EP4127075A1 - Antiviral surface coating for metal and plastic surfaces - Google Patents

Antiviral surface coating for metal and plastic surfaces

Info

Publication number
EP4127075A1
EP4127075A1 EP21712851.1A EP21712851A EP4127075A1 EP 4127075 A1 EP4127075 A1 EP 4127075A1 EP 21712851 A EP21712851 A EP 21712851A EP 4127075 A1 EP4127075 A1 EP 4127075A1
Authority
EP
European Patent Office
Prior art keywords
silver
lacquer
range
formulation
antiviral
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
EP21712851.1A
Other languages
German (de)
French (fr)
Inventor
Murray J. Height
Jens Meiser
Ralph SALATHE
Renzo RASO
Walter Nassl
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.)
HeiQ mATERIALS AG
Original Assignee
HeiQ mATERIALS AG
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 HeiQ mATERIALS AG filed Critical HeiQ mATERIALS AG
Publication of EP4127075A1 publication Critical patent/EP4127075A1/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • D06M13/507—Organic silicon compounds without carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

  • the invention relates to a lacquer comprising a base substance and an antiviral substance, a film made therefrom and the use of a lacquer and a film.
  • protective masks can be worn. Alternatively or additionally, a distance of 1-2m from other people can be maintained. Companies can have their employees work in shifts so that personal contact is minimized. However, even then, due to the lifespan of the viruses, there is a risk of smear infection if, for example, an employee on the first shift is ill and touches a surface, e.g. in a recreation room or on a machine, and on the following shift another employee touches the same surface and puts their hand to their face.
  • compositions having antimicrobial activity containing surface functionalized particles comprising an inorganic copper salt which has low water solubility. These types of inorganic salts may also be introduced in porous particles to yield antimicrobial compositions.
  • the compositions may optionally comprise additional antimicrobial agents, salts with high water solubility, organic acids, salts of organic acids and their esters.
  • the compositions may be added to various fluids used in the petroleum extraction industry, or used as coatings on components used in this industry. These antimicrobial materials may be used for reducing both anaerobic and aerobic bacteria and are also useful for reducing corrosion of ferrous components caused by anaerobic bacteria. Although such compositions may be used for any antimicrobial application, and some of the other important uses of these compositions are in wound care, personal care and waste processing.
  • US-B-8569396 proposes antimicrobial coatings with anti-staining properties that exhibit broad range adhesion characteristics.
  • the coating compositions comprise a mixture of water-borne resins that can be cross-linked through use of a suitable crosslinking agent.
  • the coating compositions can be used on a variety of substrates and are highly flexible, thereby permitting their use on flexible and stretchable materials. Testing has shown the coatings to exhibit excellent antimicrobial characteristics against a broad class of particularly virulent pathogens.
  • US-A-2010293994 discloses a hydrophilic composition and a hydrophilic member obtained by using the composition, which composition contains a hydrophilic polymer having a specific structure of having a hydrolysable group in the side chain thereof in a content of 50% by weight or more based on the weight of the solid components and further contains an additive having an antifungal property, and which composition shows excellent water resistance and maintains the high hydrophilicity even after being stored for a long period under an environment of high temperature and high humidity.
  • US-A-2017022370 discloses an aqueous ink composition including water; an optional co solvent; an optional colorant; and a composite nanoparticle comprising a core and a shell; wherein the core comprises a styrene/acrylate polymer core resin, optionally comprising a metal; and wherein the shell comprises a metal.
  • An aqueous ink composition including water; an optional co-solvent; an optional colorant; and an ionic polymer-metal composite; wherein the ionic-polymer metal composite nanoparticle acts as a reservoir for the delivery of metal ions for anti-bacterial effect, antifungal effect, antiviral biocide effect, or a combination thereof.
  • a process comprising incorporating an aqueous ink into an ink jet printing apparatus; ejecting droplets of ink in an imagewise pattern onto an intermediate transfer member or directly onto a final image receiving substrate; optionally, heating the image; and optionally, when an intermediate transfer member is used, transferring the ink in the imagewise pattern from the intermediate transfer member to a final substrate.
  • the task of the present invention is to provide a means of reducing the risk of smear infections.
  • a lacquer with a base substance and an antiviral substance comprising a booster, in particular liposomes and/or surfactants, as well as silver chloride and/or silver salts and/or silver adsorbed on silicon dioxide.
  • a lacquer is a liquid coating material which is applied thinly to objects and is built up by chemical or physical processes (for example evaporation of solvent and/or cross-linking) to form a continuous, solid film.
  • the coating according to the invention may comprise a solvent.
  • This solvent may be a high-boiling or low-boiling solvent based on synthesised or non-synthesised chemical substances, or may consist of or comprise water.
  • a booster in the sense of the invention is suitable for attacking viruses, in particular their viral membrane, and in particular for freeing them from their cholesterol.
  • a liposome is a vesicle which encloses an aqueous phase and whose membrane envelope consists of a double layer of molecules which have both a non-polar (lipophilic, fat-loving) and a polar (hydrophilic, water-loving) part and are thus termed amphiphilic.
  • the membrane-forming molecules may be substances from the lipid substance class, such as phospholipids, non-phospholipids, and fatty acids.
  • the vesicle-forming non-phospholipid can be selected from the group consisting of, the values in brackets indicating the hydrocarbon chain: fatty alcohol (C12-C20), fatty acid (C12-C20), ethoxylated (C12-C20) fatty alcohol, glycol ester of (C12-C20) fatty acid, ethoxylated of (C12-C20) fatty acid, glycerol fatty acid (C12-C20) monoester, glycerol fatty acid diester (C12-C18), ethoxylated glycerol fatty acid ester (C16-C18), fatty acid diethanolamide (C12-C20), fatty acid dimethyl amide (C12-C20), fatty acid sarcosinates (C12-C20), or a combination thereof.
  • the vesicle-forming non-phospholipid system does not contain any cholesterol or cholesterol based system.
  • the vesicle-forming non-phospholipid is selected from a polyoxyethylene cetyl ether, palmitic acid, hexadecyl trimethylammonium bromide or chloride, oleic acid or a combination thereof.
  • Said vesicle formulation additives may comprise enhancers for the antiviral effect, e.g. selected from the group consisting of: poly- or oligosaccharides such as xylitol, in particular cyclodextrin or derivatives thereof, or a steroidogenic acute regulatory protein.
  • enhancers for the antiviral effect e.g. selected from the group consisting of: poly- or oligosaccharides such as xylitol, in particular cyclodextrin or derivatives thereof, or a steroidogenic acute regulatory protein.
  • the lacquer according to the invention based on silver chloride ions, silver salts and/or silver adsorbed on silicon dioxide together with a booster, in particular liposomes and/or surfactants, can open and destroy the lipid membranes of viruses and kill the virus within minutes.
  • the silver components attract the oppositely charged viruses and bind permanently to their Sulphur groups.
  • the fat-containing spherical vesicles (liposomes) help to free the virus membrane from its cholesterol content within seconds and thus destroy the virus.
  • Non-phospholipid vesicle (liposome) components and silver-based components that are blended into the lacquer formulation distribute throughout the formulation mixture and are present homogeneously in the subsequent lacquer layer applied to the surface being coated.
  • Vesicle formulation components such as non-phospholipid vesicle components and cyclodextrin components that are present at the surface-air interface of the lacquer coating matrix are in proximity to microorganisms that may subsequently come into contact with the surface thereby enabling an interaction between microorganisms and the vesicle and cyclodextrin components in the layer. These components may interact with microorganisms to aid or boost the effect of the silver-based components.
  • the vesicle and cyclodextrin components may act upon the cholesterol layer surrounding enveloped viruses to deplete the envelope of cholesterol weakening the structure and enabling increased efficacy of the silver-based components.
  • the lacquer with the desired properties in terms of its processing can be produced particularly easily if the base substance comprises a plastic material.
  • the base substance can comprise at least one of the following: Polyurethane, polyester, epoxy, acrylate, polyvinyl alcohol (PVA) plastics, PVC, nitrocellulose, alkyd, silicone.
  • PVA polyvinyl alcohol
  • the proportion of the antiviral substance in the lacquer should be 5-30%. This results in a particularly good effectiveness of the lacquer even over several days or weeks.
  • the lacquer has antibacterial properties. This means that people can be protected not only from viruses but also from bacteria.
  • the lacquer inhibits the growth and persistence of bacteria and enveloped viruses, such as corona viruses.
  • the lacquer can comprise a cross-linking agent, in particular isocyanates or melamine- containing cross-linking agents.
  • a cross-linking agent in particular isocyanates or melamine- containing cross-linking agents.
  • crosslinked plastics in particular elastomers and/or thermosets, can be produced from the lacquer by curing and gelling epoxy resins with amines or polyurethanes with blocked isocyanates.
  • Cross-linked plastics have a wide range of properties that depend on the degree of cross-linking and can thus be varied, e.g. electrical insulation capacity, dimensional stability, temperature resistance, chemical resistance, fire behaviour.
  • the varnish can be brushed, sprayed or applied with a roller, it can be applied particularly easily to surfaces that are frequently touched by hands.
  • the applied lacquer can dry at room temperature. Alternatively, it can be dried and/or cured by a hot air blower. It is conceivable for initial and subsequent finishing of surfaces.
  • the surfaces, to which the lacquer can be applied can be hard or soft surfaces, and includes metal, plastic, wood and other natural hard surfaces like stone, ceramics, glass, as well as combinations thereof.
  • the lacquers can be applied hard surfaces but also to soft surfaces, so the above materials, apart from taking the form of solid objects, can also take the form soft objects including woven, knitted or nonwoven textiles, leather, foils, paper, and combinations thereof.
  • Plastic materials include for example polyamide, polyester, polyethylene, polypropylene, polyurethane, polycarbonate as well as combinations thereof.
  • the lacquer can be transparent or colored. Thus, in the case of transparent lacquer, the design and color of the surface coated with lacquer can be preserved or, if colored, the lacquer can be used for surface design. In addition, the colored lacquer can signal that a surface is protected from viruses.
  • a film made from or with a lacquer according to the invention is also be applied to surfaces.
  • the film also exhibits antiviral properties.
  • lacquer can be applied to a carrier, such as silicone or a release liner, in a desired film thickness. After drying, a film can then be removed from the carrier.
  • a film with lacquer it is conceivable to coat a film with lacquer.
  • the coating remains on the film so that the coated side of the film has antiviral properties. it is particularly advantageous if the film is self-adhesive. This means that it can be easily applied to surfaces.
  • the coating, when dry, and the film may be washable, especially water resistant.
  • the antiviral effect can be maintained at elevated temperatures, e.g. up to 30°C, preferably up to 50°C.
  • the film is peelable.
  • the dried lacquer may also be peelable.
  • the film or lacquer can be removed from the surface after some time and a new lacquer or film with antiviral properties can be applied to the surface.
  • the film may have a thickness in the range 0.0001 to 5mm, preferably in the range 0.001mm to 3.0mm.
  • a thicker film may be used for areas where heavy use is expected.
  • a thinner film may be used if the surface disposed under the film has a particular tactile feel that a person needs to feel.
  • the antiviral substance which comprises a booster, in particular liposomes and/or surfactants, as well as silver chloride and/or silver salts and/or silver adsorbed on silicon dioxide is an antiviral product such as HeiQ Viroblock NPJ03 (or another formulation as given in HeiQ patent application EP20176229.1).
  • Suitable aqueous antibacterial and antiviral formulations acting as the antiviral substance in combination contain silver particles as well as non-phospholipid vesicles.
  • the proposed formulation acting as the antiviral substance may combine two separately- produced functional formulation components:
  • Formulation A Silver-based particles in aqueous suspension
  • Formulation B An aqueous vesicle emulsion, preferably with cyclodextrin-based components.
  • Formulation A and formulation B may be blended in various proportions, and with other formulation components to form a stable Product formulation.
  • Formulation A it is specifically pointed out that while being described in the following often times in combination with formulation B, the corresponding formulations A are also independently and without being mixed with formulation B considered as separate inventions. Also a separate invention is any kind of description being given in the following of methods preparing such formulations of the type A.
  • the combined product formulation may be applied to solid substrates, in particular in a lacquer formulation, or to any object to be protected as defined above, in order to achieve antimicrobial and antiviral functionality.
  • Application onto the various substrates may variously be achieved through industrial processes (e.g. padding, dipping, coating, spraying, printing etc.).
  • Typical applications for hard surfaces such as foils and objects based on foils treated with the formulation include structural or protective articles for use in sensitive environments including coverings, shieldings, housings, floors etc.
  • a method for the preparation of an aqueous antibacterial and antiviral formulation acting as the antiviral substance in particular for lacquer formulations comprising silver micro or nanoparticles, preferably silver-silica micro composite particles or silver chloride particles as well as non-phospholipid lipid vesicles (nPLV) or without such non-phospholipid lipid vesicles.
  • the proposed method in case of the combination of both formulations is characterised in that separately
  • a first aqueous formulation comprising silver nano or micro particles, preferably silver-silica micro composite particles and/or silver chloride particles, and no nonphospholipid lipid vesicles (formulation A) and
  • a second aqueous formulation comprising non-phospholipid lipid vesicles and no silver particles (formulation B) are prepared.
  • first and second aqueous solutions are blended, optionally with addition of water and additional additives, at a temperature of at most 40°C, for the combination formulation acting as the antiviral substance.
  • Said first aqueous formulation (formulation A) can be prepared in that silver micro or nanoparticles, preferably silver-silica micro composite or silver chloride particles, are added to water, together with at least one cationic or non-ionic surfactant, optionally with addition of further silver formulation additives, until a stable homogenous dispersion is formed containing silver micro or nanoparticles, preferably silver chloride particles or silver-silica micro composite particles, in association with said cationic or non-ionic polymeric or nonpolymeric surfactant.
  • a cationic surfactant is used
  • silver chloride particles a non-ionic surfactant is used.
  • the surfactants are polymeric surfactants.
  • silver chloride particles as such but also composite particles, in which silver chloride is embedded or in the form of aggregates with other particles, e.g. in the form of titanium dioxide particles which are aggregated with silver chloride particles.
  • Said second aqueous formulation if used, is prepared in that at least one vesicle-forming non-phospholipid and optionally further vesicle formulation additives are added to water, are mixed at elevated temperature of more than 50°C, until homogeneous mixture is obtained, and subsequently cooled to a temperature of at most 40°C under formation of homogeneous emulsion.
  • the preferred silver component used in the formulation acting as the antiviral substance is based on a silver-silica composite powder.
  • the particles particularly useful for use in the proposed invention can be obtained using the method as disclosed in US2009131517, the disclosure of which in terms of the making process is expressly included into this disclosure.
  • the weight proportion of silver in relation with the amorphous silica in these particles is in the range of 1:8-1 :2, preferably in the range of 1 :4, and/or the silver-silica micro composite particles preferably have an average size in the range of 0.1-10 pm, preferably in the range of 0.5 - 5.0 pm, and the silver is preferably embedded in these particles in the form of particles with an average diameter in the range of 1 - 10 nm. Averages are given as number averages.
  • the silver component used in the formulation acting as the antiviral substance is based on silver chloride, preferably in the form of a combined silver chloride titanium dioxide composite product.
  • the proportion (by weight) of silver chloride to titanium dioxide is preferably in the range of 10:90-30:70, and the particle size of the corresponding composite powder is above 100 nm, preferably in the range of 200-1000 nm (d50).
  • the silver material is formulated together with additional components to facilitate formulation properties such as stability, compatibility, ease of processing, durability etc., wherein of particular importance there is a cationic or non-ionic surfactant. So also non ionic surfactants can be added, particularly preferably if silver chloride titanium dioxide composite particles are used.
  • silver-based solids such as particulate nanosilver, silver chloride particles either suspended directly or supported as part of a titanium dioxide composite (e.g. Clariant JMAC).
  • the vesicle formulation component is based on a non-phospholipid vesicle structure that interacts with enveloped virus types to render removal of the lipid envelop and subsequent denaturing of the virus RNA or DNA internal genetic materials.
  • This technology as such is known in the art and has shown to be efficient for example from US 5,561 ,062 or US 8,889,398.
  • the problem associated with the co-formulation of a silver particle based antibacterial/antiviral formulation with a vesicle based formulation is that adding active silver particles simply to a vesicle based formulation will negatively influence the vesicles and/or silver materials and will mutually degrade them at the moment of mixing and in particular upon storage. Preparing a stable combined formulation with silver particles and antiviral vesicles is therefore not simply possible.
  • silver particles and vesicle based antiviral formulations by separately preparing a silver micro or nano particle based dispersion and vesicle based antiviral emulsion/formulation, and to then combine them essentially at room temperature only and to use such a formulation in a lacquer.
  • the silver particle dispersion to this end is prepared in that the silver particles are co-formulated with a cationic or non-ionic surfactant, which forms a micro composite with a polymeric resin matrix or non-ionic matrix in close local proximity surrounding the micro composite structure effectively enveloping the silver particles.
  • the negative interaction between the vesicle components and the silver particles and also between the cationic or non-ionic surfactants on the vesicles is surprisingly reduced and stable formulations can be obtained that can be used for lacquer formulations and that, e.g. on a hard surface, have a high antiviral and antibacterial effect.
  • the principle of the preparation is to surround the silver-silica microcomposite or silver chloride particle with polymeric resin matrix or a non-ionic matrix that contains a cationic /non-ionic surfactant component.
  • the close association of the cationic/non-ionic surfactant component and the (polymeric) matrix is advantageous from a perspective of formulation stability and also efficacy of the formulated product.
  • a nonionic surfactant is first surrounding the micro composite and is then stabilised for example with ethylene glycol.
  • the initial step of the procedure involves blending the silver-silica microcomposite or silver chloride into a solution of the matrix components e.g. followed by high intensity mixing through bead milling (typically for a time span in the range of 4 - 12 hours).
  • the matrix preparation procedure generates a homogeneous mixture where the matrix components penetrate into and surround the silver-silica microcomposite particles.
  • the balance of ingredients can be formulated together prior to introduction of the matrix preparation via in-line high shear mixer.
  • the resulting formulation acting as the antiviral substance is a homogeneous dispersion with excellent storage and operational stability.
  • cationic or non-ionic surfactant component in the matrix a wide range of alternatives is given, including cosmetic cationic or non-ionic surfactants and amino-based surfactants and polymers.
  • the silver-based component in the example is a silver-silica composite, however alternative silver forms may be used separately or in combination (e.g. nanoparticulate silver, silver colloids, silver chloride particles, silver chloride supported on titanium dioxide, etc.). It is also possible to introduce further antimicrobial metal or metal oxide forms such as based on copper as an alternative or in combination with the silver material(s).
  • silver silica particles is one preferred embodiment, however according to another preferred embodiment the silver in the formulation acting as the antiviral substance is in the form of a micro composite or nano composite particle comprising silver chloride and titanium dioxide.
  • a micro composite or nano composite particle comprising silver chloride and titanium dioxide.
  • the titanium dioxide particles preferably have a particle size (d50) in the range of 0.2 to 0.8 pm.
  • using the above-mentioned cationic surfactant can still be beneficial but is not necessarily required any more.
  • Matrix and auxiliary reagents may be substituted for various functionally similar components.
  • the final functionality of the product formulation acting as the antiviral substance requires stability of both vesicle structures and silver particles within the final product formulation. While the vesicle structures are stable in the separately prepared vesicle formulation and the silver formulation, respectively, it is not obvious that a blended formulation of the two component formulations would achieve stability and be suitable for acting as the antiviral substance in a lacquer.
  • a stable combined formulation needs to preserve the vesicle structures and to maintain a homogeneous distribution of the silver particles throughout the mixture acting as the antiviral substance.
  • a significant feature of the present invention is that it has been possible to achieve a stable formulation of the vesicle and silver particle components together in the same formulation acting as the antiviral substance.
  • the formulation stability may be achieved across a range of blend ratios that cannot be predicted a priori.
  • a principle for achieving the blended formulation stability is the unique role of the silver formulation where the silver ingredients are embedded within a resinous matrix with close association with a cationic surfactant. This approach results in keeping cationic or non-ionic surfactants in close proximity with the silver ingredient rather than distributing homogenously in the final blended product formulation where it may be available for interacting with and potentially disrupting the vesicle structures.
  • a further principle for achieving stability of the combined formulation is maintaining similar pH character for each component formulation prior to blending.
  • the combined interaction of the silver (together with selected co-ingredients) and the non phospholipid vesicle enables an enhanced level of antiviral activity against both enveloped viruses and also non-enveloped viruses when acting as the antiviral substance in a lacquer.
  • Silver via silver ions and/or silver metal
  • the lipid layer of enveloped viruses provides greater resistance to diffusion of silver ions and subsequent interaction with the RNA or DNA material compared to non-enveloped viruses.
  • the lipid-mediating mechanism of the vesicle technology is specific to enveloped viruses.
  • the combined action of silver and vesicle structure therefore acts to enable greater activity of silver against enveloped viruses while also providing action against non-enveloped viruses.
  • the selected formulation co-ingredients in principle lead to greater level of proximity of the silver materials with the virus materials, leading to enhanced antiviral action of the silver ions and/or silver-based particles.
  • Some of the components may also have a basis for direct degrading action against viruses.
  • the silver materials are formulated with a range of co-ingredients including cationic surfactants (e.g. Cocobis(2-hydroxyethyl) methylammonium chloride) or non-ionic surfactants.
  • cationic surfactants e.g. Cocobis(2-hydroxyethyl) methylammonium chloride
  • non-ionic surfactants e.g. Cocobis(2-hydroxyethyl) methylammonium chloride
  • Cationic but also non-ionic surfactants in particular have shown potential for interaction with enveloped viruses, including in the presence of proteins.
  • the apparent binding tendency of cationic surfactants with enveloped virions means that for silver components that are closely surrounded by the cationic surfactants, the virions may be actively brought into closer proximity to the silver source, leading in principle to greater antiviral efficacy of the silver.
  • said cationic surfactant is a quaternary surfactant, preferably a polymeric quaternary ammonium surfactant, in particular based on fatty acid based building blocks, polyacrylate building blocks, polymethacrylate building blocks, C10- C20 alkyl building blocks, benzyl building blocks, or a combination or mixture thereof.
  • Said cationic surfactant is preferably selected from the group consisting of: quaternary ammonium polyacrylate, quaternary ammonium ethoxylate, quaternary ammonium propoxylate, quaternary ammonium fatty acid derivative, and is most preferably selected from the group consisting of: poly(2-(trimethylamino)ethyl methacrylate), coconut bis-(2- hydroxyethyl) methyl ammonium, oleyl bis-(2-hydroxyethyl)methyl ammonium, erucyl bis(2- hydroxyethyl)(methyl)ammonium, benzyl(2-hydroxyethyl)dimethylammonium chloride, dodecylbis(2-hydroxyethyl)methylammonium, or a combination or mixture thereof.
  • the negatively charged counterions for the ammonium cation in these systems can e.g. be chloride or bromide or combinations thereof, but also other inorganic systems such as sulfates, phosphates are possible or organic counterions such as acetates, or polymeric organic anions.
  • said non-ionic surfactant can be a polyethoxylated and/or polypropoxylated surfactant, in particular based on fatty acid based building blocks, C10-C40 alkyl, aryl or arylalkyl building blocks, or a combination or mixture thereof.
  • the non-ionic surfactant is selected from the group consisting of: alcohol C10- C28, preferably alcohol C10 - C20, most preferably alcohol C12 - C18 or alcohol C16-18, tristyrylphenol tridecyl ether, ethoxylated in each case with 3-70 EO units, preferably with 20-60 EO units, most preferably with 30-50 EO units, wherein most preferably a system of the type alcohol C16-C18+50EO is used.
  • the first aqueous formulation can be prepared in that the silver-silica micro composite particles are added to water together with said cationic surfactant, wherein the proportion of silver-silica micro composite particles is in the range of 0.1-1 %(w/w), preferably in the range of 0.2-0.5 %(w/w) and wherein the proportion of the cationic surfactant is in the range of 0.5-7.5% (w/w), preferably in the range of 1.5-5% (w/w) .
  • the proportion of the cationic surfactant if chosen as an ammonium compound is given for the chloride or bromide form. The concentrations in this case are given for the final formulation A.
  • the first aqueous formulation can alternatively be prepared in that the in that the silver- chloride particles are added to water together with said non-ionic surfactant, wherein the proportion of silver-chloride particles is in the range of 5-15 %(w/w), preferably in the range of 7-12 %(w/w) and wherein the proportion of the non-ionic surfactant is in the range of 0.5- 12% (w/w), preferably in the range of 1-10% (w/w), and wherein the resulting mixture is mixed, preferably through milling, preferably through bead milling, for a time span of at least an hour, more preferably for a time span of more than 5 hours, at a temperature of at least 20°C, preferably at a temperature at or above room temperature.
  • concentrations in this case are given for the final formulation A acting as the antiviral substance.
  • the silver formulation can be prepared in a two-step process, in a first step phase A is produced by suspending silver-containing particles within the cationic or non-ionic surfactant under intensive mixing, separately prepare an aqueous formulation with stabilising components such as rheology thickeners et cetera (phase B) and then introduce phase A into phase B in a manner to achieve homogeneous distribution within phase B, wherein phase B is the larger proportion of the final blend weight and forms more than 50% of the final formulation weight of formulation A.
  • phase A is produced by suspending silver-containing particles within the cationic or non-ionic surfactant under intensive mixing, separately prepare an aqueous formulation with stabilising components such as rheology thickeners et cetera (phase B) and then introduce phase A into phase B in a manner to achieve homogeneous distribution within phase B, wherein phase B is the larger proportion of the final blend weight and forms more than 50% of the final formulation weight of formulation A.
  • the resulting mixture is mixed, preferably through milling, preferably through bead milling, for a time span of at least an hour, more preferably for a time span of more than 5 hours, at a temperature of at least 20°C, preferably at a temperature at or above room temperature.
  • additives can be added selected from the group consisting of: alcohols, glycols, polyols, diols, phosphates, acids such as acetic acid, fragrance, colorants, nonionic surfactants, odorants, anti-foaming agents, foaming agents, rheology modifiers such as thickeners or a combination thereof.
  • additives or just some of them may also be added only after the mixing of the silver (silica) particles and the cationic or non-ionic surfactant, in particular additives such as thickeners are of this kind.
  • composition and the method of preparing formulation A is also regarded as an independent invention independent of formulation B and the combined product involving formulation A as well as B.
  • the vesicle-forming non-phospholipid can be selected from the group consisting of, the values in brackets indicating the hydrocarbon chain: fatty alcohol (C12-C20), fatty acid (C12-C20), ethoxylated (C12-C20) fatty alcohol, glycol ester of (C12-C20) fatty acid, ethoxylated of (C12-C20) fatty acid, glycerol fatty acid (C12-C20) monoester, glycerol fatty acid diester (C12-C18), ethoxylated glycerol fatty acid ester (C16-C18), fatty acid diethanolamide (C12-C20), fatty acid dimethyl amide (C12-C20), fatty acid sarcosinates (C12-C20), or a combination thereof.
  • the vesicle-forming non-phospholipid is selected from a polyoxyethylene cetyl ether, palmitic acid, hexadecyl trimethylammonium bromide or chloride, oleic acid or a combination thereof.
  • Said vesicle formulation additives may comprise enhancers for the antiviral effect, e.g. selected from the group consisting of: poly- or oligosaccharides such as xylitol, in particular cyclodextrin or derivatives thereof, or a steroidogenic acute regulatory protein.
  • the second aqueous formulation can be prepared in that said vesicle-forming non phospholipid and optionally further vesicle formulation additives are added to water, are mixed at elevated temperature of more than 55°C, until homogeneous mixture is obtained, and subsequently cooled to a temperature of at most 30°C under formation of homogeneous emulsion.
  • the proportion of the at least one vesicle-forming non phospholipid is in the range of 1-8 %(w/w), preferably in the range of 2-5 %(w/w) and wherein the proportion of the enhancer if present is in the range of 1-8 % (w/w), preferably in the range of 2-6 % (w/w).
  • the second aqueous formulation preferably comprises, as non-phospholipid, a mixture of polyoxyethylene (2) cetyl ether with hexadecyltrimethylammonium (which can be in the chloride or bromide form, preferably in the bromide form), preferably in a weight proportion of 20: 1-5:1 , most preferably 12:1-8:1 , in a total concentration (taking the sum of polyoxyethylene (2) cetyl ether with hexadecyltrimethylammonium (bromium)) in the range of 3-5% (w/w).
  • a mixture of polyoxyethylene (2) cetyl ether with hexadecyltrimethylammonium which can be in the chloride or bromide form, preferably in the bromide form
  • a weight proportion of 20: 1-5:1 most preferably 12:1-8:1
  • a total concentration taking the sum of polyoxyethylene (2) cetyl ether with hexadecyltrimethylammonium (bromium)
  • the second aqueous formulation comprises, as enhancer, cyclodextrin, preferably (2-hydroxypropyl)-beta-cyclodextrin, in a proportion of 1-7% (w/w), preferably in the range of 3-6% (w/w).
  • the first and second aqueous solutions can be blended at a temperature of at most 40°C, preferably around room temperature, and wherein preferably 5-20% (w/w) of said first aqueous formulation are combined with 70-90% (w/w) of said second aqueous formulation, supplemented with water to a total of 100% (w/w) to form the formulation acting as the antiviral substance.
  • the present invention further relates to an aqueous antibacterial and antiviral formulation acting as the antiviral substance in particular in a lacquer as claimed comprising silver-silica micro composite particles or silver chloride particles alone or in combination with, i.e. as well as non-phospholipid lipid vesicles (nPLV), preferably obtained using a method as described above.
  • aqueous antibacterial and antiviral formulation acting as the antiviral substance in particular in a lacquer as claimed comprising silver-silica micro composite particles or silver chloride particles alone or in combination with, i.e. as well as non-phospholipid lipid vesicles (nPLV), preferably obtained using a method as described above.
  • nPLV non-phospholipid lipid vesicles
  • Such a formulation acting as the antiviral substance comprises the silver-silica micro composite particles or silver chloride particles in association with said cationic or non-ionic polymeric surfactant, wherein preferably the silver-silica micro composite particles are present in a proportion in the range of 0.01-0.1% (w/w), preferably in a proportion in the range of 0.02-0.05% (w/w), wherein the at least one cationic polymeric surfactant is present in a proportion in the range of 0.1 -0.5% (w/w), preferably in the range of 0.2-0.4% (w/w), and wherein said at least one vesicle-forming non-phospholipid is present in a proportion in the range of 2-5% (w/w), preferably in the range of 2.5-4% (w/w).
  • silver-chloride particles these are preferably present in a proportion 5-15 %(w/w), preferably in the range of 7-12 %(w/w), and wherein the at least one non-ionic polymeric surfactant is present in a proportion in the range of 0.5-12% (w/w), preferably in the range of 1-10% (w/w).
  • the present invention relates to the use of a formulation acting as the antiviral substance, formulation A alone or the combined product comprising formulation A as well as formulation B, as detailed above or as obtained using a method as detailed above for the treatment of objects in a lacquer formulation, in particular leather, fibrous materials such as paper and cardboard articles, polymeric surfaces including polyurethane, tarps, tents, bags, luggage, or of textiles, even for the treatment of woven, knitted or nonwoven textiles, or in the field of textiles for antiviral and/or antibacterial applications including masks, filters, gowns, drapes, coverings, carpets et cetera in particular for healthcare/hospital uses.
  • a formulation acting as the antiviral substance formulation A alone or the combined product comprising formulation A as well as formulation B, as detailed above or as obtained using a method as detailed above for the treatment of objects in a lacquer formulation, in particular leather, fibrous materials such as paper and cardboard articles, polymeric surfaces including polyurethane, tarps, tents, bags
  • the present invention relates to an object in particular an object to wear, touch or to carry by a human to be protected, in particular leather, fibrous materials such as paper and cardboard articles, polymeric surfaces including polyurethane, tarps, tents, bags, luggage, a woven or knitted or nonwoven textile treated with a formulation (formulation A alone or combined product), preferably in a lacquer formulation, obtained using a method as detailed above or treated with the formulation as detailed above, preferably in the field of hard surfaces but also textiles for antiviral and/or antibacterial applications including masks, filters, gowns, drapes, coverings, carpets et cetera in particular for hospital uses.
  • a formulation formulation A alone or combined product
  • Last but not least the present invention relates to a method for rendering an object to be protected, in particular an object based on leather, fibrous materials such as paper and cardboard articles, polymeric surfaces including polyurethane, tarps, tents, bags, luggage, woven or nonwoven textile antibacterial and/or antiviral by treating it with a formulation (again formulation A alone or the combined product in each case) acting as the antiviral substance in particular in a lacquer formulation obtained using a method as detailed above, or with a formulation as described above, wherein the formulation is preferably applied by padding, dipping, coating, spraying, printing or a combination thereof, and wherein the formulation is further preferably added to the textile in the range of 2-30% (weight of fabric basis), preferably in the range of 5-20%.
  • a formulation (again formulation A alone or the combined product in each case) acting as the antiviral substance in particular in a lacquer formulation obtained using a method as detailed above, or with a formulation as described above, wherein the formulation is preferably applied by padding
  • a preferred antiviral coating acting as the antiviral substance is based on a blend of the following components:
  • Antiviral product such as HeiQ Viroblock NPJ03 (or another formulation as given in HeiQ patent application EP20176229.1)
  • the lacquer formulation has no organic solvents inside and is 100% waterborne.
  • soft PU is used with adjusted viscosity for film building properties.
  • Possible polyurethane components are selected from one or a combination of the following systems:
  • the basis can be 100% PU, but it can also be 100% Acrylate, it can be a silicon base, a vinyl dispersion base or a latex base.
  • retarder agents to control the point of film building. This is particularly for spraying or high solid contents.
  • lacquer or film according to the invention, wherein the lacquer or film is applied to a surface, in particular of plastic or metal, in order to provide it with an antiviral finish. In this way, effective virus killing can take place on surfaces and the risk of the spread of viral diseases can be reduced.
  • the lacquer or film can be removed from the surface and the lacquer or film can be reapplied to the surface. Lacquer or film that is no longer active can thus be replaced with antivirally active lacquer or film. This can be done at a predetermined time interval.
  • the lacquer or film can be applied, for example, to door handles, table tops, car doors and/or buttons, for example in buses, trains and lifts.
  • the lacquer or foil can be applied in a thickness in the range 0.0001 to 5mm, preferably in the range 0.001mm to 3.0mm.
  • the coating formulation was prepared with the following components and composition:
  • the HeiQ Viroblock NPJ03 product comprises the following constituents and was prepared using the following procedure: Vesicle formulation (2):
  • An illustrative vesicle formulation composition is as follows:
  • Polysiloxane defoamer may optionally be added
  • Preparation procedure Blending of components at elevated temperature (e.g. >60°C) until homogeneously mixed. Cool to ambient temperature while mixing and/or high shear in-line mixer.
  • elevated temperature e.g. >60°C
  • the resulting formulation is a homogeneous emulsion with excellent storage and operational stability.
  • Non-phospholipid components may be substituted.
  • (2-hydroxypropyl)-beta-cyclodextrin (B3) may be substituted or used in combination with other cyclodextrin-based compounds as detailed above.
  • other sugars, oligosaccharides and polysaccharides may be used as substitutes for or in combination with the cyclodextrin-based compounds.
  • An example silver formulation composition is as follows.
  • the silver chloride - titanium dioxide microcomposite particles are, generally speaking, prepared as follows:
  • Titanium dioxide particles are suspended in aqueous solution of silver nitrate
  • silver chloride - titanium dioxide microcomposite particles used here were processed using the following recipe:
  • the principle of the preparation is to surround the silver chloride - titanium dioxide microcomposite with either a cationic surfactant or non-ionic surfactant component.
  • a polymeric matrix component may be added to give additional material surrounding the microcomposite.
  • the close association of the cationic surfactant or non ionic surfactant components and the polymeric matrix is advantageous from a perspective of formulation stability and also efficacy of the formulated product.
  • the initial step of the procedure involves blending the silver chloride - titanium dioxide microcomposite and additional titanium dioxide particles into a solution of the matrix components (ethylene glycol, alcohol C16C18, ethoxylated, and polysiloxane) followed by high intensity mixing through bead milling (ca. 8 hours).
  • the matrix components ethylene glycol, alcohol C16C18, ethoxylated, and polysiloxane
  • the matrix preparation procedure generates a homogeneous mixture where the matrix components penetrate into and surround the silver chloride - titanium dioxide microcomposite particles.
  • the balance of ingredients surfactants and viscosity modifier components, i.e. ethylene glycol, ethyl cellulose (thickener) and additional polysiloxane defoamer are formulated together prior to introduction of the matrix preparation via in-line high shear mixer.
  • the resulting formulation is a homogeneous dispersion with excellent storage and operational stability.
  • Silver and vesicle product formulation (4) Another example formulation for the combined product formulation, using the above first, silver chloride - titanium dioxide formulation (HeiQ Viroblock NPJ03) is as follows:
  • the silver and vesicle product formulation (4) is produced by blending the silver particle formulation (3) and the vesicle formulation (2) together with addition of water (that may optionally contain additional auxiliary or functional components).
  • the blending procedure (with simple vessel agitation) proceeds in the following order.
  • the blending ratio reflects the ratios needed to produce the exemplar product composition above.
  • Steps 2 and 3 may optionally be reversed.
  • the resulting formulation is a homogeneous emulsion with excellent storage and operational stability.
  • the preparation of the coating formulation was conducted as follows:
  • a flexible Vinyl sheet (e.g 3M) of up to 0,5 mm thickness was used as the test substrate.
  • the substrate was cleaned with ethanol and air dried to ensure the surface was free of soil and contaminants prior to coating with the prepared formulation.
  • the coating formulation was applied to the surface of the test substrate using a spray applicator (Model Wagner AirlessVector pro). The coating was applied so as to achieve a dry solids coverage of 70 g/m2. The applied formulation was observed to form a homogeneous and level film on the surface of the substrate.
  • the substrate was dried in an over (ThermoFischer Scientific OMH180) at 120° Celsius for 3 min.
  • the stability of the coated surface was assessed by immersing (5 cm square) samples of the coated material in volumes (100 ml) of water and organic solvents (including ethanol, toluene, ). After a set period of time (30 seconds) the samples were removed and the stability of the coating layer was observed through visual observation. The coating was observed to be stable to exposure to water and the tested organic solvents. No haze appeared.
  • the adhesion of the coating to the surface of the substrate was examined by manual scratching of the surface with a metal blade and observing the ease of delamination of the coating layer.
  • the coating was observed to have excellent adhesion to the surface, there was no delamination.
  • the treated sample shows significantly higher antiviral effect compared to the untreated surface.

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Abstract

A lacquer comprises a base substance and an antiviral substance comprising a booster and silver chloride and/or silver salts and/or silver adsorbed on silica.

Description

TITLE
ANTIVIRAL SURFACE COATING FOR METAL AND PLASTIC SURFACES
TECHNICAL FIELD
The invention relates to a lacquer comprising a base substance and an antiviral substance, a film made therefrom and the use of a lacquer and a film.
PRIOR ART
During the Corona pandemic, awareness was raised about how viral infection can occur. Besides droplet infection, smear infection plays a crucial role.
To prevent droplet infection, protective masks can be worn. Alternatively or additionally, a distance of 1-2m from other people can be maintained. Companies can have their employees work in shifts so that personal contact is minimized. However, even then, due to the lifespan of the viruses, there is a risk of smear infection if, for example, an employee on the first shift is ill and touches a surface, e.g. in a recreation room or on a machine, and on the following shift another employee touches the same surface and puts their hand to their face.
US-A-2014271757 discloses compositions having antimicrobial activity containing surface functionalized particles comprising an inorganic copper salt which has low water solubility. These types of inorganic salts may also be introduced in porous particles to yield antimicrobial compositions. The compositions may optionally comprise additional antimicrobial agents, salts with high water solubility, organic acids, salts of organic acids and their esters. The compositions may be added to various fluids used in the petroleum extraction industry, or used as coatings on components used in this industry. These antimicrobial materials may be used for reducing both anaerobic and aerobic bacteria and are also useful for reducing corrosion of ferrous components caused by anaerobic bacteria. Although such compositions may be used for any antimicrobial application, and some of the other important uses of these compositions are in wound care, personal care and waste processing.
US-B-8569396 proposes antimicrobial coatings with anti-staining properties that exhibit broad range adhesion characteristics. The coating compositions comprise a mixture of water-borne resins that can be cross-linked through use of a suitable crosslinking agent. The coating compositions can be used on a variety of substrates and are highly flexible, thereby permitting their use on flexible and stretchable materials. Testing has shown the coatings to exhibit excellent antimicrobial characteristics against a broad class of particularly virulent pathogens.
US-A-2010293994 discloses a hydrophilic composition and a hydrophilic member obtained by using the composition, which composition contains a hydrophilic polymer having a specific structure of having a hydrolysable group in the side chain thereof in a content of 50% by weight or more based on the weight of the solid components and further contains an additive having an antifungal property, and which composition shows excellent water resistance and maintains the high hydrophilicity even after being stored for a long period under an environment of high temperature and high humidity.
US-A-2017022370 discloses an aqueous ink composition including water; an optional co solvent; an optional colorant; and a composite nanoparticle comprising a core and a shell; wherein the core comprises a styrene/acrylate polymer core resin, optionally comprising a metal; and wherein the shell comprises a metal. An aqueous ink composition including water; an optional co-solvent; an optional colorant; and an ionic polymer-metal composite; wherein the ionic-polymer metal composite nanoparticle acts as a reservoir for the delivery of metal ions for anti-bacterial effect, antifungal effect, antiviral biocide effect, or a combination thereof. A process comprising incorporating an aqueous ink into an ink jet printing apparatus; ejecting droplets of ink in an imagewise pattern onto an intermediate transfer member or directly onto a final image receiving substrate; optionally, heating the image; and optionally, when an intermediate transfer member is used, transferring the ink in the imagewise pattern from the intermediate transfer member to a final substrate.
SUMMARY OF THE INVENTION
The task of the present invention is to provide a means of reducing the risk of smear infections.
This task is solved by a lacquer with a base substance and an antiviral substance comprising a booster, in particular liposomes and/or surfactants, as well as silver chloride and/or silver salts and/or silver adsorbed on silicon dioxide. A lacquer is a liquid coating material which is applied thinly to objects and is built up by chemical or physical processes (for example evaporation of solvent and/or cross-linking) to form a continuous, solid film. Accordingly, the coating according to the invention may comprise a solvent. This solvent may be a high-boiling or low-boiling solvent based on synthesised or non-synthesised chemical substances, or may consist of or comprise water.
A booster in the sense of the invention is suitable for attacking viruses, in particular their viral membrane, and in particular for freeing them from their cholesterol.
A liposome is a vesicle which encloses an aqueous phase and whose membrane envelope consists of a double layer of molecules which have both a non-polar (lipophilic, fat-loving) and a polar (hydrophilic, water-loving) part and are thus termed amphiphilic. The membrane-forming molecules may be substances from the lipid substance class, such as phospholipids, non-phospholipids, and fatty acids.
The vesicle-forming non-phospholipid can be selected from the group consisting of, the values in brackets indicating the hydrocarbon chain: fatty alcohol (C12-C20), fatty acid (C12-C20), ethoxylated (C12-C20) fatty alcohol, glycol ester of (C12-C20) fatty acid, ethoxylated of (C12-C20) fatty acid, glycerol fatty acid (C12-C20) monoester, glycerol fatty acid diester (C12-C18), ethoxylated glycerol fatty acid ester (C16-C18), fatty acid diethanolamide (C12-C20), fatty acid dimethyl amide (C12-C20), fatty acid sarcosinates (C12-C20), or a combination thereof.
Preferably the vesicle-forming non-phospholipid system does not contain any cholesterol or cholesterol based system.
Preferably, the vesicle-forming non-phospholipid is selected from a polyoxyethylene cetyl ether, palmitic acid, hexadecyl trimethylammonium bromide or chloride, oleic acid or a combination thereof.
Said vesicle formulation additives may comprise enhancers for the antiviral effect, e.g. selected from the group consisting of: poly- or oligosaccharides such as xylitol, in particular cyclodextrin or derivatives thereof, or a steroidogenic acute regulatory protein.
The lacquer according to the invention based on silver chloride ions, silver salts and/or silver adsorbed on silicon dioxide together with a booster, in particular liposomes and/or surfactants, can open and destroy the lipid membranes of viruses and kill the virus within minutes. The silver components attract the oppositely charged viruses and bind permanently to their Sulphur groups. The fat-containing spherical vesicles (liposomes) help to free the virus membrane from its cholesterol content within seconds and thus destroy the virus.
When this lacquer is applied to a surface, the viruses die on this surface and the surface of the lacquer has an additional virus-killing effect. In this way, the risk of smear infections can be prevented in the long term. The effectiveness lasts for a few days/weeks and can then be completely renewed by removing and renewing the lacquer or a film made from it. A further possibility is to apply another layer of the lacquer or film to the surface after a few days. This makes the surface fully effective again. Another option is to apply several layers of lacquer or film and always remove the "worn" layer of lacquer or film after a few days to restore full effectiveness. This principle is known from a lint roller for cleaning textiles. Non-phospholipid vesicle (liposome) components and silver-based components that are blended into the lacquer formulation distribute throughout the formulation mixture and are present homogeneously in the subsequent lacquer layer applied to the surface being coated. Vesicle formulation components, such as non-phospholipid vesicle components and cyclodextrin components that are present at the surface-air interface of the lacquer coating matrix are in proximity to microorganisms that may subsequently come into contact with the surface thereby enabling an interaction between microorganisms and the vesicle and cyclodextrin components in the layer. These components may interact with microorganisms to aid or boost the effect of the silver-based components. For example the vesicle and cyclodextrin components may act upon the cholesterol layer surrounding enveloped viruses to deplete the envelope of cholesterol weakening the structure and enabling increased efficacy of the silver-based components.
The lacquer with the desired properties in terms of its processing can be produced particularly easily if the base substance comprises a plastic material.
Depending on the desired processing and field of application of the lacquer, the base substance can comprise at least one of the following: Polyurethane, polyester, epoxy, acrylate, polyvinyl alcohol (PVA) plastics, PVC, nitrocellulose, alkyd, silicone.
The proportion of the antiviral substance in the lacquer should be 5-30%. This results in a particularly good effectiveness of the lacquer even over several days or weeks.
Further advantages result if the lacquer has antibacterial properties. This means that people can be protected not only from viruses but also from bacteria. In particular, the lacquer inhibits the growth and persistence of bacteria and enveloped viruses, such as corona viruses.
The lacquer can comprise a cross-linking agent, in particular isocyanates or melamine- containing cross-linking agents. Thus, crosslinked plastics, in particular elastomers and/or thermosets, can be produced from the lacquer by curing and gelling epoxy resins with amines or polyurethanes with blocked isocyanates. Cross-linked plastics have a wide range of properties that depend on the degree of cross-linking and can thus be varied, e.g. electrical insulation capacity, dimensional stability, temperature resistance, chemical resistance, fire behaviour.
If the varnish can be brushed, sprayed or applied with a roller, it can be applied particularly easily to surfaces that are frequently touched by hands. The applied lacquer can dry at room temperature. Alternatively, it can be dried and/or cured by a hot air blower. It is conceivable for initial and subsequent finishing of surfaces.
The surfaces, to which the lacquer can be applied, can be hard or soft surfaces, and includes metal, plastic, wood and other natural hard surfaces like stone, ceramics, glass, as well as combinations thereof. The lacquers can be applied hard surfaces but also to soft surfaces, so the above materials, apart from taking the form of solid objects, can also take the form soft objects including woven, knitted or nonwoven textiles, leather, foils, paper, and combinations thereof. Plastic materials include for example polyamide, polyester, polyethylene, polypropylene, polyurethane, polycarbonate as well as combinations thereof. The lacquer can be transparent or colored. Thus, in the case of transparent lacquer, the design and color of the surface coated with lacquer can be preserved or, if colored, the lacquer can be used for surface design. In addition, the colored lacquer can signal that a surface is protected from viruses.
Also within the scope of the invention is a film made from or with a lacquer according to the invention. The film can also be applied to surfaces. The film also exhibits antiviral properties. For example, lacquer can be applied to a carrier, such as silicone or a release liner, in a desired film thickness. After drying, a film can then be removed from the carrier. Alternatively, it is conceivable to coat a film with lacquer. The coating remains on the film so that the coated side of the film has antiviral properties. it is particularly advantageous if the film is self-adhesive. This means that it can be easily applied to surfaces. The coating, when dry, and the film may be washable, especially water resistant. Furthermore, the antiviral effect can be maintained at elevated temperatures, e.g. up to 30°C, preferably up to 50°C.
Preferably, the film is peelable. The dried lacquer may also be peelable. Thus, the film or lacquer can be removed from the surface after some time and a new lacquer or film with antiviral properties can be applied to the surface.
Advantageously, the film may have a thickness in the range 0.0001 to 5mm, preferably in the range 0.001mm to 3.0mm. In particular, a thicker film may be used for areas where heavy use is expected. However, if the surface disposed under the film has a particular tactile feel that a person needs to feel, a thinner film may be used.
Preferably the antiviral substance which comprises a booster, in particular liposomes and/or surfactants, as well as silver chloride and/or silver salts and/or silver adsorbed on silicon dioxide is an antiviral product such as HeiQ Viroblock NPJ03 (or another formulation as given in HeiQ patent application EP20176229.1).
Suitable aqueous antibacterial and antiviral formulations acting as the antiviral substance in combination contain silver particles as well as non-phospholipid vesicles.
The proposed formulation acting as the antiviral substance may combine two separately- produced functional formulation components:
Formulation A: Silver-based particles in aqueous suspension
Formulation B: An aqueous vesicle emulsion, preferably with cyclodextrin-based components.
Formulation A and formulation B may be blended in various proportions, and with other formulation components to form a stable Product formulation. As concerns Formulation A, it is specifically pointed out that while being described in the following often times in combination with formulation B, the corresponding formulations A are also independently and without being mixed with formulation B considered as separate inventions. Also a separate invention is any kind of description being given in the following of methods preparing such formulations of the type A.
The combined product formulation, but also the formulation A alone, may be applied to solid substrates, in particular in a lacquer formulation, or to any object to be protected as defined above, in order to achieve antimicrobial and antiviral functionality.
Application onto the various substrates may variously be achieved through industrial processes (e.g. padding, dipping, coating, spraying, printing etc.).
Typical applications for hard surfaces such as foils and objects based on foils treated with the formulation include structural or protective articles for use in sensitive environments including coverings, shieldings, housings, floors etc.
A method for the preparation of an aqueous antibacterial and antiviral formulation acting as the antiviral substance in particular for lacquer formulations comprising silver micro or nanoparticles, preferably silver-silica micro composite particles or silver chloride particles as well as non-phospholipid lipid vesicles (nPLV) or without such non-phospholipid lipid vesicles. The proposed method in case of the combination of both formulations is characterised in that separately
• a first aqueous formulation comprising silver nano or micro particles, preferably silver-silica micro composite particles and/or silver chloride particles, and no nonphospholipid lipid vesicles (formulation A) and
• a second aqueous formulation comprising non-phospholipid lipid vesicles and no silver particles (formulation B) are prepared.
Subsequently the first and second aqueous solutions are blended, optionally with addition of water and additional additives, at a temperature of at most 40°C, for the combination formulation acting as the antiviral substance.
Said first aqueous formulation (formulation A) can be prepared in that silver micro or nanoparticles, preferably silver-silica micro composite or silver chloride particles, are added to water, together with at least one cationic or non-ionic surfactant, optionally with addition of further silver formulation additives, until a stable homogenous dispersion is formed containing silver micro or nanoparticles, preferably silver chloride particles or silver-silica micro composite particles, in association with said cationic or non-ionic polymeric or nonpolymeric surfactant. Preferably, in case of silver-silica micro composite particles a cationic surfactant is used, and in case of silver chloride particles a non-ionic surfactant is used. Preferably, the surfactants are polymeric surfactants. When talking about silver chloride particles in this application this includes silver chloride particles as such but also composite particles, in which silver chloride is embedded or in the form of aggregates with other particles, e.g. in the form of titanium dioxide particles which are aggregated with silver chloride particles.
Said second aqueous formulation, if used, is prepared in that at least one vesicle-forming non-phospholipid and optionally further vesicle formulation additives are added to water, are mixed at elevated temperature of more than 50°C, until homogeneous mixture is obtained, and subsequently cooled to a temperature of at most 40°C under formation of homogeneous emulsion.
The preferred silver component used in the formulation acting as the antiviral substance is based on a silver-silica composite powder. The particles particularly useful for use in the proposed invention can be obtained using the method as disclosed in US2009131517, the disclosure of which in terms of the making process is expressly included into this disclosure. Typically, the weight proportion of silver in relation with the amorphous silica in these particles is in the range of 1:8-1 :2, preferably in the range of 1 :4, and/or the silver-silica micro composite particles preferably have an average size in the range of 0.1-10 pm, preferably in the range of 0.5 - 5.0 pm, and the silver is preferably embedded in these particles in the form of particles with an average diameter in the range of 1 - 10 nm. Averages are given as number averages.
Alternatively, the silver component used in the formulation acting as the antiviral substance is based on silver chloride, preferably in the form of a combined silver chloride titanium dioxide composite product. The proportion (by weight) of silver chloride to titanium dioxide is preferably in the range of 10:90-30:70, and the particle size of the corresponding composite powder is above 100 nm, preferably in the range of 200-1000 nm (d50).
The silver material is formulated together with additional components to facilitate formulation properties such as stability, compatibility, ease of processing, durability etc., wherein of particular importance there is a cationic or non-ionic surfactant. So also non ionic surfactants can be added, particularly preferably if silver chloride titanium dioxide composite particles are used.
In addition or as an alternative to the silver metal - silicon dioxide composite material, therefore other silver-based solids may be employed such as particulate nanosilver, silver chloride particles either suspended directly or supported as part of a titanium dioxide composite (e.g. Clariant JMAC).
The vesicle formulation component is based on a non-phospholipid vesicle structure that interacts with enveloped virus types to render removal of the lipid envelop and subsequent denaturing of the virus RNA or DNA internal genetic materials. This technology as such is known in the art and has shown to be efficient for example from US 5,561 ,062 or US 8,889,398.
The problem associated with the co-formulation of a silver particle based antibacterial/antiviral formulation with a vesicle based formulation is that adding active silver particles simply to a vesicle based formulation will negatively influence the vesicles and/or silver materials and will mutually degrade them at the moment of mixing and in particular upon storage. Preparing a stable combined formulation with silver particles and antiviral vesicles is therefore not simply possible.
What has been found now is that surprisingly it is possible to co-formulate silver particles and vesicle based antiviral formulations by separately preparing a silver micro or nano particle based dispersion and vesicle based antiviral emulsion/formulation, and to then combine them essentially at room temperature only and to use such a formulation in a lacquer. The silver particle dispersion to this end is prepared in that the silver particles are co-formulated with a cationic or non-ionic surfactant, which forms a micro composite with a polymeric resin matrix or non-ionic matrix in close local proximity surrounding the micro composite structure effectively enveloping the silver particles. By first preparing these micro composites the negative interaction between the vesicle components and the silver particles and also between the cationic or non-ionic surfactants on the vesicles is surprisingly reduced and stable formulations can be obtained that can be used for lacquer formulations and that, e.g. on a hard surface, have a high antiviral and antibacterial effect.
So the principle of the preparation is to surround the silver-silica microcomposite or silver chloride particle with polymeric resin matrix or a non-ionic matrix that contains a cationic /non-ionic surfactant component. The close association of the cationic/non-ionic surfactant component and the (polymeric) matrix is advantageous from a perspective of formulation stability and also efficacy of the formulated product. In case of surrounding silver chloride particles, in particular silver chloride titanium dioxide composite particles, preferably a nonionic surfactant is first surrounding the micro composite and is then stabilised for example with ethylene glycol.
The initial step of the procedure involves blending the silver-silica microcomposite or silver chloride into a solution of the matrix components e.g. followed by high intensity mixing through bead milling (typically for a time span in the range of 4 - 12 hours).
The matrix preparation procedure generates a homogeneous mixture where the matrix components penetrate into and surround the silver-silica microcomposite particles.
The balance of ingredients (surfactants and viscosity modifier components) can be formulated together prior to introduction of the matrix preparation via in-line high shear mixer.
The resulting formulation acting as the antiviral substance is a homogeneous dispersion with excellent storage and operational stability.
For the cationic or non-ionic surfactant component in the matrix a wide range of alternatives is given, including cosmetic cationic or non-ionic surfactants and amino-based surfactants and polymers.
The silver-based component in the example is a silver-silica composite, however alternative silver forms may be used separately or in combination (e.g. nanoparticulate silver, silver colloids, silver chloride particles, silver chloride supported on titanium dioxide, etc.). It is also possible to introduce further antimicrobial metal or metal oxide forms such as based on copper as an alternative or in combination with the silver material(s).
The use of silver silica particles is one preferred embodiment, however according to another preferred embodiment the silver in the formulation acting as the antiviral substance is in the form of a micro composite or nano composite particle comprising silver chloride and titanium dioxide. Preferably, such a system is generated by precipitating silver chloride on the surface of titanium dioxide particles, and the titanium dioxide particles preferably have a particle size (d50) in the range of 0.2 to 0.8 pm. In case one uses such silver chloride and titanium dioxide composite particles, using the above-mentioned cationic surfactant can still be beneficial but is not necessarily required any more.
Matrix and auxiliary reagents may be substituted for various functionally similar components.
The final functionality of the product formulation acting as the antiviral substance requires stability of both vesicle structures and silver particles within the final product formulation. While the vesicle structures are stable in the separately prepared vesicle formulation and the silver formulation, respectively, it is not obvious that a blended formulation of the two component formulations would achieve stability and be suitable for acting as the antiviral substance in a lacquer.
A stable combined formulation needs to preserve the vesicle structures and to maintain a homogeneous distribution of the silver particles throughout the mixture acting as the antiviral substance.
For a blended formulation involving vesicle structures, it is known art that there are many surfactants and auxiliary reagents that may disrupt the stability and structural integrity of the vesicles. Furthermore, agglomeration and flocculation of particulate dispersions such as the silver formulation can be induced through introduction of surfactants and other reagents.
A significant feature of the present invention is that it has been possible to achieve a stable formulation of the vesicle and silver particle components together in the same formulation acting as the antiviral substance. The formulation stability may be achieved across a range of blend ratios that cannot be predicted a priori.
A principle for achieving the blended formulation stability is the unique role of the silver formulation where the silver ingredients are embedded within a resinous matrix with close association with a cationic surfactant. This approach results in keeping cationic or non-ionic surfactants in close proximity with the silver ingredient rather than distributing homogenously in the final blended product formulation where it may be available for interacting with and potentially disrupting the vesicle structures.
A further principle for achieving stability of the combined formulation is maintaining similar pH character for each component formulation prior to blending.
The combined interaction of the silver (together with selected co-ingredients) and the non phospholipid vesicle enables an enhanced level of antiviral activity against both enveloped viruses and also non-enveloped viruses when acting as the antiviral substance in a lacquer. Silver (via silver ions and/or silver metal) provides antiviral action against both enveloped and non-enveloped viruses. It would be expected that the lipid layer of enveloped viruses provides greater resistance to diffusion of silver ions and subsequent interaction with the RNA or DNA material compared to non-enveloped viruses. In contrast, the lipid-mediating mechanism of the vesicle technology is specific to enveloped viruses.
The combined action of silver and vesicle structure therefore acts to enable greater activity of silver against enveloped viruses while also providing action against non-enveloped viruses.
The selected formulation co-ingredients in principle lead to greater level of proximity of the silver materials with the virus materials, leading to enhanced antiviral action of the silver ions and/or silver-based particles. Some of the components may also have a basis for direct degrading action against viruses.
The silver materials are formulated with a range of co-ingredients including cationic surfactants (e.g. Cocobis(2-hydroxyethyl) methylammonium chloride) or non-ionic surfactants.
Cationic but also non-ionic surfactants in particular have shown potential for interaction with enveloped viruses, including in the presence of proteins. The apparent binding tendency of cationic surfactants with enveloped virions means that for silver components that are closely surrounded by the cationic surfactants, the virions may be actively brought into closer proximity to the silver source, leading in principle to greater antiviral efficacy of the silver. According to a preferred embodiment, said cationic surfactant is a quaternary surfactant, preferably a polymeric quaternary ammonium surfactant, in particular based on fatty acid based building blocks, polyacrylate building blocks, polymethacrylate building blocks, C10- C20 alkyl building blocks, benzyl building blocks, or a combination or mixture thereof.
Said cationic surfactant is preferably selected from the group consisting of: quaternary ammonium polyacrylate, quaternary ammonium ethoxylate, quaternary ammonium propoxylate, quaternary ammonium fatty acid derivative, and is most preferably selected from the group consisting of: poly(2-(trimethylamino)ethyl methacrylate), coconut bis-(2- hydroxyethyl) methyl ammonium, oleyl bis-(2-hydroxyethyl)methyl ammonium, erucyl bis(2- hydroxyethyl)(methyl)ammonium, benzyl(2-hydroxyethyl)dimethylammonium chloride, dodecylbis(2-hydroxyethyl)methylammonium, or a combination or mixture thereof. The negatively charged counterions for the ammonium cation in these systems can e.g. be chloride or bromide or combinations thereof, but also other inorganic systems such as sulfates, phosphates are possible or organic counterions such as acetates, or polymeric organic anions.
Preferably in case of silver chloride particles, said non-ionic surfactant can be a polyethoxylated and/or polypropoxylated surfactant, in particular based on fatty acid based building blocks, C10-C40 alkyl, aryl or arylalkyl building blocks, or a combination or mixture thereof.
Preferably the non-ionic surfactant is selected from the group consisting of: alcohol C10- C28, preferably alcohol C10 - C20, most preferably alcohol C12 - C18 or alcohol C16-18, tristyrylphenol tridecyl ether, ethoxylated in each case with 3-70 EO units, preferably with 20-60 EO units, most preferably with 30-50 EO units, wherein most preferably a system of the type alcohol C16-C18+50EO is used.
The first aqueous formulation can be prepared in that the silver-silica micro composite particles are added to water together with said cationic surfactant, wherein the proportion of silver-silica micro composite particles is in the range of 0.1-1 %(w/w), preferably in the range of 0.2-0.5 %(w/w) and wherein the proportion of the cationic surfactant is in the range of 0.5-7.5% (w/w), preferably in the range of 1.5-5% (w/w) . Preferably the proportion of the cationic surfactant if chosen as an ammonium compound is given for the chloride or bromide form. The concentrations in this case are given for the final formulation A.
The first aqueous formulation can alternatively be prepared in that the in that the silver- chloride particles are added to water together with said non-ionic surfactant, wherein the proportion of silver-chloride particles is in the range of 5-15 %(w/w), preferably in the range of 7-12 %(w/w) and wherein the proportion of the non-ionic surfactant is in the range of 0.5- 12% (w/w), preferably in the range of 1-10% (w/w), and wherein the resulting mixture is mixed, preferably through milling, preferably through bead milling, for a time span of at least an hour, more preferably for a time span of more than 5 hours, at a temperature of at least 20°C, preferably at a temperature at or above room temperature. The concentrations in this case are given for the final formulation A acting as the antiviral substance.
According to another preferred embodiment, the silver formulation can be prepared in a two-step process, in a first step phase A is produced by suspending silver-containing particles within the cationic or non-ionic surfactant under intensive mixing, separately prepare an aqueous formulation with stabilising components such as rheology thickeners et cetera (phase B) and then introduce phase A into phase B in a manner to achieve homogeneous distribution within phase B, wherein phase B is the larger proportion of the final blend weight and forms more than 50% of the final formulation weight of formulation A. Preferably, the resulting mixture is mixed, preferably through milling, preferably through bead milling, for a time span of at least an hour, more preferably for a time span of more than 5 hours, at a temperature of at least 20°C, preferably at a temperature at or above room temperature.
Preferably as further silver formulation additives prior to mixing, or in the above process involving phase B, additives can be added selected from the group consisting of: alcohols, glycols, polyols, diols, phosphates, acids such as acetic acid, fragrance, colorants, nonionic surfactants, odorants, anti-foaming agents, foaming agents, rheology modifiers such as thickeners or a combination thereof. These additives or just some of them may also be added only after the mixing of the silver (silica) particles and the cationic or non-ionic surfactant, in particular additives such as thickeners are of this kind.
It is again to be stressed that all this description above about the composition and the method of preparing formulation A is also regarded as an independent invention independent of formulation B and the combined product involving formulation A as well as B.
The vesicle-forming non-phospholipid can be selected from the group consisting of, the values in brackets indicating the hydrocarbon chain: fatty alcohol (C12-C20), fatty acid (C12-C20), ethoxylated (C12-C20) fatty alcohol, glycol ester of (C12-C20) fatty acid, ethoxylated of (C12-C20) fatty acid, glycerol fatty acid (C12-C20) monoester, glycerol fatty acid diester (C12-C18), ethoxylated glycerol fatty acid ester (C16-C18), fatty acid diethanolamide (C12-C20), fatty acid dimethyl amide (C12-C20), fatty acid sarcosinates (C12-C20), or a combination thereof.
Preferably, the vesicle-forming non-phospholipid is selected from a polyoxyethylene cetyl ether, palmitic acid, hexadecyl trimethylammonium bromide or chloride, oleic acid or a combination thereof.
Said vesicle formulation additives may comprise enhancers for the antiviral effect, e.g. selected from the group consisting of: poly- or oligosaccharides such as xylitol, in particular cyclodextrin or derivatives thereof, or a steroidogenic acute regulatory protein. The second aqueous formulation can be prepared in that said vesicle-forming non phospholipid and optionally further vesicle formulation additives are added to water, are mixed at elevated temperature of more than 55°C, until homogeneous mixture is obtained, and subsequently cooled to a temperature of at most 30°C under formation of homogeneous emulsion. Typically the proportion of the at least one vesicle-forming non phospholipid is in the range of 1-8 %(w/w), preferably in the range of 2-5 %(w/w) and wherein the proportion of the enhancer if present is in the range of 1-8 % (w/w), preferably in the range of 2-6 % (w/w).
The second aqueous formulation preferably comprises, as non-phospholipid, a mixture of polyoxyethylene (2) cetyl ether with hexadecyltrimethylammonium (which can be in the chloride or bromide form, preferably in the bromide form), preferably in a weight proportion of 20: 1-5:1 , most preferably 12:1-8:1 , in a total concentration (taking the sum of polyoxyethylene (2) cetyl ether with hexadecyltrimethylammonium (bromium)) in the range of 3-5% (w/w).
Further preferably, the second aqueous formulation comprises, as enhancer, cyclodextrin, preferably (2-hydroxypropyl)-beta-cyclodextrin, in a proportion of 1-7% (w/w), preferably in the range of 3-6% (w/w).
The first and second aqueous solutions can be blended at a temperature of at most 40°C, preferably around room temperature, and wherein preferably 5-20% (w/w) of said first aqueous formulation are combined with 70-90% (w/w) of said second aqueous formulation, supplemented with water to a total of 100% (w/w) to form the formulation acting as the antiviral substance.
The present invention further relates to an aqueous antibacterial and antiviral formulation acting as the antiviral substance in particular in a lacquer as claimed comprising silver-silica micro composite particles or silver chloride particles alone or in combination with, i.e. as well as non-phospholipid lipid vesicles (nPLV), preferably obtained using a method as described above.
Such a formulation acting as the antiviral substance comprises the silver-silica micro composite particles or silver chloride particles in association with said cationic or non-ionic polymeric surfactant, wherein preferably the silver-silica micro composite particles are present in a proportion in the range of 0.01-0.1% (w/w), preferably in a proportion in the range of 0.02-0.05% (w/w), wherein the at least one cationic polymeric surfactant is present in a proportion in the range of 0.1 -0.5% (w/w), preferably in the range of 0.2-0.4% (w/w), and wherein said at least one vesicle-forming non-phospholipid is present in a proportion in the range of 2-5% (w/w), preferably in the range of 2.5-4% (w/w).
In case of silver-chloride particles these are preferably present in a proportion 5-15 %(w/w), preferably in the range of 7-12 %(w/w), and wherein the at least one non-ionic polymeric surfactant is present in a proportion in the range of 0.5-12% (w/w), preferably in the range of 1-10% (w/w).
Also the present invention relates to the use of a formulation acting as the antiviral substance, formulation A alone or the combined product comprising formulation A as well as formulation B, as detailed above or as obtained using a method as detailed above for the treatment of objects in a lacquer formulation, in particular leather, fibrous materials such as paper and cardboard articles, polymeric surfaces including polyurethane, tarps, tents, bags, luggage, or of textiles, even for the treatment of woven, knitted or nonwoven textiles, or in the field of textiles for antiviral and/or antibacterial applications including masks, filters, gowns, drapes, coverings, carpets et cetera in particular for healthcare/hospital uses.
In addition to that, the present invention relates to an object in particular an object to wear, touch or to carry by a human to be protected, in particular leather, fibrous materials such as paper and cardboard articles, polymeric surfaces including polyurethane, tarps, tents, bags, luggage, a woven or knitted or nonwoven textile treated with a formulation (formulation A alone or combined product), preferably in a lacquer formulation, obtained using a method as detailed above or treated with the formulation as detailed above, preferably in the field of hard surfaces but also textiles for antiviral and/or antibacterial applications including masks, filters, gowns, drapes, coverings, carpets et cetera in particular for hospital uses. Last but not least the present invention relates to a method for rendering an object to be protected, in particular an object based on leather, fibrous materials such as paper and cardboard articles, polymeric surfaces including polyurethane, tarps, tents, bags, luggage, woven or nonwoven textile antibacterial and/or antiviral by treating it with a formulation (again formulation A alone or the combined product in each case) acting as the antiviral substance in particular in a lacquer formulation obtained using a method as detailed above, or with a formulation as described above, wherein the formulation is preferably applied by padding, dipping, coating, spraying, printing or a combination thereof, and wherein the formulation is further preferably added to the textile in the range of 2-30% (weight of fabric basis), preferably in the range of 5-20%.
A preferred antiviral coating acting as the antiviral substance is based on a blend of the following components:
20% Antiviral product such as HeiQ Viroblock NPJ03 (or another formulation as given in HeiQ patent application EP20176229.1)
79% Polyurethane (PU)
1% Defoaming and wetting agent
According to a preferred embodiment, the lacquer formulation has no organic solvents inside and is 100% waterborne.
According to a preferred embodiment, soft PU is used with adjusted viscosity for film building properties. Some Acrylate for stiffness. Antifoaming agent. Dispersing agent. Possible polyurethane components are selected from one or a combination of the following systems:
Carbonic acid, polymer with 1 ,6-hexanediol, 3-hydroxy-2-(hydroxymethyl)-2- methylpropanoic acid, 2-ethyl-2-(hydroxymethyl)-1 , 3-propanediol, 5-isocyanato-1- (isocyanatomethyl)-1 ,3,3-trimethylcyclohexane and hexanedioic acid 1 ,6-dihydrazide, compd. with N,N-diethylethanamine.The basis can be 100% PU, but it can also be 100% Acrylate, it can be a silicon base, a vinyl dispersion base or a latex base.
Also possible are formulations containing inert additional crosslinking systems based on isocyanate, blocked isocyanate, formaldehydes, or mixtures with a content between 0.1% up to 3%.
Other varieties can be coloring, optical brightener or coding/marking of the substance for e.g with colour agents which are only visible under e.g. special light or conditions.
An option for the systems would as well to include retarder agents, to control the point of film building. This is particularly for spraying or high solid contents.
Also within the scope of the invention is the use of a lacquer or film according to the invention, wherein the lacquer or film is applied to a surface, in particular of plastic or metal, in order to provide it with an antiviral finish. In this way, effective virus killing can take place on surfaces and the risk of the spread of viral diseases can be reduced.
The lacquer or film can be removed from the surface and the lacquer or film can be reapplied to the surface. Lacquer or film that is no longer active can thus be replaced with antivirally active lacquer or film. This can be done at a predetermined time interval.
The lacquer or film can be applied, for example, to door handles, table tops, car doors and/or buttons, for example in buses, trains and lifts.
The lacquer or foil can be applied in a thickness in the range 0.0001 to 5mm, preferably in the range 0.001mm to 3.0mm.
Further embodiments of the invention are laid down in the dependent claims.
DESCRIPTION OF PREFERRED EMBODIMENTS
Example 1: Coating on blue film substrate
Preparation of the coating formulation (1):
The coating formulation was prepared with the following components and composition:
The HeiQ Viroblock NPJ03 product comprises the following constituents and was prepared using the following procedure: Vesicle formulation (2):
An illustrative vesicle formulation composition is as follows:
Polysiloxane defoamer may optionally be added
Preparation procedure Blending of components at elevated temperature (e.g. >60°C) until homogeneously mixed. Cool to ambient temperature while mixing and/or high shear in-line mixer.
The resulting formulation is a homogeneous emulsion with excellent storage and operational stability.
Variations and extensions Non-phospholipid components may be substituted.
(2-hydroxypropyl)-beta-cyclodextrin (B3) may be substituted or used in combination with other cyclodextrin-based compounds as detailed above. Furthermore, other sugars, oligosaccharides and polysaccharides may be used as substitutes for or in combination with the cyclodextrin-based compounds.
Silver particle formulation (3):
An example silver formulation composition is as follows.
Preparation procedure in more detail:
The silver chloride - titanium dioxide microcomposite particles are, generally speaking, prepared as follows:
1. Titanium dioxide particles are suspended in aqueous solution of silver nitrate;
2. Addition of sodium chloride leading to precipitation of silver chloride on the surface of the titanium dioxide particles;
3. Addition of other formulation components such as surfactants and stabilizers.
More specifically, the silver chloride - titanium dioxide microcomposite particles used here were processed using the following recipe:
The principle of the preparation is to surround the silver chloride - titanium dioxide microcomposite with either a cationic surfactant or non-ionic surfactant component. Optionally a polymeric matrix component may be added to give additional material surrounding the microcomposite. The close association of the cationic surfactant or non ionic surfactant components and the polymeric matrix is advantageous from a perspective of formulation stability and also efficacy of the formulated product.
The initial step of the procedure involves blending the silver chloride - titanium dioxide microcomposite and additional titanium dioxide particles into a solution of the matrix components (ethylene glycol, alcohol C16C18, ethoxylated, and polysiloxane) followed by high intensity mixing through bead milling (ca. 8 hours).
The matrix preparation procedure generates a homogeneous mixture where the matrix components penetrate into and surround the silver chloride - titanium dioxide microcomposite particles.
The balance of ingredients (surfactants and viscosity modifier components, i.e. ethylene glycol, ethyl cellulose (thickener) and additional polysiloxane defoamer are formulated together prior to introduction of the matrix preparation via in-line high shear mixer. The resulting formulation is a homogeneous dispersion with excellent storage and operational stability.
Silver and vesicle product formulation (4): Another example formulation for the combined product formulation, using the above first, silver chloride - titanium dioxide formulation (HeiQ Viroblock NPJ03) is as follows:
* As part of silver chloride - titanium dioxide microcomposite particle.
Preparation procedure The silver and vesicle product formulation (4) is produced by blending the silver particle formulation (3) and the vesicle formulation (2) together with addition of water (that may optionally contain additional auxiliary or functional components).
The blending procedure (with simple vessel agitation) proceeds in the following order. The blending ratio reflects the ratios needed to produce the exemplar product composition above.
Steps 2 and 3 may optionally be reversed. The resulting formulation is a homogeneous emulsion with excellent storage and operational stability. Coating formulation preparation:
The preparation of the coating formulation was conducted as follows:
1. Measure required quantity of polyurethane (1 ) component into a mixing vessel
2. Add required quantity of the antiviral component (4) into the vessel containing the polyurethane while stirring with a mechanical mixer (Model SBS-MR-2500) for 4 minutes.
3. Add required quantity of hardener to the blended mixture while stirring with a mechanical mixer (Model SBS-MR-2500) for another 4-5 minutes.
4. The coating preparation was applied onto the surface.
Preparation of the surface:
A flexible Vinyl sheet (e.g 3M) of up to 0,5 mm thickness was used as the test substrate. The substrate was cleaned with ethanol and air dried to ensure the surface was free of soil and contaminants prior to coating with the prepared formulation.
Application of the coating formulation to the surface:
The coating formulation was applied to the surface of the test substrate using a spray applicator (Model Wagner AirlessVector pro). The coating was applied so as to achieve a dry solids coverage of 70 g/m2. The applied formulation was observed to form a homogeneous and level film on the surface of the substrate.
Drying of the coating:
Following application of the liquid the substrate was dried in an over (ThermoFischer Scientific OMH180) at 120° Celsius for 3 min.
Observed properties of the coating:
The stability of the coated surface was assessed by immersing (5 cm square) samples of the coated material in volumes (100 ml) of water and organic solvents (including ethanol, toluene, ...). After a set period of time (30 seconds) the samples were removed and the stability of the coating layer was observed through visual observation. The coating was observed to be stable to exposure to water and the tested organic solvents. No haze appeared.
The adhesion of the coating to the surface of the substrate was examined by manual scratching of the surface with a metal blade and observing the ease of delamination of the coating layer. The coating was observed to have excellent adhesion to the surface, there was no delamination. Measured properties of the coating:
Testing for antiviral activity of the coating was conducted according to ISO 21702:2019 (Measurement of antiviral activity on plastics and other non-porous surfaces).
The treated sample shows significantly higher antiviral effect compared to the untreated surface.

Claims

1. Lacquer with a base substance and an antiviral substance which comprises a booster, in particular liposomes and/or surfactants, as well as silver chloride and/or silver salts and/or silver adsorbed on silicon dioxide.
2. Lacquer according to claim 1 , characterized in that the base substance comprises a plastic.
3. Lacquer according to any one of the preceding claims, characterized in that the base substance comprises at least one of the following: Polyurethane, acrylate, polyvinyl alcohol (PVA) plastics, PVC, silicone.
4. Lacquer according to one of the preceding claims, characterized in that the proportion of the antiviral substance in the lacquer is 5-30%, wherein preferably the antiviral substance added to the base substance is an aqueous antibacterial and antiviral formulation, comprising silver nano or micro particles, preferably silver-silica micro composite particles or silver chloride particles, as well as non-phospholipid lipid vesicles (nPLV), wherein the antiviral substance preferably comprises the silver-silica micro composite particles or silver chloride particles in association with said cationic or non-ionic polymeric surfactant, wherein the silver-silica micro composite particles are present in a proportion in the range of 0.01-0.1% (w/w), preferably in a proportion in the range of 0.02- 0.05% (w/w), and wherein the at least one cationic polymeric surfactant is present in a proportion in the range of 0.1 -0.5% (w/w), preferably in the range of 0.2-0.4% (w/w), and/or the silver-chloride particles are present in the antiviral substance in a proportion 5-15 %(w/w), preferably in the range of 7-12 %(w/w), and wherein the at least one non-ionic polymeric surfactant is present in a proportion in the range of 0.5-12% (w/w), preferably in the range of 1-10% (w/w), and wherein said at least one vesicle-forming non-phospholipid is present in the antiviral substance in a proportion in the range of 2-5% (w/w), preferably in the range of 2.5- 4% (w/w).
5. Lacquer according to one of the preceding claims, characterized in that it has antibacterial properties.
6. Lacquer according to one of the preceding claims, characterised in that it comprises a cross-linking agent, in particular isocyanates or melamine-containing cross- linking agents.
7. Lacquer according to one of the preceding claims, characterised in that it can be applied by brush, spray or roller.
8. Lacquer according to one of the preceding claims, characterized in that it is transparent or coloured.
9. Foil made of or with a lacquer according to one of the preceding claims.
10. Foil according to claim 9, characterized in that it is self-adhesive.
11. Film according to any one of the preceding claims 9 or 10, characterized in that it is peelable.
12. Film according to any one of the preceding claims, characterized in that it has a thickness in the range 0.0001 to 5mm, preferably in the range 0.001mm to 3.0mm.
13. Use of a lacquer or a foil according to one of the preceding claims, wherein the lacquer or the foil is applied to a surface, in particular of plastic or metal, in order to provide it with an antiviral finish.
14. Use according to claim 12, characterized in that the lacquer or film is removed from the surface and the lacquer or film is reapplied to the surface.
15. Use according to any one of the preceding claims, characterized in that the lacquer or film is applied to door handles, door knobs, table tops, water taps, mobile phones, car doors and/or push buttons, for example in buses, trains and lifts.
16. Use according to any one of the preceding claims, characterised in that the lacquer or film is applied in a thickness in the range 0.0001 to 5mm, preferably in the range 0.001mm to 3.0mm.
17. Soft or solid object coated at least partially with at least one layer based on a lacquer according to any of the preceding claims 1-8, wherein preferably a solid object is based on metal, ceramics, plastic, wood or another natural hard surface including stone, glass, as well as combinations thereof, and a soft object takes the form of a woven, knitted or nonwoven textile, leather, foil, paper or a combination thereof.
EP21712851.1A 2020-03-26 2021-03-22 Antiviral surface coating for metal and plastic surfaces Pending EP4127075A1 (en)

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EP20165963 2020-03-26
DE102020110027 2020-04-09
EP20176229 2020-05-25
PCT/EP2021/057255 WO2021191141A1 (en) 2020-03-26 2021-03-22 Antiviral surface coating for metal and plastic surfaces

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EP21712549.1A Pending EP4127304A1 (en) 2020-03-26 2021-03-22 Antiviral and antimicrobial fabric treatment as well as fabrics treated therewith
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