WO2012013695A1 - Article en verre a proprietes antimicrobiennes - Google Patents
Article en verre a proprietes antimicrobiennes Download PDFInfo
- Publication number
- WO2012013695A1 WO2012013695A1 PCT/EP2011/062868 EP2011062868W WO2012013695A1 WO 2012013695 A1 WO2012013695 A1 WO 2012013695A1 EP 2011062868 W EP2011062868 W EP 2011062868W WO 2012013695 A1 WO2012013695 A1 WO 2012013695A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- article according
- nanoparticles
- silver
- article
- Prior art date
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Classifications
-
- 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
-
- 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
- C03C4/00—Compositions for glass with special properties
-
- 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
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/04—Particles; Flakes
-
- 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
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/08—Metals
Definitions
- the present invention relates to a glass article in which at least one of the surfaces has antimicrobial properties which are resistant to a temperature treatment, in particular to a temperature treatment with a view to their subsequent quenching.
- glass substrates with a surface with antimicrobial properties There are different types of glass substrates with a surface with antimicrobial properties and they all have at least one antimicrobial agent. This is often located on the surface of said article.
- antimicrobial agents are silver (Ag), copper (Cu) or zinc (Zn).
- a glass substrate with a known antimicrobial property in particular of the application WO2005 / 042437 A1, is obtained by diffusion of the antimicrobial agent, in particular silver (Ag), from one of the surfaces of the substrate towards the mass. substrate, to a depth of about 2 microns.
- the antimicrobial agent is then present under the glass surface.
- Another type of glass substrate known antimicrobial property comprises, on one of its surfaces, a coating or "coating” consisting of a binder and the antimicrobial agent dispersed in said binder.
- a coating or "coating” consisting of a binder and the antimicrobial agent dispersed in said binder.
- Such substrate examples are given in WO03 / 056924 A1 and WO2006 / 064060 A1.
- the antimicrobial properties withstand very little treatment at temperatures above 400 ° C. Indeed, because of the rapid spread of the Ag element at these temperatures, it migrates progressively from the surface or an area close to the surface, where it is effective to neutralize microbes, to the mass of the glass substrate where it is no longer available to play its antimicrobial role. Such temperatures, which are typically those required to effect quenching of the glass ( ⁇ 650-700 ° C), therefore result in a drastic decrease in the antimicrobial properties of the glass that has been heat treated.
- the invention particularly aims to overcome these disadvantages by solving the technical problem, namely the decrease or slowing of the diffusion of silver in the glass due to a heat treatment of a glass substrate with properties antimicrobial.
- an objective of the invention in at least one of its embodiments, is to provide a glass substrate with antimicrobial properties whose antimicrobial properties remain stable at temperatures above 400 ° C.
- an object of the invention is to provide a glass substrate with antimicrobial properties whose antimicrobial properties remain stable to a temperature treatment for their subsequent quenching.
- Another object of the invention is to provide a glass substrate with antimicrobial properties that does not include a layer and / or does not require a layer deposition step.
- a final objective of the invention is to provide a solution to the disadvantages of the prior art that is simple, fast and economical.
- the invention relates to a glass article comprising
- nanoparticles at least partially incorporated in the glass mass close to said surface and consisting of at least one inorganic compound.
- the invention is based on a completely new and inventive approach because it solves the disadvantages of glass products of the prior art and solve the technical problem.
- the inventors have indeed demonstrated that it was possible to obtain a glass substrate having temperature-resistant antimicrobial properties, without the use of layers, by combining a diffused antimicrobial agent, in a known manner, under the surface of the glass. with nanoparticles consisting of at least one inorganic compound and which are totally and / or partially incorporated in the mass of said glass close to its surface.
- the inventors have thus demonstrated that the presence of nanoparticles included in the surface or under the surface of the glass article used to block or slow the diffusion of silver under the effect of temperature.
- FIG. represents, by way of comparison, a silver concentration profile in the depth of the glass of glass articles with antimicrobial properties according to the state of the art
- FIG. 2 represents, by way of comparison, a silver concentration profile in the depth of the glass of an article, in the absence of nanoparticles
- FIG. 3 represents a silver concentration profile in the depth of the glass of an article according to the invention, obtained by flame-assisted spraying
- FIG. 4 represents a photograph obtained by transmission electron microscopy of a section of a glass article according to the invention.
- FIG. 5 represents a silver concentration profile in the depth of the glass of an article according to the invention, obtained by flame-assisted spraying
- FIG. 6 represents a silver concentration profile in the depth of the glass of another article according to the invention, obtained by flame-assisted sputtering.
- the glass article according to the invention is formed of an inorganic type of glass that can belong to various categories.
- the inorganic glass may thus be a soda-lime type glass, a boron glass, a lead glass, a glass comprising one or more additives homogeneously distributed in its mass, such as, for example, at least one inorganic dye. an oxidizing compound, a viscosity controlling agent and / or a melt facilitating agent.
- the glass article according to the invention is formed of a soda-lime type glass which can be clear or colored in the mass.
- soda-lime glass is used here in its broad sense and refers to any glass that contains the following basic components (expressed as percentages by total weight of glass):
- the glass of the article according to the invention consists of a flat glass sheet.
- the flat glass may, for example, be a float glass, a drawn glass or a printed glass.
- the flat glass sheet may be the subject of the treatment according to the invention on one side or, alternatively, on both sides.
- the treatment according to the invention is advantageously carried out on the non-printed face of the sheet if it is printed on one side.
- the glass of the article according to the invention consists of a flat glass sheet of soda-lime type.
- the glass article has not been covered by any layer prior to the treatment of the present invention, at least on the surface to be treated.
- the glass article according to the invention can be covered by any layer after the treatment of the present invention, preferably on the surface opposite to that which has been treated according to the invention.
- the glass article according to the invention has antimicrobial properties.
- microorganisms microscopically sized single-cell living organisms such as bacteria, yeasts, micro-algae, fungi or viruses.
- neutralize is meant at least the maintenance of the starting quantity of microorganisms (static effect); the invention excludes an increase of this quantity. The development and proliferation of microorganisms are thus prevented and, in almost all cases, the surface area of microorganisms decreases, even when maintaining their quantity.
- the neutralization of microorganisms can go, according to the invention, until their partial destruction and even total (microbicidal effect).
- the glass article according to the invention has an antibacterial effect (bactericidal or bacteriostatic) on a large number of bacteria, be it gram positive or gram negative bacteria, in particular on at least one of the following bacteria : Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Enterococcus hirae.
- the glass article according to the invention also has antifungal effect (fungicidal or fungiostatic), in particular on Candida albicans, and / or Aspergillus niger.
- the glass article according to the invention comprises at least one antimicrobial agent in at least one surface of the glass, in the mass of the glass close to said surface.
- the antimicrobial agent is chosen from the elements silver (Ag), copper (Cu), tin (Sn) and zinc (Zn).
- the antimicrobial agent is present either in the form of very small particles of metal or oxide, or dissolved in the matrix of the glass.
- the antimicrobial agent according to the invention is the silver element (Ag).
- the silver is diffused below the surface, so that the ratio of intensities I (CsAg) / I (CsSi), measured on the surface according to the dynamic SIMS method, is greater than 0.002, and of preference greater than or equal to 0.010.
- Such values of intensity ratios I (CsAg) / I (CsSi) make it possible to obtain a sufficient antimicrobial effect.
- I (CsAg) is the intensity the peak obtained for the ions
- I (CsSi) is the intensity of the peak obtained for the CsSi + ions, after bombardment of the surface of the substrate by a Cs + ion beam which progressively etches the surface of the sample.
- the energy of the Cs + ion beam reaching the substrate is 5.5 keV.
- the angle of incidence of the beam is 42 ° relative to the normal to the substrate.
- the values, on the surface mean that the values are taken for as small a depth as possible, as soon as the value obtained is significant.
- the first significant values may correspond to maximum depths of about 1 to 5 nm.
- the surface values correspond to a depth of 2 nm maximum.
- the ratio of the isotope intensities I (Agl07) / I (Agl09) must be close to the theoretical value (1.0722), in particular between 1.01 and 1.13.
- the concentration of antimicrobial agent is distributed in the depth of the glass according to a conventional diffusion profile, that is to say a profile which decreases continuously from the surface of the glass and tends to zero at a given depth.
- the concentration of antimicrobial agent is distributed in the depth of the glass in a profile which has a minimum. Preferably, the minimum is at a distance from the surface of between 10 and 4000 nm.
- the nanoparticles are (i) partially incorporated into the mass of the glass; and or
- nanoparticle partially incorporated into the mass of the glass means a nanoparticle which is both in the mass of the glass and outside the mass of the glass. In other words, the nanoparticle is not completely surrounded by glass.
- nanoparticle totally incorporated in the mass of the glass is meant a nanoparticle which lies beneath the glass surface of the article, at a close distance therefrom.
- the nanoparticles of the invention consist of at least one inorganic compound.
- the composition may be homogeneous or heterogeneous.
- the inorganic compound may be totally foreign to the composition of the glass mass of the article. It may also, alternatively, already be present in the composition of the glass mass of the article.
- the inorganic compound constituting the nanoparticles is chosen from oxides, nitrides, carbides and mixtures thereof.
- the inorganic compound is selected from magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, vanadium, niobium, tantalum, aluminum, gallium, indium, silicon, germanium, and combinations of at least two of the aforementioned compounds.
- the inventors have demonstrated that the resistance of the antimicrobial properties to the temperature is particularly good when the inorganic compound is an aluminum compound and in particular an aluminum oxide.
- the nanoparticles are at least partially crystallized, that is to say that they comprise at least a proportion of 5% of their weight constituted by crystals.
- the crystals may belong to several different crystallization systems. Alternatively, they can all be of the same crystallization system.
- Preferably, at least 50% of the weight of the nanoparticles is in a crystallized form. Most preferably, all the nanoparticles are in the crystallized form.
- the shape of the nanoparticles is quasi-spherical.
- quasi-spherical is meant a three-dimensional shape whose volume is close to that of a sphere whose diameter would be equal to the largest dimension of an object having this quasi-spherical shape.
- the nanoparticles of the invention have a size which is not smaller than 2 nm and preferably not less than 10 nm.
- the nanoparticles have a size which is not greater than 1000 nm and preferably not greater than 500 nm and, more preferably, no greater than 300 nm. intends to designate the largest dimension of nanoparticles.
- the glass article according to the invention may be heat treated, in particular it may be heat treated for quenching.
- the invention covers both the untreated glass article and the thermally treated glass article.
- the glass article has both antimicrobial properties and properties of tempered glass.
- Glass with tempered glass property means a glass which has an increased mechanical strength compared to a conventional untreated glass of the same thickness and composition.
- the glass article according to the invention can be obtained according to a process comprising two main stages:
- an exemplary method comprises (a) the production of nanoparticles, (b) the deposition of the nanoparticles on the surface of the article, and (c) the supply of energy to the nanoparticles and / or to said surface of such that the nanoparticles diffuse / incorporate into the glass.
- the formation and deposition of nanoparticles on the glass surface can be carried out in a single step by known methods such as chemical vapor deposition (or CVD), wet deposition such as for example sol-gel deposition , or flame-assisted spraying (or flame spraying) from a liquid, gaseous or solid precursor.
- the nanoparticles are generated by atomizing a solution of at least one chemical precursor into an aerosol transported in a flame where combustion occurs. to form solid nanoparticles. These nanoparticles can then be deposited directly on a surface placed near the end of the flame.
- the formation and deposition of nanoparticles on the surface of the glass article can be carried out consecutively in two steps.
- the nanoparticles are previously generated in solid form or in the form of suspension in a liquid by vapor, wet (sol-gel, precipitation, hydrothermal synthesis, ...) or dry (mechanical grinding, mechanochemical synthesis, ).
- An example of a method for generating nanoparticles in solid form in advance is the method known as Combustion-Vapor Combined Chemical Chilling (or CCVC). This method consists in converting into a flame a precursor solution in the vapor phase which undergoes a combustion reaction to provide nanoparticles which are finally collected.
- the previously generated nanoparticles can be transferred to the glass surface by various known methods.
- the energy required for the diffusion / incorporation of the nanoparticles into the mass of the glass can, for example, be provided by heating the glass or its surface to a suitable temperature.
- the energy necessary for the diffusion / incorporation of the nanoparticles in the mass of the glass can be provided at the time of the deposition of the nanoparticles or later. Flame-assisted sputtering is particularly advantageous in this case because the energy required for the diffusion / incorporation of the nanoparticles in the mass of the glass is provided at the time of deposition of the nanoparticles by the heat of the flame itself.
- the nanoparticles of the glass article according to the invention are obtained according to such a method.
- Various methods known per se may be suitable for obtaining a microbial agent beneath the surface of a glass article.
- the two steps of deposition of the antimicrobial agent and diffusion thereof below the surface can also be almost simultaneous if the glass article or its surface is preheated.
- the glass article according to the invention can be obtained in a single main step, via a flame-assisted spraying technique starting from a solution of a salt of the inorganic compound and a salt of the agent. antimicrobial.
- the glass article according to the invention has many applications. For example, it can be used as a container for consumables or as a bathroom, kitchen or laboratory element (mirror, partition, floor, worktop, door). It can also be used as an element of appliances such as refrigerator shelves or oven doors. It also has many applications in hospital.
- the treated leaves were finally cleaned with acid (solution of HNO 3 and Fe (NO 3 ) 3 ) to remove excess silver remained on the surface and thus not diffused during the heat treatment.
- the glass sheets treated as described above were analyzed by secondary ion mass spectrometry.
- FIG. 1 shows the quantity of silver (intensity ratio I (CsAg) / I (CsSi)) diffused below the surface of the glass as a function of the depth (d) in the substrate for each of the heat treatments (a), (b) and (c).
- I (CsAg) is the peak intensity obtained for CsAg + and I (CsSi) is the peak intensity obtained for CsSi + ions after bombardment of the substrate surface by a beam of Cs + ions with a "cameca ims-4f" type of equipment (5.5 keV beam and 42 ° angle of attack relative to the normal to the substrate).
- These analyzes illustrate the drastic effect of temperature, for the same duration of treatment, on the amount of silver present on the surface of the glass.
- a 4mm thick, 20cm x 20cm soda-lime float glass sheet was washed consecutively with running water, deionized water and isopropyl alcohol and finally dried.
- Hydrogen and oxygen were introduced into a spot burner to generate a flame at the outlet of said burner.
- the washed glass sheet was preheated in an oven at a temperature of 600 ° C. and one of its surfaces was placed under the burner near the end of the flame, at a distance of 130 mm.
- the point burner is movable in both directions of the space included in the plane of said sheet.
- the burner head moved continuously in one of two directions at a speed of 3 meters per minute and in the other direction perpendicular to the first, with jumps of 2 centimeters. After this treatment, the glass sheet was then cooled in a controlled manner.
- the glass sheet treated as described above was analyzed by secondary ion mass spectrometry.
- Figure 2 shows the amount of silver scattered (ratio of intensities I (CsAg) / I (CsSi) in logarithmic scale) as a function of the depth (d) in the glass sheet from the treated surface. It illustrates the diffusion of silver under the glass surface. The silver concentration is distributed over a depth of more than 1 micron in a profile that has a minimum at a depth from the surface of about 150 nm. In addition, the ratio of intensities I (CsAg) / I (CsSi) at the surface is 0.002.
- Hydrogen and oxygen were introduced into a linear burner to generate a flame at the outlet of said burner.
- the burner used had a width of 20 cm and had 2 atomization ramps for the introduction of the precursor solution.
- the washed glass sheet was preheated in an oven at a temperature of 600 ° C and then run at this temperature at a speed of about 8 m / min under the burner placed above the glass sheet at a distance of 90 mm.
- the total flow of the solution was 360 ml / min. After this treatment, the glass sheet was then cooled in a controlled manner.
- the glass sheet treated as described above was analyzed by scanning and transmission electron microscopy, X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy and secondary ion mass spectrometry.
- the analyzes carried out showed that aluminum was incorporated into the mass of the glass near the surface in the form of aluminum oxide nanoparticles, Al 2 O 3 .
- the nanoparticles are predominantly crystalline and have a size ranging from 10 to 100 nm.
- Figure 3 shows the ratio of intensities I (CsAg) / I (CsSi) (logarithmic scale) as a function of the depth (d) in the glass sheet from the treated surface. It illustrates the diffusion of silver under the glass surface. The silver concentration is distributed in the depth of the glass according to a profile that has a maximum value at the surface, a progressive decrease to a minimum centered around 200 nm, followed by a slight growth ending in a plateau from about 0.8 micron.
- the ratio I (CsAg) / I (CsSi) at the surface is 0.015, which shows that, starting from the same process to diffuse the silver, the presence of nanoparticles makes it possible to get a much higher silver concentration at the glass surface, which favors antimicrobial activity.
- An article according to the invention has been obtained in an installation intended to continuously manufacture soda-lime type flat glass.
- This installation includes a melting furnace, a tin bath and a cooling gallery.
- the glass in the molten state, was cast as a ribbon from the melting furnace onto the tin bath.
- the glass ribbon had an average thickness of 8 mm. It then ran with a constant speed of about 7.75 m / min and with a temperature of 615 ° C to a linear burner 20 cm wide.
- the burner was supplied with hydrogen and oxygen to generate a flame at the outlet of said burner and was placed above the glass sheet at a distance of 145 mm.
- the glass sheet finally marched to the cooling gallery where it was cooled in a controlled manner under the conditions usually used for flat float glass.
- the glass sheet treated as described above was analyzed by the same techniques as those described in Example 3.
- FIG. 4 represents a photograph obtained by electron microscopy transmitting a section of the treated glass sheet. It shows several aluminum oxide nanoparticles incorporated in the mass of the glass, partially (1) or totally (2).
- Figure 5 shows the ratio of intensities I (CsAg) / I (CsSi) (log scale) versus depth (d) in the glass sheet from the treated surface. It illustrates the diffusion of silver under the glass surface. The silver concentration is distributed in the depth of the glass according to a profile that has a maximum value at the surface, a gradual decrease to a plateau between 150 and 400 nm, followed by a slight growth ending in another plateau at from about 0.6 micron.
- the ratio I (CsAg) / I (CsSi) at the surface (maximum value of the profile) for Example 4 is 0.010, which again shows that the presence of nanoparticles makes it possible to obtain a higher silver concentration at the surface of the surface. glass.
- Example 5 (in accordance with the invention)
- An article according to the invention has been obtained in an installation intended for the continuous manufacture of printed soda-lime type flat glass.
- This installation includes a melting furnace, a laminator and a cooling gallery.
- the glass, in the molten state, was cast as a ribbon from the melting furnace into the laminator where it passed between two superimposed rollers, one of which is smooth and the other is engraved in a printing pattern. .
- This printing pattern has since been reproduced on one side of the glass, the one facing down the horizontal ribbon.
- the glass ribbon passed through the laminator had an average thickness of 4 mm (3.5-4.5 mm). It then ran with a constant speed of about 3.7 m / min and with a temperature of 710 ° C to a linear burner 2 m wide.
- the burner was supplied with hydrogen and oxygen to generate a flame at the outlet of said burner and was placed on top of the sheet of glass on the unprinted side, at a distance of 120 mm.
- the glass sheet then passed to the cooling gallery where it was cooled in a controlled manner under the conditions usually used for printed flat glass.
- the glass sheet was then covered with a thin layer of silver by the vacuum deposition method, also known as magnetron sputtering, in a manner known per se, using a metallic silver target in a plasma atmosphere. 'argon.
- the amount of silver deposited is 100 mg / m 2 of treated surface.
- the glass sheet was then treated at 300 ° C for 15 minutes to spread the silver under the surface.
- the treated sheet was then cleaned with acid (HNO 3 and Fe (NO 3 ) 3 solution ) to remove the excess silver remaining on the surface and thus not diffusing during the heat treatment.
- acid HNO 3 and Fe (NO 3 ) 3 solution
- the analyzes carried out have shown that aluminum has been incorporated in the form of aluminum oxide particles partially and totally incorporated in the mass of the glass.
- the particles have an almost spherical shape and have a size that varies from 170 to 850 nm.
- the particles are predominantly crystalline.
- Figure 6 shows the ratio of intensities I (CsAg) / I (CsSi) (logarithmic scale) versus depth (d) in the glass sheet from the treated surface. It illustrates the diffusion of silver under the glass surface.
- the ratio I (CsAg) / I (CsSi) at the surface is 0.0026, which shows that the presence of nanoparticles also makes it possible to maintain a certain concentration of silver on the surface even after quenching (compared with to the sample of Example 1 without nanoparticle for which the silver concentration at the surface after a similar heat treatment is zero).
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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- Organic Chemistry (AREA)
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- Dispersion Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013521120A JP5771273B2 (ja) | 2010-07-27 | 2011-07-27 | 抗菌特性を有するガラス物品 |
EA201291385A EA024442B1 (ru) | 2010-07-27 | 2011-07-27 | Лист стекла с противомикробными свойствами |
EP11735879.6A EP2598451A1 (fr) | 2010-07-27 | 2011-07-27 | Article en verre a proprietes antimicrobiennes |
US13/810,971 US9040163B2 (en) | 2010-07-27 | 2011-07-27 | Glass article with antimicrobial properties |
BR112013002067A BR112013002067A2 (pt) | 2010-07-27 | 2011-07-27 | artigo de vidro com propriedades antimicrobianas |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10170847 | 2010-07-27 | ||
EP10170847.7 | 2010-07-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012013695A1 true WO2012013695A1 (fr) | 2012-02-02 |
Family
ID=43480869
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/062868 WO2012013695A1 (fr) | 2010-07-27 | 2011-07-27 | Article en verre a proprietes antimicrobiennes |
Country Status (6)
Country | Link |
---|---|
US (1) | US9040163B2 (fr) |
EP (1) | EP2598451A1 (fr) |
JP (1) | JP5771273B2 (fr) |
BR (1) | BR112013002067A2 (fr) |
EA (1) | EA024442B1 (fr) |
WO (1) | WO2012013695A1 (fr) |
Citations (8)
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FI954370A (fi) | 1995-09-15 | 1997-03-16 | Juha Tikkanen | Menetelmä ja laite materiaalin ruiskuttamiseksi |
EP0806401A1 (fr) * | 1996-05-07 | 1997-11-12 | Thomson Csf | Utilisation d'une barrière en nitrure pour éviter la diffusion d'argent dans du verre |
US20030097858A1 (en) * | 2001-11-26 | 2003-05-29 | Christof Strohhofer | Silver sensitized erbium ion doped planar waveguide amplifier |
WO2003056924A1 (fr) | 2001-12-21 | 2003-07-17 | Milliken & Company | Films sol-gel antimicrobiens contenant des agents antimicrobiens specifiques renfermant du metal |
WO2005042437A2 (fr) | 2003-09-30 | 2005-05-12 | Schott Ag | Surfaces antimicrobiennes en verre et vitroceramique et leur production |
WO2006064059A1 (fr) * | 2004-12-16 | 2006-06-22 | Glaverbel | Substrat presentant des proprietes antimicrobiennes |
EP1985592A1 (fr) * | 2007-04-26 | 2008-10-29 | AGC Flat Glass Europe SA | Article en verre à résistance chimique améliorée |
WO2010046336A1 (fr) | 2008-10-20 | 2010-04-29 | Agc Flat Glass Europe Sa | Article en verre a resistance chimique amelioree |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US20050119105A1 (en) * | 2002-01-18 | 2005-06-02 | Schott Ag | Glass-ceramic composite containing nanoparticles |
DE10201747C1 (de) * | 2002-01-18 | 2003-08-14 | Schott Glas | Glas-Keramik-Komposit, Verfahren zu seiner Herstellung und Verwendungen |
FI20060288A0 (fi) * | 2006-03-27 | 2006-03-27 | Abr Innova Oy | Pinnoitusmenetelmä |
-
2011
- 2011-07-27 EA EA201291385A patent/EA024442B1/ru not_active IP Right Cessation
- 2011-07-27 BR BR112013002067A patent/BR112013002067A2/pt not_active IP Right Cessation
- 2011-07-27 WO PCT/EP2011/062868 patent/WO2012013695A1/fr active Application Filing
- 2011-07-27 JP JP2013521120A patent/JP5771273B2/ja not_active Expired - Fee Related
- 2011-07-27 EP EP11735879.6A patent/EP2598451A1/fr not_active Withdrawn
- 2011-07-27 US US13/810,971 patent/US9040163B2/en not_active Expired - Fee Related
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
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FI954370A (fi) | 1995-09-15 | 1997-03-16 | Juha Tikkanen | Menetelmä ja laite materiaalin ruiskuttamiseksi |
EP0806401A1 (fr) * | 1996-05-07 | 1997-11-12 | Thomson Csf | Utilisation d'une barrière en nitrure pour éviter la diffusion d'argent dans du verre |
US20030097858A1 (en) * | 2001-11-26 | 2003-05-29 | Christof Strohhofer | Silver sensitized erbium ion doped planar waveguide amplifier |
WO2003056924A1 (fr) | 2001-12-21 | 2003-07-17 | Milliken & Company | Films sol-gel antimicrobiens contenant des agents antimicrobiens specifiques renfermant du metal |
WO2005042437A2 (fr) | 2003-09-30 | 2005-05-12 | Schott Ag | Surfaces antimicrobiennes en verre et vitroceramique et leur production |
WO2006064059A1 (fr) * | 2004-12-16 | 2006-06-22 | Glaverbel | Substrat presentant des proprietes antimicrobiennes |
WO2006064060A1 (fr) | 2004-12-16 | 2006-06-22 | Glaverbel | Substrat avec propriétés antimicrobiennes |
EP1985592A1 (fr) * | 2007-04-26 | 2008-10-29 | AGC Flat Glass Europe SA | Article en verre à résistance chimique améliorée |
WO2008132173A1 (fr) | 2007-04-26 | 2008-11-06 | Agc Flat Glass Europe Sa | Article en verre à résistance chimique améliorée |
WO2010046336A1 (fr) | 2008-10-20 | 2010-04-29 | Agc Flat Glass Europe Sa | Article en verre a resistance chimique amelioree |
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US20130123091A1 (en) | 2013-05-16 |
JP2013532624A (ja) | 2013-08-19 |
US9040163B2 (en) | 2015-05-26 |
JP5771273B2 (ja) | 2015-08-26 |
EA024442B1 (ru) | 2016-09-30 |
BR112013002067A2 (pt) | 2016-05-24 |
EP2598451A1 (fr) | 2013-06-05 |
EA201291385A1 (ru) | 2013-05-30 |
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