshake, an automatic shaker, a share mixer, a pot mill, and the like.
  • the degree of stirring such as the stirring speed and the stirring time may be adjusted according to the amount and concentration of the delamination-treated product to be treated.
  • the acid solution When the above acid solution is mixed and stirred, it does not matter whether it is heated or not.
  • the acid solution may be mixed and stirred without heating, or may be stirred while heating within a range where the liquid temperature is 80 ° C. or lower.
  • centrifugation can be performed to remove the supernatant liquid, and an acid-treated product can be obtained as a slurry.
  • the operation of mixing with the acid solution and stirring may be performed at least once. From the viewpoint of reducing the Li content in the MXene particles, it is preferable to perform the operation of mixing with the acid solution and stirring the mixture twice or more, for example, 10 times or less.
  • the operation of mixing with the acid solution and stirring is performed a plurality of times, (i) the acid solution (with the delamination-treated product or the remaining precipitate obtained in (iii) below) is mixed and stirred.
  • the steps (i) to (iii) of (ii) centrifuging the agitated material and (iii) discarding the supernatant after centrifugation may be performed twice or more, for example, 10 times or less.
  • the pH of the acid-treated product obtained by the acid treatment is preferably 2.5 or less.
  • the pH is more preferably 2.0 or less, still more preferably 1.5 or less, still more preferably 1.2 or less.
  • the lower limit of pH is not particularly limited, but is about 1.0.
  • the acid-treated product obtained by acid treatment is washed with water to obtain MXene particles.
  • the amount of water to be mixed with the acid-treated product and the cleaning method are not particularly limited.
  • water may be added for stirring, centrifugation and the like.
  • the stirring method include stirring using a handshake, an automatic shaker, a share mixer, a pot mill, and the like.
  • the degree of stirring such as the stirring speed and the stirring time may be adjusted according to the amount and concentration of the acid-treated product to be treated.
  • the washing with water may be performed at least once. It is preferable to wash with water a plurality of times.
  • ⁇ Process (g) The MXene particles obtained as described above are mixed with a liquid medium to obtain a virus-inactivated liquid agent.
  • the details of the liquid medium are as described above.
  • the liquid medium is water
  • the water used in the washing in the step (f) (the water used in the final washing when the washing with water is performed twice or more) is the liquid medium used in the step (g). It may also serve as.
  • the pH of the liquid medium can be 2.7 or more and 7.0 or less, preferably 2.7 or more and 6.0 or less, more preferably 3.0, as described above. It is 5.0 or more and 5.0 or less.
  • a virus inactivating liquid agent having a Li content of 20% by mass or less in MXene particles can be produced.
  • the Li content in MXene particles can be measured by elemental (atomic) analysis such as inductively coupled plasma emission spectroscopy (ICP-AES) or X-ray fluorescence spectrometry (XRF).
  • elemental analysis such as inductively coupled plasma emission spectroscopy (ICP-AES) or X-ray fluorescence spectrometry (XRF).
  • the total content of chlorine and bromine in MXene particles is preferably 1500 mass ppm or less.
  • the content of chlorine and bromine among halogens is suppressed to a certain level or less, that is, so-called "halogen-free". Since the virus inactivating liquid agent of the present embodiment suppresses the total content of chlorine and bromine in MXene particles, it can be suitably used for applications requiring halogen-free.
  • the total content of chlorine and bromine is preferably 900 mass ppm or less, and most preferably 0 mass ppm or less.
  • the lower limit of the total content of chlorine and bromine in MXene particles is not particularly limited and may be zero.
  • a virus inactivated liquid agent in which the total content of chlorine and bromine is suppressed can be produced, for example, by the following third production method.
  • the third method for producing a virus-inactivated liquid agent is (A) Preparing a precursor composed of the MAX phase, (B3) Etching of A atom from the precursor using an etching solution, wherein the etching solution has an H 3 PO 4 concentration of 5.5 M or more, a HI concentration of 5.0 M or more, and H 2 It comprises satisfying at least one selected from the group consisting of SO 4 concentration of 5.0 M or more, and (g3) mixing the obtained MXene particles with a liquid medium to obtain a virus inactivating liquid agent.
  • a precursor composed of the MAX phase is prepared. This step is the same as the first manufacturing method and the second manufacturing method.
  • An etching solution is used to etch (remove and optionally layer) A atoms (and possibly some M atoms) from the precursor.
  • an etching solution satisfying at least one selected from the group consisting of an H 3 PO 4 concentration of 5.5 M or more, a HI concentration of 5.0 M or more, and an H 2 SO 4 concentration of 5.0 M or more. Use.
  • step (b3) the A atom (and optionally a portion of the M atom) from the MAX phase is present in the etching solution on the surface of the exposed MmXn layer after etching (removal and possibly layer separation).
  • At least one selected from the group consisting of PO 4 3- , I, and SO 4-2 is adsorbed and bound. It is considered that when these PO 4 3- and the like are adsorbed on the surface of the Mm Xn layer, the distance between the MXene layers is widened due to steric hindrance, and the van der Waals force between the Mm Xn layers is weakened.
  • the MmXn layer can be easily made into a single layer without applying strong shear to the multi-layered MmXn layer. Further, since it is not necessary to apply strong shear, the fracture of the MmXn layer in the plane is suppressed, and as a result, a single MmXn layer having a large two-dimensional surface can be obtained.
  • the above etching solution does not contain hydrochloric acid, that is, does not contain chlorine atoms.
  • chlorine atom-free in the etching solution means that the chlorine concentration in the etching solution is 10 mass ppm or less when measured by, for example, combustion-ion chromatography.
  • the etching solution does not contain hydrochloric acid and may contain at least one of the above-mentioned predetermined amounts of H 3 PO 4 , etc., and other configurations of the etching solution are not particularly limited, and known conditions may be adopted. can. For example, it can be carried out using an etching solution further containing F ⁇ , and examples thereof include a method using a mixed solution of hydrofluoric acid (HF) and at least one of the above-mentioned predetermined amounts of H 3 PO 4 .
  • the concentration of hydrofluoric acid in this mixed solution may be 1% by mass or more and 50% by mass or less.
  • the H 3 PO 4 concentration is 13.2 M or less, and the HI concentration. Can be 6.5 M or less, and the H 2 SO 4 concentration can be 16.5 M or less.
  • the process after the etching is not particularly limited, and MXene particles can be obtained by a known method.
  • the slurry after etching may be washed by repeating centrifugation-removal of supernatant liquid-addition of pure water to the remaining precipitate-centrifugation again, and then performing intercalation treatment and delamination treatment. ..
  • the above-mentioned steps (c) to (f) may be carried out by the second manufacturing method.
  • a virus inactivating liquid agent having a total content of chlorine and bromine in MXene particles of 1500 mass ppm or less can be produced.
  • the Li content in the MXene particles can be reduced to 20% by mass or less.
  • Each content of chlorine and bromine in MXene particles can be measured by combustion-ion chromatography.
  • ultrasonic treatment is not performed as delamination after etching. Since no ultrasonic treatment is performed, particle destruction is unlikely to occur, and MXene particles containing a single-layer / small-layer MXene having a large two-dimensional surface can be obtained.
  • MXene particles may carry at least one of a metal and a metal oxide. This makes it possible to improve the virus inactivating ability and / or add other functions (antibacterial property, catalytic function, etc.) depending on the metal and / or metal oxide to be carried.
  • the metal constituting the metal or the metal oxide may be, for example, Ag.
  • the MXene particles may carry the metal particles.
  • MXene particles carry a metal oxide
  • the metal (M) constituting the MXene layer is partially oxidized to the MXene particles (the above-mentioned partial oxidation).
  • a metal oxide (generated by) may be carried.
  • MXene particles carry metals and / or metal oxides means that in the XRD profile obtained by subjecting the particles to X-ray diffraction (XRD) measurements, MXene-specific peaks and metals and / or metals. It can be confirmed by detecting the peak peculiar to the oxide.
  • XRD X-ray diffraction
  • the detection of peaks specific to metals and / or metal oxides in the XRD profile is due to the content of the metal and / or metal oxides (overall standard for metal and / or metal oxide-bearing MXene particles). It means that it is mass% or more.
  • MXene particles may carry titanium oxide. By supporting titanium oxide on the MXene particles, it becomes possible to add antibacterial properties to the virus inactivating liquid agent.
  • the MXene particles may be supported by titanium oxide particles, or the Ti constituting the MXene layer may be partially oxidized to cause the MXene particles to be supported by titanium oxide (produced by the above partial oxidation). ..
  • the present embodiment is not limited, but specifically, the above partial oxidation is carried out in the presence of oxygen, for example, at 60 to 80 ° C. (typically about 70 ° C.) for 50 to 250 hours (representative). It can be carried out by heating for 70 to 200 hours).
  • Titanium oxide is not particularly limited, but may be anatase type.
  • the MXene particles are Ti 3 C 2 T s
  • the Ti contained therein is partially oxidized to generate TIO 2
  • the TIO 2 -supported Ti 3 C 2 T s particles are obtained by X-ray diffraction of the particles.
  • partial oxidation in MXene particles progresses excessively, it is not desirable from the viewpoint of dispersion stability, but as described above, even if partial oxidation occurs to some extent, the effect of virus inactivation is not significantly inactivated.
  • partial oxidation may be appropriately promoted to achieve both the virus inactivating effect and the antibacterial property.
  • the virus inactivated article 20 of the present embodiment is Base material 11 and It includes a virus inactivating layer 13 arranged on a substrate 11, and the virus inactivating layer 13 contains particles 10 of a predetermined layered material (MXene).
  • MXene a predetermined layered material
  • the substrate 11 can be any suitable article that may be desired to be imparted with a virus inactivating function.
  • the substrate 11 can also be understood as a support that supports the virus inactivated layer 13.
  • the material and form of the base material 11 are not particularly limited.
  • the base material 11 may be composed of fibers, glass, a polymer / polymer composition (resin, plastic, etc.), ceramics, metals, and the like.
  • the substrate 11 is selected from the group consisting of filters, masks, face shields, bandages, gloves, gowns, touch panels, displays (including monitors), films (including protective films) and stickers.
  • the filter may be a filter used in an air purifier or an air conditioner, a filter (Membrane) used in a water purifier or a wastewater treatment facility, or the like.
  • Masks, face shields, bandages, gloves, gowns, touch panels, displays, films and stickers can be common. Among them, masks, face shields, bandages, gloves, gowns, touch panels, and displays can be medical ones (those used in the medical field), and are particularly preferably used when they are easily exposed to a virus.
  • Films and seals may have an adhesive layer on the opposite side of the surface on which the virus inactivated layer is placed, through which any other article or other (eg, touch panel, display, numerous humans can touch). It may be possible to attach it to a place where there is a possibility.
  • the film may not have an adhesive layer and may be, for example, a porous film.
  • the virus inactivating layer 13 can be formed by using the virus inactivating liquid agent described above in the first embodiment. More specifically, the virus inactivated article 20 of the present embodiment is (A) A virus inactivating liquid agent is applied onto the substrate 11 to form a precursor of a virus inactivating layer containing MXene particles, and (b) the precursor is dried (in other words,). , At least partially removed) to form the virus inactivated layer 13.
  • the method of applying the virus inactivating liquid agent on the base material 11 is not particularly limited, and for example, spraying, spin casting, blade method, printing, brush coating, dipping and the like can be used.
  • the above (a) and (b) may be repeated twice or more in total until the desired virus inactivated layer thickness is obtained.
  • the virus inactivating layer 13 may be composed substantially only of MXene particles 10 (and optionally residual liquid medium), but in addition to MXene particles 10 (and optionally residual liquid medium), a dispersant. , Binders, antioxidants, viscosity modifiers and fragrances may further contain at least one additive (not shown) selected from the group.
  • the MXene particles 10 are oriented as parallel as possible to the substrate surface 11a (flat). It is preferable, but not limited to, to form the virus inactivated layer 13 by being present in the state of). For example, when the surface of the substrate is not flat (the surface roughness is large), the MXene particles 10 may exist in a state of being oriented along the state of the surface of the substrate to form the virus inactivated layer 13. ..
  • the surface 11a of the base material 11 is coated with the virus inactivated layer 13.
  • the virus inactivated layer 13 may be coated on the entire surface of the substrate surface 11a or may be coated on a part of the substrate surface 11a.
  • the thickness of the virus inactivated layer 13 may vary depending on the use of the virus inactivated article 20, and may be, for example, 0.1 ⁇ m or more and 1 mm or less.
  • MXene particles can inactivate the virus by the same mechanism as described above in the first embodiment, and the effect of virus inactivation can be sustained for a long period of time. It can be demonstrated.
  • Example 1 relates to one example of the virus inactivated liquid agent described above in Embodiment 1.
  • Example 1 preparation of precursor (MAX), (2) etching of precursor, (3) cleaning, (4) delamination and (5) concentration adjustment are performed in order. This was carried out to prepare a virus inactivating liquid.
  • precursor (MAX) TiC powder, Ti powder and Al powder (all manufactured by High Purity Chemical Laboratory Co., Ltd.) are put into a ball mill containing zirconia balls at a molar ratio of 2: 1: 1. And mixed for 24 hours. The obtained mixed powder was calcined at 1350 ° C. for 2 hours in an Ar atmosphere. The fired body (block) thus obtained was crushed with an end mill to a maximum size of 40 ⁇ m or less. As a result, Ti 3 AlC 2 particles were obtained as a precursor (MAX).
  • the virus inactivating liquid agent of Example 1 was prepared, which contained single-layer / small-layer MXene (Ti 3C 2T s ) particles in pure water at 5 mg / mL.
  • the pH of the liquid medium in this virus-inactivated liquid agent was 4.3. In this virus inactivating liquid agent, it was visually confirmed that the particles were well dispersed without agglomeration / sedimentation.
  • Example 2 [Evaluation: Inactivation against enveloped virus] Using the virus inactivating liquid agent obtained in Example 1 as a sample (sample), an inactivation test for the enveloped virus of this sample was performed to evaluate the virus inactivating ability. Influenza virus was used as the envelope virus. The details of the test are as follows.
  • Viruses used in the test Test virus Influenza A virus (H1N1) A / PR / 8/34 ATCC VR-1469 Cells used: MDCK (NBL-2) cell JCRB 9029 strain Medium used: -Cell proliferation medium Eagle MEM medium "Nissui” (1) (Nissui Pharmaceutical Co., Ltd.) supplemented with 10% fetal bovine serum was used. -Cell maintenance medium The following composition was used. Eagle MEM medium "Nissui” (1) 100 mL 10% sodium bicarbonate 14mL L-Glutamine (30g / L) 9.8mL Vitamin solution for MEM (100x) 30mL 10% albumin 20mL 0.25% Trypsin 20mL
  • the virus infectivity titer can be measured without being affected by the sample by diluting the action solution 1000 times with the cell maintenance medium.
  • the same test was performed using purified water as a control, and the virus infectivity titer was measured at the start (immediately after the start) and 1 minute, 5 minutes, 15 minutes, and 24 hours after the start.
  • TCID 50 50% tissue culture infection amount
  • the virus inactivating liquid agent (sample) of Example 1 had a virus infectivity value below the lower limit of detection within only 1 minute from the start of action, and could inactivate the virus in a short time. Was done. Furthermore, it was confirmed that the virus inactivating liquid agent (sample) of Example 1 had a virus infectivity value below the lower limit of detection even 24 hours after the start of action, and could sustainably inactivate the virus. Such a result showed that the virus inactivating liquid agent of Example 1 had a high virus inactivating ability against enveloped virus.
  • the virus inactivating liquid agent of Example 1 is considered to have a high virus inactivating ability against non-enveloped viruses.
  • Example 2 relates to a modified example of Example 1.
  • Example 2 Preparation of virus inactivated liquid agent
  • partial oxidation is carried out as an additional step, and then (5') concentration adjustment is carried out to inactivate the virus.
  • a liquid agent was prepared.
  • Example 2 First, the same operations as (1) preparation of the precursor (MAX), (2) etching of the precursor, (3) cleaning, and (4) delamination described in detail in Example 1 are carried out. A layer / small layer MXene (Ti 3 C 2 T s ) particle-containing liquid was obtained.
  • the monolayer / small layer MXene (Ti 3C 2T s ) particle-containing liquid thus obtained had a solid particle concentration of 125 mg / mL.
  • the single-layer / small-layer MXene (Ti 3 C 2 Ts) particle-containing liquid (before treatment) and the treatment liquid (after treatment) ) The solid content (particles) was collected and observed with a scanning electron microscope (SEM). The obtained SEM photograph is shown in FIG. Compared with the state before the treatment shown in FIG . 3 (a), in the state after the treatment shown in FIG. Observed) was observed. Further, the solid content (particles) was subjected to X-ray diffraction (XRD) measurement to obtain an XRD profile.
  • XRD X-ray diffraction
  • a virus-inactivated liquid agent of Example 2 was prepared, which contained single-layer / small-layer MXene (Ti 3 C 2 T s ) particles carrying TiO 2 in pure water at 5 mg / mL.
  • the pH of the liquid medium in this virus-inactivated liquid agent was 4.3. In this virus inactivating liquid agent, it was visually confirmed that the particles were well dispersed without agglomeration / sedimentation.
  • Example 2 [Evaluation: Inactivation against enveloped virus] Using the virus inactivating liquid agent obtained in Example 2 as a sample (sample), an inactivation test for the enveloped virus of this sample was carried out in the same manner as in Example 1 to evaluate the virus inactivating ability. The results obtained thereby showed that the virus inactivating liquid agent of Example 2 had a high virus inactivating ability against enveloped viruses.
  • the virus inactivating liquid agent of Example 2 is considered to have a high virus inactivating ability against non-enveloped viruses.
  • Example 3 relates to the virus inactivated article described above in the second embodiment.
  • Example 3 [Manufacturing of virus inactivated products]
  • a virus inactivating liquid agent was applied onto the substrate to form a virus inactivating layer, whereby the virus inactivating layer was arranged on the substrate.
  • Manufactured virus inactivated articles Manufactured virus inactivated articles.
  • Example 2 the same operation as in Example 1 was carried out except that the dilution with pure water was changed by adjusting the concentration in (5) above, and the single-layer / small-layer MXene (Ti 3 C 2 T s ) particles were carried out.
  • the average value of the thickness of the MXene particles was 1 nm or more and 10 nm or less, and the average size of the MXene particles in the two-dimensional sheet surface was 3 ⁇ m.
  • This virus inactivating liquid agent is a dispersion liquid in which MXene (Ti 3C 2T s ) particles are dispersed in pure water, and does not contain additives such as binders and dispersants.
  • a glass substrate whose surface was hydrophilized by UV treatment was prepared as a base material.
  • the operation of spraying the virus inactivating liquid agent prepared above on the hydrophilic surface of the glass substrate and then blowing warm air with a desiccant is repeated 30 times, and then further, in a normal pressure oven at 80 ° C. After pre-drying for 2 hours and main drying at 150 ° C. for 18 hours in a vacuum oven (drying substantially removed pure water as a liquid medium).
  • a virus inactivated layer composed of single-layer / small-layer MXene (Ti 3C 2T s ) particles was formed on the hydrophilic surface of the glass substrate.
  • the thickness of the virus inactivated layer was about 2 ⁇ m.
  • Example 3 As described above, the virus inactivated article of Example 3 in which the virus inactivated layer composed of single-layer / small-layer MXene (Ti 3 C 2 T s ) particles was arranged on a glass substrate was obtained.
  • the virus inactivating article of Example 3 is considered to have a high virus inactivating ability against enveloped viruses.
  • the virus inactivating article of Example 3 is considered to have a high virus inactivating ability against non-enveloped viruses.
  • Example 4 relates to another example of the virus inactivated liquid agent described above in Embodiment 1.
  • Example 4 (1) preparation of precursor (MAX), (2) etching of precursor, (3) cleaning after etching, (4) intercalation of Li, and (5) described in detail below. Delamination was carried out in order to prepare a virus inactivating liquid agent.
  • the supernatant was centrifuged at 4300 G for 2 hours using a centrifuge, and then the supernatant was discarded to obtain a single-layer / small-layer MXene-containing clay. 1 mg of the clay thus obtained was taken and redistributed in 10 mL of pure water.
  • a virus-inactivated liquid agent of Example 4 was prepared, which contained single-layer / small-layer MXene (Ti 3 C 2 T s ) particles in pure water at about 3 mg / mL.
  • the pH of the liquid medium in this virus-inactivated liquid agent was 2.7. In this virus inactivating liquid agent, it was visually confirmed that the particles were well dispersed without agglomeration / sedimentation.
  • Example 5 relates to a modified example of Example 4.
  • Example 5 a virus inactivating liquid agent was prepared in the same manner as in Example 4 except that the charged composition under the conditions of Li intercalation was as follows in the above (4) Li intercalation. did. ⁇ Preparation composition: MXene (Ti 3 C 2 T s ) Particle-Moisture Medium Clay: Solid Content 0.75 g LiCl 0.97g LiOH + H 2 O about 0.03g Pure water 20.00g
  • Example 5 a virus-inactivated liquid agent of Example 5 containing single-layer / small-layer MXene (Ti 3 C 2 T s ) particles in pure water at about 2 mg / mL was prepared.
  • the pH of the liquid medium in this virus-inactivated liquid agent was 6.9.
  • Example 6 relates to yet another example of the virus inactivating liquid agent described above in the first embodiment.
  • Example 6 in the above-mentioned (4) Li intercalation, the charged composition under the conditions of the Li intercalation was set as follows, and instead of the above-mentioned (5) delamination, the following (5') de-decalation was performed. Except for the fact that lamination was performed, the same procedure as in Example 4 was carried out, and then (6) acid treatment and (7) water washing were carried out in order to prepare a virus inactivating liquid agent. (Conditions for Li intercalation) ⁇ Preparation composition: MXene (Ti 3 C 2 T s ) Particle-Moisture Medium Clay: Solid Content 0.75 g LiCl 0.75g
  • Example 6 a virus-inactivated liquid agent of Example 6 containing single-layer / small-layer MXene (Ti 3 C 2 T s ) particles in pure water at about 3 mg / mL was prepared.
  • the pH of the liquid medium in this virus-inactivated liquid agent was 4.3.
  • this virus inactivating liquid agent it was visually confirmed that the particles were well dispersed without agglomeration / sedimentation.
  • MXene was liquefied by an alkaline melting method, and the Li content was measured by ICP-AES (using iCAP7400 manufactured by Thermo Fisher Scientific Co., Ltd.) using inductively coupled plasma emission spectroscopy. As a result, the Li content was 4 mass ppm.
  • Example 7 relates to yet another example of the virus inactivated liquid agent described above in Embodiment 1.
  • Example 7 (1) preparation of precursor (MAX), (2) etching of precursor, (3) cleaning after etching, (4) intercalation of Li, and (5) described in detail below. Delamination was carried out in order to prepare a virus inactivating liquid agent.
  • a virus-inactivated liquid agent of Example 7 was prepared, which contained single-layer / small-layer MXene (Ti 3 C 2 T s ) particles in pure water at about 3 mg / mL.
  • the pH of the liquid medium in this virus-inactivated liquid agent was 4.3. In this virus inactivating liquid agent, it was visually confirmed that the particles were well dispersed without agglomeration / sedimentation.
  • virus inactivating liquid agent and the virus inactivating article of the present disclosure can inactivate the virus, they can be used to prevent humans and other organisms from being infected with the virus.

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WO2023112778A1 (ja) * 2021-12-16 2023-06-22 株式会社村田製作所 ２次元粒子、導電性膜、導電性ペーストおよび複合材料

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009526828A (ja) * 2006-02-16 2009-07-23 クイーン メアリー アンド ウェストフィールド カレッジ 殺ウイルス材料
CN111905829A (zh) * 2020-09-08 2020-11-10 陈兵 一种除病毒用改性Mn掺杂PCN-222@Ti3C2光催化剂及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102373455B1 (ko) * 2015-09-24 2022-03-11 삼성전자주식회사 멕신(MXene) 나노시트 및 그 제조방법
US11202398B2 (en) * 2017-09-28 2021-12-14 Murata Manufacturing Co., Ltd. Electromagnetic shielding material and method for producing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009526828A (ja) * 2006-02-16 2009-07-23 クイーン メアリー アンド ウェストフィールド カレッジ 殺ウイルス材料
CN111905829A (zh) * 2020-09-08 2020-11-10 陈兵 一种除病毒用改性Mn掺杂PCN-222@Ti3C2光催化剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
UNAL MEHMET ALTAY; BAYRAKDAR FATMA; FUSCO LAURA; BESBINAR OMUR; SHUCK CHRISTOPHER E.; YALCIN SüLEYMAN; ERKEN MINE TURKTAS; OZ: "2D MXenes with antiviral and immunomodulatory properties: A pilot study against SARS-CoV-2", NANO TODAY, ELSEVIER, AMSTERDAM, NL, vol. 38, 18 March 2021 (2021-03-18), NL , XP086616454, ISSN: 1748-0132, DOI: 10.1016/j.nantod.2021.101136 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023112778A1 (ja) * 2021-12-16 2023-06-22 株式会社村田製作所 ２次元粒子、導電性膜、導電性ペーストおよび複合材料
CN118382599A (zh) * 2021-12-16 2024-07-23 株式会社村田制作所 二维粒子、导电性膜、导电性糊剂和复合材料

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