WO2023017834A1 - Disinfectant, disinfectant film, and disinfectant beads - Google Patents

Disinfectant, disinfectant film, and disinfectant beads Download PDF

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Publication number
WO2023017834A1
WO2023017834A1 PCT/JP2022/030526 JP2022030526W WO2023017834A1 WO 2023017834 A1 WO2023017834 A1 WO 2023017834A1 JP 2022030526 W JP2022030526 W JP 2022030526W WO 2023017834 A1 WO2023017834 A1 WO 2023017834A1
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Prior art keywords
surfactant
disinfectant
iodine
disinfecting
film
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PCT/JP2022/030526
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French (fr)
Japanese (ja)
Inventor
成和 矢野
美宗 野々村
昌敏 遠藤
千莉 寺田
貴弘 佐藤
聡 浅倉
裕之 川本
航平 柚木崎
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国立大学法人山形大学
伊勢化学工業株式会社
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Priority to JP2023541456A priority Critical patent/JPWO2023017834A1/ja
Publication of WO2023017834A1 publication Critical patent/WO2023017834A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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 containing liquids as carriers, diluents or solvents
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/18Vapour or smoke emitting compositions with delayed or sustained release
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/12Iodine, e.g. iodophors; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00Disinfectants; Antimicrobial compounds or mixtures thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • A61K33/18Iodine; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02Inorganic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/10Alcohols; Phenols; Salts thereof, e.g. glycerol; Polyethylene glycols [PEG]; Poloxamers; PEG/POE alkyl ethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/50Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
    • A61K47/69Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/08Solutions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/14Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/70Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04Antibacterial agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10Antimycotics
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12Antivirals

Definitions

  • the present invention relates to disinfectants, disinfecting films and disinfecting beads.
  • Povidone-iodine is a complex of polyvinylpyrrolidone and polyiodide ions, and disinfectants containing povidone-iodine are shipped as products at a concentration of about 10 w/v %.
  • iodine-based disinfectants include iodine tincture containing iodine and potassium iodide in ethanol, and compound iodine-glycerin containing iodine and potassium iodide in glycerin.
  • Patent Document 1 discloses a cleaning disinfectant for contact lenses containing a nonionic surfactant and iodine.
  • Patent Document 2 discloses a disinfectant containing an iodine-based bactericidal component, potassium iodide, and a zwitterionic compound.
  • An object of the present invention is to provide a novel iodine-based disinfectant, a disinfecting film and disinfecting beads containing such a disinfectant.
  • ⁇ Aspect 7>> A method for producing a disinfectant, comprising mixing in a medium such that iodine is 10 ppm or more and surfactant is 0.05 w/v% or more, wherein the surfactant is a nonionic surfactant
  • a method for producing a disinfectant comprising mixing in a medium such that iodine is 10 ppm or more and surfactant is 0.05 w/v% or more, wherein the surfactant is a nonionic surfactant
  • a method for producing a disinfectant A method for producing a disinfectant.
  • ⁇ Aspect 8>> A disinfecting film containing iodine and a surfactant in a binder resin, wherein the surfactant is a nonionic surfactant.
  • the disinfecting film according to 9. ⁇ Aspect 11>> 11.
  • a sanitizing laminate comprising: ⁇ Aspect 14>> A method for producing a disinfecting film according to aspect 10 or 11, wherein the binder resin, iodine, surfactant, and gelation accelerator are dissolved in an aqueous medium, and the resulting dissolved product is put into a mold or a substrate A method for producing an antiseptic film that is applied on top and then dried.
  • FIG. 1 shows the results of the absorbance test for each disinfectant produced in Experiment 1.
  • FIG. FIG. 2 shows the test results of the storage stability of each disinfectant produced in Experiment 2.
  • FIG. 3 shows the test results of the bactericidal performance of each disinfectant produced in Experiment 3.
  • FIG. 4 shows the results of the virus inactivation test for each disinfectant produced in Experiment 4.
  • FIG. 5 shows the results of the virus inactivation test for each disinfecting film produced in Experiment 5.
  • FIG. 6 shows an actual photograph of one example of the antiseptic film of the present invention.
  • FIG. 7 shows the results of the absorbance test and sterilization performance test of each disinfectant containing Tween 20 produced in Experiment 6.
  • FIG. 8 shows the results of the absorbance test and sterilization performance test of each disinfectant containing Tween 60 produced in Experiment 6.
  • FIG. 9 shows the absorbance test results of each disinfectant containing PEG and/or SDS produced in Experiment 6.
  • FIG. 10 shows the storage stability test results of each disinfectant containing Tween 80 produced in Experiment 7.
  • FIG. 11 shows the storage stability test results of each disinfectant containing polyoxyethylene alkyl ether produced in Experiment 7.
  • FIG. Figure 12 shows an actual photograph of one example of the disinfecting beads of the present invention.
  • the disinfectant of the present invention is a disinfectant containing 10 ppm or more of iodine and 0.05 w/v% or more of a surfactant in a medium, wherein the surfactant is a nonionic surfactant.
  • concentration and content of a component in the disinfectant mean the amount of the component added to manufacture the disinfectant.
  • unit of "ppm” means “mg/L” in this specification.
  • 95% by mass or more of the iodine added to produce the disinfectant can be complexed with a nonionic surfactant as described later.
  • the present invention is a method for producing a disinfectant, comprising mixing in a medium such that iodine is 10 ppm or more and a surfactant is 0.05 w/v% or more, wherein the surfactant is a nonionic It also relates to a method of making a disinfectant, which is a surfactant.
  • "containing 10 ppm or more of iodine” means that simple iodine is added to 10 ppm or more, and as a result of adding simple iodine, the form of iodine changes. However, the above contents are not affected.
  • the amount of iodide to be added which will be described later, is calculated separately from the amount of iodine to be added.
  • the present inventors have found that when a disinfectant contains iodine and a surfactant at a concentration above a certain level, the iodine and the surfactant are complexed, and the disinfecting effect can be exhibited while remaining in the complexed state. Found it. This was unexpected based on the prior art, which derives its disinfecting action from the presence or absence of free iodine. It has been found that this disinfectant is particularly effective in inactivating enveloped viruses such as coronaviruses and influenza viruses.
  • the disinfectant of the present invention can obtain not only a bactericidal action due to iodine cations due to free iodine, but also a disinfecting action due to a complex of iodine and a surfactant.
  • the state in which iodine and the surfactant in the disinfectant of the present invention are combined can be stably maintained for a long period of time, at least at relatively low temperatures.
  • Povidone-iodine is usually used in a diluted form, because when povidone-iodine is at a high concentration, iodine is not liberated from povidone-iodine, resulting in a lower disinfecting effect.
  • povidone-iodine is diluted from the beginning, a large amount of iodine is liberated and sublimated, resulting in a decrease in iodine, which is a sterilizing component.
  • the disinfectant of the present invention is very useful because it does not need to be diluted immediately before use and can be stored for a long period of time.
  • Iodine can be added to the disinfectant so that the weight ratio of the disinfectant is 10 ppm or more.
  • the medium is an aqueous medium
  • iodine can be mixed with a liquid containing an iodide to improve the water solubility of iodine.
  • Iodine may be, for example, 10 ppm or more, 20 ppm or more, 40 ppm or more, 50 ppm or more, 80 ppm or more, 100 ppm or more, 150 ppm or more, or 200 ppm or more, 2000 ppm or less, 1000 ppm or less, 500 ppm or less, 300 ppm or less, or 200 ppm or less. It can be included in disinfectants.
  • the content may be 10 ppm to 2000 ppm, 40 ppm to 500 ppm, or 50 ppm to 300 ppm.
  • iodide itself does not have a disinfecting effect, depending on the iodide ion concentration, the form of iodine changes to free iodine, triiodide ion, etc., and the form of iodine can affect disinfection performance. is adjusted and mixed with the disinfectant.
  • the appropriate amount of iodide to be added varies depending on the amount of iodine to be added. For example, when iodine is about 10 ppm, iodide may not be added.
  • the weight ratio of the iodide content to the iodine content may be 0 or more, 0.1 or more, 1 or more, 3 or more, 5 or more, or 7 or more, 30 or less, 20 or less, 15 or less, or 10 or less.
  • This weight ratio may be, for example, 0 to 30, 1 to 20, or 3 to 15.
  • the type of iodide is not particularly limited as long as it is an ionic compound that forms an ionic bond with iodide ions.
  • iodide ions lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, beryllium iodide, magnesium iodide, strontium iodide, barium iodide, zinc iodide, cobalt iodide, nickel iodide, ammonium iodide, methylammonium iodide, and the like.
  • the disinfectant of the present invention can contain a nonionic surfactant. According to the studies of the present inventors, it has been found that nonionic surfactants and iodine can be compounded by containing them at a certain content or more. By combining these, the absorbance in water changes, and an aqueous solution of only a normal nonionic surfactant does not have bactericidal performance and / or disinfecting performance, but by combining with iodine , can provide disinfectants with high bactericidal and/or disinfecting performance.
  • this high sterilization performance and/or disinfection performance is higher than that of an aqueous solution containing only iodine, and is due to the synergistic effect of combining iodine and a nonionic surfactant.
  • polyiodide ions are stabilized by forming a charge transfer complex with the hydrophilic portion of the nonionic surfactant, and free iodine interacts with the hydrophobic portion of the surfactant to form an O/W emulsion. is considered to form and stably disperse.
  • iodine in water can be maintained in a stable state to provide a disinfectant that maintains high sterilization performance and/or disinfection performance and long-term performance.
  • the disinfectant of the present invention contains a nonionic surfactant at a critical micelle concentration or higher. It is believed that this emulsifies the free iodine and prevents it from vaporizing.
  • the content of the nonionic surfactant in the disinfectant of the present invention is 0.05 w/v% or more, 0.08 w/v% or more, 0.10 w/v% 0.30 w/v% or more, 0.50 w/v% or more, or 0.80 w/v% or more, 5.0 w/v% or less, 3.0 w/v% or less; It may be 0 w/v% or less, or 1.5 w/v% or less.
  • the content is 0.05 w/v% or more and 5.0 w/v% or less, 0.08 w/v% or more and 3.0 w/v% or less, or 0.30 w/v% or more and 1.5 w/v% or less may be Such a range is preferable because it can be combined with iodine.
  • I 3 - derived from the added elemental iodine may be reduced to I - and the iodine and surfactant may not form a complex.
  • the weight ratio of iodine to nonionic surfactant may be 0.001 or more, 0.005 or more, 0.01 or more, or 0.05 or more, and may be 0.10 or less, 0.05 or less, 0.05 or more. 03 or less, or 0.01 or less. This weight ratio may be, for example, between 0.001 and 0.10, or between 0.005 and 0.05.
  • nonionic surfactant is not particularly limited as long as it can be combined with iodine to substantially change the absorbance in water.
  • a surfactant having a terminal hydroxyl group such as a polyoxyalkylene addition type surfactant, particularly a polyoxyethylene (POE) addition type surfactant.
  • POE polyoxyethylene
  • ester type or ester ether type surfactants are particularly preferable.
  • nonionic surfactants include C1-C20 alkanols, phenols, naphthols, bisphenols, (poly)C1-C25 alkylphenols, (poly)arylalkylphenols, C1-C25 alkylnaphthols, C1-C25 alkoxylated phosphoric acids ( salt), sorbitan fatty acid ester, polyalkylene glycol, C1-C22 aliphatic amine, C1-C22 aliphatic amide, etc., and ethylene oxide (EO) and/or propylene oxide (PO) in an amount of 2 to 300 mol, 5 to 100 mol or 10 Addition condensation of up to 60 moles, C1-C25 alkoxylated phosphoric acid (salt), and the like can be mentioned.
  • EO ethylene oxide
  • PO propylene oxide
  • the HLB value of the nonionic surfactant may be 7.0 or more, 8.0 or more, 9.0 or more, 10.0 or more, or 11.0 or more, 20 or less, 18.0 or less, 16 .0 or less, or 15.0 or less.
  • the HLB value is 9.0 or more. If the HLB value is too low, it becomes difficult to form an O/W emulsion, which is undesirable because it prevents the formation of a complex with iodine.
  • the disinfectant of the present invention contains iodine and surfactant in the medium.
  • the medium is not particularly limited, but may be liquid or solid, such as cream or gel.
  • Liquid media can include water and water-miscible media, such as water, alcohols, or mixtures thereof.
  • well-known media such as ethanol, glycerin, propylene glycol, dipropylene glycol, can be mentioned as alcohol.
  • An aqueous solvent is preferred.
  • the disinfectant of the present invention can be made into a disinfectant with a predetermined concentration by preparing a concentrated disinfectant in which the medium is adjusted in advance to less than a predetermined amount, and then adding the medium to adjust the concentration.
  • the medium used for adjustment and the medium used for density adjustment need not be the same, but must be mixed.
  • the description of the content of each component described in this specification is a description of the content of each component when using the disinfectant, and the disinfectant is manufactured by concentrating these in the range of 10 to 500 times can also
  • the disinfectant of the present invention may contain other ingredients as long as they do not impair the effects of the present invention.
  • medicinal ingredients for example, medicinal ingredients, surfactants other than the above, diluents commonly used in the preparation of disinfectants, viscosity modifiers, stabilizers such as glycerol, preservatives, flavoring agents (including sweeteners), flavorings agents (including fragrances), colorants, monodisperse solid particles such as zeolite, and various other additives.
  • the disinfectant of the present invention does not need to contain an iodine-dissipating component, such as ethylenediaminetetraacetic acid, for dissipating iodine after using the disinfectant.
  • an iodine-dissipating component such as ethylenediaminetetraacetic acid
  • the iodine dissipating component can be 0.01 w/v% or less, 0.001 w/v% or less, 0.0005 w/v% or less, or 0.0001 w/v% or less, or even not included at all. good.
  • the disinfectant of the present invention need not contain polyvinylpyrrolidone.
  • polyvinylpyrrolidone may be 0.01 w/v% or less, 0.001 w/v% or less, 0.0005 w/v% or less, 0.0001 w/v% or less, or may be completely absent. .
  • the disinfectant of the present invention may contain pH buffers such as borate buffers, phosphate buffers, citrate buffers, lactic acid buffers, etc. for pH stabilization.
  • the content of the buffering agent in the disinfectant is not particularly limited as long as the pH of the disinfectant can be stabilized in a suitable range, such as a neutral to weakly acidic range, but for example, 0.02 to 3.0 w/v. %, or 0.1 to 1.5 w/v %.
  • the disinfectant of the present invention contains ionic surfactants such as cationic surfactants such as alkyltrimethylammonium iodide and dialkyldimethylammonium chloride, N-acylglutamate, An anionic surfactant such as N-methyl-acyl taurine salt may be contained.
  • the content of the ionic surfactant in the disinfectant is 0.1 to 50 mol/mol, or 3 to 20 mol/mol as a molar amount relative to the nonionic surfactant in the emulsion.
  • the disinfecting film of the present invention contains iodine and a surfactant in a binder resin, and the surfactant is a nonionic surfactant.
  • a film containing iodine and a surfactant can inactivate viruses in the form of a film.
  • Films having antibacterial properties existed in the prior art, but the present inventors were the first to discover such an iodine-based antiseptic film.
  • the antiseptic film of the present invention By attaching the antiseptic film of the present invention to the surfaces of buttons, touch panels, etc., it is possible to prevent the spread of bacteria and viruses, which is very useful.
  • the disinfecting film of the present invention to a wound or the like, it is possible to prevent infection with bacteria and viruses.
  • the disinfectant film of the present invention can be applied to the udder of a dairy cow.
  • the effect of disinfection can also be maintained for a long time.
  • iodine and surfactants those used in the above disinfectants can be used.
  • the content of iodine and surfactant in the film is not particularly limited as long as it can provide disinfecting properties, but the content contained in the above disinfectant can be referred to.
  • the film of the present invention contains 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more of a nonionic surfactant with respect to 100 parts by mass of the binder resin. 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, 80 parts by mass or less, or 60 parts by mass or less.
  • the film of the present invention may contain 1 part by mass or more and 200 parts by mass or less, or 20 parts by mass or more and 80 parts by mass or less of a nonionic surfactant with respect to 100 parts by mass of the binder resin.
  • the weight ratio of iodine to the nonionic surfactant can be the same as that of the disinfectant of the present invention.
  • the binder resin is not particularly limited as long as it can provide the advantageous effects of the present invention and can be used as a binder resin for films, but water-soluble polymers can be mentioned in consideration of ease of production.
  • water-soluble polymers examples include polyvinyl alcohols, polyvinylpyrrolidones, polyalkylene oxides such as polyethylene oxide and polypropylene oxide, water-soluble (meth)acrylic resins such as polyacrylic acid and polyacrylamide, and water-soluble acetic acid.
  • Vinyl resins and salts thereof, gelatin, and thickening polysaccharides can be mentioned.
  • thickening polysaccharides include food additive polysaccharides such as gellan gum, alginic acid such as sodium alginate or salts thereof, xanthan gum, agar, agarose, and locust bean gum.
  • a disinfecting film When using a water-soluble polymer, a disinfecting film can be obtained simply by dissolving the water-soluble polymer in the above disinfectant and drying it.
  • the antiseptic film of the present invention can further contain a gelling accelerator depending on the type of water-soluble polymer.
  • gelling accelerators include salts of alkali metals or alkaline earth metals, such as calcium salts, magnesium salts, sodium salts and potassium salts.
  • salts include organic salts or inorganic salts. Halogen salts such as chlorides and fluorides are preferred.
  • the above disinfectant and water-soluble polymer are dissolved in an aqueous medium, and this is spread evenly in a container such as a petri dish, and an aqueous system containing the gelation accelerator is placed thereon. Spread out the medium on top of each other. Then, the film of the present invention can be produced by removing the liquid phase by drying or the like and solidifying the film.
  • the water content of the antiseptic film of the present invention is not particularly limited, but can be 50 w/v% or less, 10 w/v% or less, 1 w/v% or less, or 0.1 w/v% or less, and does not contain any may
  • the thickness of the antiseptic film of the present invention is not particularly limited, but may be 1 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, 30 ⁇ m or more, 50 ⁇ m or more, 100 ⁇ m or more, 500 ⁇ m or more, or 1 mm or more. 1 mm or less, 500 ⁇ m or less, 300 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less.
  • the thickness of the antiseptic film may be between 1 ⁇ m and 5 mm, between 30 ⁇ m and 1 mm, or between 100 ⁇ m and 500 ⁇ m.
  • the antiseptic film of the present invention can be used as one layer of the antiseptic laminate by preparing the above antiseptic, putting it into a mold or coating it on a substrate, and then drying it.
  • the base material is not particularly limited as long as it is not gas or liquid.
  • it may be a form-retaining substrate such as paper, cloth, film, foam, fiber, glass, rubber, and the like.
  • the antiseptic laminate thus comprises a substrate and an antiseptic film on the substrate.
  • the antiseptic film may be in the form of a coating, or may be a self-supporting film adhered to the substrate with an adhesive or the like.
  • the disinfecting beads of the present invention contain iodine and a surfactant in a binder resin, and the surfactant is a nonionic surfactant.
  • Disinfectant beads like the disinfectant film above, can inactivate viruses in the form of beads, which is very useful. It is also possible to use it by attaching it to a base material, or put it in a container and use it as it is.
  • iodine, surfactant, and binder resin those used in the above disinfectant or disinfectant film can be used, respectively.
  • the contents of the iodine, surfactant and binder resin in the beads are not particularly limited as long as they can provide disinfecting properties, but the contents contained in the above film can be referred to.
  • the water content of the beads of the present invention is not particularly limited, but may be 50 w/v% or less, 10 w/v% or less, 1 w/v% or less, or 0.1 w/v% or less, and may be completely free of water. good too.
  • binder resin and the gelling accelerator those that can be used in the above film can be used.
  • Disinfectant beads can be obtained by dissolving a water-soluble polymer in the above disinfectant and dropping it into an aqueous medium containing a gelling accelerator. Immediately after production, gel-like beads are obtained, but even if the water content of the gel-like beads is removed, the beads of the present invention do not lose their disinfecting properties because iodine and surfactant are complexed.
  • the disinfecting beads of the present invention can be used by being present on or in a substrate.
  • the base material include the base material used for the disinfecting laminate described above.
  • the antiseptic beads may be adhered onto a substrate with an adhesive or the like, or may be used by being contained in a fiber substrate or the like.
  • the disinfecting films and disinfecting beads of the present invention are colored, in particular have a light brown color. It is derived from iodine, which has disinfecting properties, and has a characteristic absorption of visible light. In other words, it is possible to detect that the disinfecting performance of the disinfecting film, the disinfecting laminate including the disinfecting film, and the disinfecting beads has deteriorated due to fading.
  • the detection method is not particularly limited as long as it is an inspection method that identifies the colors of the film and beads. For example, the appearance may be confirmed by visual observation or by a spectrophotometer.
  • Experiment 1 Experiment of Compositing Polyoxyethylene Sorbitan Monooleate and Iodine
  • polyoxyethylene sorbitan monooleate Teween 80
  • iodine and potassium iodide were mixed in a weight ratio of 1:8 so that the iodine content was 20 ppm to obtain a disinfectant.
  • Fig. 1 shows the light absorption spectrum (absorbance) of these disinfectants in the range of 270 nm to 500 nm.
  • Experiment 2 Stability test of disinfectant Disinfectant containing no surfactant and containing 200 ppm iodine (Comparative Example 1); containing 1.0 w/v% surfactant (Tween 80) and 200 ppm iodine Disinfectant (Example 1); Disinfectant containing 5.0 w/v % glycerol as stabilizer and 200 ppm iodine and potassium iodide (Comparative Example 2); An antiseptic with the additional addition of 0 w/v % glycerol (Example 2); and a povidone-iodine mouthwash (Comparative Example 3) diluted to an iodine concentration of 200 ppm showing effective bactericidal activity were prepared.
  • FIG. 2 shows how much the peak decreased when the absorbance immediately after preparation of each example was taken as 100%.
  • the disinfectants of Examples 1 and 2 did not decrease in absorbance even after about 30 days, whereas the disinfectants of Comparative Examples 1-3 showed a few days to 10 days. It can be seen that the absorbance peak is lost in about a day.
  • the sanitizers of Examples 1 and 2 did not change color after about 30 days, whereas the sanitizers of Comparative Examples 1-3 became colorless as the absorbance peak was lost. became.
  • Bacteriophage Q ⁇ can be used as a virus model such as norovirus that does not have an envelope
  • bacteriophage ⁇ 6 can be used as a virus model that has an envelope such as influenza virus and coronavirus.
  • Escherichia coli NBRC13965 and Pseudomonas syringae NBRC14084 were used. A portion of the colony of the strain used was inoculated into the autoclaved 702 liquid medium prepared using a platinum loop, and shake culture was performed overnight at 30° C. and 150 rpm. Two types of medium were used, a liquid medium, an upper layer agar medium and a lower layer agar medium.
  • For the upper agar medium soft agar medium
  • 4 ml of 702 liquid medium containing 0.7% agar powder was dispensed into each test tube, covered with an aluminum cap, autoclaved, and placed in a water bath at 52°C for 15 minutes. I kept it warm for about a minute and used it.
  • 702 liquid medium containing 1.5% agar powder was autoclaved and spread in a deep petri dish.
  • the phage stock solution was diluted 10-fold with 10 mM potassium phosphate buffer (KPB), treated with 1 ml of disinfectant for 5 minutes, and added with 9 ml of 702 liquid medium to inactivate iodine.
  • KPB potassium phosphate buffer
  • a 10 3 -fold, 10 4 -fold, 10 5 -fold or 10 6 -fold diluted phage dilution was prepared with KPB, and 100 ⁇ l of these phage dilutions and 100 ⁇ l of the pre-cultured bacterial solution were added to the warmed upper agar medium. After gently stirring, the mixture was uniformly poured into the lower layer agar medium which had been returned to room temperature. The number of plaques was counted after culturing overnight with the plate facing upward, and the phage concentration (PFU) was calculated according to the following formula.
  • Phage concentration (PFU/ml) Number of plaques x (dilution rate x 1,000 ( ⁇ l))/(volume of phage dilution ( ⁇ l))
  • PFU Protein Forming Unit
  • the iodine-Tween80 complex solution was prepared so that the Tween80 concentration was 0 or 1% and the iodine concentration was 0-200 ppm.
  • the culture temperature is 37° C. for Escherichia coli infected with bacteriophage Q ⁇ , and 25° C. for Pseudomonas bacteria infected with bacteriophage ⁇ 6.
  • FIG. 4(a) The results for bacteriophage Q ⁇ are shown in FIG. 4(a), and the results for bacteriophage ⁇ 6 are shown in FIG. 4(b).
  • the disinfectant containing iodine concentration of 100 ppm or more can reduce the number of plaques by more than two orders of magnitude. Also, looking at FIG. 4(b), the disinfectant containing iodine concentration of 10 ppm or more can reduce the number of plaques by three orders of magnitude or more, and the disinfection of the present invention against viruses such as enveloped coronaviruses. agents have been found to be particularly effective.
  • means that the turbidity was 99.9% or more lower than the blank test using water instead of disinfectant and was below the lower limit of detection.
  • means that the turbidity was 90.0% to 99.9% lower than water.
  • X means that the turbidity did not decrease by 90.0% or more with respect to water.
  • Experiment 6 Experiment of disinfecting film containing disinfectant 1 w / v% of gellan gum, which is a water-soluble polymer, 1.0 w / v% of surfactant (Tween 80), 200 ppm of iodine and potassium iodide are mixed in water, These aqueous solutions were obtained. A thin film was formed by putting 10 ml of this aqueous solution into a ⁇ 90 mm glass petri dish. Further, a 0.5% by weight calcium chloride solution was added in layers and allowed to solidify. Then, the film of Example 4 was formed by removing moisture after air-drying for 5 days. A film of Comparative Example 6 was formed in the same manner as in Example 4, except that iodine was not included. Further, a film of Comparative Example 7 was formed in the same manner as in Example 4, except that iodine and surfactant were not included.
  • a virus-containing liquid was dropped onto these films, and after about 10 minutes, the films were washed out, and the liquid was used to infect E. coli with the virus. Then, in the same manner as in Experiment 4, the virus inactivation performance was tested.
  • FIG. 5(a) The results for bacteriophage Q ⁇ are shown in FIG. 5(a), and the results for bacteriophage ⁇ 6 are shown in FIG. 5(b).
  • the film of Example 4 was able to reduce the number of plaques by one digit or more. Moreover, referring to FIG. 5(b), the film of Example 4 showed no plaques within the measurable range, and was able to reduce the number of plaques by at least four orders of magnitude. Therefore, it was found that the antiseptic film of the present invention can inactivate viruses simply by contacting them. In particular, it was found that the antiseptic film of the present invention is very effective against viruses such as enveloped coronaviruses.
  • FIG. 6 shows an actual photograph of a film obtained using 2 w/v % sodium alginate instead of 1 w/v % gellan gum in Example 4.
  • FIG. 6 shows an actual photograph of a film obtained using 2 w/v % sodium alginate instead of 1 w/v % gellan gum in Example 4.
  • Experiment 7 Experiment of disinfectants containing various surfactants Except for changing the surfactant polyoxyethylene sorbitan monooleate (Tween 80, C18; 1 (n-9)) to another surfactant, In the same manner as in Experiments 1 and 3, the surfactant and iodine were combined and the bactericidal performance thereof was tested.
  • the surfactant polyoxyethylene sorbitan monooleate Teween 80, C18; 1 (n-9)
  • Fig. 7 shows the results of disinfectants containing polyoxyethylene sorbitan monolaurate (Tween 20, C12), and Fig. 8 shows the results of disinfectants containing polyoxyethylene sorbitan monostearate (Tween 60, C18).
  • (a) is the result of the absorbance test, and (b) is the result of the bactericidal performance test.
  • Figure 9(a) shows the absorbance test results for disinfectants containing polyethylene glycol (PEG) of various molecular weights
  • Figure 9(b) shows sodium lauryl sulfate (SDS), an anionic surfactant.
  • the results of the absorbance test of the disinfectant are shown
  • FIG. 9(c) shows the result of the absorbance test of the disinfectant containing PEG and SDS.
  • A means that there is no bactericidal property of the surfactant alone, and the bactericidal property is improved by adding the surfactant to iodine alone
  • B is iodine.
  • the single substance and surfactant alone show bactericidal activity, it means that the bactericidal activity is equal to or lower than that of iodine alone. In contrast, it means that the bactericidal activity is equal to or lower than that.
  • the disinfectant using a nonionic surfactant was able to demonstrate both long-term bactericidal retention and high bactericidal performance.
  • the synergistic effect with iodine was not clear for cationic surfactants and amphoteric surfactants, since the surfactants themselves also have bactericidal properties.
  • Experiment 7 Complex Stability Experiment A disinfectant was obtained by adding 20 ppm of iodine to various concentrations of surfactant (Tween 80) aqueous solutions. This was stored at 30° C., and the change in absorbance of the peak near 350 nm was observed over time.
  • surfactant Teween 80
  • a disinfectant was obtained by adding 20 ppm of iodine to a surfactant (polyoxyethylene alkyl ether (C8: HLB 11.5) aqueous solution of various concentrations. It was stored at 30 ° C. and the peak near 350 nm The change in absorbance was observed over time, and the disinfectant stored at 18° C. was also observed. At 30°C, an emulsion is formed, making it difficult to measure the light absorption spectrum.
  • a surfactant polyoxyethylene alkyl ether (C8: HLB 11.5) aqueous solution of various concentrations. It was stored at 30 ° C. and the peak near 350 nm The change in absorbance was observed over time, and the disinfectant stored at 18° C. was also observed. At 30°C, an emulsion is formed, making it difficult to measure the light absorption spectrum.
  • Experiment 8 Experiment of Disinfection Beads 2 w/v% sodium alginate, 1.0 w/v% surfactant (Tween 80), 200 ppm iodine and potassium iodide were mixed in water to obtain an aqueous solution of these. When this aqueous solution was dropped into a 0.5 mass % calcium chloride solution, gel-like beads were formed in the solution according to the size of the dropped droplet.
  • Fig. 12 shows the disinfection beads obtained by separating the beads from the solution.
  • the beads shown on the left side of FIG. 12 had a high moisture content and were yellow in color.
  • the dried beads obtained by drying the beads for 2 months are shown on the right side of FIG. This bead had a very low moisture content and was darker than the bead before drying, giving it an orange color.

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Abstract

The purpose of the present invention is to provide: a novel iodine-based disinfectant; and a disinfectant film and disinfectant beads both including such disinfectant. The disinfectant comprises a medium and, contained therein, 10 ppm or greater iodine and 0.05 w/v% or greater surfactant, wherein the surfactant is a nonionic surfactant. The disinfectant film comprises a binder resin and, contained therein, iodine and a surfactant, wherein the surfactant is a nonionic surfactant. The disinfectant beads comprise a binder resin and, contained therein, iodine and a surfactant, wherein the surfactant is a nonionic surfactant.

Description

消毒剤、消毒フィルム及び消毒ビーズDisinfectants, disinfecting films and disinfecting beads
 本発明は、消毒剤、消毒フィルム及び消毒ビーズに関する。 The present invention relates to disinfectants, disinfecting films and disinfecting beads.
 ヨウ素系の消毒剤として、ポビドンヨードを用いることが知られている。ポビドンヨードは、ポリビニルピロリドンとポリヨウ化物イオンとの複合体であり、ポビドンヨードを含む消毒剤は、10w/v%程度の濃度で製品として出荷されている。 It is known to use povidone-iodine as an iodine-based disinfectant. Povidone-iodine is a complex of polyvinylpyrrolidone and polyiodide ions, and disinfectants containing povidone-iodine are shipped as products at a concentration of about 10 w/v %.
 他のヨウ素系の消毒剤としては、ヨウ素及びヨウ化カリウムをエタノール中に含有するヨードチンキ、並びにヨウ素及びヨウ化カリウムをグリセリン中に含有する複方ヨード・グリセリンも挙げることができる。 Other iodine-based disinfectants include iodine tincture containing iodine and potassium iodide in ethanol, and compound iodine-glycerin containing iodine and potassium iodide in glycerin.
 ヨウ素を界面活性剤と共に含む消毒剤も知られており、例えば特許文献1では、ノニオン系界面活性剤とヨウ素とを含むコンタクトレンズ用の洗浄消毒剤を開示している。 A disinfectant containing iodine together with a surfactant is also known. For example, Patent Document 1 discloses a cleaning disinfectant for contact lenses containing a nonionic surfactant and iodine.
 また、特許文献2では、ヨウ素系殺菌成分、ヨウ化カリウム及び双性イオン化合物を含有する消毒剤を開示している。 In addition, Patent Document 2 discloses a disinfectant containing an iodine-based bactericidal component, potassium iodide, and a zwitterionic compound.
特開平10-108897号公報JP-A-10-108897 特開2017-066054号公報JP 2017-066054 A
 本発明は、新規なヨウ素系消毒剤、そのような消毒剤を含む消毒フィルム及び消毒ビーズを提供することを目的とする。 An object of the present invention is to provide a novel iodine-based disinfectant, a disinfecting film and disinfecting beads containing such a disinfectant.
 本発明者らは、以下の態様を有する本発明により、上記課題を解決できることを見出した。
《態様1》
 10ppm以上のヨウ素、及び0.05w/v%以上の界面活性剤を媒体中に含む消毒剤であって、前記界面活性剤が、ノニオン系界面活性剤である、消毒剤。
《態様2》
 前記ヨウ素を25ppm以上500ppm以下で含み、かつ前記界面活性剤を0.1w/v%以上1.0w/v%以下で含む、態様1に記載の消毒剤。
《態様3》
 前記ノニオン系界面活性剤のHLB値が、9.0以上である、態様1又は2に記載の消毒剤。
《態様4》
 前記ノニオン系界面活性剤が、ポリオキシエチレン付加型の界面活性剤である、態様1~3のいずれか一項に記載の消毒剤。
《態様5》
 前記媒体が、水系媒体である、態様1~4のいずれか一項に記載の消毒剤。
《態様6》
 ヨウ化物をさらに含み、前記ヨウ素の含有量に対する前記ヨウ化物の含有量の重量比が、30以下である、態様1~5のいずれか一項に記載の消毒剤。
《態様7》
 ヨウ素が10ppm以上、かつ界面活性剤が0.05w/v%以上となるように媒体中に混合することを含む、消毒剤の製造方法であって、前記界面活性剤が、ノニオン系界面活性剤である、消毒剤の製造方法。
《態様8》
 ヨウ素及び界面活性剤をバインダー樹脂中に含み、前記界面活性剤が、ノニオン系界面活性剤である、消毒フィルム。
《態様9》
 前記バインダー樹脂が、水溶性ポリマーである、態様8に記載の消毒フィルム。
《態様10》
 前記バインダー樹脂が、アルギン酸もしくはその塩、ゲランガム、キサンタンガム、寒天、アガロース及びローカストビーンガムからなる群から選ばれるいずれか一種、またはそれらの混合物であり、ゲル化促進剤をさらに含有する、態様8又は9に記載の消毒フィルム。
《態様11》
 前記ゲル化促進剤が、カルシウム塩、マグネシウム塩、ナトリウム塩及びカリウム塩からなる群から選ばれる1又は2種以上である、態様10に記載の消毒フィルム。
《態様12》
 ヨウ素及び界面活性剤をバインダー樹脂中に含み、前記界面活性剤が、ノニオン系界面活性剤である、消毒ビーズ。
《態様13》
 基材と前記基材上の態様8~11のいずれか一項に記載の消毒フィルムとから構成され、あるいは基材と前記基材上又は前記基材中に含まれる態様12に記載の消毒ビーズとから構成される、消毒積層体。
《態様14》
 態様10又は11に記載の消毒フィルムの製造方法であって、バインダー樹脂、ヨウ素、界面活性剤、及びゲル化促進剤を水系媒体に溶解させ、得られた溶解物を型に投入し又は基材上に塗布し、その後乾燥する、消毒フィルムの製造方法。
《態様15》
 ヨウ素残量に応じて退色することで消毒効果の低下を検出する、態様8~11のいずれか一項に記載の消毒フィルム、態様12に記載の消毒ビーズ、又は態様13に記載の消毒積層体の消毒効果の判別方法。
The inventors have found that the above problems can be solved by the present invention having the following aspects.
<<Aspect 1>>
A disinfectant containing 10 ppm or more of iodine and 0.05 w/v% or more of a surfactant in a medium, wherein the surfactant is a nonionic surfactant.
<<Aspect 2>>
The disinfectant according to aspect 1, which contains the iodine at 25 ppm or more and 500 ppm or less and the surfactant at 0.1 w/v% or more and 1.0 w/v% or less.
<<Aspect 3>>
The disinfectant according to aspect 1 or 2, wherein the nonionic surfactant has an HLB value of 9.0 or more.
<<Aspect 4>>
The disinfectant according to any one of aspects 1 to 3, wherein the nonionic surfactant is a polyoxyethylene addition type surfactant.
<<Aspect 5>>
The disinfectant according to any one of aspects 1 to 4, wherein the medium is an aqueous medium.
<<Aspect 6>>
The disinfectant according to any one of aspects 1 to 5, further comprising iodide, wherein the weight ratio of the iodide content to the iodine content is 30 or less.
<<Aspect 7>>
A method for producing a disinfectant, comprising mixing in a medium such that iodine is 10 ppm or more and surfactant is 0.05 w/v% or more, wherein the surfactant is a nonionic surfactant A method for producing a disinfectant.
<<Aspect 8>>
A disinfecting film containing iodine and a surfactant in a binder resin, wherein the surfactant is a nonionic surfactant.
<<Aspect 9>>
9. The antiseptic film of aspect 8, wherein the binder resin is a water-soluble polymer.
<<Aspect 10>>
Embodiment 8 or wherein the binder resin is any one selected from the group consisting of alginic acid or a salt thereof, gellan gum, xanthan gum, agar, agarose and locust bean gum, or a mixture thereof, and further contains a gelling accelerator. 9. The disinfecting film according to 9.
<<Aspect 11>>
11. The disinfecting film according to aspect 10, wherein the gelling accelerator is one or more selected from the group consisting of calcium salts, magnesium salts, sodium salts and potassium salts.
<<Aspect 12>>
Disinfecting beads containing iodine and a surfactant in a binder resin, wherein the surfactant is a nonionic surfactant.
<<Aspect 13>>
Disinfecting beads according to aspect 12, consisting of a substrate and the antiseptic film according to any one of aspects 8-11 on said substrate, or comprising a substrate and on or in said substrate. A sanitizing laminate, comprising:
<<Aspect 14>>
A method for producing a disinfecting film according to aspect 10 or 11, wherein the binder resin, iodine, surfactant, and gelation accelerator are dissolved in an aqueous medium, and the resulting dissolved product is put into a mold or a substrate A method for producing an antiseptic film that is applied on top and then dried.
<<Aspect 15>>
The disinfecting film according to any one of aspects 8 to 11, the disinfecting beads according to aspect 12, or the disinfecting laminate according to aspect 13, which detects a decrease in disinfection effect by fading according to the remaining amount of iodine. Disinfection effect determination method.
図1は、実験1で製造した各消毒剤の吸光度試験の結果を示している。FIG. 1 shows the results of the absorbance test for each disinfectant produced in Experiment 1. FIG. 図2は、実験2で製造した各消毒剤の保存安定性の試験結果を示している。FIG. 2 shows the test results of the storage stability of each disinfectant produced in Experiment 2. 図3は、実験3で製造した各消毒剤の殺菌性能の試験結果を示している。FIG. 3 shows the test results of the bactericidal performance of each disinfectant produced in Experiment 3. 図4は、実験4で製造した各消毒剤のウィルス不活化試験の結果を示している。FIG. 4 shows the results of the virus inactivation test for each disinfectant produced in Experiment 4. 図5は、実験5で製造した各消毒フィルムのウィルス不活化試験の結果を示している。FIG. 5 shows the results of the virus inactivation test for each disinfecting film produced in Experiment 5. 図6は、本発明の消毒フィルムの1つの例の実際の写真を示している。FIG. 6 shows an actual photograph of one example of the antiseptic film of the present invention. 図7は、実験6で製造したTween20を含む各消毒剤の吸光度試験及び殺菌性能試験の結果を示している。FIG. 7 shows the results of the absorbance test and sterilization performance test of each disinfectant containing Tween 20 produced in Experiment 6. 図8は、実験6で製造したTween60を含む各消毒剤の吸光度試験及び殺菌性能試験の結果を示している。FIG. 8 shows the results of the absorbance test and sterilization performance test of each disinfectant containing Tween 60 produced in Experiment 6. 図9は、実験6で製造したPEG及び/又はSDSを含む各消毒剤の吸光度試験の結果を示している。FIG. 9 shows the absorbance test results of each disinfectant containing PEG and/or SDS produced in Experiment 6. FIG. 図10は、実験7で製造したTween80を含む各消毒剤の保存安定性の試験結果を示している。FIG. 10 shows the storage stability test results of each disinfectant containing Tween 80 produced in Experiment 7. 図11は、実験7で製造したポリオキシエチレンアルキルエーテルを含む各消毒剤の保存安定性の試験結果を示している。FIG. 11 shows the storage stability test results of each disinfectant containing polyoxyethylene alkyl ether produced in Experiment 7. FIG. 図12は、本発明の消毒ビーズの1つの例の実際の写真を示している。Figure 12 shows an actual photograph of one example of the disinfecting beads of the present invention.
《消毒剤》
 本発明の消毒剤は、10ppm以上のヨウ素、及び0.05w/v%以上の界面活性剤を媒体中に含む消毒剤であって、前記界面活性剤が、ノニオン系界面活性剤である。なお、本明細書において、消毒剤中の成分の濃度及び含有量について言及している場合、それらは、消毒剤を製造するために添加したその成分の添加量を意味する。また、「ppm」の単位は、本明細書において「mg/L」を意味する。なお、消毒薬を製造するために添加したヨウ素は、例えば、95質量%以上がノニオン界面活性剤と後述のように複合体化することができる。本発明は、ヨウ素が10ppm以上、かつ界面活性剤が0.05w/v%以上となるように媒体中に混合することを含む、消毒剤の製造方法であって、前記界面活性剤が、ノニオン系界面活性剤である、消毒剤の製造方法にも関する。本明細書において、「10ppm以上のヨウ素を含む」とは、10ppm以上となるように単体のヨウ素が添加されていることを意味しており、単体のヨウ素が添加された結果ヨウ素の形態が変化しても上記含有量は影響を受けない。また、後述するヨウ化物の添加量は、ヨウ素の添加量とは別に計算される。
"disinfectant"
The disinfectant of the present invention is a disinfectant containing 10 ppm or more of iodine and 0.05 w/v% or more of a surfactant in a medium, wherein the surfactant is a nonionic surfactant. In addition, in this specification, when referring to the concentration and content of a component in the disinfectant, they mean the amount of the component added to manufacture the disinfectant. Moreover, the unit of "ppm" means "mg/L" in this specification. In addition, 95% by mass or more of the iodine added to produce the disinfectant can be complexed with a nonionic surfactant as described later. The present invention is a method for producing a disinfectant, comprising mixing in a medium such that iodine is 10 ppm or more and a surfactant is 0.05 w/v% or more, wherein the surfactant is a nonionic It also relates to a method of making a disinfectant, which is a surfactant. In the present specification, "containing 10 ppm or more of iodine" means that simple iodine is added to 10 ppm or more, and as a result of adding simple iodine, the form of iodine changes. However, the above contents are not affected. The amount of iodide to be added, which will be described later, is calculated separately from the amount of iodine to be added.
 本発明者らは、消毒剤が一定以上の濃度でヨウ素と界面活性剤とを含む場合に、ヨウ素と界面活性剤とが複合化し、かつ複合化したままの状態で、消毒作用を発揮できることを見出した。これは、遊離ヨウ素の有無によって消毒作用を得ていた従来技術に基づくと、予想外であった。この消毒剤は、特にコロナウィルス、インフルエンザウィルス等のエンベロープを有するウィルスの不活化に非常に有効であることが分かった。すなわち、本発明の消毒剤は、遊離ヨウ素によるヨウ素カチオンによる殺菌作用だけではなく、ヨウ素と界面活性剤との複合体による消毒作用を得ることができる。 The present inventors have found that when a disinfectant contains iodine and a surfactant at a concentration above a certain level, the iodine and the surfactant are complexed, and the disinfecting effect can be exhibited while remaining in the complexed state. Found it. This was unexpected based on the prior art, which derives its disinfecting action from the presence or absence of free iodine. It has been found that this disinfectant is particularly effective in inactivating enveloped viruses such as coronaviruses and influenza viruses. That is, the disinfectant of the present invention can obtain not only a bactericidal action due to iodine cations due to free iodine, but also a disinfecting action due to a complex of iodine and a surfactant.
 また、本発明の消毒剤のヨウ素と界面活性剤とが複合化した状態は、少なくとも比較的低い温度であれば、長期間安定して維持できることがわかった。ポビドンヨードは、通常の場合には希釈して用いられるが、これは、ポビドンヨードが高濃度である場合、ヨウ素がポビドンヨードから遊離しないため、むしろ消毒作用が低くなるためである。一方で、ポビドンヨードは、最初から希釈してしまうと、多くのヨウ素が遊離し昇華することで、殺菌成分であるヨウ素が減少することから長期間の保管ができないという課題がある。それに対して、本発明の消毒剤は、使用直前で希釈する必要はなく、かつ長期間の保管も可能であるため、非常に有用である。 In addition, it was found that the state in which iodine and the surfactant in the disinfectant of the present invention are combined can be stably maintained for a long period of time, at least at relatively low temperatures. Povidone-iodine is usually used in a diluted form, because when povidone-iodine is at a high concentration, iodine is not liberated from povidone-iodine, resulting in a lower disinfecting effect. On the other hand, when povidone-iodine is diluted from the beginning, a large amount of iodine is liberated and sublimated, resulting in a decrease in iodine, which is a sterilizing component. In contrast, the disinfectant of the present invention is very useful because it does not need to be diluted immediately before use and can be stored for a long period of time.
〈ヨウ素〉
 ヨウ素は、消毒剤の重量比で10ppm以上となるように、消毒剤に添加させることができる。媒体が水系媒体である場合には、ヨウ素の水溶性向上のためヨウ化物を添加した液とヨウ素とを混合することができる。
<Iodine>
Iodine can be added to the disinfectant so that the weight ratio of the disinfectant is 10 ppm or more. When the medium is an aqueous medium, iodine can be mixed with a liquid containing an iodide to improve the water solubility of iodine.
 ヨウ素は、例えば10ppm以上、20ppm以上、40ppm以上、50ppm以上、80ppm以上、100ppm以上、150ppm以上、又は200ppm以上であってもよく、2000ppm以下、1000ppm以下、500ppm以下、300ppm以下、又は200ppm以下で消毒剤に含有させることができる。含有量は、10ppm以上2000ppm以下、40ppm以上500ppm以下、又は50ppm以上300ppm以下であってもよい。 Iodine may be, for example, 10 ppm or more, 20 ppm or more, 40 ppm or more, 50 ppm or more, 80 ppm or more, 100 ppm or more, 150 ppm or more, or 200 ppm or more, 2000 ppm or less, 1000 ppm or less, 500 ppm or less, 300 ppm or less, or 200 ppm or less. It can be included in disinfectants. The content may be 10 ppm to 2000 ppm, 40 ppm to 500 ppm, or 50 ppm to 300 ppm.
 ヨウ化物自体には消毒作用はないものの、ヨウ化物イオン濃度によって、ヨウ素の形態が遊離ヨウ素、三ヨウ化物イオン等に変化し、ヨウ素の形態は消毒性能に影響を与えうるため、ヨウ化物の量を調整して、消毒剤に混合することが好ましい。ヨウ化物の適切な添加量は、ヨウ素の添加量によって変わり、例えばヨウ素が10ppm程度である場合には、ヨウ化物を添加しなくてもよい。例えば、ヨウ素の含有量に対するヨウ化物の含有量の重量比は、0以上、0.1以上、1以上、3以上、5以上、又は7以上であってもよく、30以下、20以下、15以下、又は10以下であってもよい。この重量比は、例えば0以上30以下、1以上20以下、又は3以上15以下であってもよい。 Although iodide itself does not have a disinfecting effect, depending on the iodide ion concentration, the form of iodine changes to free iodine, triiodide ion, etc., and the form of iodine can affect disinfection performance. is adjusted and mixed with the disinfectant. The appropriate amount of iodide to be added varies depending on the amount of iodine to be added. For example, when iodine is about 10 ppm, iodide may not be added. For example, the weight ratio of the iodide content to the iodine content may be 0 or more, 0.1 or more, 1 or more, 3 or more, 5 or more, or 7 or more, 30 or less, 20 or less, 15 or less, or 10 or less. This weight ratio may be, for example, 0 to 30, 1 to 20, or 3 to 15.
 ヨウ化物の種類としては、ヨウ化物イオンとイオン結合を形成するイオン化合物であれば、特に限定されない。例えば、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化ルビジウム、ヨウ化セシウム、ヨウ化ベリリウム、ヨウ化マグネシウム、ヨウ化ストロンチウム、ヨウ化バリウム、ヨウ化亜鉛、ヨウ化コバルト、ヨウ化ニッケル、ヨウ化アンモニウム、ヨウ化メチルアンモニウムなどが挙げられる。 The type of iodide is not particularly limited as long as it is an ionic compound that forms an ionic bond with iodide ions. For example, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, beryllium iodide, magnesium iodide, strontium iodide, barium iodide, zinc iodide, cobalt iodide, nickel iodide, ammonium iodide, methylammonium iodide, and the like.
〈界面活性剤-ノニオン系界面活性剤〉
 本発明の消毒剤は、ノニオン系界面活性剤を含有することができる。本発明者らの検討によれば、ノニオン系界面活性剤とヨウ素とを一定以上の含有量で含有させることによって、これらを複合化できることが分かった。これらは複合化することによって、水中での吸光度に変化が生じ、通常のノニオン系界面活性剤のみの水溶液では、殺菌性能及び/又は消毒性能がないにも関わらず、ヨウ素と複合化させることによって、高い殺菌性能及び/又は消毒性能を消毒剤に提供できることが分かった。また、この高い殺菌性能及び/又は消毒性能は、ヨウ素のみを含む水溶液よりも高く、ヨウ素とノニオン系界面活性剤とが複合化することによる相乗効果によるものである。理論に拘束されないが、ポリヨウ化物イオンはノニオン系界面活性剤の親水部と電荷移動錯体を形成して安定し、また遊離ヨウ素は界面活性剤の疎水部と疎水性相互作用によりO/W型エマルションを形成して安定して分散すると考えられる。それにより、水中のヨウ素が、安定な状態を維持して高い殺菌性能及び/又は消毒性能と長時間の性能を維持した消毒剤を提供できると考えられる。
<Surfactant - nonionic surfactant>
The disinfectant of the present invention can contain a nonionic surfactant. According to the studies of the present inventors, it has been found that nonionic surfactants and iodine can be compounded by containing them at a certain content or more. By combining these, the absorbance in water changes, and an aqueous solution of only a normal nonionic surfactant does not have bactericidal performance and / or disinfecting performance, but by combining with iodine , can provide disinfectants with high bactericidal and/or disinfecting performance. Moreover, this high sterilization performance and/or disinfection performance is higher than that of an aqueous solution containing only iodine, and is due to the synergistic effect of combining iodine and a nonionic surfactant. Although not bound by theory, polyiodide ions are stabilized by forming a charge transfer complex with the hydrophilic portion of the nonionic surfactant, and free iodine interacts with the hydrophobic portion of the surfactant to form an O/W emulsion. is considered to form and stably disperse. As a result, it is believed that iodine in water can be maintained in a stable state to provide a disinfectant that maintains high sterilization performance and/or disinfection performance and long-term performance.
 好ましくは、本発明の消毒剤は、ノニオン系界面活性剤を臨界ミセル濃度以上で含有する。これによって、遊離ヨウ素をエマルション化して気化を防止できると考えられる。具体的には、本発明の消毒剤のノニオン系界面活性剤の含有量は、その種類にもよるが、0.05w/v%以上、0.08w/v%以上、0.10w/v%以上、0.30w/v%以上、0.50w/v%以上、又は0.80w/v%以上であってもよく、5.0w/v%以下、3.0w/v%以下、2.0w/v%以下、又は1.5w/v%以下であってもよい。その含有量は、0.05w/v%以上5.0w/v%以下、0.08w/v%以上3.0w/v%以下、又は0.30w/v%以上1.5w/v%以下であってもよい。このような範囲であれば、ヨウ素との複合化ができるため好ましい。界面活性剤の種類によっては含有量が高すぎると、添加した単体のヨウ素由来のI がIに還元されてヨウ素と界面活性剤とが複合化しなくなる場合がある。 Preferably, the disinfectant of the present invention contains a nonionic surfactant at a critical micelle concentration or higher. It is believed that this emulsifies the free iodine and prevents it from vaporizing. Specifically, the content of the nonionic surfactant in the disinfectant of the present invention, depending on the type, is 0.05 w/v% or more, 0.08 w/v% or more, 0.10 w/v% 0.30 w/v% or more, 0.50 w/v% or more, or 0.80 w/v% or more, 5.0 w/v% or less, 3.0 w/v% or less; It may be 0 w/v% or less, or 1.5 w/v% or less. The content is 0.05 w/v% or more and 5.0 w/v% or less, 0.08 w/v% or more and 3.0 w/v% or less, or 0.30 w/v% or more and 1.5 w/v% or less may be Such a range is preferable because it can be combined with iodine. Depending on the type of surfactant, if the content is too high, I 3 - derived from the added elemental iodine may be reduced to I - and the iodine and surfactant may not form a complex.
 ノニオン系界面活性剤に対するヨウ素の重量比は、0.001以上、0.005以上、0.01以上、又は0.05以上であってもよく、0.10以下、0.05以下、0.03以下、又は0.01以下であってもよい。この重量比は、例えば0.001以上0.10以下、又は0.005以上0.05以下であってもよい。 The weight ratio of iodine to nonionic surfactant may be 0.001 or more, 0.005 or more, 0.01 or more, or 0.05 or more, and may be 0.10 or less, 0.05 or less, 0.05 or more. 03 or less, or 0.01 or less. This weight ratio may be, for example, between 0.001 and 0.10, or between 0.005 and 0.05.
 ノニオン系界面活性剤の種類としては、ヨウ素と複合化して水中での吸光度に実質的な変化を与えることができれば、特に限定されない。例えば、ノニオン系界面活性剤としては、末端に水酸基を有する界面活性剤、例えばポリオキシアルキレン付加型の界面活性剤、特にポリオキシエチレン(POE)付加型の界面活性剤を用いることが好ましい。ポリオキシエチレン(POE)付加型の界面活性剤の中でも特に、エステル型又はエステルエーテル型のものが好ましい。例えば、ノニオン系界面活性剤としては、C1~C20アルカノール、フェノール、ナフトール、ビスフェノール類、(ポリ)C1~C25アルキルフェノール、(ポリ)アリールアルキルフェノール、C1~C25アルキルナフトール、C1~C25アルコキシル化リン酸(塩)、ソルビタン脂肪酸エステル、ポリアルキレングリコール、C1~C22脂肪族アミン、C1~C22脂肪族アミドなどにエチレンオキシド(EO)及び/又はプロピレンオキシド(PO)を2~300モル、5~100モル又は10~60モル付加縮合させたものや、C1~C25アルコキシル化リン酸(塩)などが挙げられる。 The type of nonionic surfactant is not particularly limited as long as it can be combined with iodine to substantially change the absorbance in water. For example, as the nonionic surfactant, it is preferable to use a surfactant having a terminal hydroxyl group, such as a polyoxyalkylene addition type surfactant, particularly a polyoxyethylene (POE) addition type surfactant. Among polyoxyethylene (POE) addition type surfactants, ester type or ester ether type surfactants are particularly preferable. For example, nonionic surfactants include C1-C20 alkanols, phenols, naphthols, bisphenols, (poly)C1-C25 alkylphenols, (poly)arylalkylphenols, C1-C25 alkylnaphthols, C1-C25 alkoxylated phosphoric acids ( salt), sorbitan fatty acid ester, polyalkylene glycol, C1-C22 aliphatic amine, C1-C22 aliphatic amide, etc., and ethylene oxide (EO) and/or propylene oxide (PO) in an amount of 2 to 300 mol, 5 to 100 mol or 10 Addition condensation of up to 60 moles, C1-C25 alkoxylated phosphoric acid (salt), and the like can be mentioned.
 ノニオン系界面活性剤のHLB値が、7.0以上、8.0以上、9.0以上、10.0以上、又は11.0以上であってもよく、20以下、18.0以下、16.0以下、又は15.0以下であってもよい。好ましくはHLB値が9.0以上である。HLB値が低すぎるとO/W型エマルションを形成しにくくなることでヨウ素と複合体を形成しなくなる点があり好ましくない。 The HLB value of the nonionic surfactant may be 7.0 or more, 8.0 or more, 9.0 or more, 10.0 or more, or 11.0 or more, 20 or less, 18.0 or less, 16 .0 or less, or 15.0 or less. Preferably, the HLB value is 9.0 or more. If the HLB value is too low, it becomes difficult to form an O/W emulsion, which is undesirable because it prevents the formation of a complex with iodine.
〈媒体〉
 本発明の消毒剤は、ヨウ素及び界面活性剤を媒体中に含む。媒体としては、特に限定されないが、液体又は固体であってもよく、例えばクリーム状、ゲル状等であってもよい。液体媒体としては、水及び水と混和性のある媒体を挙げることができ、例えば水、アルコール又はこれらの混合物であってもよい。また、アルコールとしては、エタノール、グリセリン、プロピレングリコール、ジプロピレングリコール等の周知の媒体を挙げることができる。好ましくは水系溶媒である。
<Medium>
The disinfectant of the present invention contains iodine and surfactant in the medium. The medium is not particularly limited, but may be liquid or solid, such as cream or gel. Liquid media can include water and water-miscible media, such as water, alcohols, or mixtures thereof. Moreover, well-known media, such as ethanol, glycerin, propylene glycol, dipropylene glycol, can be mentioned as alcohol. An aqueous solvent is preferred.
 本発明の消毒剤は、事前に媒体を所定より少なく調整した濃縮消毒薬を作製し、後から媒体を添加し濃度調整を行うことで所定濃度の消毒剤にすることができる。なお、調整に用いる媒体と濃度調整に用いる媒体は同一である必要はないが、混和しなければならない。本明細書に記載の各成分の含有量等の記載は、消毒剤使用時の各成分の含有量等に関する記載であり、これらを10倍~500倍等の範囲で濃縮した消毒剤を製造することもできる。 The disinfectant of the present invention can be made into a disinfectant with a predetermined concentration by preparing a concentrated disinfectant in which the medium is adjusted in advance to less than a predetermined amount, and then adding the medium to adjust the concentration. The medium used for adjustment and the medium used for density adjustment need not be the same, but must be mixed. The description of the content of each component described in this specification is a description of the content of each component when using the disinfectant, and the disinfectant is manufactured by concentrating these in the range of 10 to 500 times can also
〈その他の成分〉
 本発明の消毒剤には、本発明の効果を損なわない範囲であれば、他の成分を配合することができる。例えば、薬効成分、上記以外の界面活性剤、消毒剤の調製に一般的に使用される希釈剤、粘度調整剤、グリセロール等の安定化剤、防腐剤、矯味剤(甘味料を含む)、矯臭剤(香料を含む)、着色料、ゼオライト等の単分散固体粒子等の各種添加剤を挙げることができる。
<Other ingredients>
The disinfectant of the present invention may contain other ingredients as long as they do not impair the effects of the present invention. For example, medicinal ingredients, surfactants other than the above, diluents commonly used in the preparation of disinfectants, viscosity modifiers, stabilizers such as glycerol, preservatives, flavoring agents (including sweeteners), flavorings agents (including fragrances), colorants, monodisperse solid particles such as zeolite, and various other additives.
 本発明の消毒剤は、例えば消毒剤を使用したあとにヨウ素を消散させるためのヨウ素消散成分、例えばエチレンジアミンテトラ酢酸等を含む必要がない。例えば、ヨウ素消散成分は、0.01w/v%以下、0.001w/v%以下、0.0005w/v%以下、又は0.0001w/v%以下とすることができ、全く含まなくてもよい。 The disinfectant of the present invention does not need to contain an iodine-dissipating component, such as ethylenediaminetetraacetic acid, for dissipating iodine after using the disinfectant. For example, the iodine dissipating component can be 0.01 w/v% or less, 0.001 w/v% or less, 0.0005 w/v% or less, or 0.0001 w/v% or less, or even not included at all. good.
 本発明の消毒剤は、ポリビニルピロリドンを含む必要がない。例えば、ポリビニルピロリドンは、0.01w/v%以下、0.001w/v%以下、0.0005w/v%以下、又は0.0001w/v%以下とすることができ、全く含まなくてもよい。 The disinfectant of the present invention need not contain polyvinylpyrrolidone. For example, polyvinylpyrrolidone may be 0.01 w/v% or less, 0.001 w/v% or less, 0.0005 w/v% or less, 0.0001 w/v% or less, or may be completely absent. .
 本発明の消毒剤は、pHの安定化のためにpH緩衝剤、例えばホウ酸塩緩衝剤、リン酸塩緩衝剤、クエン酸塩緩衝剤、乳酸緩衝液等を含有していてもよい。消毒剤における緩衝剤の含有量は、消毒剤のpHを好適な範囲、例えば中性から弱酸性の範囲に安定化させることができれば特に限定されないが、例えば、0.02~3.0w/v%、又は0.1~1.5w/v%である。 The disinfectant of the present invention may contain pH buffers such as borate buffers, phosphate buffers, citrate buffers, lactic acid buffers, etc. for pH stabilization. The content of the buffering agent in the disinfectant is not particularly limited as long as the pH of the disinfectant can be stabilized in a suitable range, such as a neutral to weakly acidic range, but for example, 0.02 to 3.0 w/v. %, or 0.1 to 1.5 w/v %.
 本発明の消毒剤は、静電反発力による分散安定性を高めるためにイオン性界面活性剤、例えばヨウ化アルキルトリメチルアンモニウム、塩化ジアルキルジメチルアンモニウム等のカチオン系界面活性剤、N-アシルグルタミン酸塩、N-メチル-アシルタウリン塩等のアニオン系界面活性剤を含有していてもよい。消毒剤におけるイオン性界面活性剤の含有量は、エマルションのノニオン系界面活性剤に対するモル分量として0.1~50mol/mol、又は3~20mol/molである。 The disinfectant of the present invention contains ionic surfactants such as cationic surfactants such as alkyltrimethylammonium iodide and dialkyldimethylammonium chloride, N-acylglutamate, An anionic surfactant such as N-methyl-acyl taurine salt may be contained. The content of the ionic surfactant in the disinfectant is 0.1 to 50 mol/mol, or 3 to 20 mol/mol as a molar amount relative to the nonionic surfactant in the emulsion.
《消毒フィルム》
 本発明の消毒フィルムは、ヨウ素及び界面活性剤をバインダー樹脂中に含み、前記界面活性剤が、ノニオン系界面活性剤である。
《Disinfection film》
The disinfecting film of the present invention contains iodine and a surfactant in a binder resin, and the surfactant is a nonionic surfactant.
 本発明者らは、ヨウ素及び界面活性剤を含むフィルムが、フィルムの状態でウィルスを不活化できることを見出した。抗菌性を有するフィルムは、従来技術においても存在していたが、このようなヨウ素系の消毒フィルムは、本発明者らが初めて見出した。本発明の消毒フィルムをボタン、タッチパネル等の表面に貼り付けることで、細菌やウィルスの拡散を防止することができるため、非常に有用である。また、本発明の消毒フィルムを傷口等に貼り付けることで細菌やウィルスへの感染も防止することができる。さらに、ヨウ素系の液体消毒剤の代わりに、例えば乳牛の乳房炎を防止するために用いられているヨウ素系の消毒剤の代わりに、本発明の消毒フィルムを乳牛の乳房に貼り付けることで、消毒の効果も長期間持続できる。 The inventors found that a film containing iodine and a surfactant can inactivate viruses in the form of a film. Films having antibacterial properties existed in the prior art, but the present inventors were the first to discover such an iodine-based antiseptic film. By attaching the antiseptic film of the present invention to the surfaces of buttons, touch panels, etc., it is possible to prevent the spread of bacteria and viruses, which is very useful. In addition, by attaching the disinfecting film of the present invention to a wound or the like, it is possible to prevent infection with bacteria and viruses. Furthermore, instead of an iodine-based liquid disinfectant, for example, instead of an iodine-based disinfectant used to prevent mastitis in dairy cows, the disinfectant film of the present invention can be applied to the udder of a dairy cow. The effect of disinfection can also be maintained for a long time.
 ヨウ素及び界面活性剤は、上記の消毒剤で用いられるものをそれぞれ用いることができる。ヨウ素及び界面活性剤のフィルム中の含有量も、消毒性を提供できるのであれば特に限定されないが、上記の消毒剤に含まれる含有量を参照することができる。 For iodine and surfactants, those used in the above disinfectants can be used. The content of iodine and surfactant in the film is not particularly limited as long as it can provide disinfecting properties, but the content contained in the above disinfectant can be referred to.
 例えば、本発明のフィルムは、バインダー樹脂100質量部に対して、ノニオン界面活性剤を1質量部以上、5質量部以上、10質量部以上、20質量部以上、又は30質量部以上含んでいてもよく、200質量部以下、150質量部以下、100質量部以下、80質量部以下、又は60質量部以下で含んでいてもよい。例えば、本発明のフィルムは、バインダー樹脂100質量部に対して、ノニオン界面活性剤を、1質量部以上200質量部以下、又は20質量部以上80質量部以下で含んでいてもよい。なお、ノニオン系界面活性剤に対するヨウ素の重量比は、上記の本発明の消毒剤と同じとすることができる。 For example, the film of the present invention contains 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more of a nonionic surfactant with respect to 100 parts by mass of the binder resin. 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, 80 parts by mass or less, or 60 parts by mass or less. For example, the film of the present invention may contain 1 part by mass or more and 200 parts by mass or less, or 20 parts by mass or more and 80 parts by mass or less of a nonionic surfactant with respect to 100 parts by mass of the binder resin. The weight ratio of iodine to the nonionic surfactant can be the same as that of the disinfectant of the present invention.
 バインダー樹脂としては、本発明の有利な効果を提供でき、かつフィルム用のバインダー樹脂として使用できれば特に限定されないが、製造の容易さを考慮した場合には、水溶性ポリマーを挙げることができる。 The binder resin is not particularly limited as long as it can provide the advantageous effects of the present invention and can be used as a binder resin for films, but water-soluble polymers can be mentioned in consideration of ease of production.
 水溶性ポリマーとしては、例えば、ポリビニルアルコール類、ポリビニルピロリドン類、ポリエチレンオキシド、ポリプロピレンオキシド等のポリアルキレンオキシド類、ポリアクリル酸、ポリアクリルアミド等の水溶性(メタ)アクリル系樹脂類、水溶性の酢酸ビニル系樹脂類及びこれらの塩、ゼラチン、並びに増粘多糖類を挙げることができる。増粘多糖類としては、ゲランガム、アルギン酸ナトリウム等のアルギン酸又はその塩、キサンタンガム、寒天、アガロース、ローカストビーンガム等の食品添加物系の多糖類を特に挙げることができる。 Examples of water-soluble polymers include polyvinyl alcohols, polyvinylpyrrolidones, polyalkylene oxides such as polyethylene oxide and polypropylene oxide, water-soluble (meth)acrylic resins such as polyacrylic acid and polyacrylamide, and water-soluble acetic acid. Vinyl resins and salts thereof, gelatin, and thickening polysaccharides can be mentioned. Examples of thickening polysaccharides include food additive polysaccharides such as gellan gum, alginic acid such as sodium alginate or salts thereof, xanthan gum, agar, agarose, and locust bean gum.
 水溶性ポリマーを使用する場合、上記の消毒剤に水溶性ポリマーを溶解し、これを乾燥させるだけで消毒フィルムを得ることができる。 When using a water-soluble polymer, a disinfecting film can be obtained simply by dissolving the water-soluble polymer in the above disinfectant and drying it.
 本発明の消毒フィルムは、水溶性ポリマーの種類等に応じて、ゲル化促進剤をさらに含有することができる。ゲル化促進剤としては、アルカリ金属又はアルカリ土類金属の塩、例えばカルシウム塩、マグネシウム塩、ナトリウム塩及びカリウム塩を挙げることができ、塩としては、有機塩又は無機塩を挙げることができ、好ましくはハロゲン塩、例えば塩化物、フッ化物等を挙げることができる。 The antiseptic film of the present invention can further contain a gelling accelerator depending on the type of water-soluble polymer. Examples of gelling accelerators include salts of alkali metals or alkaline earth metals, such as calcium salts, magnesium salts, sodium salts and potassium salts. Examples of salts include organic salts or inorganic salts. Halogen salts such as chlorides and fluorides are preferred.
 ゲル化促進剤を用いる場合、例えば、上記の消毒剤と水溶性ポリマーとを水系媒体に溶解し、これをシャーレ等の容器に均一に広げて入れて、その上にゲル化促進剤を含む水系媒体を重ねて広げる。そして、液相を乾燥等によって除去させて、フィルムを固化させることで、本発明のフィルムを製造することができる。 When a gelation accelerator is used, for example, the above disinfectant and water-soluble polymer are dissolved in an aqueous medium, and this is spread evenly in a container such as a petri dish, and an aqueous system containing the gelation accelerator is placed thereon. Spread out the medium on top of each other. Then, the film of the present invention can be produced by removing the liquid phase by drying or the like and solidifying the film.
 本発明の消毒フィルムの含水量は、特に限定されないが、50w/v%以下、10w/v%以下、1w/v%以下、又は0.1w/v%以下とすることができ、全く含まなくてもよい。 The water content of the antiseptic film of the present invention is not particularly limited, but can be 50 w/v% or less, 10 w/v% or less, 1 w/v% or less, or 0.1 w/v% or less, and does not contain any may
 本発明の消毒フィルムの厚さは、特に限定されないが、1μm以上、5μm以上、10μm以上、30μm以上、50μm以上、100μm以上、500μm以上、又は1mm以上とすることができ、また5mm以下、3mm以下、1mm以下、500μm以下、300μm以下、100μm以下、50μm以下、又は30μm以下とすることができる。例えば、消毒フィルムの厚さは、1μm以上5mm以下、30μm以上1mm以下、又は100μm以上500μm以下であってもよい。 The thickness of the antiseptic film of the present invention is not particularly limited, but may be 1 μm or more, 5 μm or more, 10 μm or more, 30 μm or more, 50 μm or more, 100 μm or more, 500 μm or more, or 1 mm or more. 1 mm or less, 500 μm or less, 300 μm or less, 100 μm or less, 50 μm or less, or 30 μm or less. For example, the thickness of the antiseptic film may be between 1 μm and 5 mm, between 30 μm and 1 mm, or between 100 μm and 500 μm.
 本発明の消毒フィルムは、上記の消毒剤を作製し、それを型に投入し又は基材上に塗布し、その後に乾燥して、消毒積層体の1層として使用することができる。基材は気体や液体でなければ特に限定されない。例えば、紙、布、フィルム、発泡体、繊維、ガラス、ゴム等の形を保っている基材であってよい。したがって、消毒積層体は、基材及び基材上の消毒フィルムを含む。この場合、消毒フィルムは、コーティングのような形態であってもよく、基材と接着剤等で接着された自立性のフィルムであってもよい。 The antiseptic film of the present invention can be used as one layer of the antiseptic laminate by preparing the above antiseptic, putting it into a mold or coating it on a substrate, and then drying it. The base material is not particularly limited as long as it is not gas or liquid. For example, it may be a form-retaining substrate such as paper, cloth, film, foam, fiber, glass, rubber, and the like. The antiseptic laminate thus comprises a substrate and an antiseptic film on the substrate. In this case, the antiseptic film may be in the form of a coating, or may be a self-supporting film adhered to the substrate with an adhesive or the like.
 《消毒ビーズ》
 本発明の消毒ビーズは、ヨウ素及び界面活性剤をバインダー樹脂中に含み、前記界面活性剤が、ノニオン系界面活性剤である。
《Disinfection beads》
The disinfecting beads of the present invention contain iodine and a surfactant in a binder resin, and the surfactant is a nonionic surfactant.
 消毒ビーズも、上記の消毒フィルムと同様に、ビーズの状態でウィルスを不活化でき、非常に有用である。これを基材に貼り付けて使用したり、容器に入れてそのまま使用したりすることも可能である。 Disinfectant beads, like the disinfectant film above, can inactivate viruses in the form of beads, which is very useful. It is also possible to use it by attaching it to a base material, or put it in a container and use it as it is.
 ヨウ素、界面活性剤及びバインダー樹脂は、上記の消毒剤又は消毒フィルムで用いられるものをそれぞれ用いることができる。ヨウ素、界面活性剤及びバインダー樹脂のビーズ中の含有量も、消毒性を提供できるのであれば特に限定されないが、上記のフィルムに含まれる含有量を参照することができる。 For the iodine, surfactant, and binder resin, those used in the above disinfectant or disinfectant film can be used, respectively. The contents of the iodine, surfactant and binder resin in the beads are not particularly limited as long as they can provide disinfecting properties, but the contents contained in the above film can be referred to.
 本発明のビーズの含水量は、特に限定されないが、50w/v%以下、10w/v%以下、1w/v%以下、又は0.1w/v%以下とすることができ、全く含まなくてもよい。 The water content of the beads of the present invention is not particularly limited, but may be 50 w/v% or less, 10 w/v% or less, 1 w/v% or less, or 0.1 w/v% or less, and may be completely free of water. good too.
 バインダー樹脂及びゲル化促進剤としても、上記のフィルムで使用できるものを用いることができる。 As the binder resin and the gelling accelerator, those that can be used in the above film can be used.
 消毒ビーズは、上記の消毒剤に水溶性ポリマーを溶解し、これを、ゲル化促進剤を含む水系媒体に滴下させることによって得ることができる。製造した直後は、ゲル状のビーズが得られるが、このゲル状ビーズの水分を除去しても、本発明のビーズではヨウ素と界面活性剤とが複合化しているため消毒性が失われない。 Disinfectant beads can be obtained by dissolving a water-soluble polymer in the above disinfectant and dropping it into an aqueous medium containing a gelling accelerator. Immediately after production, gel-like beads are obtained, but even if the water content of the gel-like beads is removed, the beads of the present invention do not lose their disinfecting properties because iodine and surfactant are complexed.
 本発明の消毒ビーズは、基材上又は基材中に存在させて、用いることができる。基材としては、上記の消毒積層体に用いられる基材を挙げることができる。消毒ビーズは、接着剤等で基材上に接着させてもよく、繊維基材等に含有させて用いることもできる。 The disinfecting beads of the present invention can be used by being present on or in a substrate. Examples of the base material include the base material used for the disinfecting laminate described above. The antiseptic beads may be adhered onto a substrate with an adhesive or the like, or may be used by being contained in a fiber substrate or the like.
《消毒効果の判別検出方法》
 本発明の消毒フィルム及び消毒ビーズは着色しており、特に薄い褐色を有している。これは消毒性能を有するヨウ素に由来するものであり、可視光に特有の吸光を有している。つまり、消毒フィルム及びそれを含む消毒積層体並びに消毒ビーズが退色することでそれらの消毒性能が低下したことを検出できる。検出方法はフィルム及びビーズの色を識別する検査方法であれば特に限定されない。例えば、目視による外観確認、分光光度計であってよい。
<<Disinfection effect detection method>>
The disinfecting films and disinfecting beads of the present invention are colored, in particular have a light brown color. It is derived from iodine, which has disinfecting properties, and has a characteristic absorption of visible light. In other words, it is possible to detect that the disinfecting performance of the disinfecting film, the disinfecting laminate including the disinfecting film, and the disinfecting beads has deteriorated due to fading. The detection method is not particularly limited as long as it is an inspection method that identifies the colors of the film and beads. For example, the appearance may be confirmed by visual observation or by a spectrophotometer.
 本発明を以下の実施例でさらに具体的に説明をするが、本発明はこれによって限定されるものではない。 The present invention will be described more specifically in the following examples, but the present invention is not limited by these.
実験1:ポリオキシエチレンソルビタンモノオレートとヨウ素との複合化の実験
 界面活性剤として、ノニオン系界面活性剤のポリオキシエチレンソルビタンモノオレート(Tween80)を水に様々な濃度で混合した。これに、ヨウ素が20ppmとなるように、ヨウ素及びヨウ化カリウムを重量比で1:8の比率で混合して消毒剤を得た。
Experiment 1: Experiment of Compositing Polyoxyethylene Sorbitan Monooleate and Iodine As a surfactant, polyoxyethylene sorbitan monooleate (Tween 80), which is a nonionic surfactant, was mixed with water at various concentrations. To this, iodine and potassium iodide were mixed in a weight ratio of 1:8 so that the iodine content was 20 ppm to obtain a disinfectant.
 これらの消毒液の270nm~500nmの範囲の光吸収スペクトル(吸光度)を図1に示す。 Fig. 1 shows the light absorption spectrum (absorbance) of these disinfectants in the range of 270 nm to 500 nm.
 図1を参照すると、界面活性剤を0.1w/v%以上含有すると、吸光度の上昇及びピークシフトが観察され、ヨウ素と界面活性剤による複合体が形成されていることが確認される。 Referring to FIG. 1, when the surfactant content is 0.1 w/v% or more, an increase in absorbance and a peak shift are observed, confirming that a complex is formed by iodine and the surfactant.
実験2:消毒剤の安定性試験
 界面活性剤を含まず、200ppmのヨウ素を含有する消毒剤(比較例1);1.0w/v%の界面活性剤(Tween80)と200ppmのヨウ素を含有する消毒剤(実施例1);安定剤として5.0w/v%のグリセロールと200ppmのヨウ素及びヨウ化カリウムを含有する消毒剤(比較例2);実施例1の消毒剤に安定剤として5.0w/v%のグリセロールをさらに添加した消毒剤(実施例2);及び有効な殺菌性を示す200ppmのヨウ素濃度まで希釈したポビドンヨードのうがい用消毒剤(比較例3)を調製した。
Experiment 2: Stability test of disinfectant Disinfectant containing no surfactant and containing 200 ppm iodine (Comparative Example 1); containing 1.0 w/v% surfactant (Tween 80) and 200 ppm iodine Disinfectant (Example 1); Disinfectant containing 5.0 w/v % glycerol as stabilizer and 200 ppm iodine and potassium iodide (Comparative Example 2); An antiseptic with the additional addition of 0 w/v % glycerol (Example 2); and a povidone-iodine mouthwash (Comparative Example 3) diluted to an iodine concentration of 200 ppm showing effective bactericidal activity were prepared.
 これらを蓋の開いた瓶に保管して、その保存安定性の試験を行った。具体的には、吸収スペクトルにおける280nm~300nm付近のピークを経時観察した。各例の調製直後の吸光度を100%とした場合に、ピークがどの程度減少したかを図2に示す。 We stored these in a jar with an open lid and tested its storage stability. Specifically, the peak near 280 nm to 300 nm in the absorption spectrum was observed over time. FIG. 2 shows how much the peak decreased when the absorbance immediately after preparation of each example was taken as 100%.
 図2を参照すると、実施例1及び2の消毒剤は、約30日が経過しても、吸光度が減少していないのに対して、比較例1~3の消毒剤は、数日~10日程度で、吸光度のピークが失われていることが分かる。実際に、実施例1及び2の消毒剤は、約30日が経過しても色の変化がなかったのに対し、比較例1~3の消毒剤は、吸光度のピークが失われるにつれて無色になっていった。 Referring to FIG. 2, the disinfectants of Examples 1 and 2 did not decrease in absorbance even after about 30 days, whereas the disinfectants of Comparative Examples 1-3 showed a few days to 10 days. It can be seen that the absorbance peak is lost in about a day. In fact, the sanitizers of Examples 1 and 2 did not change color after about 30 days, whereas the sanitizers of Comparative Examples 1-3 became colorless as the absorbance peak was lost. became.
実験3:消毒剤の殺菌性試験
 界面活性剤として、界面活性剤(Tween80)を水に様々な濃度で混合し、そのそれぞれに様々な含有量でヨウ素及びヨウ化カリウムを添加して消毒剤を得た。
Experiment 3: Bactericidal activity test of disinfectant As a surfactant, a surfactant (Tween 80) was mixed with water at various concentrations, and iodine and potassium iodide were added to each of them at various contents to make a disinfectant. Obtained.
 この消毒剤を用いて、シュードモナス細菌に対する殺菌性能を試験した。ここで、1/10倍濃度のLB液体培地をオートクレーブし、白金耳を用いて被験菌を植菌し、30℃、150rpmで一晩振盪培養を行った。これを前培養液とした。1/5倍濃度のLB液体培地(2.5mL)をオートクレーブ処理したのちに、目的の終濃度になるよう調製したヨウ素-界面活性剤複合体溶液(2.5mL)を加えた。調整した培地に、前培養液5μLを添加して、30℃、150rpmで振盪培養を1日行った。培養の前後で濁度測定し、濁度増加から被験菌の増殖を調べた。 Using this disinfectant, we tested its bactericidal performance against Pseudomonas bacteria. Here, a 1/10-fold concentration LB liquid medium was autoclaved, the test bacteria were inoculated using a platinum loop, and shaking culture was performed overnight at 30° C. and 150 rpm. This was used as a pre-culture solution. After autoclaving a 1/5-fold concentration LB liquid medium (2.5 mL), an iodine-surfactant complex solution (2.5 mL) adjusted to the desired final concentration was added. 5 μL of the preculture solution was added to the adjusted medium, and shaking culture was performed at 30° C. and 150 rpm for one day. Turbidity was measured before and after culture, and the growth of the test bacteria was examined from the increase in turbidity.
 その結果を図3に示す。 The results are shown in Figure 3.
 図3を参照すると、界面活性剤の含有量が高ければ、ヨウ素濃度は低くても高い殺菌性を占めることが分かる。また、ヨウ素が含まれていない場合で比較すると、界面活性剤の含有量が高いと濁度が高くなり、殺菌性が低くなっていることが分かる。これらの結果から、界面活性剤の含有量とヨウ素濃度との間に相乗効果があることが分かった。 Referring to Fig. 3, it can be seen that if the surfactant content is high, even if the iodine concentration is low, it accounts for high bactericidal activity. In addition, when compared with the case where iodine is not contained, it can be seen that the higher the surfactant content, the higher the turbidity and the lower the bactericidal activity. These results indicate that there is a synergistic effect between the surfactant content and the iodine concentration.
実験4:消毒剤のウィルス不活化試験
 界面活性剤として、1.0w/v%の界面活性剤(Tween80)に様々な含有量でヨウ素及びヨウ化カリウムを添加して消毒剤を得た。
Experiment 4: Virus inactivation test of disinfectant As a surfactant, iodine and potassium iodide were added to 1.0 w/v% surfactant (Tween 80) at various contents to obtain disinfectants.
 この消毒剤及び参考としてヨウ素及びヨウ化カリウムのみを含む水を用いて、バクテリオファージQβ(Escherichia coli phage Qβ:NBRC20012)及びバクテリオファージΦ6(Pseudomonas syringae phageφ6:NBRC105899)にそれぞれ感染させた大腸菌あるいはシュードモナス細菌を用いてウィルスの不活化性能を試験した。それらを用いて、二重平板法によるプラーク計測によって、ウィルスの不活化試験を行った。なお、バクテリオファージQβは、エンベロープを持たないノロウィルス等のウィルスモデルとして用いることができ、バクテリオファージΦ6は、エンベロープを持つインフルエンザウィルス、コロナウィルス等のウィルスモデルとして用いることができる。 Escherichia coli or Pseudomonas bacteria infected with bacteriophage Qβ (Escherichia coli phage Qβ: NBRC20012) and bacteriophage Φ6 (Pseudomonas syringae phage Φ6: NBRC105899), respectively, using this disinfectant and water containing only iodine and potassium iodide as a reference was used to test the virus inactivation performance. Using them, a virus inactivation test was performed by plaque counting by the double plate method. Bacteriophage Qβ can be used as a virus model such as norovirus that does not have an envelope, and bacteriophage Φ6 can be used as a virus model that has an envelope such as influenza virus and coronavirus.
 具体的には、Escherichia coli NBRC13965とPseudomonas syringae NBRC14084を用いた。調製した702液体培地をオートクレーブ処理したものに、使用菌株のコロニーの一部を白金耳を用いて植菌し、30℃、150rpmで一晩振盪培養を行った。培地は、液体培地の他に上層寒天培地と下層寒天培地との2種類を使用した。上層寒天培地(軟寒天培地)は、寒天粉末0.7%を加えた702液体培地を試験管に4mlずつ分注し、アルミキャップをかぶせたのちオートクレーブ処理を行い、52℃のウォーターバスで15分ほど保温し使用した。下層寒天培地は、寒天粉末1.5%を加えた702液体培地をオートクレーブ処理後に深型のシャーレにまいた。 Specifically, Escherichia coli NBRC13965 and Pseudomonas syringae NBRC14084 were used. A portion of the colony of the strain used was inoculated into the autoclaved 702 liquid medium prepared using a platinum loop, and shake culture was performed overnight at 30° C. and 150 rpm. Two types of medium were used, a liquid medium, an upper layer agar medium and a lower layer agar medium. For the upper agar medium (soft agar medium), 4 ml of 702 liquid medium containing 0.7% agar powder was dispensed into each test tube, covered with an aluminum cap, autoclaved, and placed in a water bath at 52°C for 15 minutes. I kept it warm for about a minute and used it. For the lower layer agar medium, 702 liquid medium containing 1.5% agar powder was autoclaved and spread in a deep petri dish.
 次に、ファージ原液を10mMカリウムリン酸緩衝液(KPB)で10倍希釈したものに、消毒剤1mlを5分間作用させ、702液体培地9mlを加えることでヨウ素を不活化させた。KPBで10倍、10倍、10倍、又は10倍希釈のファージ希釈液となるよう調製し、これらファージ希釈液100μlと前培養菌液100μlを保温していた上層寒天培地に加え静かに撹拌後、室温に戻した下層寒天培地に均一になるよう流し込んだ。上向きにして1晩培養後にプラーク数を計測し、以下の式でファージ濃度(PFU)を計算した。 Next, the phage stock solution was diluted 10-fold with 10 mM potassium phosphate buffer (KPB), treated with 1 ml of disinfectant for 5 minutes, and added with 9 ml of 702 liquid medium to inactivate iodine. A 10 3 -fold, 10 4 -fold, 10 5 -fold or 10 6 -fold diluted phage dilution was prepared with KPB, and 100 μl of these phage dilutions and 100 μl of the pre-cultured bacterial solution were added to the warmed upper agar medium. After gently stirring, the mixture was uniformly poured into the lower layer agar medium which had been returned to room temperature. The number of plaques was counted after culturing overnight with the plate facing upward, and the phage concentration (PFU) was calculated according to the following formula.
ファージ濃度(PFU/ml)=
 プラークの数×(希釈倍率×1,000(μl))/(ファージ希釈液の容量(μl))
Phage concentration (PFU/ml) =
Number of plaques x (dilution rate x 1,000 (μl))/(volume of phage dilution (μl))
 ここで、PFU(Plaque Forming Unit)は、プラークを形成することのできたファージ粒子の数を表す。なお、ヨウ素-Tween80複合体溶液は、Tween80濃度が0、1%、ヨウ素濃度が0-200ppmとなるよう調製した。培養温度はバクテリオファージQβを感染させた大腸菌が37℃、バクテリオファージφ6を感染させたシュードモナス細菌が25℃である。 Here, PFU (Plaque Forming Unit) represents the number of phage particles that were able to form plaques. The iodine-Tween80 complex solution was prepared so that the Tween80 concentration was 0 or 1% and the iodine concentration was 0-200 ppm. The culture temperature is 37° C. for Escherichia coli infected with bacteriophage Qβ, and 25° C. for Pseudomonas bacteria infected with bacteriophage φ6.
 バクテリオファージQβについての結果を、図4(a)に示し、バクテリオファージΦ6についての結果を、図4(b)に示す。 The results for bacteriophage Qβ are shown in FIG. 4(a), and the results for bacteriophage Φ6 are shown in FIG. 4(b).
 図4(a)を見ると、ヨウ素濃度を100ppm以上含む消毒剤は、プラーク数を2桁以上減少させることができている。また、図4(b)を見ると、ヨウ素濃度を10ppm以上含む消毒剤は、プラーク数を3桁以上減少させることができており、エンベロープを持つコロナウィルス等のウィルスに対して本発明の消毒剤が特に有効であることが分かった。 Looking at Figure 4 (a), the disinfectant containing iodine concentration of 100 ppm or more can reduce the number of plaques by more than two orders of magnitude. Also, looking at FIG. 4(b), the disinfectant containing iodine concentration of 10 ppm or more can reduce the number of plaques by three orders of magnitude or more, and the disinfection of the present invention against viruses such as enveloped coronaviruses. agents have been found to be particularly effective.
実験5:消毒薬の抗微生物スペクトル
 界面活性剤として、1.0w/v%の界面活性剤(Tween80)にヨウ素濃度を25ppmを添加して実施例3を得た。参考として、界面活性剤を添加せずにヨウ素濃度25ppmを添加した比較例4、1.0w/v%の界面活性剤(Tween80)にヨウ素を添加しない比較例5を得た。
Experiment 5: Antimicrobial spectrum of disinfectant Example 3 was obtained by adding an iodine concentration of 25 ppm to a surfactant (Tween 80) of 1.0 w/v% as a surfactant. For reference, Comparative Example 4 in which 25 ppm of iodine was added without adding a surfactant, and Comparative Example 5 in which iodine was not added to a 1.0 w/v% surfactant (Tween 80) were obtained.
 これらの消毒薬を用いて、様々な細菌に対する殺菌試験を試験した。その結果を表1に示す。 Using these disinfectants, we tested sterilization tests against various bacteria. Table 1 shows the results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 上記表のうち、「○」は、消毒薬の代わりに水を用いたブランク試験に対して濁度が99.9%以上低く、且つ、検出下限以下であったことを意味している。「△」は水に対して濁度が90.0%~99.9%低かったことを意味している。「×」は水に対して濁度が90.0%以上低くならなかったことを意味している。 In the above table, "○" means that the turbidity was 99.9% or more lower than the blank test using water instead of disinfectant and was below the lower limit of detection. "Δ" means that the turbidity was 90.0% to 99.9% lower than water. "X" means that the turbidity did not decrease by 90.0% or more with respect to water.
 表1を見ると、ヨウ素や界面活性剤のみの消毒薬では殺菌性が低い、又は見られなかったが、二つを複合体にすることで殺菌効果が相乗効果により大幅に向上している。また、この消毒薬は非常に広い抗微生物スペクトルを有していることが分かった。 Looking at Table 1, disinfectants containing only iodine and surfactants had low or no bactericidal activity, but by combining the two, the bactericidal effect is greatly improved due to the synergistic effect. It was also found that this disinfectant has a very broad antimicrobial spectrum.
実験6:消毒剤を含む消毒フィルムの実験
 水溶性ポリマーであるゲランガムを1w/v%、界面活性剤(Tween80)を1.0w/v%、ヨウ素を200ppm及びヨウ化カリウムを水中で混合し、これらの水溶液を得た。この水溶液10mlをΦ90mmのガラスシャーレに投入し薄膜を形成した。さらに0.5質量%の塩化カルシウム溶液を重層して加え、固化させた。そして、5日間風乾させた水分を除去して実施例4のフィルムを形成した。また、ヨウ素を含めないこと以外は実施例4と同様にして、比較例6のフィルムを形成した。さらに、ヨウ素と界面活性剤とを含めないこと以外は実施例4と同様にして、比較例7のフィルムを形成した。
Experiment 6: Experiment of disinfecting film containing disinfectant 1 w / v% of gellan gum, which is a water-soluble polymer, 1.0 w / v% of surfactant (Tween 80), 200 ppm of iodine and potassium iodide are mixed in water, These aqueous solutions were obtained. A thin film was formed by putting 10 ml of this aqueous solution into a φ90 mm glass petri dish. Further, a 0.5% by weight calcium chloride solution was added in layers and allowed to solidify. Then, the film of Example 4 was formed by removing moisture after air-drying for 5 days. A film of Comparative Example 6 was formed in the same manner as in Example 4, except that iodine was not included. Further, a film of Comparative Example 7 was formed in the same manner as in Example 4, except that iodine and surfactant were not included.
 これらのフィルム上に、ウィルスを含む液を滴下して、約10分経過後にそのフィルムを洗い出して、その液でウィルスを大腸菌に感染させた。その後、上記実験4と同様にして、用いてウィルスの不活化性能を試験した。 A virus-containing liquid was dropped onto these films, and after about 10 minutes, the films were washed out, and the liquid was used to infect E. coli with the virus. Then, in the same manner as in Experiment 4, the virus inactivation performance was tested.
 具体的には、1×1cmのヨウ素フィルムにファージ原液10μlをのせ、10分間放置した。その後、702液体培地10ml入り試験管をオートクレーブ処理したものにフィルムを入れ撹拌した。これを10倍ファージ希釈液とし、同様に702液体培地を用いて10倍と10倍ファージ希釈液を調製した。10~10ファージ希釈液をそれぞれ100μlと、前培養菌液100μlとを、保温していた上層寒天培地に加え静かに撹拌後、室温に戻した下層寒天培地に均一になるよう流し込んだ。1晩培養後にプラーク数を計測し、ファージ濃度(PFU)を計算した。 Specifically, 10 μl of the phage stock solution was placed on an iodine film of 1×1 cm 2 and allowed to stand for 10 minutes. Then, the film was placed in an autoclaved test tube containing 10 ml of 702 liquid medium and stirred. This was used as a 10 3 -fold phage dilution, and 10 4 and 10 5 -fold phage dilutions were similarly prepared using 702 liquid medium. 100 μl each of the 10 3 to 10 5 phage dilutions and 100 μl of the pre-cultured bacterial solution were added to the warmed upper layer agar medium, stirred gently, and poured uniformly into the lower layer agar medium that had been returned to room temperature. After overnight culture, the number of plaques was counted and the phage concentration (PFU) was calculated.
 バクテリオファージQβについての結果を、図5(a)に示し、バクテリオファージΦ6についての結果を、図5(b)に示す。 The results for bacteriophage Qβ are shown in FIG. 5(a), and the results for bacteriophage Φ6 are shown in FIG. 5(b).
 図5(a)を見ると、実施例4のフィルムは、プラーク数を1桁以上減少させることができている。また、図5(b)を見ると、実施例4のフィルムは、計測できる範囲でプラークが確認できず、プラーク数を少なくとも4桁以上減少させることができた。したがって、本発明の消毒フィルムは、ウィルスと接触するだけでウィルスを不活化できることが分かった。また、特に、本発明の消毒フィルムは、エンベロープを持つコロナウィルス等のウィルスに対して非常に有効であることが分かった。 Looking at FIG. 5(a), the film of Example 4 was able to reduce the number of plaques by one digit or more. Moreover, referring to FIG. 5(b), the film of Example 4 showed no plaques within the measurable range, and was able to reduce the number of plaques by at least four orders of magnitude. Therefore, it was found that the antiseptic film of the present invention can inactivate viruses simply by contacting them. In particular, it was found that the antiseptic film of the present invention is very effective against viruses such as enveloped coronaviruses.
 同様に、ゲランガムに代えて、アルギン酸ナトリウム及びポリアクリルアミドでも同様のフィルム化を行ったところ、これらのフィルムでも消毒性能があることが分かった。図6は、実施例4の1w/v%のゲランガムの代わりに、2w/v%のアルギン酸ナトリウムを用いて得られたフィルムの実際の写真を示す。 Similarly, instead of gellan gum, sodium alginate and polyacrylamide were also used to form a similar film, and it was found that these films also had antiseptic properties. FIG. 6 shows an actual photograph of a film obtained using 2 w/v % sodium alginate instead of 1 w/v % gellan gum in Example 4. FIG.
実験7:様々な界面活性剤を含む消毒剤の実験
 界面活性剤のポリオキシエチレンソルビタンモノオレート(Tween80、C18;1(n-9))を、他の界面活性剤に変更したこと以外は、上記実験1及び実験3と同様にして、界面活性剤とヨウ素との複合化とそれによる殺菌性能を試験した。
Experiment 7: Experiment of disinfectants containing various surfactants Except for changing the surfactant polyoxyethylene sorbitan monooleate (Tween 80, C18; 1 (n-9)) to another surfactant, In the same manner as in Experiments 1 and 3, the surfactant and iodine were combined and the bactericidal performance thereof was tested.
 図7に、ポリオキシエチレンソルビタンモノラウレート(Tween20、C12)を含む消毒剤の結果を示し、図8に、ポリオキシエチレンソルビタンモノステアレート(Tween60、C18)を含む消毒剤の結果を示す。それぞれにおいて、(a)は吸光度試験の結果であり、(b)は殺菌性能試験の結果である。 Fig. 7 shows the results of disinfectants containing polyoxyethylene sorbitan monolaurate (Tween 20, C12), and Fig. 8 shows the results of disinfectants containing polyoxyethylene sorbitan monostearate (Tween 60, C18). In each, (a) is the result of the absorbance test, and (b) is the result of the bactericidal performance test.
 図7及び図8を参照すると、これらの界面活性剤は、Tween80と同様にヨウ素と複合化することができ、かつそれらを含む消毒剤は殺菌性能も高いことがわかる。  With reference to Figures 7 and 8, it can be seen that these surfactants can be combined with iodine in the same way as Tween 80, and disinfectants containing them have high bactericidal performance.
 図9(a)に、様々な分子量のポリエチレングリコール(PEG)を含む消毒剤の吸光度試験の結果を示し、図9(b)に、アニオン系界面活性剤であるラウリル硫酸ナトリウム(SDS)を含む消毒剤の吸光度試験の結果を示し、図9(c)に、PEG及びSDSを含む消毒剤の吸光度試験の結果を示す。 Figure 9(a) shows the absorbance test results for disinfectants containing polyethylene glycol (PEG) of various molecular weights, and Figure 9(b) shows sodium lauryl sulfate (SDS), an anionic surfactant. The results of the absorbance test of the disinfectant are shown, and FIG. 9(c) shows the result of the absorbance test of the disinfectant containing PEG and SDS.
 図9を参照すると、これらの物質を添加しても吸光度に実質的な差がなく、ヨウ素との複合化がされていないことが分かった。 Referring to FIG. 9, it was found that there was no substantial difference in absorbance even when these substances were added, and they were not complexed with iodine.
 さらに様々な界面活性剤を試験した結果をまとめると、以下の表のとおりとなった。 Furthermore, the results of testing various surfactants are summarized in the table below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 上記表のうち、「○」は、Tween80等と同様に、吸光度が大きく変化をして複合化されている場合及び長時間の殺菌性を保持する場合、具体的には吸光度においてヨウ素に起因する350nmのピークトップの波長が10~20nm長波長側にシフトしている場合(図1の光吸収スペクトルにおいて、「1.0%」及び「0.1%」の例のようなシフトが観察される場合)を意味しており、「△」は、吸光度が変化をして複合化が示唆されている場合及び殺菌性を保持する場合、具体的には吸光度においてヨウ素に起因する350nmのピークトップの波長が1~10nm長波長側にシフトし、その半値幅が増加する場合(図1の光吸収スペクトルにおいて、「0.01%」の例のようなシフトが観察される場合)を意味しており、「×」は、吸光度が実質的に変化をしない場合及び殺菌性をほとんど保持しない場合を意味している。 In the above table, "○" is similar to Tween 80, etc., when the absorbance changes greatly and is compounded and when the long-term sterilization is maintained, specifically due to iodine in absorbance When the wavelength of the peak top at 350 nm is shifted to the long wavelength side by 10 to 20 nm (in the light absorption spectrum in FIG. 1, shifts such as "1.0%" and "0.1%" are observed. When the absorbance changes and the compounding is suggested, and when the bactericidal property is maintained, specifically, the peak top at 350 nm due to iodine in the absorbance The wavelength shifts to the long wavelength side by 1 to 10 nm, and the half width increases (in the light absorption spectrum of FIG. 1, a shift such as "0.01%" is observed) "X" means that the absorbance does not change substantially and that the bactericidal activity is hardly maintained.
 上記表のうち、「A」は界面活性剤単体の殺菌性がなく、ヨウ素単体に対して界面活性剤を入れることで殺菌性が向上している場合を意味しており、「B」はヨウ素単体、界面活性剤単体で殺菌性を示すものの、ヨウ素単体に対して殺菌性が同等以下である場合を意味しており、「C」は界面活性剤単体の殺菌性がなく、且つヨウ素単体に対して殺菌性が同等以下である場合を意味している。 In the above table, "A" means that there is no bactericidal property of the surfactant alone, and the bactericidal property is improved by adding the surfactant to iodine alone, and "B" is iodine. Although the single substance and surfactant alone show bactericidal activity, it means that the bactericidal activity is equal to or lower than that of iodine alone. In contrast, it means that the bactericidal activity is equal to or lower than that.
 この結果から分かるように、ノニオン系界面活性剤を用いた消毒剤については、長時間の殺菌性保持と高い殺菌性能を同時に示すことができた。また、カチオン系界面活性剤、両性界面活性剤については、界面活性剤自体にも殺菌性があるため、ヨウ素との相乗効果が明確ではなかった。 As can be seen from these results, the disinfectant using a nonionic surfactant was able to demonstrate both long-term bactericidal retention and high bactericidal performance. In addition, the synergistic effect with iodine was not clear for cationic surfactants and amphoteric surfactants, since the surfactants themselves also have bactericidal properties.
 さらに、ポリオキシエチレンアルキルエーテルについて、HLBの違いによって、吸光度と殺菌性相乗効果にどのような影響が出るかを試験した。その結果を表3に示す。 Furthermore, for polyoxyethylene alkyl ethers, we tested how differences in HLB affect absorbance and bactericidal synergistic effects. Table 3 shows the results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表3の評価基準は、表2における評価基準と同一である。 The evaluation criteria in Table 3 are the same as those in Table 2.
 この結果、HLB値が高い方が、複合体形成に伴う長時間の殺菌性保持と高い殺菌性能を同時に示すことが分かった。これは、HLB値が高いほうが、O/W型のエマルションを形成するのを促進するためであると考えられる。 As a result, it was found that the higher the HLB value, the longer the bactericidal activity associated with complex formation and the higher the bactericidal performance. This is probably because a higher HLB value promotes the formation of an O/W emulsion.
実験7:複合体の安定性の実験
 様々な濃度の界面活性剤(Tween80)水溶液に20ppmのヨウ素を添加して消毒剤を得た。これを30℃で保管をして、350nm付近のピークの吸光度変化を、経時観察した。
Experiment 7: Complex Stability Experiment A disinfectant was obtained by adding 20 ppm of iodine to various concentrations of surfactant (Tween 80) aqueous solutions. This was stored at 30° C., and the change in absorbance of the peak near 350 nm was observed over time.
 その結果を、図10に示す。 The results are shown in FIG.
 Tween80が0%の場合において、7日目でヨウ素は揮発し、外観は透明になり吸光度が観察できなくなった。これに対して、Tween80が1.0w/v%又は2.0w/v%の溶液では、外観は褐色を維持したまま逆に吸光度の上昇が観察された。これは溶液の水分が蒸発し、Tween80が凝縮された際にヨウ素がTween80に結合したままであり、ヨウ素の濃度が上昇したためだと考えられる。 When Tween 80 was 0%, iodine volatilized on the 7th day, the appearance became transparent, and the absorbance could not be observed. On the other hand, in a solution containing 1.0 w/v % or 2.0 w/v % Tween 80, an increase in absorbance was observed while maintaining a brown appearance. This is probably because iodine remained bound to Tween 80 when the water in the solution evaporated and Tween 80 was condensed, increasing the concentration of iodine.
 様々な濃度の界面活性剤(ポリオキシエチレンアルキルエーテル(C8:HLB11.5)水溶液に20ppmのヨウ素を添加して消毒剤を得た。これを30℃で保管をして、350nm付近のピークの吸光度変化を、経時観察した。同様に、18℃で保管をした消毒剤についても観察をした。なお、界面活性剤を2.0w/v%及び4.0w/v%で含む界面活性剤については、30℃ではエマルションが形成され、光吸収スペクトルが測定しにくくなるため吸光度計を曇点以下の12℃に調整してから測定した。 A disinfectant was obtained by adding 20 ppm of iodine to a surfactant (polyoxyethylene alkyl ether (C8: HLB 11.5) aqueous solution of various concentrations. It was stored at 30 ° C. and the peak near 350 nm The change in absorbance was observed over time, and the disinfectant stored at 18° C. was also observed. At 30°C, an emulsion is formed, making it difficult to measure the light absorption spectrum.
 30℃で保管した場合の結果を図11(a)に示し、18℃で保管した場合の結果を図11(b)に示す。 The results of storage at 30°C are shown in Fig. 11(a), and the results of storage at 18°C are shown in Fig. 11(b).
 図11(a)を参照すると、図10のTween80による消毒剤の吸光度と比較して、ポリオキシエチレンアルキルエーテルを各濃度で含む消毒剤は、吸光度が非常に高く、曇点以上でヨウ素の結合量が非常に多いことが分かった。一方で、7日目及び14日目になると吸光度は激減し、複合体が消失することが分かった。 Referring to FIG. 11(a), compared to the absorbance of the disinfectant with Tween 80 in FIG. It turned out to be very large. On the other hand, it was found that the absorbance decreased sharply on the 7th and 14th days, indicating that the complex disappeared.
 図11(b)を参照すると、18℃で保管をすれば、7日目及び14日目になっても吸光度は減少しておらず、むしろ初期状態から高くなっており、複合体が安定に存在していることが分かった。 Referring to FIG. 11 (b), if stored at 18 ° C., the absorbance did not decrease even on the 7th and 14th days, but rather increased from the initial state, indicating that the complex was stable. found to exist.
 Tween80が0%で1日目の褐色な消毒剤と7日目の外観が透明になった消毒剤、Tween80が1.0w/v%で1日目の褐色な消毒剤と7日目の褐色を維持した消毒剤を用いて実験3と同様の手順で殺菌性を評価した。その結果、褐色の消毒剤はいずれも高い殺菌性能を示したが、透明な消毒剤は殺菌性を全く示さなかった。 Brown disinfectant at 0% Tween 80 on day 1 and disinfectant with clear appearance at 7 days, brown disinfectant at 1.0 w/v% Tween 80 on day 1 and brown disinfectant on day 7. Bactericidal activity was evaluated in the same procedure as in Experiment 3 using a disinfectant that maintained As a result, all of the brown disinfectants showed high bactericidal performance, but the transparent disinfectant did not show any bactericidal activity.
 つまり、吸光度測定や目視による外観検査により定性・定量的に殺菌作用があることを検出することができる。これは消毒フィルムも同様の検出を行うことができる。 In other words, it is possible to qualitatively and quantitatively detect the presence of a bactericidal action through absorbance measurements and visual appearance inspections. This can also detect disinfecting films as well.
実験8:消毒ビーズの実験
 アルギン酸ナトリウムを2w/v%、界面活性剤(Tween80)を1.0w/v%、ヨウ素を200ppm及びヨウ化カリウムを水中で混合し、これらの水溶液を得た。この水溶液を、0.5質量%の塩化カルシウム溶液に滴下したところ、滴下した液滴のサイズに応じてゲル状のビーズが溶液中で形成された。
Experiment 8: Experiment of Disinfection Beads 2 w/v% sodium alginate, 1.0 w/v% surfactant (Tween 80), 200 ppm iodine and potassium iodide were mixed in water to obtain an aqueous solution of these. When this aqueous solution was dropped into a 0.5 mass % calcium chloride solution, gel-like beads were formed in the solution according to the size of the dropped droplet.
 そのビーズを溶液中から分離して得られた消毒ビーズを図12に示す。図12の左側に示すビーズは、水分も含水率が高く、黄色い色をしていた。このビーズを、2ヶ月乾燥させて得られた乾燥ビーズを図12の右側に示す。このビーズは、含水率が非常に低く、乾燥前のビーズよりも色が濃くなっており、オレンジ色になっていた。 Fig. 12 shows the disinfection beads obtained by separating the beads from the solution. The beads shown on the left side of FIG. 12 had a high moisture content and were yellow in color. The dried beads obtained by drying the beads for 2 months are shown on the right side of FIG. This bead had a very low moisture content and was darker than the bead before drying, giving it an orange color.
 これらのビーズの消毒性能を確認したところ、図12の両方の形態において、消毒性能は上記の消毒フィルムのように十分に高いということを確認することができた。 When the disinfection performance of these beads was confirmed, it was confirmed that the disinfection performance of both forms in Fig. 12 was sufficiently high like the above disinfection film.

Claims (15)

  1.  10ppm以上のヨウ素、及び0.05w/v%以上の界面活性剤を媒体中に含む消毒剤であって、前記界面活性剤が、ノニオン系界面活性剤である、消毒剤。 A disinfectant containing 10 ppm or more of iodine and 0.05 w/v% or more of a surfactant in a medium, wherein the surfactant is a nonionic surfactant.
  2.  前記ヨウ素を25ppm以上500ppm以下で含み、かつ前記界面活性剤を0.1w/v%以上1.0w/v%以下で含む、請求項1に記載の消毒剤。 The disinfectant according to claim 1, comprising 25 ppm or more and 500 ppm or less of said iodine and 0.1 w/v% or more and 1.0 w/v% or less of said surfactant.
  3.  前記ノニオン系界面活性剤のHLB値が、9.0以上である、請求項1又は2に記載の消毒剤。 The disinfectant according to claim 1 or 2, wherein the nonionic surfactant has an HLB value of 9.0 or more.
  4.  前記ノニオン系界面活性剤が、ポリオキシエチレン付加型の界面活性剤である、請求項1~3のいずれか一項に記載の消毒剤。 The disinfectant according to any one of claims 1 to 3, wherein the nonionic surfactant is a polyoxyethylene-added surfactant.
  5.  前記媒体が、水系媒体である、請求項1~4のいずれか一項に記載の消毒剤。 The disinfectant according to any one of claims 1 to 4, wherein the medium is an aqueous medium.
  6.  ヨウ化物をさらに含み、前記ヨウ素の含有量に対する前記ヨウ化物の含有量の重量比が、30以下である、請求項1~5のいずれか一項に記載の消毒剤。 The disinfectant according to any one of claims 1 to 5, further comprising iodide, wherein the weight ratio of said iodide content to said iodine content is 30 or less.
  7.  ヨウ素が10ppm以上、かつ界面活性剤が0.05w/v%以上となるように媒体中に混合することを含む、消毒剤の製造方法であって、前記界面活性剤が、ノニオン系界面活性剤である、消毒剤の製造方法。 A method for producing a disinfectant, comprising mixing in a medium such that iodine is 10 ppm or more and surfactant is 0.05 w/v% or more, wherein the surfactant is a nonionic surfactant A method for producing a disinfectant.
  8.  ヨウ素及び界面活性剤をバインダー樹脂中に含み、前記界面活性剤が、ノニオン系界面活性剤である、消毒フィルム。 A disinfecting film containing iodine and a surfactant in a binder resin, wherein the surfactant is a nonionic surfactant.
  9.  前記バインダー樹脂が、水溶性ポリマーである、請求項8に記載の消毒フィルム。 The disinfecting film according to claim 8, wherein the binder resin is a water-soluble polymer.
  10.  前記バインダー樹脂が、アルギン酸もしくはその塩、ゲランガム、キサンタンガム、寒天、アガロース及びローカストビーンガムからなる群から選ばれるいずれか一種、またはそれらの混合物であり、ゲル化促進剤をさらに含有する、請求項8又は9に記載の消毒フィルム。 8. The binder resin is any one selected from the group consisting of alginic acid or its salt, gellan gum, xanthan gum, agar, agarose and locust bean gum, or a mixture thereof, and further contains a gelling accelerator. Or the disinfecting film according to 9.
  11.  前記ゲル化促進剤が、カルシウム塩、マグネシウム塩、ナトリウム塩及びカリウム塩からなる群から選ばれる1又は2種以上である、請求項10に記載の消毒フィルム。 The disinfecting film according to claim 10, wherein the gelling accelerator is one or more selected from the group consisting of calcium salts, magnesium salts, sodium salts and potassium salts.
  12.  ヨウ素及び界面活性剤をバインダー樹脂中に含み、前記界面活性剤が、ノニオン系界面活性剤である、消毒ビーズ。 Disinfection beads containing iodine and a surfactant in a binder resin, wherein the surfactant is a nonionic surfactant.
  13.  基材と前記基材上の請求項8~11のいずれか一項に記載の消毒フィルムとから構成され、あるいは基材と前記基材上又は前記基材中に含まれる請求項12に記載の消毒ビーズとから構成される、消毒積層体。 Consisting of a substrate and the antiseptic film according to any one of claims 8 to 11 on said substrate, or comprising a substrate and contained on or in said substrate according to claim 12 antiseptic laminate, comprising antiseptic beads;
  14.  請求項10又は11に記載の消毒フィルムの製造方法であって、バインダー樹脂、ヨウ素、界面活性剤、及びゲル化促進剤を水系媒体に溶解させ、得られた溶解物を型に投入し又は基材上に塗布し、その後乾燥する、消毒フィルムの製造方法。 12. The method for producing the antiseptic film according to claim 10 or 11, wherein the binder resin, iodine, surfactant, and gelling accelerator are dissolved in an aqueous medium, and the resulting dissolved product is put into a mold or A method for producing a disinfecting film that is applied onto a material and then dried.
  15.  ヨウ素残量に応じて退色することで消毒効果の低下を検出する、請求項8~11のいずれか一項に記載の消毒フィルム、請求項12に記載の消毒ビーズ、又は請求項13に記載の消毒積層体の消毒効果の判別方法。 The disinfecting film according to any one of claims 8 to 11, the disinfecting beads according to claim 12, or the disinfecting beads according to claim 13, which detects a decrease in the disinfecting effect by fading according to the remaining amount of iodine. A method for determining the disinfecting effect of a disinfecting laminate.
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