EP1718571A2 - Glasplatte zum aufbringen einer metallabscheidung, die gegenüber einer möglicherweise durch eine derartige abscheidung induzierten verfärbung beständig ist - Google Patents

Glasplatte zum aufbringen einer metallabscheidung, die gegenüber einer möglicherweise durch eine derartige abscheidung induzierten verfärbung beständig ist

Info

Publication number
EP1718571A2
EP1718571A2 EP05728064A EP05728064A EP1718571A2 EP 1718571 A2 EP1718571 A2 EP 1718571A2 EP 05728064 A EP05728064 A EP 05728064A EP 05728064 A EP05728064 A EP 05728064A EP 1718571 A2 EP1718571 A2 EP 1718571A2
Authority
EP
European Patent Office
Prior art keywords
glass
plate according
species
equal
bath
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP05728064A
Other languages
English (en)
French (fr)
Inventor
Sylvie Abensour
Géraldine DUISIT
Catherine Goulas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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
Application filed by Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP1718571A2 publication Critical patent/EP1718571A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00Shaping glass in contact with the surface of a liquid
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3607Coatings of the type glass/inorganic compound/metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00Shaping glass in contact with the surface of a liquid
    • C03B18/02Forming sheets
    • C03B18/18Controlling or regulating the temperature of the float bath; Composition or purification of the float bath
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00Shaping glass in contact with the surface of a liquid
    • C03B18/02Forming sheets
    • C03B18/20Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3642Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3655Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3668Surface 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
    • C03C17/3673Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C19/00Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/31Pre-treatment
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20Constructional details
    • H01J2211/34Vessels, containers or parts thereof, e.g. substrates
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth 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)
EP05728064A 2004-02-19 2005-02-18 Glasplatte zum aufbringen einer metallabscheidung, die gegenüber einer möglicherweise durch eine derartige abscheidung induzierten verfärbung beständig ist Withdrawn EP1718571A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0450314A FR2866644B1 (fr) 2004-02-19 2004-02-19 Plaque de verre destinee a recevoir un depot metallique et resistant a la coloration susceptible d'etre provoquee par un tel depot
PCT/FR2005/050104 WO2005080278A2 (fr) 2004-02-19 2005-02-18 Plaque de verre destinee a recevoir un depot metallique et resistant a la coloration susceptible d'etre provoquee par un tel depot.

Publications (1)

Publication Number Publication Date
EP1718571A2 true EP1718571A2 (de) 2006-11-08

Family

ID=34834217

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05728064A Withdrawn EP1718571A2 (de) 2004-02-19 2005-02-18 Glasplatte zum aufbringen einer metallabscheidung, die gegenüber einer möglicherweise durch eine derartige abscheidung induzierten verfärbung beständig ist

Country Status (8)

Country Link
US (1) US20080038543A1 (de)
EP (1) EP1718571A2 (de)
JP (1) JP2007523038A (de)
KR (1) KR20060129020A (de)
CN (1) CN1980868A (de)
FR (1) FR2866644B1 (de)
TW (1) TW200531947A (de)
WO (1) WO2005080278A2 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5282572B2 (ja) * 2006-11-10 2013-09-04 旭硝子株式会社 フラットパネルディスプレイ用ガラス基板およびその製造方法、ならびにそれを用いたディスプレイパネル
EP2371775A1 (de) * 2008-12-25 2011-10-05 Asahi Glass Company Limited Glassubstrat und herstellungsverfahren dafür
JP2011011951A (ja) * 2009-07-03 2011-01-20 Asahi Glass Co Ltd フラットパネルディスプレイ用ガラス基板およびその製造方法、ならびにそれを用いたディスプレイパネル
BE1019988A3 (fr) * 2011-05-24 2013-03-05 Agc Glass Europe Substrat verrier transparent portant un revetement de couches successives.
CN103619764B (zh) * 2011-07-01 2017-03-01 旭硝子株式会社 化学强化用浮法玻璃
JP7306502B2 (ja) * 2019-07-12 2023-07-11 Agc株式会社 膜付きガラス基板及びその製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2748469B1 (fr) * 1996-05-07 1998-07-31 Thomson Csf Utilisation d'une barriere en nitrure pour eviter la diffusion d'argent dans du verre
JPH10302648A (ja) * 1997-04-30 1998-11-13 Asahi Glass Co Ltd プラズマディスプレイ用ガラス基板
JP2001270740A (ja) * 2000-01-19 2001-10-02 Nippon Sheet Glass Co Ltd ガラス物品及びディスプレイ用ガラス基板
FR2803843B1 (fr) * 2000-01-19 2004-06-25 Nippon Sheet Glass Co Ltd Article en verre et substrat en verre pour un ecran

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005080278A2 *

Also Published As

Publication number Publication date
FR2866644B1 (fr) 2007-02-09
WO2005080278A3 (fr) 2007-03-08
WO2005080278A2 (fr) 2005-09-01
FR2866644A1 (fr) 2005-08-26
CN1980868A (zh) 2007-06-13
US20080038543A1 (en) 2008-02-14
KR20060129020A (ko) 2006-12-14
JP2007523038A (ja) 2007-08-16
WO2005080278A8 (fr) 2007-04-26
TW200531947A (en) 2005-10-01

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