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WO2003056924A1 - Films sol-gel antimicrobiens contenant des agents antimicrobiens specifiques renfermant du metal - Google Patents

Films sol-gel antimicrobiens contenant des agents antimicrobiens specifiques renfermant du metal Download PDF

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Publication number
WO2003056924A1
WO2003056924A1 PCT/US2002/038287 US0238287W WO03056924A1 WO 2003056924 A1 WO2003056924 A1 WO 2003056924A1 US 0238287 W US0238287 W US 0238287W WO 03056924 A1 WO03056924 A1 WO 03056924A1
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Prior art keywords
sol
metal
hard surface
surface substrate
gel film
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PCT/US2002/038287
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English (en)
Inventor
Delwin Jackson
Leland G. Close
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Milliken and Co
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Milliken and Co
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Priority claimed from US10/027,433 external-priority patent/US20030118733A1/en
Priority claimed from US10/036,652 external-priority patent/US6797278B2/en
Application filed by Milliken and Co filed Critical Milliken and Co
Priority to AU2002364513A priority Critical patent/AU2002364513A1/en
Publication of WO2003056924A1 publication Critical patent/WO2003056924A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • A01N25/24—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 containing ingredients to enhance the sticking of the active ingredients
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5027—Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes

Definitions

  • This invention relates to broadly defined sol-gel films for the coating of solid substrates, wherein such sol-gel films provide effective and durable antimicrobial properties.
  • the utilization of such films permits relatively low-temperature production of antimicrobial substrates, such as ceramics, metals (e.g., stainless steel, brass, and the like), plastics (e.g., polyimides, polyamides, polyacrylics, and the like), glass (e.g., borosilicates, and the like), as compared with typical glazes for ceramics and the like.
  • inventive films comprise, as the primary antimicrobial active ingredients, certain metal-containing inorganic or organic antimicrobial compounds, such as, preferably, metal-containing ion-exchange, oxide, glass, sulfadiazine, and/or zeolite compounds (most preferably, including silver therein as the metal component).
  • certain metal-containing inorganic or organic antimicrobial compounds such as, preferably, metal-containing ion-exchange, oxide, glass, sulfadiazine, and/or zeolite compounds (most preferably, including silver therein as the metal component).
  • the particular solid substrate to which such films are applied should exhibit substantially high melting and/or heat distortion temperatures to permit high temperature curing of the films to the solid substrate surface (in the range of 100-800°C, for example). If the solid substrate melts or distorts, the antimicrobial activity of the ultimate composite is drastically reduced.
  • End uses for such film-coated articles include bathroom fixtures, appliances, kitchen articles and fixtures, furniture, glass, and any other surface that exhibits the high melt and/or heat distortion temperatures noted above and requires antimicrobial characteristics, including certain polymeric films.
  • the specific method of producing such films is also encompassed within this invention.
  • triclosan is a chlorinated compound which may, under certain conditions, release chlorine atoms from the substrate surface.
  • Such ions are potentially hazardous to humans, due to skin irritation upon contact, as well as within environmental effluents, and the like.
  • harmful microbes have shown, on occasion, an ability to develop an immunity to the bactericidal properties of triclosan.
  • surface treatments with triclosan have proven ineffective as well since such compounds are easily washed from surfaces when topically applied thereto.
  • metal-containing (more specifically and preferably, specific silver-containing) inorganic microbiocides e.g., ion-exchange, oxide, glass, sulfadiazine, and/or zeolite compounds
  • metal-containing microbiocides e.g., ion-exchange, oxide, glass, sulfadiazine, and/or zeolite compounds
  • ion-exchange, oxide, glass, sulfadiazine, and/or zeolite compounds have recently been developed and or utilized as antimicrobial agents on and within a plethora of different substrates and surfaces, h particular, such microbiocides have been adapted for incorporation within plastic compositions and fibers in order to provide household and consumer products which inherently exhibit antimicrobial characteristics.
  • Such a glaze although providing excellent antimicrobial activity to target ceramic substrates " , also exhibits a serious drawback in that the use thereof is limited to ceramic surfaces, and that the temperatures required to cure and thus effectuate the adhesion of such a glaze to the target ceramic is very high (in the range of 1200°C).
  • the temperatures required to cure and thus effectuate the adhesion of such a glaze to the target ceramic is very high (in the range of 1200°C).
  • there is a requirement for the generation of and exposure to such very high temperatures From both safety and cost perspectives, there is thus a need to improve upon such a surface treatment.
  • the development of a lower-temperature method of treating selected surfaces with durable antimicrobial coatings would also permit an expansion in the type of substrates to which such a coating or film maybe applied.
  • sol- gel coating films can provide improvements in terms of durable, low-temperature processing, articles, as discussed in greater detail below. Therefore, it remains highly desirable to provide a more versatile surface coating for hard surface substrates, particularly those that are consistently utilized for human hygienic and or sanitation purposes (such as bathroom and/or kitchen fixtures; e.g., sinks, toilets, showers, and the like) that exhibits effective, and preferably durable, antimicrobial activity. To date, such a coating or film has heretofore been nonexistent within the pertinent prior art and industries.
  • Another object of the invention is to provide an antimicrobial hard surface substrate coated with a sol-gel film comprising at least one inorganic silver-based ion-exchange compound, oxide, or zeolite compound.
  • Another object of the invention is to provide an antimicrobial sol-gel film that retains a high degree of antimicrobial activity in the presence of highly caustic solvents (and other standard cleaning agents) and that does not exhibit any aesthetically displeasing discolorations over time.
  • this invention encompasses an antimicrobial sol-gel film comprising at least one inorganic antimicrobial agent, wherein said film exhibits a log kill rate for Klebsiella pneumoniae of at least 0.5 (preferably, at least 1.5, more preferably, at least 2.5, and most preferably, at least 3.5) as measured under a modified plate contact method very similar to JIS Z2801 :2000 (the Japanese Industrial testing protocol) utilizing a phosphate buffer solution instead of a dilute nutrient solution (as the simple modification).
  • this invention also encompasses a hard surface substrate (such as ceramic, steel, brass, silica, glass, plastic) that exhibits a melt and/or heat distortion temperature of at least 100°C, preferably, at least 200°C, more preferably at least 300°C, and most preferably at least 400°C, to which such an inventive sol-gel fihn as noted above has been applied. Also, this invention encompasses such a sol-gel film coated hard surface substrate exhibiting the same log kill rate as noted above after said substrate has been immersed in a heated caustic bath, having a pH level of at least 12, for 48 hours.
  • a hard surface substrate such as ceramic, steel, brass, silica, glass, plastic
  • this invention encompasses a method of producing an antimicrobial hard surface substrate comprising the steps of a) providing a hard surface substrate; b) providing a sol-gel film precursor formulation comprising a host precursor and at least one metal-containing inorganically based antimicrobial agent; c) applying said sol-gel film precursor to at least a portion of said hard surface substrate; and d) exposing said coated hard surface substrate to a temperature of at most about 800°C to form a finished sol-gel film-coated hard surface substrate, wherein said finished substrate exhibits a log kill rate for Klebsiella pneumoniae of at least 0.5 (with higher log kill rates preferred) as measured under a modified plate contact method similar to that pursuant to JIS Z2801 :2000 (with, as noted above, the only difference being the utilization of a phosphate buffer solution instead of a dilute nutrient solution).
  • hard surface substrate is intended to encompass any hard surface to which a sol-gel film can effectively be applied, and thus that can withstand the temperatures required to effectively adhere such a film to such a surface.
  • Such particular solid substrates to which the inventive sol-gel films may be applied should exhibit substantially high melting and/or heat distortion temperatures to permit high temperature curing of the films to the specific solid substrate surface (in the range of 100-800°C, for example).
  • such a term encompasses such specific substrates as metals (such as, again, steel, stainless steel, brass, enameled metal, such as enameled steel, and the like, particularly metals utilized within or as the basis of bathroom fixtures, including wash basins, commodes, toilet stalls, sinks, pipes, countertops, and the like, as well as furniture, tableware, eating utensils, appliances, such as stoves, ovens, refrigerators, etc.), ceramics (including vitreous china, tiles, and the like, covering the same types of specific end-uses as for metals as noted above), plastics (e.g., polyimides, polyamides, polyacrylics, and other plastics that can withstand such requisite high temperatures, for the same end-use categories as listed above), glasses (e.g., silica, silicates, borosilicates, and the like, for various uses involving human contact
  • metals such as, again, steel, stainless steel, brass, enameled metal, such as enameled steel, and
  • sol-gel films are properly applied to such surfaces. If the substrate melts or overly distorts i shape and/or constitution during sol-gel film application, then the substrate will not exhibit the desired antimicrobial activity, not to mention retain its desired shape thereafter, and thus is not encompassed within the definition of the term. Also, it is noted that this invention is limited in scope to articles treated with sol-gel films, and not to sol-gel composites (e.g., glasses, monoliths, dental implants, prostheses, and the like).
  • sol-gel film then is intended to encompass any type of ceramic coating that is formed (or is produced on a substrate surface) through the standard sol-gel methods described below and that is cured or adhered to a hard surface substrate through exposure to low temperatures (e.g., at most 800°C, preferably at most 700°C). Thus, such a term does not encompass (specifically, though not solely) ceramic glazes that require high temperature curing for adhesion (e.g., 900°C and above).
  • metal-containing (primarily) inorganic antimicrobial agent is intended to encompass any particulate formulation comprising a maj ority of a metal-based compound exhibiting excellent antimicrobial characteristics, even after being subjected to the high temperatures required for curing and setting of the target sol-gel film to the target hard surface substrate.
  • a metal-based compound is preferably primarily inorganic in nature (some organic component is permitted, although the primary antimicrobial portion must be inorganic, in order to withstand the aforementioned high temperatures), is a solid at standard temperature and pressure, and which exhibits antimicrobial activity.
  • such material is a metal oxide, such as silver oxide, zinc oxide, and the like, a metal-containing (preferably silver-containing) ion-exchange compound, a metal-containing (preferably silver-containing) zeolite, or a metal-containing (preferably silver-containing) glass, and any combinations thereof.
  • a metal oxide such as silver oxide, zinc oxide, and the like
  • a metal-containing (preferably silver-containing) ion-exchange compound such as silver oxide, zinc oxide, and the like
  • a metal-containing (preferably silver-containing) ion-exchange compound such as silver oxide, zinc oxide, and the like
  • a metal-containing (preferably silver-containing) ion-exchange compound such as silver oxide, zinc oxide, and the like
  • a metal-containing (preferably silver-containing) ion-exchange compound such as silver oxide, zinc oxide, and the like
  • a metal-containing (preferably silver-containing) ion-exchange compound such as silver oxide, zinc oxide, and the like
  • silver-containing solid inorganic antimicrobials in this invention is a silver-substituted zeolite available from Sinanen under the tradename ZEOMIC®, or alternatively marketed under the tradename Aglon® by the company of the same name, or a silver-substituted glass available from Ishizuka Glass under the tradename IONPURE®, may be utilized either in addition to or as a substitute for the preferred species.
  • Other possible compounds again without limitation, are silver-based materials such as MICROFREE®, a mark denoting products developed by DuPont, as well as JMAC®, available from Johnson Mathey.
  • compounds, such as silver sulfadiazine which are generally organic in nature but provide excellent antimicrobial activity and can withstand high sintering temperatures in certain applications.
  • such a metal-based inorganic antimicrobial agent compound is added (and thus is present) within the sol-gel film precursor formulation added in an amount of from about
  • the precursor composition preferably from about 0.001 to about 5%; more preferably from about 0.01 to about 1%; and most preferably from about 0.1 to about 1.0%.
  • inventive films comprising such ion-exchange or zeolite compounds appear to provide more durable antimicrobial levels, particularly when coated hard surface substrates are subjected to highly caustic cleaning preparations, and do not exhibit discoloration over time.
  • antistatic compounds such as antistatic compounds, fillers, such as calcium carbonate (to provide strength and hardness to the film), flame retardants, such as antimony oxide, available from Great Lakes Chemical, and dyes and other colorants to impart desirable colorations therein.
  • fillers such as calcium carbonate (to provide strength and hardness to the film)
  • flame retardants such as antimony oxide, available from Great Lakes Chemical, and dyes and other colorants to impart desirable colorations therein.
  • a “sol” is a dispersion of colloidal particles in a liquid, and the term “gel” connotes an interconnected, rigid network with pores of submicrometer dimensions and polymeric chains whose average length is greater than a micrometer.
  • the film-forming sol-gel process involves mixing of host precursors (e.g., alkyl metal oxides, as dicussed in greater detail below) and any additives into a sol; applying the sol to a selected surface; gelation of the mixture, whereby the colloidal particles link together to become a porous three- dimensional network in film form; aging of the gel to increase its strength; drying the liquid from the interconnected pore network within the film; dehydration or chemical stabilization of the pore network; and densification, to produce structures with ranges of physical properties.
  • host precursors e.g., alkyl metal oxides, as dicussed in greater detail below
  • the inventive antimicrobial sol-gel films can be prepared from gels by sintering between 300 and 800°C, well below the temperatures required for glassmaking and glazing. Accordingly, these procedures afford cost-effective production for preparing effective antimicrobial hard surface substrates.
  • Such a sol-gel process also permits use of very small colloidal particles (on the order of one nanometer or less) as glass precursors, thereby ensuring a high degree of homogeneity and purity in the final film product.
  • the films of the present invention are prepared from any number of base host precursors, including, without limitation, alkoxysilanes, preferably tetramethoxysilane ("TMOS"), tetraethoxysilane (“TEOS”), and the like, as well as acetylacetonates, such, again, without limitation, titanium acetylacetonate, zirconium acetylacetonate, and aluminum acetylacetonate.
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • Such host precursors were then converted to the metal oxide through standard sol-gel preparation techniques, namely and preferably
  • the sol-gel film producing process entails the conversion of a sol component to a gel component which can then be heated to a sufficiently high temperature in order to generate the desired film.
  • the sol generally consists of metal alkoxide in the presence of water. Such a component then undergoes hydrolysis to form the correlated metal hydroxide species. Condensation of two metal hydroxides then combine such species to form a single (di)metal oxide (with water released in such a reaction). More and more metal oxides form together and increase in molecular weight to form a three-dimensional network, particularly in the presence of a necessary solvent to liquefy the sol to the extent that gel formation is permitted. The sol then becomes the desired three-dimensional gel composition.
  • the inorganic antimicrobial may be introduced within the sol (metal alkoxide) initially and then applied, with the sol, to a hard surface substrate prior to gel formation, at which point the gel can be formed with the antimicrobial present therein creating an antimicrobial film on the target hard surface substrate after exposure to sufficient heat for sintering of the film to the surface.
  • the inorganic antimicrobial component may be combined with the initial sol component, for further gel formation therewith, after which the solvent within the gel is then removed. After solvent removal, the resultant friable gel can then be ground into a powder that can be resuspended with addition of solvent thereto. Sintering of the resultant dispersion can then be easily performed to provide the desired hard surface substrate.
  • this invention permits unique flexibility in providing antimicrobial low-temperature films for hard surface substrates.
  • inventive films are thus produced through the initial compounding of the base compounds together, or providing a powder which can be modified to a gel upon introduction of solvents, and drying to form a film precursor formulation (e.g., gel) exhibiting a certain degree of adhesiveness or tackiness.
  • This precursor formulation can then be applied through coating procedures, sprayings, immersions, or any like process, to the target hard surface substrate after which the coated substrate is then exposed to a sufficiently high temperature to effectuate the substantially uniform film production over the coated portion of the substrate.
  • the desired antimicrobial agents as discussed above, are thus added prior to the formation of the film precursor formulation and are present within such a coated formulation during the heating step.
  • the resultant inventive film and thus the resultant coated hard surface substrate, exhibits excellent antimicrobial properties, again, as discussed above and further presented within the preferred embodiments provided below. Adding such solid antimicrobial agents after film production is extremely difficult without the production of highly undesirable discolorations (e.g., darkening, particularly due to the high temperatures utilized for film formation).
  • the particular metal-based antimicrobial agent e.g., silver-containing inorganic antimicrobial compound
  • Such an acceptable level log kill rate is tested for Klebsiella pneumoniae (as well as for Staphylococcus aureus, Eschericia coli, and any other standard, commonly found bacteria; for test purposes, the results for K. pneumoniae are used most prominently) of at least 0.1 increase over baseline (with at least a log kill rate of 0.5 and above, preferred).
  • an acceptable level will exist if the log kill rate is greater than the log kill rate for non-treated (i.e., no solid inorganic antimicrobial added) films (such as about 0.5 log kill rate increase over control, antimicrobial-free latices).
  • this log kill rate baseline increase is at least 0.3 and 0.3, respectively for S. aureus and K. pneumoniae; more preferably these log kill rate is 0.5; and more preferably is 1.0, respectively.
  • the high end of such log il rates are much higher than the baseline, on the magnitude of 5.0 (99.999% kill rate). Any rate in between is thus, of course, acceptable as well, hi such an instance, the antimicrobial material present within the films at least exhibits a hindrance to microbe growth.
  • the preferred inventive sol-gel films were produced in accordance with the compositions denoted within the Table below with all of the components admixed together.
  • the basic procedure entailed the production of preferred alumina oxide, titania oxide, zirconia oxide, or silica oxide host thin films via sol-gel processes.
  • a host precursor component selected from the preferred, non-limiting group of either aluminum acetylacetonate, titanium acetylacetonate, zirconium acetylacetonate, was added to a mixture of 20 g of acetic acid and 10 g (28%) methanol (which have already been heated and stirred at 65°C for 15 minutes).
  • the powder was then added with 2% (of the total weight of metal components within the host precursor) of either silver oxide (available from Aldrich under catalog # 22,683-1), RC 5000 (an ALPHASAN® antimicrobial available from Milliken & Company), IONPURE®, silver sulfadiazine, or ZEOMIC®, to the acid/methanol mixture.
  • the resultant mixture was then heated at 65°C and stirred for an additional 15 minutes.
  • the sol was prepared by adding from 5-10% by weight of methanol, as well as 2% of the antimicrobial agent in powder form (as defined above) to the TMOS liquid composition and stirring the resultant formulation at 65°C for 15 minutes.
  • the resultant composition was sonicated for 15 minutes and applied to the target hard surface substrate (noted below) through drip coating while maintaining the same temperature as before.
  • the coated substrate was then fired in a kiln at a ramp of 2°C until the desired high temperature (300, 500, or 700°C, as noted below) was reached. Upon reaching such a high temperature, the substrate remained exposed at the same high temperature for a 30 minute dwell time.
  • the substrate was then removed and tested for antimicrobial activity, both directly after cooling as well as after exposure to a caustic solution at elevated temperature (about 50°C) for 48 hours.
  • the components, firing temperatures, substrates being either 1 inch by 1 inch ceramic tiles
  • such a test protocol required immersion of the plate (substrate) within a solution comprising 0.4 mL of 1 X 10 5 of cells/mL of Klebsiella pneumoniae ATCC #4352 bacteria for 22 hours in a Na/K phosphate buffer solution. The number of killed cells was then calculated and recorded as the log kill rate after this 22 hour exposure test.
  • the results are as follows in tabular form:
  • the inventive adhesive sol-gel films and coated substrates exhibit excellent antimicrobial properties and durable properties as well.
  • the silver-containing ion-exchange compounds also provide excellent durability as well as low levels of discoloration after caustic treatments.
  • aesthetically pleasing, antimicrobial substrates may be provided via low-temperature sol-gel processes.

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Abstract

D'une façon générale, cette invention a trait à des films sol-gel destinés à revêtir des substrats solides. Ces films ont des propriétés antimicrobiennes efficaces et durables. L'emploi de ces films permet de produire à basse température des substrats antimicrobiens, notamment des substrats céramiques, métalliques (par exemple, en acier inoxydable, en laiton et analogue), en matière plastique (par exemple, des polyimides, des polyamides, des polyacryliques et analogue) et en verre (des verres borosilicatés et analogue) et ce, en comparaison des glaçures types pour céramiques et analogue. Les films selon l'invention contiennent, comme principaux ingrédients actifs antimicrobiens, certains composés antimicrobiens inorganiques ou organiques contenant du métal, notamment et, de préférence, des composés échangeurs d'ions contenant du métal, des oxydes, du verre de la sulfadiazine et/ou des composés à base de zéolite (mieux, contenant de l'argent comme composant métallique). De préférence, également, les substrats solides spécifiques sur lesquels sont déposés ces films ont des températures sensiblement élevées de point de fusion et/ou de déformation thermique, ce qui permet de les laisser durcir à une température élevée sur ces substrats (dans une plage comprise, par exemple, entre 100 et 800°C). Si les substrats solides fondent ou se déforment, l'activité antimicrobienne du composite final est fortement réduite. Parmi les utilisations dernières des articles revêtus de ces films, figurent des accessoires de salle de bain, des appareils électroménagers, des articles et des accessoires de cuisine, du mobilier, du verre et toute autre surface susmentionnée ayant des températures de fusion et ou de déformation thermique élevées et devant faire montre de propriétés antimicrobiennes, certains films polymères y compris. L'invention porte également sur un procédé spécifique de production de ces films.
PCT/US2002/038287 2001-12-21 2002-12-02 Films sol-gel antimicrobiens contenant des agents antimicrobiens specifiques renfermant du metal Ceased WO2003056924A1 (fr)

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US10/027,433 US20030118733A1 (en) 2001-12-21 2001-12-21 Low-temperature method of producing an antimicrobial, durable coating for hard surface substrates
US10/027,433 2001-12-21
US10/036,652 US6797278B2 (en) 2001-12-21 2001-12-21 Antimicrobial sol-gel films comprising specific metal-containing antimicrobial agents
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005115151A1 (fr) * 2004-05-25 2005-12-08 Etc Products Gmbh Agents de revetement sol-gel fonctionnels
WO2006099906A1 (fr) * 2005-03-24 2006-09-28 Schott Ag Objet presentant un revetement antibacterien, procede pour le produire et utilisation de celui-ci
WO2007147842A3 (fr) * 2006-06-21 2008-03-06 Agc Flat Glass Europe Sa Substrat doté de propriétés antimicrobiennes et procédé de production d'un substrat antimicrobien
EP1917934A1 (fr) * 2006-10-30 2008-05-07 Ethicon Endo-Surgery, Inc. Bande gastrique réglable ayant des revêtements antimicrobiens
WO2009004158A3 (fr) * 2007-05-29 2009-07-16 Lainiere De Picardie Bc Procédé de fonctionnalisation d'un substrat textile à propriété antiseptique et/ou virucide
EP2169092A3 (fr) * 2004-12-16 2010-08-25 AGC Glass Europe Substrat doté de propriétés antimicrobiennes
WO2012013696A1 (fr) 2010-07-27 2012-02-02 Agc Glass Europe Article en verre a proprietes antimicrobiennes
WO2012013695A1 (fr) 2010-07-27 2012-02-02 Agc Glass Europe Article en verre a proprietes antimicrobiennes
WO2012013863A1 (fr) 2010-07-27 2012-02-02 Beneq Oy Objet de verre ayant des propriétés antimicrobiennes
WO2015164475A1 (fr) * 2014-04-23 2015-10-29 Corning Incorporated Articles antimicrobiens comportant un revêtement à base de silicate alcalin contenant de l'argent et leurs procédés de fabrication

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5882808A (en) * 1993-05-31 1999-03-16 Sumitomo Osaka Cement Co., Ltd. Anti-bacterial and anti-fungal ceramic product

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5882808A (en) * 1993-05-31 1999-03-16 Sumitomo Osaka Cement Co., Ltd. Anti-bacterial and anti-fungal ceramic product

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005115151A1 (fr) * 2004-05-25 2005-12-08 Etc Products Gmbh Agents de revetement sol-gel fonctionnels
EP2169092A3 (fr) * 2004-12-16 2010-08-25 AGC Glass Europe Substrat doté de propriétés antimicrobiennes
WO2006099906A1 (fr) * 2005-03-24 2006-09-28 Schott Ag Objet presentant un revetement antibacterien, procede pour le produire et utilisation de celui-ci
WO2007147842A3 (fr) * 2006-06-21 2008-03-06 Agc Flat Glass Europe Sa Substrat doté de propriétés antimicrobiennes et procédé de production d'un substrat antimicrobien
EP1917934A1 (fr) * 2006-10-30 2008-05-07 Ethicon Endo-Surgery, Inc. Bande gastrique réglable ayant des revêtements antimicrobiens
WO2009004158A3 (fr) * 2007-05-29 2009-07-16 Lainiere De Picardie Bc Procédé de fonctionnalisation d'un substrat textile à propriété antiseptique et/ou virucide
WO2012013696A1 (fr) 2010-07-27 2012-02-02 Agc Glass Europe Article en verre a proprietes antimicrobiennes
WO2012013695A1 (fr) 2010-07-27 2012-02-02 Agc Glass Europe Article en verre a proprietes antimicrobiennes
WO2012013863A1 (fr) 2010-07-27 2012-02-02 Beneq Oy Objet de verre ayant des propriétés antimicrobiennes
EP2415725A1 (fr) 2010-07-27 2012-02-08 Beneq Oy Article en verre à propriétés antimicrobiennes
WO2015164475A1 (fr) * 2014-04-23 2015-10-29 Corning Incorporated Articles antimicrobiens comportant un revêtement à base de silicate alcalin contenant de l'argent et leurs procédés de fabrication
US10364181B2 (en) 2014-04-23 2019-07-30 Corning Incorporated Antimicrobial articles with silver-containing alkali silicate coating and methods of making thereof
US10981825B2 (en) 2014-04-23 2021-04-20 Corning Incorporated Antimicrobial articles with silver-containing alkali silicate coating and methods of making thereof

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