EP4146748A1 - Utilisation d'un revêtement antimicrobien - Google Patents

Utilisation d'un revêtement antimicrobien

Info

Publication number
EP4146748A1
EP4146748A1 EP21722233.0A EP21722233A EP4146748A1 EP 4146748 A1 EP4146748 A1 EP 4146748A1 EP 21722233 A EP21722233 A EP 21722233A EP 4146748 A1 EP4146748 A1 EP 4146748A1
Authority
EP
European Patent Office
Prior art keywords
coating
elements
antimicrobial
antimicrobial coating
tio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21722233.0A
Other languages
German (de)
English (en)
Inventor
Ralph BRÜCKNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hecosol GmbH
Original Assignee
Hecosol GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hecosol GmbH filed Critical Hecosol GmbH
Publication of EP4146748A1 publication Critical patent/EP4146748A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/03—Discharge apparatus, e.g. electrostatic spray guns characterised by the use of gas, e.g. electrostatically assisted pneumatic spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B05D2601/24—Titanium dioxide, e.g. rutile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface

Definitions

  • the present invention relates to the use of an antimicrobial coating of a substrate for inactivating an infectious agent, especially a virus, the coating being obtained by applying the coating on a surface of the substrate by means of an electrostatic spraying method.
  • Such surfaces can be represented, for example, by articles of clothing, lounges of buildings and public means of transport as well as their furnishings, medical implants, hygiene articles, face shields, means of payment or medical devices, etc.
  • DE 102012 103064 A1 discloses a hydrophilic composite with at least one carrier material and at least one antimicrobially active agent in the form of a metal or metal compound.
  • DE 10 2013 114 575A shows a method for producing an antimicrobially active composite material in which at least one molybdenum- and/or tungsten- containing inorganic compound is bonded to at least one further material.
  • DE 102013 114573 A1 also shows a method for producing an antimicrobially active furniture and/or interior component, in which at least one molybdenum-containing inorganic compound is arranged at least in the region of a surface of the furniture and/or interior component. Furthermore, DE 10 2013 104 284 A1 discloses a method for producing a doped or undoped mixed oxide for a composite material which serves to form antimicrobially active surfaces.
  • DE 10 2011 085 862 A1 further discloses a composition
  • a composition comprising at least one antimicrobially active substance which acts as a proton donor on contact with an aqueous medium, with the at least one active substance being at least partially encased with at least one coating material, the coating material having a lower water solubility than the active substance.
  • WO 2008/058707 A2 shows the use of an inorganic substance which, in contact with an aqueous medium, forms hydrogen cations which trigger an antimicrobial effect, the substance containing molybdenum and/or tungsten.
  • a cooling tower is known from DE 10 2007 061 965 A1 in which contamination with microorganisms and their proliferation can be avoided by means of internals made of composite materials and/or material composites and an antimicrobially active substance containing tungsten and/or molybdenum.
  • DE 60022 344 T2 relates to a personal care product which has antimicrobial activity and is selected from antimicrobial, disposable absorbent articles, toothbrushes or baby soothers.
  • an antimicrobial coating to be used for inactivation of infectious agents, such as specific types of viruses, bacteria, fungi mould fungi and/or yeasts, in order to prevent infection of subjects. It is therefore the task of the present invention to provide an antimicrobial coating of the type mentioned above in a beneficial manner, in particular, the antimicrobial coating should be usable for inactivation of infectious agents, in particular enveloped viruses.
  • the invention is based on the fundamental idea that by applying an aqueous solution (which contains the metal oxide and/or metal salt) in micro-droplet form on the substrate, the solid antimicrobial coating is formed by evaporation.
  • the metal oxide and/or the metal salt is/are very well soluble or suspendible in the aqueous solution.
  • the aqueous solution / suspension has a nitrate content of about 28 %.
  • metal oxides e.g. TiO 2
  • metal salts have particularly good and effective antimicrobial properties, making these types of compounds particularly suitable for an improved antimicrobial effect of the coating by a targeted alteration of their composition.
  • the great advantage of this coating method is also that the droplets charged during the spraying method find a suitable discharge partner on the oppositely charged coating surfaces and hence are automatically attracted by this partner. This significantly improves the adhesion properties of the micro-droplets and the antimicrobial coating resulting therefrom. This also reduces the undesirable effect of aerosol or fine dust pollution during and/or after application. As a result, the area-specific density of the antimicrobial coating is improved, on the one hand, and its adhesion properties and durability on the other hand.
  • an antimicrobial coating may be characterized by e.g. bactericidal, fungicidal, virucidal, sporicidal and/or levurocidal properties.
  • a major advantage of the present invention is the permanent germ reduction on surfaces by using antimicrobial coating.
  • the coating comprises at least one complex compound.
  • the complex compound can be used to create new properties of the antimicrobial coating. In this context, for example, it is conceivable that the antimicrobial effectiveness of the coating is enhanced by the complex compound.
  • the structure of the metal oxide is described by the formula A c O d , where A is selected from the elements of group 4 of the periodic table of the elements (lUPAC nomenclature) and 0 is the element oxygen, wherein c and d, independently of each other, can assume a value between 0 and 24.
  • A is selected from the elements of group 4 of the periodic table of the elements (lUPAC nomenclature) and 0 is the element oxygen, wherein c and d, independently of each other, can assume a value between 0 and 24.
  • PSE the use of a metal oxide with the metals of group 4 of the periodic table of the elements (in brief: PSE) ensures a very good antimicrobial effectiveness of this coating. These properties can be influenced even more freely and specifically by a targeted selection of the composition, characterized by the indices c and d.
  • group 4 of the PSE refers to the current convention of lUPAC. All other designations of PSE groups listed in this disclosure also refer to the current l
  • the structure of the metal oxide is described by the formula AO 2 , wherein A is selected from the elements of Group 4 of the periodic table of the elements (lUPAC nomenclature) and 0 is the element oxygen, the metal oxide being in particular TiO 2 , ZrC>2 or HfO 2.
  • the metal dioxides of group 4 of the PSE have a very good antimicrobial effectiveness and are therefore suited for use in antimicrobial coating in a particularly advantageous way. Consequently, the antimicrobial effectiveness of the coating can be further increased.
  • the structure of the metal oxide is described by the formula Me e O d , wherein Me is selected from the elements of group 6 of the periodic table of the elements (lUPAC nomenclature) and 0 is the element oxygen, wherein d and e, independently of each other, can assume a value between 0 and 100, preferably 0 and 40, most preferably 0 and 24.
  • d and e independently of each other, can assume a value between 0 and 100, preferably 0 and 40, most preferably 0 and 24.
  • metal oxides composed of molybdenum Mo and tungsten W should be mentioned in particular, since corresponding chromium compounds have a very pronounced toxicity.
  • the structure of the complex compound is described by the formula A c B d X n Me e B f or X n Me e B f , wherein A is selected from the elements of group 4, B is selected from the elements of group 15 or 16, X is selected from the elements of groups 5, 7, 8, 9, 10, 11 , 12, 13, 14, 15 from the lanthanides or the actinides, and Me is selected from the elements of group 6 of the periodic table of the elements (lUPAC nomenclature), and wherein c, d, n, e and f, independently of one another, can assume a value between 0 and 1000, preferably 0 and 24.
  • complex compounds of this type also have good antimicrobial properties
  • the use of this type of complex compound in an antimicrobial coating is also particularly advantageous.
  • complex compounds are added to lacquers and paints (e.g. anti-fouling lacquers or paints) or sol gels or synthetic resins such as melamine resin, polyurethane or silicone in the form of a suspension or as a solid after drying, which thus acquire antimicrobial properties.
  • the complex compound is mixed with a (solid) matrix (e.g. elastomers, duromers or thermoplastics) either as a suspension or by compounding, melting or grinding.
  • a (solid) matrix e.g. elastomers, duromers or thermoplastics
  • the antimicrobial matrices obtained may be brought into their final form by brushing, spraying, thermoplastic processing or 3D printing.
  • the structure of the complex compound is described by the formula AC ⁇ XnMeO y or X n MeO y , wherein A is selected from the elements of group 4, X is selected from the elements of groups 5, 7, 8, 9, 10, 11 , 12, 13, 14, 15 from the lanthanides or the actinides, and Me is selected from the elements of group 6 of the periodic table of the elements (lUPAC nomenclature) and O is the element oxygen, wherein n can assume a value between 0 and 24 and/or wherein y can assume a value between 0 and 1000, and the complex compound comprising in particular molybdates, polyoxomolybdates, tungstates (wolframates) or chromates.
  • the complex compound of formula AC ⁇ XnMeO 4 has in particular a synergetic effect with a view to enhancing the antimicrobial properties or effects of the antimicrobial coating. This is because a complex compound of the formula AC ⁇ XnMeO 4 has a stronger antimicrobial activity than its constituents with the formulae AO 2 or XnMeO 4 .
  • the complex compounds with this composition are present in particular partially in the form of colorless complexes of the form TiO 2 * X n MeO 4 and can be incorporated particularly advantageously into plastics (e.g. silicone, PU, etc.) or building materials (e.g. cement), which thereby exhibit antimicrobial properties at least on their surface.
  • the structure of the complex compound is described by the formula AO 2 Me e 0 d , wherein A is selected from the elements of group 4, Me is selected from the elements of group 6 of the periodic table of the elements (lUPAC nomenclature) and 0 is the element oxygen, wherein d and e, independently of each other, can assume a value between 0 and 100, preferably 0 and 40, most preferably 0 and 24. Since also this type of complex compound has enhancing effects on the antimicrobial effectiveness of the antimicrobial coating, its use is also particularly advantageous in this respect.
  • the structure of the metal oxide and/or metal salt is described by the formula AO 2 XBO 3 orXBO 3 , wherein A is selected from the elements of group 4, X is selected from the elements of groups 5, 7, 8, 9, 10, 11, 12, 13, 14, from the lanthanides or the actinides, and B is selected from the elements of group 15 or 16 of the periodic table of the elements (lUPAC nomenclature) and O is the element oxygen, and the metal oxide and/or metal salt being in particular TiC ⁇ AgNO 3 or AgNO 3 .
  • This type of metal oxide and/or metal salt has in particular enhancing effects on the antimicrobial effectiveness of the antimicrobial coating under darkened environmental conditions and/or total darkness. Especially in situations where the coating is used under low light incidence or no light incidence, e.g. for the internal coating of pipelines or in the case of implants, their use is particularly advantageous.
  • the coating is designed in the form of a matrix structure which comprises a plurality of islands spaced apart from one another, and wherein the islands have a diameter in a range in particular from about 0.1 pm to about 500 pm, preferably from about 1 pm to about 200 pm, particularly preferably from about 2 pm to about 100 pm, and wherein the islands are each spaced apart from one another in accordance with their diameter.
  • the close spacing of the individual islands relative to each other allows their homogeneous distribution on the substrate and, as a result, a high antimicrobial effectiveness of the coating with a simultaneously optimized material input of the metal oxides or metal salts used. Since the islands are applied on the substrate by means of the aforementioned electrostatic spraying method, their adhesion to the substrate can also be improved. ln this respect, the sprayed and deposited micro-droplets evaporate very quickly (e.g. at room temperature) within only 1 to 2 minutes and leave a transparent TiO 2 matrix in the form of said islands.
  • the islands comprise clusters formed by TiO 2 and ZnMoO 4 .
  • the very effective antimicrobial properties of TiO 2 have been known for a long time.
  • ZnMoO 4 these antimicrobial properties can be synergetically increased compared to the two individual components, whereby the antimicrobial effectiveness of the coating can be further increased on the whole.
  • a further essential aspect of applying water-soluble titanium dioxide on the substrate by means of the suspension or aqueous solution and thus working as a basic matrix, is the positive charge in the solid state. It retains this positive charge of the titanium dioxide even in the dry state, especially after separation from the aqueous-acidic environment (pH ⁇ 6.8).
  • species of the form Ti-0(H + )-Ti as well as 0-Ti + -0 occur.
  • compounds with a permanent positive charge e.g. quaternary ammonium compounds such as PHMB
  • PHMB quaternary ammonium compounds
  • the positive charge leads to a structural change of the bacterial membrane and to a dysfunction of the ion channels. As a result, cell homeostasis is brought out of balance and the microorganism dies even more effectively.
  • the islets have a surface which is formed like a pan with a central region and an edge region rising radially outwards with respect thereto.
  • This way of shaping increases the surface of the islands in particular, which makes it possible, on the one hand, to create a larger effective surface of the individual islands.
  • the total effective surface of the antimicrobial coating is also increased.
  • the pan-like structure of the individual island surfaces also provides better protection, especially for the lowered central region of the individual islands, against mechanical influences, e.g. by means of a cleaning cloth, which allows to further increase the durability of the antimicrobial coating.
  • the islands have a convex surface which is formed with a central region and an edge region that flattens out radially outwards with respect thereto.
  • This way of convex shaping also increases the surface area of the individual islands, which makes it possible to create a larger effective surface of the individual islands, on the one hand.
  • the total effective surface of the antimicrobial coating is also increased.
  • the surface of the islands has a wrinkled structure, the wrinkles each having a width of about 10 pm, preferably about 5 pm, particularly preferably about 2 pm, so that the surface of the islands of the matrix structure is enlarged.
  • the wrinkles additionally increase the effective surface of the individual islands and consequently also the entire surface of the antimicrobial coating. The antimicrobial effectiveness of the entire coating can thus be improved or increased.
  • the surface of the coating has hydrophilic properties.
  • the hydrophilic properties of the coating further improve its antimicrobial effectiveness. This circumstance can be explained by the fact that hydrophilic surfaces, in contrast to hydrophobic surfaces, bind bacteria or microorganisms on the surface and prevent a retransfer to their habitat, for instance room air or water.
  • the hydrophilic properties facilitate the cleaning of the antimicrobial coating, since a monomolecular water layer forms between the dirt (e.g. cell debris) and the surface.
  • the antimicrobial properties of the coating are available independently of light incidence, in particular UV light incidence.
  • the independence of certain coating compounds from light incidence has considerable advantages, especially under darkened environmental conditions and/or total darkness of the antimicrobial coating (e.g. TiO 2 *AgNO 3 ).
  • the use of antimicrobial coating can be made much more variable and its application conditions can be extended. In this context, for example, application conditions in objects or components are conceivable that are only partially or never exposed to light.
  • light incidence can also be understood to mean, in particular, UV light incidence from a natural and/or non-natural light source (e.g. outdoors).
  • these can be, for example, coatings of pipelines or containers, implants, filters, hygiene articles, catheters, adhesives, personal care products, varnishes, polymer materials, prostheses, stents, silicone membranes, wound dressings, fittings, credit cards, housings, coins, bank notes, parts of the interior equipment of public means of transport, etc.
  • the antimicrobial properties of the coating can be enhanced by light incidence, especially UV light incidence.
  • the enhancement of the antimicrobial coating by UV light incidence especially has the advantage of an even stronger antimicrobial effect of this coating. Since the antimicrobial coating is often used under exposed or partially exposed conditions, the use of the antimicrobial coating can be made even more variable or extended.
  • electrostatic spraying method described above is used for coating at least one substrate, and that this method comprises at least the following steps:
  • the aqueous solution or suspension comprising at least one metal oxide and/or at least one metal salt soluble therein, whereby the aqueous solution or suspension has antimicrobial properties;
  • the electrostatic spraying method is particularly advantageous with regard to improved properties in terms of adhesion of the antimicrobial coating on the substrate.
  • the charged droplets first find an oppositely charged discharge partner on the oppositely charged substrate, so that they are automatically attracted by it. This also reduces the risk of fine dust pollution during application.
  • the micro-droplets deposited on it evaporate (e.g. at room temperature) very quickly within only 1 to 2 minutes, leaving behind a transparent matrix of the coating components (especially a TiO 2 matrix) in the form of small islands.
  • the metal oxide is present in the form of nanoparticles with an average size of in particular smaller than about 100 nm, preferably smaller than about 20 nm, particularly preferably smaller than about 10 nm, and wherein the aqueous solution or suspension has a pH value of in particular smaller than or equal to about 6.8, preferably smaller than or equal to about 2, particularly preferably smaller than or equal to about 1.5. Since the metal oxide, e.g. TiO 2 , is present in the form of nanoparticles before being added to the aqueous solution or suspension, it is very readily soluble in water.
  • the good water solubility is further enhanced by the decreasing size of the individual nanoparticles, which means that a size of the nanoparticles smaller than about 10 nm is particularly advantageous in this context.
  • a suitable metal oxide e.g. TiO 2
  • TiO 2 can retain this positive charge even in the dry state after separation from the aqueous-acidic environment (pH ⁇ 6.8). This results in an even better effectiveness of the antimicrobial coating.
  • the metal oxide is contained in the aqueous solution or suspension in a range in particular from about 0.005 % to about 20 %, preferably from about 0.01 % to about 10 %, particularly preferably from about 0.1 % to about 5 %.
  • the electrostatic spraying method allows to apply aqueous solutions especially with a metal oxide content from 0.01 to 10%.
  • using a content of 1.5% (15 g/l) is particularly advantageous.
  • the aqueous solution or suspension contains at least one complex compound.
  • the germ reducing or antimicrobial properties of the coating can be varied or extended advantageously by complex compounds.
  • the antimicrobial effectiveness of the coating can be improved or adapted to external conditions such as light incidence or UV light incidence or no light incidence.
  • the substrate is electrically positively or negatively charged and the droplets of the aqueous solution or suspension are electrically positively or negatively charged. It is particularly important to note in this context that the droplets must always have a charge which is opposite to that of the substrate, so that an improved and particularly advantageous application of the coating can be achieved and the resulting improved adhesion properties of the coating in the solid state can be obtained in the first place.
  • an antimicrobial coating of a substrate for inactivation of an infectious agent may be provided, wherein the coating is obtained by applying the coating on a surface of the substrate by means of an electrostatic spraying method, and wherein the coating comprises at least one metal oxide and/or at least one metal salt.
  • metal oxides e.g. T1O 2
  • metal salts have particularly good and effective antimicrobial properties, whereby these types of compounds are suitable in a particularly advantageous way for an improved and more varied antimicrobial effect of the coating.
  • the coating material may also be available in the form of an anti-fouling lacquer and/or an anti-fouling paint, a sol-gel or synthetic resin such as melamine resin, silicone or polyurethane, wherein at least one complex, in particular at least one TiO 2* X n MeO 4 complex, is added to the coating material in the form of a suspension or as a solid after drying.
  • a sol-gel or synthetic resin such as melamine resin, silicone or polyurethane
  • the infectious agent may be a bacterium, especially one of Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus or Listeria monocytogenes, and/or a fungus, especially one of Candida albicans, Candida auris, Aspergillus fumigatus or Penicillium sp.) and/or a parasite.
  • a bacterium especially one of Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus or Listeria monocytogenes
  • a fungus especially one of Candida albicans, Candida auris, Aspergillus fumigatus or Penicillium sp.
  • the infections agent may also be a virus, such as rhinovirus, norovirus or coronavirus.
  • a virus may be a ssDNA virus, dsDNA virus, dsRNA virus, (+)ssRNA virus, (-)ssRNA virus, ssRNA-RT virus, dsDNA-RT virus.
  • a virus may be an enveloped virus or a naked virus.
  • the virus may be characterized by an icosahedral capsid symmetry or helical capsid symmetry or complex capsid symmetry.
  • the virus may be of the family of Reoviridae, Picornaviridae, Caliciviridae, Togaviridae, Arenaviridae, Flaviviridae, Orthomyxoviridae, Paramyxoviridae, Bunyaviridae, Rhabdoviridae, Filoviridae, Coronaviridae, Astroviridae Bornaviridae, Arteriviridae, Hepeviridae.
  • the virus may be of the subfamily of Orthocoronavirinae or Letovirinae.
  • the virus may be a coronavirus species, especially a severe acute respiratory syndrome coronavirus, severe acute respiratory syndrome coronavirus 2, or Middle East respiratory syndrome-related coronavirus.
  • Inactivation of an infectious agent may be understood as reducing completely or reducing partially the infectiousness of an infectious agent.
  • inactivation of an infectious agent may be understood as rendering an infectious agent non-viable and/or no longer capable of growing, replicating, infecting a subject or causing disease.
  • the object of viral inactivation is to improve viral safety so that transmissions no longer occur.
  • the coating is an antimicrobial coating as described above.
  • the great advantage of this coating method is that the droplets charged during the spraying procedure find an effective discharge partner on the oppositely charged substrate and are thus automatically attracted by it. This significantly improves the adhesion properties of the micro-droplets and the resulting antimicrobial coating.
  • a coating material for producing an antimicrobial coating on a surface of a substrate for inactivation of an infectious agent wherein the coating comprises at least one metal oxide and/or at least one metal salt, is provided.
  • a surface of the coating is a working surface and/or is at least temporarily in contact with ambient air and/or fluids and/or liquids.
  • the antimicrobial coating according to the invention can noticeably reduce a user's microbial load, which has a particularly positive effect on the user's well-being and health.
  • the antimicrobial coating according to the invention is also very advantageous, as the reduced particle load in the air has a positive effect on the production conditions in the clean rooms (fewer defective components) or allows the air quality in the living rooms to be further improved.
  • the antimicrobial coating can be applied, for example, as an internal coating on drinking water pipes, containers and fittings.
  • FIG. 1 shows in an enlarged SEM illustration a top view of a first exemplary embodiment of an antimicrobial coating according to the invention
  • Fig. 2 shows in two enlarged illustrations in each case a top view of the first exemplary embodiment of the coating according to Fig. 1;
  • FIG. 3 shows in two enlarged perspective illustrations the hydrophilic properties of the first example of the coating according to Fig. 1 ;
  • Fig. 4 shows a general tabular characterization of the antimicrobial effectiveness (according to ISO 22196) of antimicrobial coatings
  • Fig. 5 shows a tabular illustration of the antimicrobial effectiveness of further exemplary embodiments of an antimicrobial coating according to the invention.
  • Fig. 6 shows two further tabular illustrations of the antimicrobial effectiveness of further exemplary embodiments of an antimicrobial coating according to the invention.
  • Fig. 7 shows a further tabular illustration of the antimicrobial effectiveness of further exemplary embodiments of an antimicrobial coating according to the invention.
  • Fig. 8 shows a further tabular illustration of the antimicrobial effectiveness of further exemplary embodiments of an antimicrobial coating according to the invention.
  • Fig. 9a shows a schematic illustration of an exemplary embodiment of an electrostatic spraying method for obtaining an antimicrobial coating according to the invention
  • Fig. 9b is an enlarged illustration of an island
  • Fig. 10 shows a diagram of a comparison of the temporal germ reduction of an exemplary embodiment of the coating of the invention according to Fig. 5 in darkness and light;
  • Fig. 11 is a bar chart of the antimicrobial effectiveness of an exemplary embodiment of the coating of the invention according to Fig. 5 for a 2-fold, 3-fold and 4-fold coating of a Petri dish
  • Fig. 12 is a bar chart with a comparison of the temporal germ reduction of three exemplary embodiments of the coating of the invention according to Fig. 5 in darkness and light;
  • Fig. 13a is a diagram of a comparison of the temporal germ reduction of two exemplary embodiments of the coating of the invention according to Fig. 5 in darkness and light;
  • Fig. 13b shows selected data points from Fig. 13a in tabular illustration
  • Fig. 14a is a tabular illustration of the antimicrobial effectiveness of an exemplary embodiment of the coating according to Fig. 5 against the germ Staphylococcus aureus
  • Fig. 14b shows a temporal reduction development of the germ Aspergillus fumigatus on an uncoated Petri dish and one coated with an exemplary embodiment of the coating according to Fig. 5;
  • Fig. 15 shows a temporal reduction development of the germ Candida albicans on an uncoated petri dish and one coated with an exemplary embodiment of the coating according to Fig. 5;
  • Fig. 16a is a bar chart with a comparison of the temporal germ reduction of E. coli for six exemplary embodiments of the coating of the invention according to Fig. 5 and Fig. 6 in darkness.
  • Fig. 17 shows examples for the effect of the use of an antimicrobial coating according to the present invention for inactivating different infectious agents
  • Fig. 18 shows an example of a workflow for testing the effect of the use of an antimicrobial coating 10 of a substrate 12 for inactivation of human rhinovirus 16 FIRV;
  • FIG. 19 the effect of the use of an antimicrobial coating 10 of a substrate 12 for inactivation of human rhinovirus 16 HRV.
  • Fig. 1 shows an enlarged plan view of a first embodiment of an anti-microbial coating 10 of a substrate 12 according to the invention.
  • the anti-microbial coating 10 of the substrate 12 is obtained by applying the coating 10 to a surface 14 of the substrate 12 by means of an electrostatic spray method.
  • the coating 10 contains at least one metal oxide.
  • the structure of the metal oxide is described by the formula A c Od.
  • A is selected from the elements of group 4 of the periodic table of the elements (lUPAC nomenclature) and O is the element oxygen.
  • the indices c and d can independently of each other have a value between 0 and 24.
  • the structure of the metal oxide is described even more specifically by the formula AO 2.
  • Flere A is also selected from the elements of group 4 of the periodic table of the elements (lUPAC nomenclature) and O is the element oxygen.
  • the metal oxide is particularly TiO 2 (or ZrO 2 or HfO 2 ).
  • the coating 10 according to Fig. 1 is formed in the form of a matrix structure in which the TiO 2 is contained.
  • this matrix structure has several islands 16 spaced apart to one another.
  • These islands 16 have a diameter in a range particularly from about 2 pm to about 100 pm.
  • the islands 16 are each spaced apart according to their diameter.
  • the islands 16 also contain AgNO 3 .
  • the islands 16 can comprise comprise clusters formed by TiO 2 and ZnMoO 4 .
  • Fig. 2 shows two further enlarged representations of a respective plan view of the first embodiment of the coating according to Fig. 1.
  • a SEM analysis of an island shows a flat pan in the central area 18 with a clear elevation at the edges of the TiO 2 - islands.
  • the islands 16 have a surface that is pan-like with a central area 18 and an edge area 20 radially outwardly elevating thereto.
  • the islands 16 have a convex surface.
  • This surface is also formed with a central area and an edge area radially outwardly flattening thereto.
  • Fig. 2 shows the surfaces of the islands 16, which have a furrowed structure.
  • the furrowed structure is especially formed in the edge area 20 of the individual islands 16.
  • the furrows 22 each have a width of about 2 pm, so that the surface of the islands 16 of the matrix structure is enlarged.
  • Fig. 3 also shows in two enlarged perspective views the hydrophilic properties of the first embodiment of coating 10 according to Fig. 1.
  • Fig. 3 show a comparison of an uncoated surface 12 (left) and a coated surface 12 (right).
  • the surface of coating 10 with the hydrophilic properties (right) has a clearly recognisable hydrophilic effect.
  • Fig. 4 shows a tabular characterization of the anti-microbial effectiveness of anti- microbial coatings in general.
  • the anti-microbial or anti-bacterial effectiveness of different coatings can be classified according to Fig. 4 as “none”, “slight”, “significant” and “strong”.
  • the reduction factor R L is used to quantify the anti-microbial effectiveness.
  • R L log (A/B).
  • A corresponds to an average value of so-called colony forming units (CFU) per ml on a reference surface without anti-microbial coating.
  • B corresponds to an average value of colony forming units (CFU) per ml on a reference surface with an anti-microbial coating according to the present invention.
  • the colony-forming units can also be interpreted as the specific total germ count per ml.
  • JIS Z 2801 Japanese Industrial Standard Test, JIS Z 2801
  • ISO standard 22196 in Europe is used for objective assessment of the germ reducing effect of surfaces.
  • Petri dishes coated with the test substance are first wetted with a germ suspension (e.g. E. coli or Staphylococcus aureus), covered with a foil and then incubated at 35°C and 95% humidity.
  • a germ suspension e.g. E. coli or Staphylococcus aureus
  • the experiments can be performed in the dark or under defined lighting conditions (e.g. by means of LED light at 1600 lux).
  • Fig. 5 shows a tabular representation of the anti-microbial effectiveness of further embodiments of an anti-microbial coating 10’ according to the invention.
  • the anti-microbial effectiveness against E. coli bacteria is shown in Fig. 5 for a duration of 5 min in darkness and under defined light conditions at 1600 lux.
  • inventions of the respective anti-microbial coating 10’ according to the invention as shown in Fig. 5 essentially have the same structural (macroscopic) and functional features as the embodiments shown in Fig. 1 and 2.
  • the structure of the metal oxide and metal salt or only the metal salt contained in the anti-microbial coating is generally described by the formula AO 2 XBO 3 or XBO 3 according to Fig. 5. Wherein A is selected from the elements of group 4, X is selected from the elements of group 11 , and B is selected from the elements of group 15 of the periodic table of the elements (lUPAC nomenclature) and 0 is the element oxygen.
  • the metal oxide and the metal salt are TiO 2 AgNO 3 or the metal salt is AgNO 3.
  • the anti-microbial effectiveness of TiO 2 against E. coli bacteria was assessed for a duration of 0.5h, 4h and 24h both in darkness and under defined light conditions at 1600 lux.
  • Fig. 6 shows a further tabular representation of the anti-microbial effectiveness of further embodiments of an anti-microbial coating 10” according to the invention.
  • the anti-microbial effectiveness against E. coli bacteria is shown in Fig. 6 for a duration of 5 min, 1 h and 24 h under defined light conditions at 1600 lux.
  • the embodiments of the respective anti-microbial coating 10” shown in Fig. 6 essentially have the same structural (macroscopic) and functional features as the embodiments shown in Fig. 1 and 2.
  • the coating 10 contains at least one complex compound.
  • the structure of the complex compound is generally described by the formula A c B d X n Me e B f or X n Me e B f.
  • A is selected from the elements of group 4
  • B is selected from the elements of group 15 or 16
  • X is selected from the elements of groups 5, 7, 8, 9, 10, 11 , 12, 13, 14, 15 of the lanthanoids, or the actinides
  • Me is selected from the elements of group 6 of the periodic table of the elements (lUPAC nomenclature).
  • c, d, n, e and f can independently of each other take a value between 0 and 1000, preferably 0 and 24.
  • the structure of the complex compound is described by the formula AO 2 X n MeO y or X n MeO y.
  • A is selected from the elements of group 4
  • X is selected from the elements of groups 5, 7, 8, 9, 10, 11, 12, 13, 14, 15 of the lanthanoids, or the actinides
  • Me is selected from the elements of group 6 of the periodic table of the elements (lUPAC nomenclature) and 0 is the element oxygen.
  • n can have a value between 0 and 24.
  • y can have a value between 0 and 1000.
  • the structure of the complex compound can be described by the formula AO 2 X n MeO 4 or XpMeO 4.
  • the complex compound contains particularly molybdates or tungstates.
  • the molybdates comprise particularly (NFU 4 ) 6 MoyO 24 , Na 2 MoO 4 , Ag 2 MoO 4 , AI 2 (MOO 4 ) 3 , CeMoO 4 , C0M0O 4 , CuMoO 4 , Fe-lll-MoO 4 , MnMoO 4 , N1M0O 4 or ZnMoO 4 .
  • the anti-microbial coating 10 can be formed either from these molybdates or from a compound of these molybdates with TiO 2.
  • the anti-microbial coating 10 can also include M0O 3 or a compound of TiO 2 and M0O 3 instead of the molybdates.
  • the tungstates comprise particularly Na 2 WO 4 , AgWO 4 , AIWO 4 , CeWO 4 , C0WO 4 , CuWO 4 , Fe-lll-WO 4 , MnWO 4 , NiW0 4 or ZnWO 4.
  • the anti-microbial coating 10 can either be formed from these tungstates or from a compound of these tungstates with TiO 2.
  • the anti-microbial coating 10 can also include WO 3 or a compound of TiO 2 and WO 3.
  • Fig. 7 shows a further tabular representation of the anti-microbial effectiveness of further embodiments of an anti-microbial coating 10’” according to the invention.
  • the anti-microbial effectiveness against E. coli bacteria is shown in Fig. 7 for a duration of 1 h and 24 h under defined light conditions at 1600 lux.
  • the embodiments of the respective anti-microbial coating 10’” shown in Fig. 7 essentially have the same structural (macroscopic) and functional features as the embodiments shown in Fig. 1 and 2. Merely the following differences shall be discussed:
  • the representation in Fig. 7 particularly serves to show the difference in the anti- microbial effectiveness of the anti-microbial coating, which on the one hand is formed from a tungstate and on the other hand is formed from this tungstate in combination with Ti02.
  • the tungstates according to Fig. 7 include particularly AgWO 4 , AIWO 4 , CeWO 4 , CuWO 4 , or ZnWO 4 or these tungstates in combination with TiO 2.
  • the second last or last line of the table shown in Fig. 7 shows another metal oxide and another complex compound.
  • Me is selected from the elements of group 6 of the periodic table of the elements (lUPAC nomenclature) and 0 is the element oxygen.
  • d and e can independently of each other have a value between 0 and 100.
  • d and e can independently of each other have a value between 0 and 40.
  • d and e can independently of each other have a value between 0 and 24.
  • the metal oxide as shown in Fig. 7 is particularly WO 3.
  • A is selected from the elements of group 4
  • Me is selected from the elements of group 6 of the periodic table of the elements (lUPAC nomenclature) and O is the element oxygen.
  • d and e can independently of each other take a value between 0 and 100.
  • d and e can independently of each other have a value between 0 and 40.
  • d and e can independently of each other have a value between 0 and 24.
  • Fig. 7 is particularly WO 3 * TIO 2 .
  • Fig. 8 shows a further tabular representation of the anti-microbial effectiveness of further embodiments of an anti-microbial coating 10’” according to the invention.
  • the anti-microbial effectiveness against E. coli bacteria is shown in Fig. 8 for a duration of 1 h under defined light conditions at 1600 lux.
  • the embodiments of the respective anti-microbial coating 10”” shown in Fig. 8 essentially have the same structural (macroscopic) and functional features as the embodiments shown in Fig. 1 and 2.
  • FIG. 8 serves particularly to show the difference in the anti- microbial effectiveness of this anti-microbial coating 10”” with different compositions.
  • This coating 10 includes particularly ZnCrO 4 , ZnMoO 4 orZnWO 4 .
  • chromium oxide has a strong toxic effect.
  • Fig. 9a shows a schematic representation of an embodiment of an electrostatic spray method for obtaining an anti-microbial coating 10, 10’, 10”, 10”’, 10”” according to the invention.
  • the electrostatic spray method for coating at least one substrate 12 comprises the following steps:
  • aqueous solution or suspension 24 containing at least one metal oxide and/or at least one metal salt soluble therein, whereby the aqueous solution or suspension 24 has anti- microbial properties;
  • the metal oxide is present in the form of nanoparticles with an average size of less than or equal to about 10 nm.
  • the aqueous solution or suspension 24 has a pH value of less than or equal to about 1.5.
  • the metal oxide is contained in the aqueous solution or suspension 24 in a range, particularly, of about 0.1% to about 5%.
  • the aqueous solution or suspension 24 may also contain a complex compound.
  • Fig. 9a it is also shown that during the coating of substrate 12 the microdroplets with the TiO 2 dissolved therein are electrically positively charged.
  • Fig. 9b shows an enlarged representation of an island 16 in this respect.
  • the moisture content is 2%.
  • this behaviour determines the basic idea of converting water-soluble TiO 2 after application in the form of small droplets 26 with the electrostatic spray method described above into a solid matrix into which both soluble and insoluble (complex) compounds with a germ reducing effect can be introduced.
  • the deposited microdroplets 26 evaporate very quickly at room temperature within only 1 - 2 min and leave a transparent TiO 2 matrix in the form of small islands 16 (of. Fig. 1 and 2).
  • Compounds with a permanent positive charge e.g. quaternary ammonium compounds such as PHMB are known to energize bacteria having a negative polar outer shell and thus preventing them from being transported back into the ambient air.
  • the positive charge leads to a structural change of the bacterial membrane and a dysfunction of the ion channels.
  • hydrophilic surfaces of the substrate 12 have the advantage, contrary to hydrophobic surfaces, that they bind bacteria on the surface and prevent back transfer away from the coating surface.
  • This property is an important first step towards improved room hygiene.
  • Fig. 10 shows a diagram with a comparison of the temporal germ reduction of E. coli for an embodiment of the coating according to the invention pursuant to Fig. 5 in the form of TiO 2.
  • Fig. 11 shows a bar chart of the anti-microbial effectiveness of an embodiment of the inventive coating 10’ according to Fig. 5 for 2-times, 3-times and 5-times coating of a Petri dish.
  • the anti-microbial coating contains a matrix of TiO 2 and silver nitrate TiO 2* AgNO 3.
  • the anti-microbial effectiveness of the coating against E. coli bacteria is shown in Fig. 11 after an incubation duration of 24 h under defined light conditions at 1600 lux.
  • silver changes the tertiary structure of the bacterial outer membrane.
  • the structure of the deposited TiO 2 *AgNO 3 matrix is stable against 1000-times wiping with an anti-septic cloth (ethanol, benzalkonium chloride).
  • Fig. 12 shows two bar diagrams with a comparison of the temporal germ reduction of a coating containing TiO 2 *AgNO 3 and its individual components according to Fig. 5 in darkness and brightness.
  • fig. 13a shows a diagram of a comparison of the temporal germ reduction of these two embodiments of the inventive coating 10’ according to Fig. 5 in darkness and brightness (about 1600 Lux).
  • 100% correspond to the respective starting concentration (about 5x10 5 CFU).
  • TiO 2 *AgNO 3 shows a very strong germ reduction within the first 5 minutes by up to > 99.99%.
  • Remarkable is the very strong germ reduction at 1600 lux of 98.1% after 1 min and 99.859% after 3 min.
  • the anti-microbial properties of this coating 10’ therefore may be enhanced by UV light incidence.
  • Fig. 13b additionally shows the data points shown in Fig. 13a in tabular form.
  • cationic silver has a very high oxidation potential and is able to attack the outer membrane of the microorganisms by fast electron transfers, whereby additional sulphur-containing enzymes are chemically inactivated.
  • Fig. 14a shows a tabular representation of the anti-microbial effectiveness of an embodiment of the coating 10’ according to Fig. 5 against a Staphylococcus aureus germ.
  • Fig. 14b shows in this respect a temporal reduction of an Aspergillus fumigatus germ on an uncoated Petri dish and a Petri dish coated with an embodiment of the coating 10’ according to Fig. 5.
  • the anti-microbial coating in Fig. 14b shows a TiO 2 *AgNO 3 matrix structure, as also shown in Fig. 11 to 14a.
  • FIG. 14b shows a significant growth control within the first 4h and a clear reduction of germs after 24h compared to the uncoated reference Petri dish (left figure in Fig. 14b).
  • Fig. 15 shows a temporal reduction of a Candida albicans germ on an uncoated Petri dish and a Petri dish coated with an embodiment of the coating 10’ as shown in Fig. 5.
  • the anti-microbial coating 10’ in Fig. 15 also shows a TiO 2 *AgNO 3 matrix structure as also shown in Fig. 11 to 14b.
  • the anti-microbial coating 10’ of substrates according to Fig. 11 to 15 with TiO 2 *AgNO 3 is conceivable e.g. in outdoor areas (e.g. building walls, surfaces of public transport vehicles or road surfaces).
  • the biological matrix was filtered off and hydrochloric acid was added to the clear aqueous solution.
  • Fig. 16a also shows a bar chart with a comparison of the temporal E. coli germ reduction of six embodiments of the inventive coating 10’, 10” according to Fig. 5 and Fig. 6 after 5 min incubation time in the darkness.
  • the anti-microbial coating contains a combination of the TiO 2 matrix with oxides and salts of group 6 (lUPAC nomenclature) of the periodic table of the elements. Since chromium compounds are characterized by a very pronounced toxicity, the focus was on the oxides and salts of the elements molybdenum (Mo) and tungsten (W).
  • the zinc molybdate (ZnMoO 4 ) was applied alone (about 5.0 g/L) and in combination with the TiO 2 matrix described above (about 15 g/L) to a substrate 12 via electrospray and tested against E. coli.
  • ammonium heptamolybdate (NH 4 ) 6 Mq 7 q24 was tested, which has an anti- microbial effectiveness of 1.4 after 1h and 4.3 after 24h under these experimental conditions.
  • the ammonium heptamolybdate (NH 4 ) 6 Mo 7 O 24 used for the synthesis has a significant effectiveness already after 1h.
  • Na 2 MoO 4 sodium molybdate
  • the sodium molybdate which is also highly soluble, shows no anti-microbial effect even after 24 h (see Fig. 6).
  • silver molybdate (Ag 2 MoO 4 ) could be determined as a further strongly germ-reducing compound.
  • the starting material for the syntheses was sodium tungstate, which reacts with the soluble salts (chloride, nitrate, sulphate) of aluminium, cerium, cobalt, copper, nickel, manganese, silver and zinc to form slightly soluble salts of the form X n WO 4 .
  • tungsten molybdate shows no antimicrobial effectiveness after an incubation period of 1h and 24h as well.
  • zinc tungstate ZnWO 4
  • TiO 2* ZnWO 4 shows a strong antimicrobial effectiveness within 24 h.
  • silver tungstate AlWO 4
  • aluminium tungstate AIWO 4
  • cerium tungstate CeWO 4
  • copper tungstate CuWO 4
  • tungsten oxide also has this strong effectiveness as well as its combination with the TiO 2 matrix.
  • a three-center complex may also be formed between the positively charged TiO 2 , the positive metal cation (e.g. Ce 2+ ) and the tungstate anion.
  • the electronic states change in such a way that the sparklingness of the original tungstates is lost.
  • the yellow tungsten oxide (WO 3 ) also leads to a colourless suspension with TiO 2 through complexation.
  • Such use of a coating material can thus be provided for producing an anti-microbial coating 10, 10’, 10”, 10’”, 10”” as described above on a surface 14 of a substrate 12, said coating 10 containing at least one metal oxide and/or metal salt as described above.
  • the coating 10, 10’, 10”, 10”’, 10” is thereby obtained by an electrostatic spray method as described above.
  • the surface 14 of the coating 10, 10’, 10”, 10”’, 10” may be a work surface or may be in contact, at least temporarily, with ambient air, fluids or liquids.
  • TiO 2 * X n MeO 4 can be added to lacquers and paints (e.g. anti-fouling) in the form of the suspension or as a solid after drying, thus giving them anti-microbial properties.
  • a TiO 2 * X n MeO 4 complex is added to the coating material, which is especially designed as an anti-fouling lacquer or anti-fouling paint, in the form of a suspension or as a solid after drying.
  • the coating material could be designed as a sol gel or a synthetic resin, for instance a melamine resin or a polyurethane.
  • the colourless complexes of the form TiO 2 *XnMeO 4 can be incorporated into plastics (e.g. silicone, PU, etc.) or building materials (e.g. cement), which thus become anti- microbial.
  • the water-soluble nano- zirconium oxide ZrO 2 can also be applied to a transparent matrix comparable to T1O 2 (same group in periodic table of the elements) by means of the electrostatic spray method.
  • hafnium oxide as a group relative of the IV. subgroup should be usable.
  • Fig. 17 shows examples for the effect of the use of an antimicrobial coating 10 of a substrate 12 for inactivation of infectious agents.
  • bar diagrams show the effect of the use of an antimicrobial coating 10 of a substrate 12 for inactivation of different infectious agents.
  • the coating 10 is obtained by applying the coating 10 on a surface 14 of the substrate 12 by means of an electrostatic spraying method.
  • the coating 10 comprises at least one metal oxide and/or at least one metal salt.
  • a surface 14 has been exposed to different infectious agents.
  • the surface 14 has been exposed to bacteria, in particular E. coli, P. aeruginosa or S aureus.
  • the surface 14 has also been exposed to a coronavirus, in particular a bovine coronavirus.
  • the surface 14 has further been exposed to an antimicrobial coating 10.
  • a control group is shown, which indicates the infectious agents not treated with any coating 10.
  • the coating 10 has been applied to the surface 14 of a substrate 12 after exposure of the surface 14 to the infectious agent.
  • the surface 14 is first coated with the antimicrobial coating and then the infections agent is applied and inactivated by the coating 10.
  • the number of bacteria on the surface 14 is reduced by more than 99.99999%, 5 minutes after application of the antimicrobial coating 10.
  • the number of bovine corona virus (in log colony forming units) is reduced significantly 5 minutes after application of the antimicrobial coating 10, and is further reduced significantly 30 minutes after application of the antimicrobial coating 10.
  • the antimicrobial coating 10 can be applied for inactivation of infectious agents, such as bacteria or viruses.
  • Fig. 17 the effect of the antimicrobial coating 10 shown for bovine coronavirus is similar or identical for other viruses of the family of Coronaviridae, especially viruses of the subfamily Orthocoronavirinae, such as the severe acute respiratory syndrome coronavirus, the severe acute respiratory syndrome coronavirus 2 or the Middle East respiratory syndrome-related coronavirus.
  • viruses of the subfamily Orthocoronavirinae such as the severe acute respiratory syndrome coronavirus, the severe acute respiratory syndrome coronavirus 2 or the Middle East respiratory syndrome-related coronavirus.
  • Fig. 17 the effect of the antimicrobial coating shown for bovine coronavirus is similar or identical for any coronavirus species, due to the comparable structure of the different coronavirus species (Alphacoronavirus type species Fluman coronavirus 229E, Human coronavirus NL63, Miniopterus bat coronavirus 1, Miniopterus bat coronavirus HKU8, Porcine epidemic diarrhea virus, Rhinolophus bat coronavirus HKU2, Scotophilus bat coronavirus 512, Betacoronavirus species Betacoronavirus 1 (Bovine Coronavirus, Human coronavirus OC43), Human coronavirus HKU1, Murine coronavirus, Pipistrellus bat coronavirus HKU5, Rousettus bat coronavirus HKU9, Severe acute respiratory syndrome-related coronavirus (SARS-CoV, SARS-CoV-2), Tylonycteris bat coronavirus HKU4, Middle East respiratory syndrome-related coronavirus, Hedgehog coron
  • an antimicrobial coating according to the present invention caused 90% inactivation of coronavirus. after 24h exposure to the antimicrobial coating.
  • the antimicrobial coating 10 can be applied for inactivation of infectious agents, such as various bacteria, fungi, moulds or viruses:
  • an antimicrobial coating 10 according to the present invention caused 99.9999% inactivation of Escherichia coli after 5 minutes exposure to the antimicrobial coating 10.
  • an antimicrobial coating 10 caused 99.9999% inactivation of Pseudomonas aeruginosa after less than 60 minutes exposure to the antimicrobial coating 10.
  • an antimicrobial coating 10 according to the present invention caused 99.9999% inactivation of staphylococcus aureus after less than 120 minutes exposure to the antimicrobial coating 10.
  • an antimicrobial coating 10 caused 99.98% inactivation of Candida albicans or Candida auris after 60 minutes exposure to the antimicrobial coating 10.
  • an antimicrobial coating 10 caused 99.9% inactivation of Aspergillus fumigatus or Penicilliums sp. after 4-24h exposure to the antimicrobial coating 10.
  • an antimicrobial coating 10 according to the present invention caused 99.999% inactivation of norovirus. after 24h exposure to the antimicrobial coating 10. Further, the use of an antimicrobial coating according to the present invention caused more than 99% inactivation of rhinovirus. after 24h exposure to the antimicrobial coating 10.
  • iinactivation of an infectious agent may be understood as reducing completely or reducing partially the infectiousness of an infectious agent.
  • inactivation of an infectious agent may be understood as rendering an infectious agent non-viable and/or no longer capable of growing, replicating, infecting a subject or causing disease.
  • the object of viral inactivation is to improve viral safety so that transmissions no longer occur.
  • Fig. 18 shows an example of a workflow for testing the effect of the use of an antimicrobial coating 10 of a substrate 12 for inactivation of human rhinovirus 16 HRV.
  • a substrate 12, in particular a plate, coated with TiO 2 AgNO 3 (here referred to as HEC 110) is exposed to human rhinovirus 16 FIRV for either 5 minutes, 15 minutes or 30 minutes.
  • a substrate 12 in particular a plate, coated with (TiO 2 ) 10 * H 4 SiWi 2 O 4o (here referred to as HEC117) is exposed to human rhinovirus 16 FIRV for either 5 minutes, 15 minutes or 30 minutes.
  • the supernatant of the coated plates comprising the human rhinovirus 16 FIRV exposed to the respective coating for the respective period of time is transferred to FleLa cells (grown in plates).
  • infection This can be referred to as “infection” of the cells with the pre-treated virus.
  • FleLa cells infected with human rhinovirus 16 FIRV previously not exposed to any coating are used as a control (non-coated group). This can also be referred to as positive control
  • Cytopathic effect was assessed by assessing cell detachment from the culture plate and assessing different cell morphology (round structures, bright boundary) after viral infection.
  • the virus previously incubated with HEC110 and HEC17 showed less cytopathic effects (compared to the virus not incubated with any antimicrobial coating) 24 hours after infection and HeLa cells could maintain the same morphology as the non- infected group.
  • HEC110 showed a fast anti-viral effect within 24 hours after virus infection (hours post infection, hpi).
  • HEC117 Compared to H EC 110, HEC117 showed a more persistent anti-viral effect.
  • HEC117 showed a persistent anti-viral effect after short-term incubation with human rhinovirus (5 and 15 minutes) compared to HEC110.
  • HEC110 and HEC17 can display a better anti-viral effect.
  • the antibacterial effect of (TiO 2 )i 2 * PW 12 O 4o was shown (for Escherichia coli).
  • the coating comprises between 0.5% and 10% of a compound comprising nano-TiO 2 , AgNO 3 and/or fumed silica, and is especially designed as a sole gel (tetrahydrosilicane/HNO 3 /alkyl alcohol), showing antimicrobial effects. The effect is, however, not dependent on the type of sole gel.
  • the coating comprises 5% (TiO 2 ) 10 * SiW 12 O 4o and is especially designed as a sole gel (tetrahydrosilicane/HNO 3 /alkyl alcohol). The effect is, however, not dependent on the type of sole gel.
  • the coating comprises 0.5-10% (TiO 2 ) 3* ZnMoO 4 and is especially designed as a synthetic resin, in particular a melamine resin.
  • This coating applied to a surface of a substrate showed antibacterial effects (significant reduction of colony forming units of Staphylococcus aureus).
  • the coating 10 comprises (T ⁇ O 2 ) 3* ZhMoq 4 and is especially designed as a polyurethane, showing antimicrobial effects.
  • the antimicrobial effect can be enhanced by grinding the surface after hardening of the coating 10.
  • (T ⁇ O 2 )*ZhMoq 4 was compounded to 1-10% with granules and processed in a 3D printing process to form a three-dimensional object, which shows a strong effectiveness against Escherichia coli.

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Abstract

La présente invention concerne l'utilisation d'un revêtement antimicrobien (10, 10', 10'', 10''', 10'''') d'un substrat (12) en vue de l'inactivation d'un agent infectieux, le revêtement (10, 10', 10'', 10''', 10'''') étant obtenu par application du revêtement (10, 10', 10'', 10''', 10'''') sur une surface (14) du substrat (12) par un procédé de pulvérisation électrostatique, et le revêtement comprenant au moins un oxyde métallique et/ou au moins un sel métallique. En outre, la présente invention concerne l'utilisation d'un matériau de revêtement pour la production d'un revêtement antimicrobien (10, 10', 10'', 10''', 10'''') sur une surface (14) d'un substrat (12) en vue de l'inactivation d'un agent infectieux, le revêtement (10, 10', 10'', 10''', 10'''') comprenant au moins un oxyde métallique et/ou au moins un sel métallique.
EP21722233.0A 2020-05-06 2021-05-02 Utilisation d'un revêtement antimicrobien Pending EP4146748A1 (fr)

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