Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B18/00—Shaping glass in contact with the surface of a liquid
• • 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
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3607—Coatings of the type glass/inorganic compound/metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B18/00—Shaping glass in contact with the surface of a liquid
  • C03B18/02—Forming sheets
  • C03B18/18—Controlling or regulating the temperature of the float bath; Composition or purification of the float bath
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B18/00—Shaping glass in contact with the surface of a liquid
  • C03B18/02—Forming sheets
  • C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
• • 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
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
• • 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
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3642—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing a metal layer
• • 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
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3655—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing at least one conducting layer
• • 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
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
  • C03C17/3673—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use in heating devices for rear window of vehicles
• • 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
  • C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
• • 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
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
• • 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
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
• • 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
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/31—Pre-treatment
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
  • H01J2211/20—Constructional details
  • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent

Definitions

• the present invention relates to a glass plate intended to constitute a plate-shaped product provided on at least part of at least one of its faces with a metallic deposit, said plate being resistant to coloration due to at least one metallic species M "* of said metallic deposit, which species, under the conditions of manufacture and / or use of the product, is liable to migrate into the glass from its surface and then to undergo a reduction in the species M ⁇ responsible for the coloration.
• the metallic species which can induce an undesirable coloration are in particular Ag, Cu and Au. Such undesirable colourations appear, due to interactions between the components of the glass and these metallic species, either during manufacturing treatments.
• products more particularly when these treatments include heating steps favoring the migration of the species responsible for the unwanted coloration da ns glass, and also throughout the aging and use of the products, in particular when the use involves high temperature and / or electronic bombardment, products in plates having received a metallic deposit presenting risks of coloring of the glass are called "substrates" in the field of electronics.
• substrates in the field of electronics.
• These are in particular the faces of television screens, computer screens, in general, emissive screens, such as plasma screens (Plasma Display Panel), electroluminescent screens and cold cathode screens (Field Emission Display). ).
• Other products include flat lamps, gradient index microlenses, as well as heated automobile rear glasses.
• This discoloration anomaly can appear at different times: - during the manufacture of the screen if it was necessary to conduct a high temperature treatment, the temperature rise favoring the migration of Ag + ions, * - during the 'use for example, where the rise in temperature or electronic bombardment will further promote coloring; by normal aging of the screen, the Ag + ions migrate more over time, in particular when they are under tension.
• the same problems as with screens arise with flat lamps, microlenses and rear glasses. There is therefore a need to have a glass plate as defined above, having no coloration, under the conditions of manufacture and use of the finished products, such as screens.
• the present invention provides a solution to this problem.
• the glass plate according to the present invention is characterized in that it comprises at least on the surface and on at least one face sensitive to coloring a composition capable of limiting or blocking said migration and / or said reduction of the Vf * species.
• a composition capable of limiting or blocking said migration and / or said reduction of the Vf * species.
• n + is likely to migrate, a quantity of reducing agent capable of reducing the species M ft + which is at most equal to 1.40 ⁇ 10 ⁇ 7 mole / cm 2 , in particular at most equal to 7 ⁇ 10 ⁇ 8 mole / cm 2 and advantageously at most equal to 3.5 x 10 -8 mole / cm 2 when the metallic species M * 1 " is Ag + .
• the reducing agent is chosen from elements with multiple oxidation degrees such as Fe, S, Sn, Sb and mixtures of these elements. Preferably, Fe, S and / or Sn are chosen.
• the protocol for this measurement is as follows; On a sheet of glass, a layer of metallic silver about 400 nm thick is deposited by sputtering. The sheet is then heated in air at 600 ° C. for 1 hour, then it is treated with nitric acid in order to remove the layer of surface silver.
• the profile of the silver in the surface layer of the glass is produced by S IMS: it has a bump corresponding to the reduction of the silver by the reducing agent.
• the quantity of reducing agent in moles per cm 2 , is obtained by measuring the silver content integrated over the thickness of the glass corresponding to the silver bump. This measurement expresses a quantity of reducing agent on the surface of the glass which should not be exceeded so that the M n + ions do not have the possibility of being reduced to the point of causing unacceptable coloring, a glass obtained by the "Float" process, on its face which has been in contact with the tin bath, has a greater content of reducing agent than on the opposite face. However, it will not be sufficient to simply apply the layer comprising the metal liable to migrate on this second face, which is less sensitive to coloring. It can also be emphasized that said quantity
• the ' of reducing agent according to the invention is that of glass as it is produced without an additional polishing step which * would have made it possible to reach the surface layer having the quantity of reducing agent sought.
• the latter is provided on the side (s) sensitive to coloring with a barrier layer to the migration of the species M n + , on which continuous or discontinuous functional layers are capable of adhering, and which is not liable to react chemically with said functional layers so as to deteriorate the properties thereof.
• the barrier layer is non-conductive.
• an additional layer of Si0 2 , SiOC or Si 3 N 4 different from the barrier layer can be applied to the barrier layer, before depositing the first functional layer.
• the anti-fouling layers of Ti0 2 and the conductive layers of iTO, of Sn0 s : F, of SnO. Sb and ZnOtAl barium does not enter the. content of alkaline earth metals only in a limited proportion, that is to say in an amount such that the content of BaO does not exceed 2% by weight of the glass composition.
• the glass plate of the present invention has an alkali metal content under conditions ensuring a so-called mixed alkali effect.
• the alkali metals are lithium, sodium and potassium.
• the alkali metals are sodium and potassium, present in the form of their corresponding oxides Na 2 0 and K 2 0 in molar quantities satisfying the following relationship: 0.35 ⁇ 2 0 / K? 0 + Na 2 0 ⁇ 0.65
• the latter has a weight content of alumina at most equal to 3% and / or a weight content of silica at least equal to 65%.
• the surface layer capable of limiting or blocking the migration or reduction of the species or species M n + advantageously has a thickness of less than 100 ⁇ m, preferably less than 50 ⁇ m, especially less than 20 ⁇ .
• the glass plate may have been produced in the form of a ribbon obtained by floating on a bath of molten metal, such as a tin bath, the face of the glass sensitive to the coloring in the finished product being that opposite to that which has been in contact
• the latter has a lower temperature of collector ("strain point") corresponding to the temperature at which the glass has a viscosity of the order of 10 14 ' 5 poises which is higher than 550 ° C, in particular higher than 580 ° C.
• strain point corresponding to the temperature at which the glass has a viscosity of the order of 10 14 ' 5 poises which is higher than 550 ° C, in particular higher than 580 ° C.
• its composition is chosen to allow its production under conditions which slow down the migration of Sn 2 * or Hz in the atmosphere side of glass ribbon.
• the H 2 content of the reducing atmosphere of Tsk + H 2 above the bath is lowered compared to normal working conditions to reduce the saturated vapor pressure of SnS and to limit the diffusion of H 2 in the atmosphere side.
• the temperature of the bath and that of the glass are also lowered compared to normal working conditions, the sulfate content of the glass being advantageously lowered compared to normal working conditions to reduce the SnS content.
• at least one of the following conditions has been met:
• the glass plate according to the present invention contains at least one element capable of coloring the glass in a color complementary to the risky color due to the diffusion of M n *, for example Co 2+ .
• a glass having the following composition corresponds to the present invention, the weight proportions of the constituents being as follows:
• the subject of the present invention is also a process for manufacturing a stain-resistant glass plate by a float process on a molten tin bath, characterized in that the float is carried out under the following conditions: glass viscosity corresponding to log ⁇
• 3.5, at a temperature at most equal to 1230 "C, preferably between 1180 and 1220 ° C ( ⁇ being expressed in dPa.s); bath temperature at most equal to 1220 ° C; - casting temperature glass on a tin bath of at most 1280 ° C.
• the present invention also relates to the application of a glass plate as defined above or obtained by the process as defined above, in the manufacture of glass products in the form of plates having received metallic deposits capable of generating coloration during treatments in particular at high temperature during their manufacture and / or during use due to interactions between the components of the glass and itself and these metals, in particular in the manufacture of emissive screens such as plasma screens, electroluminescent screens and cold cathode screens, lamps flat, microlens with index gradient and automotive rear glasses.
• emissive screens such as plasma screens, electroluminescent screens and cold cathode screens, lamps flat, microlens with index gradient and automotive rear glasses.
• EXAMPLES 1 to 3 These examples illustrate the effect of the pouring temperature of the glass and the content of f 2 in the tin bath on the coloring of the final glass.
• Classic silica-soda-lime glasses are produced in the form of a ribbon by floating on a tin bath under the defined conditions. below. These glasses have the following chromatic coordinates L *, a * and b * measured for a thickness of 6 mm, under illuminant Des by taking the colorimetric reference observer CE 1931. It is observed that the glasses of Examples 1 and 2 according to the invention have a lower value of b * than that of the glass of Example 3 (Comparative), which corresponds to a less significant yellow coloration.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Mechanical Engineering (AREA)
• Inorganic Chemistry (AREA)
• Glass Compositions (AREA)
• Surface Treatment Of Glass (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

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• 2004
  • 2004-02-19 FR FR0450314A patent/FR2866644B1/fr not_active Expired - Fee Related
• 2005
  • 2005-02-18 CN CNA2005800054706A patent/CN1980868A/zh active Pending
  • 2005-02-18 US US10/589,736 patent/US20080038543A1/en not_active Abandoned
  • 2005-02-18 EP EP05728064A patent/EP1718571A2/de not_active Withdrawn
  • 2005-02-18 JP JP2006553632A patent/JP2007523038A/ja active Pending
  • 2005-02-18 KR KR1020067016506A patent/KR20060129020A/ko not_active Withdrawn
  • 2005-02-18 WO PCT/FR2005/050104 patent/WO2005080278A2/fr not_active Ceased
  • 2005-02-21 TW TW094105057A patent/TW200531947A/zh unknown

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