WO2015040558A1 - Film antimicrobien à double action - Google Patents

Film antimicrobien à double action Download PDF

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Publication number
WO2015040558A1
WO2015040558A1 PCT/IB2014/064599 IB2014064599W WO2015040558A1 WO 2015040558 A1 WO2015040558 A1 WO 2015040558A1 IB 2014064599 W IB2014064599 W IB 2014064599W WO 2015040558 A1 WO2015040558 A1 WO 2015040558A1
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WIPO (PCT)
Prior art keywords
film
dual action
antimicrobial
coating solution
tfa
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PCT/IB2014/064599
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English (en)
Inventor
Cormac O'Keeffe
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Theta Chemicals Limited
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Publication of WO2015040558A1 publication Critical patent/WO2015040558A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof

Definitions

  • the invention relates to a dual action antimicrobial film for coating a surface to provide a long term antimicrobial effect and prevent biofilm formation.
  • Silver and copper has been used for centuries in the treatment of burns and chronic wounds due to its ability to promote crust formation on the surface of the wound and provide anti-bacterial functionality. Its antimicrobial mechanism may be due to binding to proteins and enzymes inhibiting their function.
  • the introduction of antibiotics in the 1940's led to a reduction in the use of silver in particular for bacterial infections.
  • silver has regained popularity in fighting infection and the spread of microbes.
  • Photocatalytic Ti0 2 has been shown to have, among other properties, anti-microbial activity due to its ability to breakdown organic material to C0 2 and H 2 O.Ti0 2 can physically degrade the cell wall of the microbe leading to lysis and cell death.
  • An increase in functionality of Ti0 2 can be accomplished by shifting the band onset into the visible light region via introduction of elemental dopants. However, in low lit or dark areas the photocatalytic effect is reduced or halted completed.
  • a dual action antimicrobial film comprising a visible transparency of greater than 75% transmission at visible light wavelengths of between 400 and 900nm, the film comprising a coating solution of soluble Ti0 2 and a metal species wherein the dual action antimicrobial activity comprises metal ion diffusion release and Ti0 2 photocatalytic activity.
  • the film is a smooth film displaying regulated isotropic crystal growth and comprises a roughness factor (Ra) of less than 1.5nm.
  • the antimicrobial action of the film is active under both light and dark conditions.
  • the film prevents biofilm formation when the film is deposited on a substrate.
  • the antimicrobial film comprises an even concentration distribution of Ti and metal species comprising an average Ti0 2 to metal species concentration ratio of from 1:0.005 to 1:0.1.
  • the Ti0 2 comprises doped and/or undoped Ti0 2 .
  • the Ti0 2 is doped with sulphur and/or fluorine.
  • the metal species in is elemental or oxide form. Most preferably the metal is silver or copper.
  • the antimicrobial action of the film, metal ion diffusion release and Ti0 2 photocatalytic activity provides a long term antimicrobial effect.
  • the coating solution comprises a homogenous solution of nano-particle sized soluble Ti0 2 , metal species and/or a chelating agent and/or coordinating solvent.
  • the particle size of the Ti0 2 and metal species in the coating solution is less than lOnm.
  • a method of synthesising a dual action antimicrobial film as claimed in any preceding claim comprising the steps of; preparing and solubilising hydrous Ti0 2 ,
  • the substrate coated with the coating solution is annealed at a temperature between 500 and 1000°C.
  • a substrate comprising a dual action antimicrobial film.
  • a method of promoting antimicrobial activity comprising coating a substrate with a coating solution of nano-particle sized soluble Ti0 2 , metal species and/or a chelating agent and/or coordinating solvent and annealing to form a transparent long acting dual action antimicrobial film.
  • Fig. 1 is a schematic illustration of the formation of biofilms on a silver release surface
  • Fig. 2 is a schematic illustration of the prevention of biofilm formation using the dual action antimicrobial film according to the invention
  • Fig. 3 is a schematic illustration of the dual action of the antimicrobial film via (a) photocatalytic Ti0 2 and (b) Ag + release according to the invention;
  • Fig. 4 shows X-ray diffraction (XRD) analysis of the Ti0 2 and silver components in a deposited matrix film according to the invention;
  • Fig. 5 is a photograph illustrating the hybrid nature of the films coated onto (a) ceramic and (b) steel coupons;
  • Fig. 6 is an Energy Dispersive X-ray Spectroscopy (EDS) spectra of
  • Fig. 7 is a table of the elemental concentration of Ti and Ag on coated steel films
  • Fig. 8 is an Energy Dispersive X-ray Spectroscopy (EDS) spectra of
  • Fig. 9 is a table of the elemental concentration of ceramic coated films.
  • Fig. 10 is a graph showing the % transmission between uncoated and Ag- S/F/Ti0 2 coated glass samples
  • Fig. 11 is a graph showing the % transmission between uncoated and Cu- F/Ti0 2 coated glass samples
  • Fig. 12 is a table showing silver ion release under different conditions
  • Fig. 13 is a table showing silver ion release sustained over time
  • Fig. 14 is a table showing silver ion release sustained over time when placed in a new saline solution
  • Fig. 15 is a table showing the ion diffusion of copper and silver over time
  • Fig. 16 is an atomic force microscopy measurement showing the difference between (a) Uncoated glass and (b) Ag-S/F/Ti0 2 coated glass;
  • Fig. 17 is a schematic illustration of test and control conditions prior to spiking the samples with a bacterial load;
  • Fig. 18 is a table of results of the test and controls outlined in Fig. 17 subjected to Escherichia coli and Staphylococcus aureus survival testing.
  • Antimicrobials containing titanium dioxide and silver are known.
  • US2009/0220600 Parkin et al describes a film consisting of a titanium dioxide host matrix comprising silver oxide particles. The film is prepared from a colloidal precursor solution. Silver oxide nanoparticles are deposited in or upon the titanium dioxide film. The antimicrobial effect of the films is activated by exposure to a light source. The silver nanoparticle solutions are quite unstable.
  • combining photocatalytic Ti0 2 and anti-bacterial Ag and/or Cu species into a single composite film provides a dual action coating for surfaces having enhanced properties.
  • the dual action coating has surprisingly been found to provide a sustained long term antimicrobial effect and prevent biofilm formation.
  • the antimicrobial film of the invention has been shown to maintain a long term antimicrobial action under both light and dark conditions.
  • the antimicrobial film of the invention has been shown to have a very high microbial kill rate under dark conditions.
  • the solutions of Ti0 2 and metal species are homogenous in nature with approximately less than 5nm size particles resulting in an even distribution of Ag/Cu ions among the Ti0 2 particles.
  • the particles size begins at a very low level the Ag is well distributed among the Ti0 2 particles.
  • the films of the present invention show no particle agglomeration.
  • the Ag/Cu species are evenly integrated into the Ti0 2 matrix during film formation on a 'nano-level'. This results in an increase in the anti-microbial activity of the film as there is a greater distribution of metal species on the surface leading to greater diffusion of silver/copper ions with the ability to attack microbes.
  • a biofilm layer is a combination of biomolecules that can adhere onto an artificial surface. It provides a means of survival for microbes outside of a host organism and a vehicle for re-infection of a population. It acts as an anchor surrounding the microbial cells protecting them against unfavourable conditions such as temperature or chemical attack through cleaning. Human pathogens have shown resistance to antibiotic attack through biofilm formation.
  • the anti-microbial activity of the Ag-S/F/Ti0 2 films of the present invention utilises and combines two mechanisms of action, silver and/or copper ion release and photocatalytic Ti0 2 .
  • Microbes are attacked by silver ion release as soon as they come into contact with the film killing them.
  • the silver/copper species work by diffusing from the film as metal ions that are absorbed by the microbe and attack the cellular functions via a number of methods, e.g. inhibition of protein assembly, redox cycling, membrane lipid peroxidation etc.
  • the second component of the film is Ti0 2 which is a light activated catalyst which continues to fully breakdown the organic matter of the dead microbe. In this way the dual action of the film of the present invention prevents any formation of a biofilm and enables continued and sustained metal ion release activity.
  • Fig. 2 is a schematic showing the dual action of the silver and Ti0 2 .
  • Ti0 2 employs a different mode of action by physically breaking down the structure of the cell. It attacks the organic material of the cell wall and cell contents.
  • Ti0 2 is a light activated semi-conductor material, a light activated catalyst that generates reactive oxygen species that attack the microbe reacting with it to form C0 2 and H 2 0.
  • Photocatalytic Ti0 2 is used as an effective tool against biofilm formation. Photons of light are absorbed generating electron-hole pairs that migrate to the surface of the Ti0 2 particle.
  • ROSs reactive oxygen species
  • the principle reactive species responsible for the anti-microbial action is the hydroxyl radical which attacks organic material in a highly oxidative, nonspecific fashion.
  • the hydroxyl radical causes the breakdown of the cell wall and cytoplasmic membrane where leakage of cytoplasm, including critical ions such as K + , results in cell death.
  • the breakdown of organic matter by Ti0 2 eradicates the presence of biofilms.
  • Activated Ti0 2 breaks down the biomolecules that make up the biofilms as well as the attach threads that anchor the biofilm to the surface.
  • Photocatalytic Ti0 2 requires light for activation. In areas that are not illuminated consistently or areas that are dimly lit the Ag and Cu ion diffusion provides effective antibacterial activity to boost the efficiency of the film.
  • the Ag-S/F/Ti0 2 films of the present invention provide a dual action coating for surfaces.
  • the composite Ag-S/F/Ti0 2 films according to the present invention provide a hybrid dual action coating as shown in Fig. 3. It has been found that silver and copper bind and inhibit protein function while the Ti0 2 breaks down the structure of the organic material. In areas not illuminated consistently the silver or copper ion release is utilised to boost the anti-microbial efficiency of the film. In addition the breakdown of organic matter by Ti0 2 eradicates the issue of biofilms.
  • Fig, 4 shows the results of X-ray diffraction (XRD) analysis carried out.
  • XRD X-ray diffraction
  • the silver species was believed to be in oxide form due to annealing of the films at high temperature in an oxygen environment leading to thermal oxidation of silver in the matrix film.
  • XRD analysis confirms the presence of elemental silver in films, however, this does not rule out the possibility of smaller quantities of silver species in the oxide form present in the matrix film. This is also true for copper species present in a matrix film.
  • the dual action antimicrobial film comprises a coating solution of Ti0 2 and a metal species containing silver or copper.
  • a coating solution comprising both silver and copper species in combination with Ti0 2 may also be used.
  • the coating solution is deposited onto a substrate and annealed at high temperatures to form a dual action antimicrobial film of the invention.
  • the coating solution of the invention is very stable over long periods of time.
  • the coating solution has been found to be stable after several months of storage.
  • the solution comprises very low nano-meter particles, approximately in the range of less than 5nm, so the metal species distribution in solution is very homogenous.
  • the smaller particle size results in a strong electrostatic repulsion between particles.
  • a chelating agent and/or a coordinating solvent is also added to the coating solution.
  • the combination of small particle size and chelating agent and/or coordinating solvent result in a coating solution which can be stored and used over long periods of time and in which there are high concentrations of Ti0 2 and metal species present.
  • the coating solutions are used to produce permanent films with long-term functionality.
  • the antimicrobial films of the invention are homogenous on a 'nano-level' scale and show regulated isotropic crystal growth.
  • the solutions of Ti0 2 and Ag or Cu ions are homogenous in nature with approximately less than 5nm size particles resulting in an even distribution of Ag/Cu ions among the Ti0 2 particles.
  • the coating solution contains preformed Ti0 2 particles which during film formation result in isotropic crystal growth. Isotropic crystal growth has no preferred orientation and instead grow in an even fashion in each direction producing very smooth films. As the particle size begins at a very low level the Ag and Cu species are well distributed among the Ti0 2 particles, without any agglomeration as can be found in other films comprising silver and Ti0 2 .
  • the Ag/Cu species are evenly integrated into the Ti0 2 matrix on a 'nano-level' . This results in an increase in the anti-microbial activity of the film as there is a greater distribution of metal species on the surface leading to greater diffusion of silver/copper ions with the ability to attack microbes.
  • the small particle size also provides an antimicrobial film with superior adherence to a substrate.
  • the small particle size of the components in the coating solution ensure that more particles are adhered per surface area of a substrate.
  • the films of the present invention show no cracking.
  • the films are very smooth and show enhanced transparency.
  • the antimicrobial films of the present invention may have a thickness as low as lOnm. Any thickness of film may be made depending on the application using the antimicrobial films of the invention.
  • the antimicrobial properties of the films and the films ability to prevent biofilm formation ensure that the films of the present invention have application in many different areas where microbiological cleanliness is necessary.
  • the films may be applied to any suitable surface in order to provide antimicrobial properties, for example metal surfaces such as taps and metal work surfaces, ceramic surfaces, such as wash basins, baths and toilets or glass surfaces, such as doors and windows.
  • the films may also be applied to furniture, such as beds, or medical equipment and instruments. Other applications for the films include surfaces for use in a medical environment, such as tiles, work surfaces, door handles, taps and beds.
  • the films may be used in hospitals and other places, for example in food processing facilities, dining areas, play areas, swimming pools, communal areas and nursing homes.
  • metal species described in the examples are silver and copper other suitable metal species having antimicrobial properties such as zinc may be used.
  • Ti0 2 described in the examples is doped the Ti0 2 in the dual action antimicrobial films of the invention may be doped or undoped. Both doped and undoped Ti0 2 exhibit photocatalysis and the ion diffusion from the metal species allows the dual action film to produce an anti-microbial effect in light and dark conditions.
  • the present invention will be more fully understood from the following examples.
  • the production of Ag/TFA-S/Ti0 2 /TFA involves two separate synthesis pathways for a) Ag/TFA or Cu/TFA and b) S/Ti0 2 /TFA. Formulation of both species is required with a chelating agent to generate the coating solution. The coating solution is then deposited onto a substrate and annealed at a high temperature to produce the hybrid Ag-S/F/Ti0 2 film of the invention. The following describes the synthesis process, formulation and film generation of the material.
  • the silver species to be introduced is produced from the reaction of TFA and Ag 2 0 in a polar solvent (see below).
  • the Ag/TFA species is not isolated and is formulated with soluble Ti0 2 and/or chelating agent and/or coordination solvent to the appropriate concentration.
  • the copper species to be introduced is produced in a similar fashion via the reaction of TFA and Cu(N0 3 ) 2 in a polar solvent
  • Titanium isopropoxide (Ti(OPr) 4 ) is added to water with some hydrous Ti0 2 seed and ethyl acetoacetate.
  • Ti(OPr) 4 Titanium isopropoxide
  • the amorphous Ti0 2 is required to be converted into nano-particulate hydrous-Ti0 2 due to its high absorbance to both cationic and anionic species.
  • the ability to attract donor species is crucial to the coordination of organic acetate groups during the solubilisation step.
  • the conversion of amorphous Ti0 2 to hydrous nano-particle Ti0 2 is carried out at elevated temperatures, see equation below.
  • the high temperature encourages particle growth from amorphous Ti0 2 to more crystalline nano-particulate hydrous Ti0 2 .
  • the nano-particulate hydrous Ti0 2 is dried and the solubilisation of the material involves refluxing in TFA before removal of excess TFA and isolation of Ti0 2 /TFA.
  • the doping step is carried out using sulphur to produce the S/Ti0 2 /TFA.
  • the chelating agent may be a homopolymeric polyethylenimine containing a combination of primary, secondary and tertiary amine groups with a general formula:
  • Chelating agent formula -(CH 2 -CH 2 -NH n ) m -
  • a coordinating solvent such as acetonitrile also contributes the stability of the material in solution.
  • a chelating agent and/or a coordination solvent allows the formulated coating solutions to be stored and used when required.
  • the coating solution e.g. Ag/TFA-S/Ti0 2 /TFA
  • a surface such as the surface of a ceramic tile, steel, a polymeric element, glass, a silica element or a zeolite element or any other suitable surface.
  • Deposition of the coating solution may be carried out using conventional wet chemistry methods such as dip coating, spin coating or spray coating.
  • dip and spray techniques are used on high temperature substrates.
  • the substrate with the deposited Ag/TFA-S/Ti0 2 /TFA coating solution is placed in a furnace at a high temperature.
  • the annealing conditions are amended. For example ceramic substrates have a higher annealing temperature while glass has a longer anneal duration etc.
  • the film is formed, while the nano-particulate S/Ti0 2 /TFA particles sinter together to form a dense film of crystalline anatase Ti0 2 .
  • Sulfur and fluorine doping of the Ti0 2 occurs during the annealing step (see below).
  • the Ag species is integrated with the Ti0 2 particles and evenly distributed throughout the film producing a matrix coating.
  • the chelating agent and/or coordination solvent which is organic based, is removed through decomposition at high temperature.
  • the substrate with the deposited Cu/TFA-Ti0 2 /TFA material is placed in a furnace at a high temperature.
  • Nano-particulate Ti0 2 /TFA particles sinter together to form a dense film of crystalline anatase Ti0 2 at high temperature. Fluorine doping of the Ti0 2 occurs during this annealing step.
  • the Cu species is integrated with the Ti0 2 particles and evenly distributed throughout the film producing a matrix coating.
  • Matrix film formation Cu/TFA + Ti0 2 /TFA ⁇ Cu-F/Ti0 2 Silver ion concentration
  • the silver species of the Ag-S/F/Ti0 2 film is fully integrated into the coating with an even concentration distribution.
  • the film exhibits silver ion diffusion properties giving it its anti-microbial activity.
  • the elemental analysis of the Ag-S/F/Ti0 2 films on their respective substrates was carried out using energy dispersive x-ray spectroscopy (EDS).
  • EDS energy dispersive x-ray spectroscopy
  • the concentration ratio of Ag is equivalent to Ti for samples on both substrates averaging a ratio of 1:0.078 for the ceramic samples as shown in the table in Fig. 9.
  • Fig. 10 is UV-vis spectrum showing the % transmission between uncoated and Ag-S/F/Ti0 2 coated glass samples.
  • Fig. 11 is UV-vis spectrum showing the transparency data of matrix film containing copper with Ti0 2 .
  • the films show a transmission greater than 75% over the visible light wavelengths (400 to 900nm).
  • the high transmission is an indication of the high physical qualities of the dual action film of the present invention.
  • the smoothness of the films is an indication of the uniformity of the film on the substrate surface and provides evidence for the isotropic growth of the particles during sintering to form a dense even film.
  • Film roughness can affect the adhesion of the film to the substrate as it is important that as much of the film is in contact with the substrate interface. Smooth films can also enhance the film's physical properties by reducing light diffraction in comparison to rougher films resulting in increased transparency and clarity of the film with reduced haziness and negligible impact on the aesthetic of the underlying substrate.
  • Atomic force measurements were carried out on both coated and uncoated samples and the smoothness of the film was found to be very similar. The smoothness is calculated by using a Ra value or roughness factor, the uncoated sample was found to have an Ra value of 0.99nm while the coated sample was marginally higher at 1.15nm. (Fig. 16).
  • the photocatalytic activity of the Ag-S/F/Ti0 2 films according to the present invention was quantified using indicator dyes such as methylene blue, resazurin or silver nitrate.
  • the colour of the dye changes in proportion to the activity of the photocatalytic film.
  • the rate of colour change using the Lab colour space scheme (L.a.b.), was analysed to identify any changes in the activity of the film due to adjustments in formulation, film thickness as well as from chemical and physical resistance testing.
  • the anti-microbial activity of the Ag-S/F/Ti0 2 films was assessed via microbiological survival studies.
  • the results demonstrate their exceptionally potency at killing both gram negative Escherichia coli ATCC 25922 and gram positive Staphylococcus aureus ATCC 25923 under fluorescent illumination and in dark conditions.
  • Test conditions and procedure were executed using aseptic techniques and all testing was carried out in triplicate. To ensure accuracy two parallel serial dilutions and inoculated Petri dishes were carried out where an average was taken. Samples were divided into a number of control and test categories as set out in Fig. 17.
  • Both coated and uncoated aseptic samples were spiked with a bacterial load, incubated for 15 hours at 30-35°C under fluorescent light irradiation as well as in the dark. 'Pre- activated' samples were irradiated with fluorescent lighting prior to testing.
  • the microbiological results were successful in displaying the anti-bacterial properties of Ag-S/F/Ti0 2 , as shown in the table in Fig. 18. Results reveal that environmental stresses or lack of resources cannot be attributed to the testing conditions as no significant losses ( ⁇ log 1) were encountered for any of the controls.
  • the hybrid films produce a biocidal surface that totally reduces microbial density, not a single colony forming unit was present for the coated samples for both gram negative and gram positive test regimes.
  • the Ag-S/F/Ti0 2 films according to the present invention are durable, functional coats formed by conventional coating/annealing methods and can be easily applied to common surfaces. Functional testing has demonstrated that the films according to the present invention have superior antimicrobial activity under both light and dark conditions. There is huge potential in the films ability to reduce infection transmission on surfaces of internal environments.
  • the antimicrobial action of the films of the present invention, metal ion diffusion release and Ti0 2 photocatalytic activity provide a long term antimicrobial effect. Long term may be several months if not years as the Ti0 2 is a catalyst and is not used up during the photocatalytic process. It should therefore work for the lifetime of the substrate.
  • the silver ion release is at low levels and should also continue for years.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un film antimicrobien à double action qui présente une transparence visible de plus de 75 % de transmission à des longueurs d'onde de la lumière visible comprises entre 400 et 900 nm, le film comprenant une solution de revêtement de TiO2 soluble et une espèce métallique, l'activité microbienne à double action comprenant une libération par diffusion d'ions métalliques et une activité photocatalytique par TiO2. Le film antimicrobien à double action est un film lisse présentant une croissance cristalline isotrope régulée et un facteur de rugosité (Ra) de moins de 1,5 nm. L'action antimicrobienne du film est active à la fois en conditions lumineuses et sombres, et le film antimicrobien à double action empêche la formation d'un biofilm lorsque le film est déposé sur un substrat.
PCT/IB2014/064599 2013-09-17 2014-09-17 Film antimicrobien à double action WO2015040558A1 (fr)

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EP13004531 2013-09-17
EP13004531.3 2013-09-17

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019053037A1 (fr) * 2017-09-15 2019-03-21 Hecosol Gmbh Revêtement antimicrobien
WO2021260370A1 (fr) * 2020-06-23 2021-12-30 Pilkington Group Limited Substrat antimicrobien

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002187806A (ja) * 2000-12-20 2002-07-05 Nihon Tetra Pak Kk 抗菌性材料
US20080081758A1 (en) * 2006-09-28 2008-04-03 Taketoshi Kuroda Photocatalytic titanium oxide sol, and coating composition and member using the same
US20090220600A1 (en) 2005-10-31 2009-09-03 Ivan Parkin Antimicrobial films
WO2013054860A1 (fr) * 2011-10-12 2013-04-18 Showa Denko K.K. Composition antimicrobienne et antivirale comprenant de l'oxyde de cuivre et procede de production
US20130115308A1 (en) * 2010-07-13 2013-05-09 Paul Gannon Doped material
WO2014091861A1 (fr) * 2012-12-13 2014-06-19 Showa Denko K.K. Composition antimicrobienne et antivirale et son procédé de production
WO2014112345A1 (fr) * 2013-01-16 2014-07-24 日本板硝子株式会社 Base ayant un film mince antiviral

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002187806A (ja) * 2000-12-20 2002-07-05 Nihon Tetra Pak Kk 抗菌性材料
US20090220600A1 (en) 2005-10-31 2009-09-03 Ivan Parkin Antimicrobial films
US20080081758A1 (en) * 2006-09-28 2008-04-03 Taketoshi Kuroda Photocatalytic titanium oxide sol, and coating composition and member using the same
US20130115308A1 (en) * 2010-07-13 2013-05-09 Paul Gannon Doped material
WO2013054860A1 (fr) * 2011-10-12 2013-04-18 Showa Denko K.K. Composition antimicrobienne et antivirale comprenant de l'oxyde de cuivre et procede de production
WO2014091861A1 (fr) * 2012-12-13 2014-06-19 Showa Denko K.K. Composition antimicrobienne et antivirale et son procédé de production
WO2014112345A1 (fr) * 2013-01-16 2014-07-24 日本板硝子株式会社 Base ayant un film mince antiviral

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LIGA M V ET AL: "Virus inactivation by silver doped titanium dioxide nanoparticles for drinking water treatment", WATER RESEARCH, ELSEVIER, AMSTERDAM, NL, vol. 45, no. 2, 1 January 2011 (2011-01-01), pages 535 - 544, XP027574578, ISSN: 0043-1354, [retrieved on 20100919] *
MACHIDA M ET AL: "Antibacterial activity of photocatalytic titanium dioxide thin films with photodeposited silver on the surface of sanitary ware", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, BLACKWELL PUBLISHING, MALDEN, MA, US, vol. 88, no. 1, 1 January 2005 (2005-01-01), pages 95 - 100, XP008085978, ISSN: 0002-7820 *
PAGE K ET AL: "titania and silver-titania composite films on glass", JOURNAL OF MATERIALS CHEMISTRY, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 2007, no. 17, 1 January 2007 (2007-01-01), pages 95 - 104, XP002547161, ISSN: 0959-9428, [retrieved on 20061103], DOI: 10.1039/B611740F *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019053037A1 (fr) * 2017-09-15 2019-03-21 Hecosol Gmbh Revêtement antimicrobien
CN111432638A (zh) * 2017-09-15 2020-07-17 黑克索儿有限公司 抗微生物涂层
WO2021260370A1 (fr) * 2020-06-23 2021-12-30 Pilkington Group Limited Substrat antimicrobien

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