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
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
• • 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
• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
  • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
• • 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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
• • 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

Definitions

• the present invention relates to a substrate of any type: metal, glass, glass ceramic, or plastic type substrate, wherein at least one of its surfaces has antimicrobial, in particular antibacterial or antifungal, properties.
• the present invention also relates to processes for the production of such a substrate.
• EP 653 161 describes the possibility of covering these with a glaze composed of silver to provide them with antibacterial properties.
• sol-gel type processes are known to provide an antimicrobial surface. These processes require a hardening stage of the sol-gel layer, which involves elevated temperatures in the order of 500°-600°C (sintering temperature). Processes are also known that require the substrate to be dipped in a composition comprising a silver salt. In this case, a silver layer is not deposited, but an ion exchange takes place in the solution at an elevated temperature.
• a process for producing a glass substrate having antimicrobial properties is also known from EP 1449816.
• This process uses AgNO 3 in oil and requires both a drying stage between 20° and 105 0 C and a thermal treatment at 600°-650°C.
• This thermal treatment has some disadvantages particularly with respect to cost and uniformity of the product. Moreover, it renders the process very poorly reproducible, since it has been found that at these temperatures the diffusion of the silver is very rapid and a slight variation in the duration of the thermal treatment results in a significant variation in the depth of diffusion of the silver, and therefore this causes variation in the antibacterial properties of the substrate.
• we have observed that with such a process the majority of the silver has diffused between around 1 and 2 ⁇ m and that at the surface the quantity of silver is too low to give antimicrobial properties to the glass.
• thermal treatment causes an undesirable yellow colouration of a soda-lime glass substrate.
• the thermal treatment is carried out during a tempering process, after having been treated, the product may no more be cut into particular size.
• WO 95/13704 describes anti-microbial materials, in particular for medical devices.
• separated layers of Ag and ZnO were deposited sequentially by RF magnetron sputtering in a ratio of 75-25 wt%. The total thickness of the layers is 330 nm.
• RF magnetron sputtering is a deposition method which is hardly industrialisable today.
• one aim of the invention is to provide a glass substrate which can be tempered and which keeps antimicrobial properties after accelerating ageing tests carried out after tempering process.
• the present invention relates to a substrate coated with at least one mineral layer, particularly selected from metal oxides, oxynitrides, oxycarbides, carbides, DLC (diamond like carbon) or nitrides, said layer comprising at least one antimicrobial agent, the coated substrate maintaining antimicrobial properties after accelerated ageing tests.
• the mineral layer can be selected from oxides of silicon, tin, nickel, chrome, zinc, titanium, niobium, aluminium, zirconium or mixtures thereof, for example ZnxSnyOz and NiCrOx.
• Particularly preferred nitrides are silicon, titanium and aluminium nitrides and mixtures thereof.
• the antimicrobial agent can be selected from various inorganic agents known for their antimicrobial properties, in particular silver, copper, gold and zinc.
• the antimicrobial agent is in ionic form.
• the substrate can be metallic, e.g. made of steel, or stainless steel or ceramic type or plastic or thermoplastic type substrate or a glass-type substrate, in particular a sheet of flat glass, particularly soda-lime glass which may be float glass. It may be clear glass or coloured glass. Frosted or patterned glass can also be used.
• the glass sheets can be treated on one or on both of their faces. The face opposite the treated face can be subjected to any desired type of surface treatment. It may comprise a reflective layer (to form a mirror) or a layer of enamel or painting (for wall covering), generally at the surface opposite to the antimicrobial surface.
• the substrate may have a thickness within the range of 0.2 to 12 mm.
• the substrate may have a surface area of greater than 0.8 m to 0.8m; it may be adapted to be cut to a finished size by a subsequent cutting operation.
• the antimicrobial glass substrate thus obtained is subjected to a thermal treatment stage such as, in the case of glass substrate, a thermal tempering, bending or hardening, while still retaining its antimicrobial properties.
• a substrate having antimicrobial agents present at least at one exposed surface may be a sheet of annealed glass.
• annealed sheet of glass is used herein to mean that the glass may be cut to size without breaking in the way that a tempered or hardened sheet of glass would break upon cutting.
• Such a sheet of annealed glass preferably has a surface compression of less than 5 MPa. After the eventual cutting operation, the substrate is able to be tempered and antimicrobial properties are maintained.
• the substrate can be first coated with an underlayer that blocks or slows down the diffusion of the antimicrobial agents during the tempering treatment.
• the function of the underlayer can be ascertained on a product made according to the invention by comparing the antimicrobial effect of similar products with and without undercoating and/or by analysing diffusion profiles.
• undercoat and/or mixed layers are chosen amongst titanium oxide, titanium nitride, zirconium oxide, silicon oxide or silicon oxinitride.
• the substrate according to the invention preferably has an antibacterial effect on a large number of bacteria, whether 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 antibacterial effect measured in accordance with the JIS Z 2801 standard, is in particular, at least on any one of these bacteria, higher than log 1, preferably higher than log 2 and particularly preferred higher than log 2.5.
• the substrate will be considered bactericidal according to the JIS Z 2810 standard if it has an effect higher than log 2.
• the invention also relates to substrates that have a lower effect (for example bacteriostatic effect, which means that the bacteria are not necessarily killed but can not develop any more).
• the mineral layer and the antimicrobial agent in one single step over the entire substrate, whether it is made of metal, e.g. steel, or is a glass-type substrate.
• a layer e.g. of a metal oxide doped with an antimicrobial agent, e.g. silver
• an antimicrobial agent e.g. silver
• Targets with mixed materials may be metallic but it can be particularly advantageous to mix ceramic materials for one of the cathode in the co-sputtering process or to mix ceramic materials with metals for the single cathode in the single cathode process.
• Ag, Cu, Au and Zn can be mixed with oxides of Ti, NiCr, Zr and other pure or mixed oxides in order to produce mixed ceramic-based targets which lead to highly efficient processes in terms of deposition rate and process stability.
• Layers of Ag doped metal oxide deposited in a single step by co- sputtering or sputtering of mixed targets, have been made which have antimicrobial properties with a simple process that does not require any thermal treatment.
• the substrate used is a clear glass, it can advantageously have antimicrobial properties as well as a neutral colouration in reflection.
• the colorimetric indexes (CIELAB system) in reflection a* and b* may be in the range of between -10 and 6, preferably between -8 and 3 and particularly preferred between -6 and 0, and the purity may be less than 15%, preferably less than 10% and particularly preferred less than 5%. If an underlayer is deposited a slight absorption in the visible (around 5 to 25 %) may be imparted to the underlayer. It may have a visible light reflection around 8 and 15%,
• the substrate is a coloured glass
• antimicrobial properties may be obtained without changing very much the initial colour of the substrate.
• the change of coloration is generally expressed with the colorimetric index by Delta E* ;
• Delta E* [ (L*j - L* 2 ) 2 + (a*j - a* 2 ) 2 + O ⁇ - b* 2 ) 2 ] 1/2 .
• a Delta E* lower than 3, preferably lower than 2 may be obtained for an antimicrobial substrate according to the invention.
• the substrate is transparent (glass, plastic, ...), it may be advantageous to obtain antimicrobial properties while keeping the substrate essentially transparent.
• the average light transmission in the visible range of the coated substrate according to the invention may be higher than 50%, preferably higher than 60% and most preferably higher than 65%.
• the glass substrate used is a clear glass, it may advantageously have both antimicrobial properties and a low visible light absorption.
• the substrate according to the invention has an antimicrobial effect after at least one of the following accelerated ageing tests: wet spray test (test over 20 days in a chamber with a humidity of more than 95% at 40 0 C), after 500 hours of UV irradiation (4 340A ATLAS lamps, chamber at 60 0 C), after 24 hours immersed in a solution of H 2 SO 4 (0.1 N), after 24 hours immersed in a solution of NaOH (0.1 N), 48 hours of immersion in Mr Propre® detergent followed by 5 days of drying.
• an undercoat comprising an oxide of zirconium. This may particularly be so when the mixed layer comprises an antibacterial agent and an oxide of titanium, particularly a titanium oxide in its anatase crystallised form. Additional or alternative embodiments of the present invention are also described in dependant claims.
• One sample of clear soda-lime glass having a thickness of 4 mm was coated with a layer of SiO 2 (Al) :Ag by co-sputtering.
• Two metal targets were used in a mixed atmosphere of argon and oxygen: one was composed of silicon doped with 8% Al and the second target was a metallic silver target.
• the Si(Al) target was sputtered with a pulsed DC power supply at 100 kHz while the Ag target was sputtered with DC power supply.
• the electric power supplies were regulated in order to obtain 10 mg of Ag in the layer per square meter of substrate with the totaljayer thickness of 24 nm.
• the bactericidal properties (in particular on E. CoIi) of all the samples were analysed in accordance with standard JIS Z 2801.
• a log 1 level indicates that 90% of the bacteria inoculated onto the surface of the glass were killed in 24 hours in the conditions of the standard; log 2 indicates that 99% of the bacteria were killed; log 3 indicates that 99.9% of the bacteria deposited were killed etc. If the value indicated is greater than a particular amount, this mean that the maximum of countable bacteria was killed.
• the coated sample was subjected to a common tempering treatment
• Samples of the same clear soda-lime glass (4 mm thick) were first coated with an underlayer and then coated with a layer of 24 nm of SiO 2 -Ag by co- sputtering using the same conditions as in example 1.
• the electric power supplies were regulated in order to obtain 20 mg/m 2 of Ag in the layer.
• the underlayer is a double underlayer deposited by CVD (Chemical Vapor Deposition) consisting of 75 nm of SiOxCy and 320 nm of fluorine doped tin oxide, the surface being slightly polished after deposition.
• CVD Chemical Vapor Deposition
• the underlayer is also a double SiOxCy/ SnO2:F layer but not polished.
• the antibacterial effect was measured in the same manner as in example 1. Values greater than log 4 were obtained.
• the antibacterial properties were again measured on the samples having been tempered and then subjected to the accelerated ageing tests.
• the sample of example 2 maintained a log 4.9 value after H 2 SO 4 immersion, a log 4.7 value after the wet spray test, a log 4.1 after the detergent immersion test and after the UV test.
• the sample of example 3 maintained a log 4.5 value after H 2 SO 4 immersion, a log 4.7 value after the wet spray test, a log 3.6 after the detergent immersion test and a log 4.1 after the UV test.
• Samples of the same clear soda-lime glass (4 mm thick) was first coated with a CVD underlayer of 75 nm of SiOxCy and 320 nm of fluorine doped tin oxide, and the surface has been slightly polished after deposition.
• the samples have then been coated with a layer of 15 nm of SiO 2 -Ag by co-sputtering.
• two metal targets were used in a mixed atmosphere of argon and oxygen: one was composed of silicon doped with 8% Al and the second target was a metallic silver target. Both targets were sputtered with one single AC electric power supply operating at 27 kHz and being regulated in order to obtain 15 mg of Ag in the layer per square meter of substrate.
• the antibacterial effect was measured in the same manner as in the other examples. Values greater than log 4 were obtained.
• Ag was then deposited by co-sputtering using two metallic targets (Si-Zr (10wt%Zr) and Ag). Both targets were sputtered with one single electric power supply being regulated in order to obtain a total thickness of 19 nm and 21 mg/m 2 of Ag.
• the antibacterial effect was measured in the same manner as in the previous examples. On the samples before tempering (a value greater than log 4 was obtained), after tempering (a value greater than log 4.6 was obtained). The tempered samples were subjected to accelerating ageing tests. After the H 2 SO 4 immersion test, a bactericidal value greater than log 4.9 was maintained. After the wet spray test, a value greater than log 4.7 was obtained and after the detergent immersion test, a log 4.1 was obtained.
• Samples of the same clear soda-lime glass were first coated with the same double CVD underlayer as in examples 2 and 4.
• a layer of TiAlOx doped with Ag was then deposited by co-sputtering using one Ag metal target and one ceramic target TiAlOx (12wt% AlOx) in a mixed atmosphere of argon and oxygen.
• the Ti(Al)Ox target was sputtered with a pulsed DC power supply at 100 kHz while the Ag target was sputtered with a DC power supply.
• the electric power supplies were regulated in order to obtain a thickness of 60 nm and 26 mg/m 2 of Ag in the layer.
• both targets were sputtered with one single AC power supply regulated in order to obtain a thickness of 7 nm and 30 mg/m 2 of Ag in the layer.
• the antibacterial effect was measured in the same manner as in the previous examples. On the sample before tempering a value greater than log 4 was obtained, after tempering a value greater than log 4.6 was obtained.
• the sample according to the invention maintained good antibacterial properties.
• a sand abrasion test was carried out in order to measure the mechanical resistance of the coated samples.
• a piece of felt is rubbed on the sample for 600 passes.
• a weight of 1050 g is applied on the felt while an abrasive solution is poured on the sample (160 g of sand, mesh 500 per litre of water).
• the change of reflected colour in the abraded zone is measured and expressed as delta E*.
• a delta E* of 2.2 was obtained, which means that the mechanical resistance of the layer is acceptable.
• the antibacterial properties were measured also after the abrasion test. For example 6, same very good level of antibacterial activity was obtained. For example 7, a log 2.4 was obtained which means that the sample was still bactericidal.
• One sample of clear soda-lime glass having a thickness of 4 mm was coated with a layer of ZrO 2 : Ag by co-sputtering.
• Two metal targets were used in a mixed atmosphere of argon and oxygen: one was composed of zirconium and the second target was a metallic silver target.
• An unipolar pulsed electric power supply was used and was regulated in order to obtain 7 wt% of Ag in the layer.
• the layer thickness was 225 nm.
• the bactericidal properties of the sample was analysed in accordance with Standard JIS Z 2801 before and after tempering process
• the coated sample was subjected to a tempering treatment (670 0 C during 200 sec). And the bactericidal properties were analysed. A log 3.8 was obtained which means that the sample has good bactericidal properties after tempering.
• Samples of the same clear soda-lime glass (4 mm thick) was first coated with a CVD underlayer of 75 nm of SiOxCy and 320 nm of fluorine doped tin oxide, and the surface has been slightly polished after deposition as in the previous examples 2 and 4-7.
• a layer of TiOx doped with Ag has been deposited by magnetron co- sputtering using one metal target of Ag and one ceramic target TiOx respectively in a mixed atmosphere of argon and oxygen for example 9 and in a atmosphere comprising mainly argon for example 10.
• the Ag target was sputtered with a pulsed DC power supply at 50 kHz with 50 ⁇ s one time, while the TiOx target was sputtered with DC power supply.
• the electric power supplies were regulated in order to obtain a layer of respectively 38 nm thick for example 9 and 11 nm for example 10.
• the layer comprises respectively 5 mg/m2 of Ag in example 9 and 4 mg/m2 of Ag in example 10.
• a sample of the same clear soda-lime glass was first coated with the same double CVD underlayer as in examples 2 and 4-7, 9-10.
• a layer of SiOxNy doped with Ag was then deposited by co-sputtering using one target of silicon and one target of silver in a mixed atmosphere of argon, nitrogen and oxygen.
• the Si target was sputtered with a pulsed DC power supply at 50 kHz with 5 ⁇ s while the Ag target was sputtered with a DC power supply.
• the electric power supplies were regulated in order to obtain a layer of 12 nm with 1 mg/m2 of Ag.
• a sample of the same clear soda-lime glass (4 mm thick) was first coated with a CVD underlayer of 75 nm of SiOxCy and 320 nm of fluorine doped tin oxide, and the surface has been slightly polished after deposition as in the previous examples 2 and 4-7.
• a layer of TiOx doped with Ag has been deposited by magnetron sputtering using a single target of mixed ceramic titanium and Ag (1.3 wt%).
• the single target was sputtered with a normal DC power supply in a mixed atmosphere of argon and oxygen.
• the electric power supply was regulated in order to obtain a layer of 36 nm with 2.2 mg/m2 of Ag.
• the colour in reflection was measured on the coated side for most of the samples. The results are summarized in the following table. All the values are obtained according to the Cielab system (D65, 10°). The light transmission integrated on the visible wavelengths has also been measured from some samples in D65, 2°.

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• Geochemistry & Mineralogy (AREA)
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• Surface Treatment Of Glass (AREA)
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• 2007
  • 2007-06-20 KR KR1020097001339A patent/KR101392110B1/ko not_active Expired - Fee Related
  • 2007-06-20 SG SG2011045325A patent/SG172722A1/en unknown
  • 2007-06-20 CN CN2007800230105A patent/CN101473058B/zh not_active Expired - Fee Related
  • 2007-06-20 WO PCT/EP2007/056109 patent/WO2007147832A1/en not_active Ceased
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  • 2007-06-20 AU AU2007263059A patent/AU2007263059A1/en not_active Abandoned
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• 2008
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