WO2006088468A2 - Glaçage d'email antimicrobien - Google Patents

Glaçage d'email antimicrobien Download PDF

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Publication number
WO2006088468A2
WO2006088468A2 PCT/US2005/006464 US2005006464W WO2006088468A2 WO 2006088468 A2 WO2006088468 A2 WO 2006088468A2 US 2005006464 W US2005006464 W US 2005006464W WO 2006088468 A2 WO2006088468 A2 WO 2006088468A2
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WO
WIPO (PCT)
Prior art keywords
antimicrobial
ppm
glazing composition
zinc borate
enamel
Prior art date
Application number
PCT/US2005/006464
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English (en)
Other versions
WO2006088468A3 (fr
Inventor
Anders Olsson
Howard Wayne Swofford
Original Assignee
Microban Products Company
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
Priority claimed from US11/040,379 external-priority patent/US7250178B2/en
Application filed by Microban Products Company filed Critical Microban Products Company
Publication of WO2006088468A2 publication Critical patent/WO2006088468A2/fr
Publication of WO2006088468A3 publication Critical patent/WO2006088468A3/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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof

Definitions

  • the present invention relates to the field of antimicrobial protection. More specifically, the present invention relates to a composition for imparting built-in and long lasting antimicrobial characteristics to ceramic and metal products. In particular, the present invention pertains to glazing compositions that impart built-in antimicrobial characteristics to ceramic and metal products.
  • Ceramic coatings are commonly used in products that store, treat, or transport water and liquid waste. Ceramic toilets, urinals, bidets, bathroom basins, flooring tiles and other bathroom fixtures are probably the most common example of such products. [0006] Ceramic products used to collect and transport water are often stained by scum and films of biologic origin (e.g., bacteria, fungus, mold, mildew). To date, the primary method of removing biological scum and film from these ceramic products has been to abrade the ceramic surface in the presence of topical cleaning agent. This process is time consuming and provides little or no protection against future growth. Some cleaning agents can damage the surface of the ceramic product. Therefore there is great interest in the development of ceramic coatings that have built-in protection against the growth and proliferation of microbes.
  • biologic origin e.g., bacteria, fungus, mold, mildew
  • one object of the present invention is to provide a new and useful antimicrobial ceramic coating that can impart antimicrobial characteristics in a wide range of products.
  • a still further object of the invention is to provide this ceramic coating at a cost that is acceptable to the marketplace. Furthermore, this antimicrobial ceramic coating should be safe to humans, exhibit commercially acceptable antimicrobial properties, and most importantly, be compatible with existing ceramic production processes.
  • an antimicrobial ceramic glazing composition comprising a quantity of zinc borate sufficient to achieve a commercially acceptable level of antimicrobial efficacy.
  • this ceramic glazing composition also comprises a quantity of zinc oxide.
  • the invention is a ceramic article that exhibits antimicrobial properties.
  • the ceramic article according to the invention has at least one surface and a glaze on a portion of that surface.
  • the glaze comprises a quantity of zinc borate sufficient to achieve a commercially acceptable level of antimicrobial efficacy.
  • this ceramic glazing composition also comprises a quantity of zinc oxide.
  • the invention is a method of making an antimicrobial ceramic glaze and a method of making a ceramic article comprising the antimicrobial ceramic glaze.
  • Another object of the present invention is to provide a new and useful antimicrobial enamel glaze that can impart antimicrobial characteristics in a wide range of products.
  • Still yet a further object of the invention is to provide this enamel glaze at a cost that is acceptable to the marketplace. Furthermore, this antimicrobial enamel glaze should be safe to humans, exhibit commercially acceptable antimicrobial properties, and most importantly, be compatible with existing enamel production processes.
  • an antimicrobial enamel glazing composition comprising a quantity of zinc borate sufficient to achieve a commercially acceptable level of antimicrobial efficacy.
  • this enamel glaze composition also comprises a quantity of zinc oxide.
  • the invention is an enameled article that exhibits antimicrobial properties.
  • the enameled article according to the invention has at least one surface and a glaze on a portion of that surface.
  • the glaze comprises a quantity of zinc borate sufficient to achieve a commercially acceptable level of antimicrobial efficacy.
  • this enamel glaze composition also comprises a quantity of zinc oxide.
  • microbe or "microbial” should be interpreted to encompass any of the microscopic organisms commonly studied by microbiologists. Such organisms include, but are not limited to, bacteria and fungi as well as other single-celled organisms such as mold, mildew and algae. Viral particles and other infectious agents are also included in the term microbe.
  • One embodiment of the present invention relates to ceramic coatings and in particular to ceramic glazing on the outer surfaces of ceramic products.
  • vitreous china or ceramic production is provided as an aid to the reader. This discussion is presented in the context of the production of bathroom fixtures. Those skilled in the art recognize that the production process of other ceramic products may vary from that which is presented below. The claimed invention, however, is adaptable to any such variances.
  • the initial stage of a typical ceramic production process is the production of barbotine or slip, a clay from which bathroom ceramic products are made.
  • Barbotine is made from a mixture of clays, kaolin, phyllites, feldspar and quartz.
  • the parts are formed by absorption of water contained in the barbotine through the capillary action of the gypsum. As water leaves the barbotine the part solidifies to a point where the mold can be opened. The still malleable part is then removed from the mold.
  • the parts After casting and removal from the molds, the parts go for drying in kilns under controlled humidity and temperature (approximately 90 0 C ). The drying cycle lasts about 7 hours, reducing the water content of the part from about 16% to less than 1%. Following this, the parts are inspected to detect possible flaws. The parts then go to the coating process.
  • the coating process is often referred to as the glazing step.
  • the glazing step typically comprises the manual application of ceramic glaze on the parts using guns in individual booths fitted with exhaust systems and water curtains.
  • Typical ceramic glaze is produced from a mixture of kaolin, feldspar, quartz, colorings and other additives.
  • the parts are fired in continuous kilns, reaching temperatures of about 1,250 0 C, in an approximately 15-hour cycle. The firing process gives the glazed part the color and transparent appearance that is typical of vitreous china.
  • the invention is a ceramic glazing composition that provides commercially acceptable antimicrobial efficacy after the firing process.
  • the claimed glazing reduces or substantially eliminates the growth and proliferation of microbes on the surface of ceramic articles upon removal from the firing process and without any further treatment (e.g., further coating or painting of the ceramic part).
  • the antimicrobial ceramic glazing composition according to the invention comprises components commonly utilized in the preparation of ceramic glazing plus a quantity of zinc borate sufficient to achieve a commercially acceptable level of antimicrobial efficacy.
  • Zinc borate is the common term for a hydrated mineral-like substance. Zinc Borate is most often used as. a flame retardant and smoke suppressant additive but it is sometimes used as an antifungal agent. However, zinc borate is not known as an antimicrobial agent in ceramic coatings.
  • the quantity of zinc borate required to achieve a commercially acceptable level of antimicrobial efficacy for finished ceramic products may vary depending upon the level of contamination generally associated with the product. However, the concentration of zinc borate for most commercial applications is at least about 5,000 ppm of zinc borate. Concentrations above about 100,000 ppm can have adverse impacts on the aesthetic qualities of the ceramic glaze. Concentrations of about 20,000 ppm to about 40,000 of zinc borate are preferred.
  • the glazing composition according to the invention also comprises a quantity of free zinc oxide.
  • Free zinc oxide refers to an additional amount of zinc oxide that is added to the glazing composition separate from the zinc borate.
  • the ratio of zinc borate to zinc oxide in the glazing composition may range from about 90: 10 to about 10:90.
  • a ratio of about 50:50 is preferred but may be altered depending upon cost considerations.
  • a ratio of about 50:50 of zinc borate to zinc oxide is added to the ceramic glazing composition at about 2 weight % for the combination based upon the weight of the ceramic glaze composition.
  • ceramic glazing compositions comprising zinc borate and zinc oxide may have at least about 5,000 ppm of a combination of zinc borate and zinc oxide.
  • ceramic glazing compositions comprising a combination of zinc borate and zinc oxide have about 20,000 ppm to about 40,000 ppm of the combination. More preferably, about 20,000 ppm of the combination.
  • concentrations, in varying ratios achieve at least a 90% reduction, preferably greater than a 99% reduction, of microbial species as compared to an untreated control applied to a ceramic surface coated with the glazing composition. Concentrations above 100,000 ppm may have adverse aesthetic effects on the glazing.
  • antimicrobial agents capable of surviving the high temperatures of the glazing process may be added to the glazing composition.
  • agents include, but are not limited to, silver (e.g., silver salts and silver zeolites), copper, and other known metallic antimicrobial agents.
  • silver e.g., silver salts and silver zeolites
  • copper e.g., copper
  • metallic antimicrobial agents can be added in relatively minor amounts to supplement biocidal activity against specific pathogens
  • metallic antimicrobial agents can be added in greater quantities if desired
  • the invention encompasses a ceramic article that exhibits antimicrobial properties
  • the claimed antimicrobial ceramic article comprises a ceramic substrate having at least one surface and a glaze on at least a portion of that surface
  • the glaze utilized in this embodiment of the invention is the same as that desc ⁇ bed in the first embodiment of the invention
  • the glaze comprises a quantity of zinc borate or a combination of zmc borate and zmc oxide that is sufficient to achieve a commercially acceptable level of antimicrobial efficacy
  • the glazing will compnse at least about 5,000 ppm of zinc borate Concentrations above about 100,000 ppm of zmc borate may have adverse aesthetic effects on the glazing Concentrations of about 20,000 ppm to about 40,000 ppm of zinc borate are preferred
  • the glaze comp ⁇ ses a combination of zmc borate and zmc oxide, where the combined concentration of zinc borate and zinc oxide is preferably at least about 5,000 ppm
  • the combined concentration of zinc borate and zinc oxide is in a range of about 20,000 ppm to about 40,000 ppm
  • the ratio of zinc borate to zinc oxide may be about 90 10 to about 10 90, preferably about 50 50
  • the invention encompasses a method of making an antimicrobial ceramic glaze and an article having an antimicrobial ceramic glaze
  • the antimicrobial ceramic glaze according to the invention may be made by adding zinc borate or a combination of zinc borate and zinc oxide, both of which are commercially available from a number of sources, to an existing glazing composition Those skilled in the art of preparing glazing compositions will recognize that the zinc borate and zinc oxide may be added separately or in combination at any point in the process of making the glazing composition
  • the method of making the claimed antimicrobial ceramic article closely resembles the general method for making ceramic articles set forth at the beginning of the detailed description. However, in the method according to the invention, upon removal of the article from the mold, the article is coated with the antimicrobial ceramic glazing composition according to the invention. The coated article is then fired as usual with the ceramic coating retaining its antimicrobial characteristics even after the firing.
  • the ceramic glaze according to the invention was designed to impart built-in antimicrobial protection to a variety of ceramic articles. Accordingly, the scope of the invention includes ceramic articles that incorporate the glazing according to the invention. Such articles include, but are not limited to, toilets, bidets, washbasins, towel rails, soap holders, toilet roll holders, water control fixtures (e.g., hot and cold water handles), ceramic tiles, and other ceramic applications.
  • Another embodiment of the present invention relates to enamel coatings and in particular to enamel glaze on the outer surfaces of metal products.
  • Enamel is a form of low temperature ceramic glaze that is usually applied over metal. This provides metal products with the resistance to wear and corrosion of ceramics while having the physical strength and durability of metal.
  • Typical firing temperatures for enamel glaze are approximately 600 to 1000 0 C as compared with firing temperatures of approximately 1200 to 1300 0 C for ceramic glaze.
  • Typical products that may be enameled are kitchen and bathroom sinks, bathtubs, eating utensils, pots and pans, jewelry, and decorative items, among others.
  • the product to be enameled usually metal
  • a sink will be drawn down from a sheet of metal into its final shape before applying the enamel glaze.
  • the enamel glazing components are mixed and milled to the desired particle size in water to form a slurry, and then the slurry is sprayed or otherwise coated onto the metal, dried, and then the part is fired in a kiln at approximately 800 0 C.
  • the glaze imparts color, luster, and the hardness and chemical resistance of ceramic to the metal part.
  • the coating process is often referred to as the glazing step.
  • the glazing step typically comprises the manual application of glaze on the articles or parts.
  • Typical enamel glaze may be produced from a mixture of kaolin, feldspar, quartz, colorings and other additives.
  • the invention is an enamel glazing composition that provides commercially acceptable antimicrobial efficacy after the firing process.
  • the enamel glazing reduces or substantially eliminates the growth and proliferation of microbes on the surface of metal articles upon removal from the firing process and without any further treatment (e.g., further coating or painting of the metal part).
  • the antimicrobial enamel glazing composition according to the invention comprises components commonly utilized in the preparation of enamel glazing plus a quantity of zinc borate sufficient to achieve a commercially acceptable level of antimicrobial efficacy.
  • Zinc borate is the common term for a hydrated mineral-like substance. Zinc Borate is most often used as a flame retardant and smoke suppressant additive but it is sometimes used as an antifungal agent. However, zinc borate is not known as an antimicrobial agent in ceramic coatings.
  • the quantity of zinc borate required to achieve a commercially acceptable level of antimicrobial efficacy for finished enamel products may vary depending upon the level of contamination generally associated with the product. However, the concentration of zinc borate for most commercial applications is at least about 5,000 ppm of zinc borate. Concentrations above about 100,000 ppm can have adverse impacts on the aesthetic qualities of the ceramic glaze. Concentrations of about 20,000 ppm to about 40,000 of zinc borate are preferred.
  • the enamel glazing composition according to the invention also comprises a quantity of free zinc oxide.
  • Free zinc oxide refers to an additional amount of zinc oxide that is added to the enamel glazing composition separate from the zinc borate.
  • the ratio of zinc borate to zinc oxide in the enamel glazing composition may range from about 90:10 to about 10:90.
  • a ratio of about 50:50 is preferred but may be altered depending upon cost considerations.
  • a ratio of about 50:50 of zinc borate to zinc oxide is added to the enamel glazing composition at about 2 weight % for the combination based upon the weight of the enamel glaze composition.
  • enamel glazing compositions comprising zinc borate and zinc oxide may have at least about 5,000 ppm of a combination of zinc borate and zinc oxide.
  • ceramic glazing compositions comprising a combination of zinc borate and zinc oxide have about 20,000 ppm to about 40,000 ppm of the combination. More preferably, about 20,000 ppm of the combination.
  • concentrations, in varying ratios achieve at least a 90% reduction, preferably greater than a 99% reduction, of microbial species as compared to an untreated control applied to a metal surface coated with the enamel glazing composition. Concentrations above 100,000 ppm may have adverse aesthetic effects on the glazing.
  • antimicrobial agents capable of surviving the temperatures of the enamel glazing process may be added to the enamel glazing composition.
  • agents include, but are not limited to, silver (e.g., silver salts and silver zeolites), copper, and other known metallic antimicrobial agents.
  • silver e.g., silver salts and silver zeolites
  • copper e.g., copper
  • metallic antimicrobial agents can be added in relatively minor amounts to supplement biocidal activity against specific pathogens.
  • metallic antimicrobial agents can be added in greater quantities if desired.
  • the invention encompasses an enameled article that exhibits antimicrobial properties.
  • the antimicrobial enameled article comprises a metal substrate having at least one surface and a glaze on at least a portion of that surface.
  • the glaze utilized in this embodiment of the invention is the same as that described previously for enamel glaze.
  • the enamel glaze comprises a quantity of zinc borate or a combination of zinc borate and zinc oxide that is sufficient to achieve a commercially acceptable level of antimicrobial efficacy
  • the enamel glazing will comp ⁇ se at least about 5,000 ppm of zinc borate Concentrations above about 100,000 ppm of zinc borate may have adverse aesthetic effects on the glazing Concentrations of about 20,000 ppm to about 40,000 ppm of zinc borate are preferred
  • the enamel glaze compnses a combination of zinc borate and zmc oxide, where the combined concentration of zinc borate and zmc oxide is preferably at least about 5,000 ppm
  • the combined concentration of zmc borate and zinc oxide is in a range of about 20,000 ppm to about 40,000 ppm
  • the ratio of zinc borate to zinc oxide may be about 90 10 to about 10 90, preferably about 50 50
  • the invention encompasses a method of making an antimicrobial enamel glaze and an article having an antimicrobial enamel glaze
  • the antimicrobial enamel glaze according to the invention may be made by adding zinc borate or a combination of zinc borate and zinc oxide, both of which are commercially available from a number of sources, to an existing glazing composition Those skilled in the art of preparing glazing compositions will recognize that the zinc borate and zinc oxide may be added separately or in combination at any point in the process of making the glazing composition
  • test articles were prepared to test the antimicrobial characteristics of the recited glaze which compnses a combination of zinc borate and zinc oxide
  • the test articles comprised an underlying ceramic substrate made from a standard commercial barbotine
  • the glaze used in the testing was a standard glaze comprising silica sand, feldspar, calcium carbonate, china clay, zirconium silicate, a small amount of CMC as a binder, and a small amount of zinc oxide.
  • To this basic glaze composition was added varying quantities of zinc borate and zinc oxide.
  • the glaze composition according to the invention was applied to the articles by spraying. The articles were then fired at 1200° C.
  • One test article was prepared without any additional zinc oxide or zinc borate for use as a control.
  • Metal sheet was coated with an enamel glazing composition containing an antimicrobial formulation consisting of 50% zinc oxide and 50% zinc borate (Formulation #1).
  • the antimicrobial formulation was present in the enamel glaze at 2% and 4% (20,000 ppm and 40,000 ppm, respectively) by weight based on the total dry weight of the enamel glaze.
  • the coated samples were dried and fired as described in Example 1 with the exception that the firing temperature was 800 0 C in Example 2. Samples for testing were cut from the metal sheet in 1.5 inch squares. The bare metal edges of the tile samples were sealed with paraffin to prevent rusting and contamination from other metal ions.
  • Efficacy testing was conducted in accordance with Japanese Industrial Standard Z 2801 :2000, one of the most common test methods for antimicrobial efficacy with inorganic antimicrobials. For these tests, the method was modified as follows. The inoculum was 0.1 ml of inoculum with approximately 10 6 Colony Forming Units (CFU)/ml of bacteria, and the 24 hour contact time was conducted at room temperature, as would occur in real use, rather than in an incubator at 37 0 C.
  • CFU Colony Forming Units
  • the test involved inoculating the surface of the sample with 10 5 organisms with a thin film placed on top of the inoculum to ensure even distribution and intimate contact of the inoculum on the surface of the sample.
  • the organisms used for inoculation were staph aureus (Sa) and Klebsiella pneumoniae (Kp).
  • Sa staph aureus
  • Kp Klebsiella pneumoniae
  • the inoculum was left in contact with the surface for 24 hours and then recovered into broth.
  • the recovered inoculum was then plated and incubated for 24 hours.
  • the number of surviving colony forming units was then counted using an automated colony counter.
  • the number of surviving organisms was compared to the number in the initial inoculum.
  • the number of surviving organisms for the treated samples was also compared to the number of surviving organisms on the untreated control.
  • Enameled metal samples were prepared as desc ⁇ bed in Example 2 Samples were treated with the following antimicrobial formulations a blend ratio of 50/50 of zinc oxide to zinc borate (Formulation #1), a blend ratio of 10/90 zinc oxide to zinc borate (Formulation #2), and a blend ratio of 90/10 zinc oxide to zinc borate (Formulation #3) The formulations were used at 4%, 7% and 10% (40,000 ppm, 70,000 ppm and 100,000 ppm, respectively) by weight based upon the dry weight of the enamel glaze Three tiles were tested per formulation and concentration The control was untreated with any antimicrobial formulation The bare metal edges of the tile samples were sealed with paraffin to prevent rusting and contamination from other metal ions
  • Efficacy testing was conducted by the same protocol as desc ⁇ bed in Example 2
  • the samples were inoculated with the organism Klebsiella pneumoniae
  • the initial inoculum level of each sample was 2 04E+05 CFU, determined by plating of the inoculum
  • the recovered organisms (24 Hour Recovery) for the treated samples were compared to the initial inoculum (% Reduction), and versus the control.
  • the average value from the controls was 5.08E+05 CFU, and this value was used for the comparison versus the control.
  • the "1.00E+02" represented the limit of detection for the test. This means that there was actually no growth on the plates for the 24-hour recovery.

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

Abstract

L'invention porte sur une composition de glaçage d'émail antimicrobienne contenant du borate de zinc afin d'attribuer des propriétés antimicrobiennes à de nombreux produits en émail. L'invention concerne aussi un procédé de fabrication de la composition de glaçage antimicrobienne et de revêtement d'un article au moyen de la composition de glaçage d'émail antimicrobienne.
PCT/US2005/006464 2005-01-21 2005-02-28 Glaçage d'email antimicrobien WO2006088468A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11/040,379 US7250178B2 (en) 2004-01-21 2005-01-21 Antimicrobial ceramic glaze
USPCT/US05/02002 2005-01-21
PCT/US2005/002002 WO2005069962A2 (fr) 2004-01-21 2005-01-21 Glaçure ceramique antimicrobienne
US11/040,379 2005-01-21

Publications (2)

Publication Number Publication Date
WO2006088468A2 true WO2006088468A2 (fr) 2006-08-24
WO2006088468A3 WO2006088468A3 (fr) 2009-03-19

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PCT/US2005/006464 WO2006088468A2 (fr) 2005-01-21 2005-02-28 Glaçage d'email antimicrobien

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012142681A1 (fr) 2011-04-21 2012-10-26 Polyvision, Naamloze Vennootschap Panneau de communication visuelle émaillé antimicrobien

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5677251A (en) * 1996-04-25 1997-10-14 Cerdec Corporation Partially crystallizing enamel containing crystalline zinc borate seed material
US20030030042A1 (en) * 2000-01-11 2003-02-13 Hiroshi Sawada Zinc borate, and production method and use thereof
US20030035912A1 (en) * 2000-03-07 2003-02-20 Heinrich Horacek Intumescent fire-protection strips jacketed on three sides and combined cold-and hot-gas seals

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5677251A (en) * 1996-04-25 1997-10-14 Cerdec Corporation Partially crystallizing enamel containing crystalline zinc borate seed material
US20030030042A1 (en) * 2000-01-11 2003-02-13 Hiroshi Sawada Zinc borate, and production method and use thereof
US20030035912A1 (en) * 2000-03-07 2003-02-20 Heinrich Horacek Intumescent fire-protection strips jacketed on three sides and combined cold-and hot-gas seals

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JACKSON, W.M.II.: 'Low Firing Glazes and Slips.' CERAMIC BULLETIN. vol. 68, no. I, 1989, pages 87 - 88 *
KUCHINSKI, F.A. ET AL.: 'Ceramic Films and Coatings.', 1993, NOYES PUBLICATIONS, PARK RIDGE (NEW JERSEY) article 'Corrosion Resistant Thick Films by Enameling.', pages 77 - 80 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012142681A1 (fr) 2011-04-21 2012-10-26 Polyvision, Naamloze Vennootschap Panneau de communication visuelle émaillé antimicrobien

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