• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The subject of the invention is a material comprising a glass sheet coated on at least a part of one of its faces with a stack of thin layers comprising at least one layer based on a nitride, said stack being coated on with least part of its surface of an enamel layer comprising bismuth, said stack further comprising, in contact with the enamel layer, a layer, said contact layer, which is based on an oxide.
    公开号:FR3074167A1
    申请号:FR1761391
    申请日:2017-11-30
    公开日:2019-05-31
    发明作者:Juliette JAMART
    申请人:Saint Gobain Glass France SAS；Compagnie de Saint Gobain SA；
    IPC主号:
    专利说明:

    The invention relates to the field of materials comprising a glass sheet coated with a stack of thin layers. Such materials are intended to form or be incorporated into glazing for buildings or for motor vehicles.
    Stacks of thin layers confer various properties to glazing, for example optical (reflective or anti-reflective layers), energetic (solar control and / or low-emissivity) or electrical conduction (used for example for glazing) properties. heated).
    The glass sheets are sometimes coated, on at least part of their surface, with a layer of enamel. An enamel is a mineral material formed from a composition comprising at least one pigment and at least one glass frit. A glass frit consists of fine particles of a glass with a low melting point, which under the effect of a thermal baking treatment softens and adheres to the glass sheet. This forms a mineral layer, generally opaque, with high chemical and mechanical resistance, adhering perfectly to the glass while maintaining the pigment particles. The enamel layers can have a decorative or aesthetic function, but also a protective function. The enamel layers can for example be deposited on the periphery of glazing in order to conceal and protect from ultraviolet radiation the polymeric seals used to fix the glazing to the load-bearing structure of the building or on the bodywork bay.
    Certain known glazings comprise sheets of glass coated, on the same face, with a stack of thin layers and then with a layer of enamel.
    example in
    Through the building sector, there are glazings called "lighters", used for the facades of buildings, and in which the glass sheet is entirely covered with a layer of colored and decorative enamel. Layers of solar control are sometimes placed under the enamel layer in order to limit the heating of the building under the effect of solar radiation. The enamels used in these applications do not contain bismuth, however, and few compatibility problems between
    The stack of thin layers and the enamel layer were encountered.
    On the other hand, when a glazing coated with a stack of thin layers must be provided with an enamel layer containing bismuth, it is customary to first remove the stack of thin layers at the places where the layer d enamel must be applied, for example using abrasives, so that
    The enamel is deposited in direct contact with the glass sheet and to avoid any problems of adhesion between the enamel layer and the stack of thin layers. It has furthermore been found that enamel layers comprising bismuth deposited directly on stacks of thin layers often exhibit degraded optical and chemical resistance properties.
    Alternatively, application WO 2014/133929 proposes the idea of using special glass frits capable during cooking of dissolving the stack of thin layers in order to fix themselves to the glass. However, such methods are expensive.
    The object of the invention is to provide glass sheets coated with a stack of thin layers and with an enamel layer which are less costly to produce, and such that the enamel exhibits good optical and adhesion properties. , and chemical resistance.
    To this end, the subject of the invention is a material comprising a glass sheet coated on at least part of one of its faces (hereinafter the first face) with a stack of thin layers comprising at least one base layer. of a nitride, said stack being coated on at least part of its surface with an enamel layer comprising bismuth, said stack further comprising, in contact with the enamel layer, a layer, called contact layer , which is based on an oxide.
    The invention also relates to a method of manufacturing a material according to the invention, comprising depositing a stack of thin layers comprising at least one layer based on a nitride on at least part of a face of a sheet of glass, then the deposition, on at least part of the surface of said stack, of an enamel layer comprising bismuth.
    Contrary to what is proposed in the request
    WO 2014/133929 mentioned above,
    The stack of thin layers is not degraded by the deposition of material according to the invention therefore has,
    1'émail. The superimposed, a stack of thin layers and then a layer of enamel, the latter not being in contact with the glass sheet. The presence of a contact layer makes it possible to make compatible the enamel layers comprising bismuth and the stacks of thin layers comprising at least one nitride layer, in the sense that no major optical or mechanical defect is observed after cooking the enamel. The inventors have been able to demonstrate that the defects observed when an enamel layer comprising bismuth was baked in contact with a stack of layers comprising at least one layer of nitride were due to the appearance of bubbles within the enamel, near the interface between the stack and the enamel. These bubbles cause a significant drop in adhesion of the enamel, modify its optical appearance and reduce its chemical resistance, in particular to acids. Using a contact layer removes
    The appearance of bubbles, or at least to offset the temperature of appearance of these bubbles beyond the temperatures used for cooking
    Enamel, especially beyond the bending temperatures of glass.
    The glass sheet is preferably flat, in particular when the material is intended for glazing for the building, or curved, in particular when the material is intended for glazing for the automobile. The glass sheet is generally flat when the stack of thin layers and then the enamel layer is deposited, and can then be curved. The glass is typically a soda-lime-silica glass, but other glasses, for example borosilicates or aluminosilicates can also be used. The glass sheet is preferably obtained by floating, that is to say by a process consisting in pouring molten glass onto a bath of molten tin. The glass sheet can be reinforced mechanically, in particular hardened or thermally toughened. To do this, the glass sheet is reheated to a temperature of around 600 ° C. or above, a treatment which can lead, if desired, to bending of the glass, then cooled rapidly in order to create compressive stresses on its surface. . The enamel firing preferably takes place during this heat treatment. The glass sheet can be clear or tinted, for example green, blue, gray or bronze. The glass sheet preferably has a thickness in a range from 0.7 to 19 mm, in particular from 1 to 10 mm, particularly from 2 to 6 mm, or even from 2 to 4 mm.
    The glass sheet is preferably coated with the stack of thin layers over at least 70%, in particular 80%, or even over the entire surface of the first face. The stack is preferably coated with the enamel layer on at most 40%, in particular 30% and even 20%, even 15% of its surface.
    By “contact” in this text is meant physical contact. The expression “based on” preferably means the fact that the layer in question comprises at least 50% by weight of the material considered, in particular 60%, even 70% and even 80% or 90%. The layer may even essentially consist or consist of this material. By "essentially consist", it should be understood that the layer can include impurities without influencing its properties. The terms "oxide" or "nitride" do not necessarily mean that the oxides or nitrides are stoichiometric. They can indeed be substoichiometric, over-stoichiometric or stoichiometric.
    The stack comprises at least one layer based on a nitride as well as a contact layer based on an oxide.
    The at least one layer based on a nitride preferably comprises a nitride of at least one element chosen from aluminum, silicon, zirconium, titanium. It can comprise a nitride of at least two or three of these elements, for example a silicon and zirconium nitride, or a silicon and aluminum nitride. Preferably, the layer based on a nitride is a layer based on silicon nitride, more particularly a layer consisting essentially of a silicon nitride. When the silicon nitride layer is deposited by sputtering, it generally contains aluminum, since it is customary to dop the silicon targets with aluminum in order to accelerate the deposition rates.
    The at least one nitride-based layer preferably has a physical thickness in a range from 2 to 100 nm, in particular from 5 to 80 nm.
    Nitride-based layers are commonly used in many stacks of thin layers because they have advantageous blocking properties, in that they avoid the oxidation of other layers present in the stack, in particular functional layers which will be described below. The inventors have however been able to demonstrate that the presence of these layers does not make it possible to obtain the properties required in terms of adhesion, chemical resistance and aesthetics with enamels containing bismuth, unless a layer of contact above the nitride-based layers, in direct contact with the enamel layer.
    Preferably, the contact layer comprises an oxide of at least one element chosen from aluminum, silicon, titanium, zinc, zirconium, tin. The contact layer can comprise an oxide of at least two or three of these elements, for example a zinc and tin oxide, or a silicon and aluminum oxide.
    The contact layer is advantageously a layer based on silicon oxide, more particularly a layer consisting essentially of a silicon oxide. When the silicon oxide layer is deposited by sputtering, it generally contains aluminum, since it is customary to dop the targets of silicon with aluminum in order to accelerate the deposition rates.
    The contact layer preferably has a physical thickness of at least 40 nm, or even 50 nm and even 80 or 100 nm, or even 150 or 200 nm. This thickness is preferably at most 2 μm, in particular 1 μm, even 500 nm and even 100 nm. The inventors have been able to demonstrate that the increase in the thickness of the contact layer makes it possible to shift the appearance of bubbles at the interface between the coating and the enamel towards higher temperatures. The increase in the thickness of the contact layer is therefore favorable for obtaining good properties in terms of adhesion, chemical resistance and aesthetics of the enamel containing bismuth. As detailed later in the present description, a smaller thickness can however be compensated by the choice of particular enamel compositions, called "preferred compositions".
    Preferably, at least one layer based on a nitride is in contact with the contact layer.
    The stack preferably comprises at least one functional layer, in particular an electrically conductive functional layer. The functional layer is preferably between two thin dielectric layers, at least one of which is a nitride-based layer. Other possible dielectric layers are for example layers of oxides or oxynitrides.
    At least one electrically conductive functional layer is advantageously chosen from metallic layers, in particular silver or niobium, and layers of a transparent conductive oxide, especially chosen from indium tin oxide, tin oxides doped (eg fluorine or antimony), doped zinc oxides (eg aluminum or gallium). These layers are particularly appreciated for their low emissivity, which gives the glazing excellent thermal insulation properties. In glazing fitted to land vehicles, in particular motor vehicles, railways, or even air or maritime vehicles, low-emitting glazing makes it possible, in hot weather, to reflect some of the solar radiation outwards, and therefore to limit the heating of the passenger compartment of said vehicles, and if necessary to reduce air conditioning expenses. Conversely, in cold weather, these glazings make it possible to conserve heat within the passenger compartment, and consequently to reduce the energy effort of heating. It is the same in the case of glazing fitted to buildings.
    The stack of thin layers preferably comprises at least one layer of indium tin oxide. Its physical thickness is preferably between 30 and 200 nm, in particular between 40 and 150 nm. This layer is advantageously between two layers based on nitride, in particular silicon nitride. The contact layer is preferably based on silicon oxide.
    At least part of the stack of thin layers can be deposited by various known techniques, for example by chemical vapor deposition (CVD), or by sputtering, in particular assisted by magnetic field (magnetron process).
    According to one embodiment, the entire stack of thin layers is deposited by sputtering, in particular assisted by magnetic field. In this process, a plasma is created under a high vacuum in the vicinity of a target comprising the chemical elements to be deposited. The active plasma species, by bombarding the target, tear off said elements, which are deposited on the glass sheet, forming the desired thin layer. This process is said to be “reactive” when the layer consists of a material resulting from a chemical reaction between the elements torn from the target and the gas contained in the plasma. The major advantage of this process lies in the possibility of depositing on a single line a very complex stack of layers by successively scrolling the glass sheet under different targets, this generally in a single device.
    According to another embodiment, the entire stack of thin layers, with the exception of the contact layer, is deposited by sputtering, in particular assisted by magnetic field. In this case, the contact layer is sol-gel. In the latter precursors of the glass sheet layer by spraying, the curtain, etc. The soil preferably contains deposited by process process, a soil containing to be produced is deposited on various means, such as laminar coating , the roll preferably of organometallic precursors of the layer to be produced, for example of
    The dried orthosilicate is then annealed in order to densify it. This process makes it possible to obtain thicker contact layers than by the sputtering process.
    The physical thickness of the contact layer can thus be at least 100, in particular 200 and even 500 nm, or even pm and more.
    The enamel layer is preferably formed from a composition comprising at least one pigment and at least one glass frit of bismuth borosilicate, preferably a glass frit of bismuth and zinc borosilicate, as explained in the continuation of the text. The enamel layer preferably does not include lead oxide.
    The enamel composition generally also comprises an organic medium, intended to facilitate the application of the composition to the substrate as well as its temporary adhesion to the latter, and which is eliminated during the firing of the enamel. The medium typically includes solvents, thinners, oils and / or resins. In the present text, the term “enamel composition” describes the liquid composition which is used to deposit, on the glass sheet, a layer of wet enamel. The term "enamel layer" is used to describe the final layer after baking, while the term "wet enamel layer" is used to describe the enamel layer before baking.
    The enamel layer is preferably deposited by screen printing. To do this, we have on the glass sheet a screen printing screen, which includes meshes some of which are closed, then we deposit the enamel composition on the screen, then we apply a doctor blade in order to force the composition of enamel to cross the screen in areas where the mesh of the screen is not closed, so as to form a layer of wet enamel.
    The deposition of the enamel layer comprises a baking step, preferably at a temperature of at least 600 and even 650 ° C, and at most 700 ° C, preferably during a bending treatment and / or tempering of the glass sheet.
    The pigments preferably comprise one or more oxides chosen from oxides of chromium, copper, iron, manganese, cobalt, nickel. It may, for example, be copper and / or iron chromates.
    In a preferred embodiment of the invention, the enamel layer is based on bismuth and zinc borosilicate.
    More particularly, the enamel layer advantageously has a chemical composition (“preferred composition”) comprising the following oxides, in weight contents varying within the limits mentioned below:
    b 2 o 3 1-10%, especially 2-8% SiO 2 15-40%, especially 20-35% B12O3 5-45%, especially 10-40% ZnO 7-25%, especially 8-20%. The composition advantageously comprises at least one
    alkaline oxide, in particular potassium oxide, in contents of at most 5%. The composition preferably contains titanium oxide (TiCt), in contents ranging from 1 to 10%, in particular from 2 to 7%. The composition also includes pigments, for example copper chromates. In this case the typical Cr 2 O 3 and CuO contents range from 8 to 20% and from 3 to 12% respectively. The ZnO / Bi 2 O3 mass ratio is advantageously at least 0.2, in particular between 0.2 and 1.
    The chemical composition of the enamel can be determined by conventional chemical analysis methods, in particular from the fired enamel. It is therefore a question of the chemical composition of the baked enamel layer, and not of the glass frit used to form the enamel.
    These preferred compositions have been found to be particularly compatible with stacks of thin layers comprising at least one layer of nitride. If the contact layer is still necessary, it has however been found that the use of these preferred compositions makes it possible to offset the appearance of bubbles towards high temperatures, or even to completely eliminate this appearance, and therefore to obtain excellent results in terms of adhesion, chemical resistance and optical properties, even for very small thicknesses of contact layers. Without the exact reason being known, these advantageous effects are in particular due to the presence of a minimum quantity of zinc oxide in the composition.
    Preferably the enamel layer is opaque, black in color. It advantageously forms a strip at the periphery of the glass sheet. In this way, the enamel layer is able to conceal and protect against ultraviolet radiation joints, connectors, or even sensors.
    The invention also relates to a glazing unit comprising at least one material as described above. Such glazing can be as well a glazing for a building as a glazing for a transport vehicle, land, rail, sea or air.
    This glazing is in particular a glazing for a motor vehicle roof, in which the face of the glass sheet supporting the stack of thin layers and the enamel layer is the internal face of the glazing. The glass sheet is preferably mechanically reinforced (in particular by thermal toughening) and / or laminated with at least one other glass sheet by means of a laminating interlayer. The laminating interlayer is for example a sheet of polyvinyl butyral (PVB). Such glazing can for example be composed of a sheet of thermally toughened tinted glass coated on the internal face of the glazing (that intended to be turned towards and in contact with the interior of the vehicle interior) of a stack containing a layer of indium tin oxide between two layers of silicon nitride, the contact layer being a layer of silicon oxide, then a layer of enamel deposited on the periphery of the glass sheet. The glass sheet can also be laminated by means of a PVB interlayer with another glass sheet, located more outside of the passenger compartment.
    In this case, at least one glass sheet or the PVB interlayer is preferably tinted.
    The exemplary embodiments which follow illustrate the invention without limitation.
    Glass sheets coated with stacks of thin layers were then enamelled by screen printing and then baking the enamel.
    The stack studied here, denoted El, is a low emissive stack deposited by magnetron sputtering and comprising successively, from the glass sheet a layer of silicon nitride (30 nm), a layer of silicon oxide (15-20 nm), a layer of indium tin oxide (ITO, 70-80 nm), a layer of silicon nitride (5-10 nm) and finally a contact layer of silicon oxide (variable thickness noted X below).
    The comparative stack (E2) differs from the stack El in that it does not include a contact layer within the meaning of the invention, and therefore ends in a layer of silicon nitride.
    Different enamel compositions were tested, the chemical composition by weight of which is indicated in Table 1 below.
    AT B VS D E F B2O3 7.4 6, 1 3.4 3.7 4.5 4.3 SiO 2 32.7 24.7 27, 6 28.1 29, 1 28.0 B12O3 - 32.1 28.3 33.0 24.4 14, 1 ZnO 15, 9 5.0 13.3 10, 8 12.4 16.3 Na2O 9, 9 - - - - - T1O2 5.4 3.2 3.4 3.4 4.0 4.9 A12O3 2.2 0.8 0.7 0.7 0.8 0, 6 K 2 O 2.4 2, 6 2, 6 2.2 2.7 2.7 Cr 2 O 3 16.0 16.5 12.9 11.0 12.8 17.9 MnO 2 - - - - 3, 6 - CuO 8, 0 9, 0 6, 8 6, 2 5.1 9, 0 Other 0.1 - 1.0 0.8 0, 6 2.2
    Table 1
    Enamel A (comparative) is an enamel based on zinc and not on bismuth. Enamels B to F are enamels comprising bismuth, more particularly based on bismuth and zinc borosilicate, and can therefore be used in the context of the invention. Enamels C to F also have the preferred composition described above, rich in zinc oxide. The enamel layer was deposited by screen printing, in a wet layer thickness of 25 μm.
    Table 2 below summarizes the results obtained, indicating for each example the nature of the stack, if applicable the physical thickness of the contact layer, denoted X and expressed in nanometers, the enamel used, and finally the temperature at which bubbles appear at the interface between the enamel layer and the stack, denoted Tx and expressed in ° C.
    The temperature Tx is determined by baking the enamel at different temperatures and detecting the appearance of bubbles by visual observation and measurement of the reflectance of the enamel after baking. The appearance of bubbles in fact causes a drop in the reflectance of the enamel layer.
    stacking X (nm) E-mail Tx (° C) Cl E2 - AT > 710 C2 E2 - B <600 1 El 50 B 668 2 El 33 B 653 3 El 45 B 662 4 El 50 VS > 710 5 El 50 D > 710 6 El 50 E > 710 7 El 50 F > 710
    Table 2
    A Tx temperature noted> 710 ° C means that no bubbling is observed at 710 ° C. It is therefore possible either that no bubbling occurs, or that bubbles appear, but in any event at a higher temperature.
    Comparative example Cl, which uses a zinc enamel, shows that these enamels do not pose problems of compatibility with stacks comprising nitrides, even in the absence of a contact layer. These enamels, however, are not suitable for bending processes for automobile glass, since they are liable at high temperature to adhere to the bending tools.
    Comparative example C2 shows a contrario that bismuth enamels pose compatibility problems with stacks comprising nitride layers, since bubbling appears before 600 ° C. However, bending or quenching treatments generally involve temperatures above this value.
    The examples according to the invention 1 to 3 show that the addition of a contact layer makes it possible to offset the appearance of the bubbles towards higher temperatures, and this all the more that this layer is thick. It is therefore possible to obtain good results with this combination of stacking and enamel when the bending does not involve excessively high temperatures. Some defects may appear at the edge of the glazing, where the temperatures are highest.
    For Examples 4 to 7, on the other hand, which use the preferred enamel compositions described above, no bubbling is observed at temperatures as high as 710 ° C. Good results are therefore obtained for all the bending temperatures used in practice.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Material comprising a glass sheet coated on at least part of one of its faces with a stack of thin layers comprising at least one layer based on a nitride, said stack being coated on at least part of its surface of an enamel layer comprising bismuth, said stack further comprising, in contact with the enamel layer, a layer, called contact layer, which is based on an oxide.
    [2" id="c-fr-0002]
    2. Material according to claim 1, wherein the at least one layer based on a nitride comprises a nitride of at least one element chosen from aluminum, silicon, zirconium, titanium, in particular is a layer based on silicon nitride.
    [3" id="c-fr-0003]
    3. Material according to one of the preceding claims, in which the contact layer comprises an oxide of at least one element chosen from aluminum, silicon, titanium, zinc, zirconium, tin, in particular is a layer based on silicon oxide.
    [4" id="c-fr-0004]
    4. Material according to one of the preceding claims, in which at least one layer based on a nitride is in contact with the contact layer.
    [5" id="c-fr-0005]
    5. Material according to one of the preceding claims, in which the contact layer has a physical thickness of at least 40 nm.
    [6" id="c-fr-0006]
    6. Material according to one of the preceding claims, such that the stack comprises at least one functional layer, in particular an electrically conductive functional layer.
    [7" id="c-fr-0007]
    7. Material according to the preceding claim, in which at least one electrically conductive functional layer is chosen from metal layers, in particular silver or niobium, and layers of a transparent conductive oxide, in particular chosen from indium oxide and of tin, doped tin oxides, doped zinc oxides.
    [8" id="c-fr-0008]
    8. Material according to one of the preceding claims, such that the enamel layer is based on bismuth and zinc borosilicate.
    [9" id="c-fr-0009]
    9. Material according to the preceding claim, such that the enamel layer has a chemical composition comprising the following oxides, in weight contents varying within the limits mentioned below:
    B2O3 1-10% especially 2-8% SiO 215-40% , especially 20-35% B12O3 5-45% especially 10-40% ZnO 7-25% especially 8-20%.
    [10" id="c-fr-0010]
    10. Material according to one of the preceding claims, such that the enamel layer is opaque, of black tint, and forms a strip at the periphery of the glass sheet.
    [11" id="c-fr-0011]
    11. Glazing comprising at least one material according to one of the preceding claims.
    [12" id="c-fr-0012]
    12. Glazing according to the preceding claim, which is a glazing for the roof of a motor vehicle, wherein the face of the glass sheet supporting the stack of thin layers and the enamel layer is the internal face of the glazing, said sheet of glass being mechanically reinforced and / or laminated with at least one other sheet of glass by means of a laminating interlayer.
    [13" id="c-fr-0013]
    13. A method of manufacturing a material according to one of claims 1 to 10, comprising depositing a stack of thin layers comprising at least one layer based on a nitride on at least part of a face
    5 of a glass sheet, then the deposition, on at least part of the surface of said stack, of an enamel layer comprising bismuth.
    [14" id="c-fr-0014]
    14. Method according to the preceding claim, in which at least part of the stack of layers
    10 thin is deposited by chemical vapor deposition or by sputtering.
    [15" id="c-fr-0015]
    15. Method according to one of claims 13 and 14, in which the deposition of the enamel layer comprises a firing step at a temperature of at least 600 ° C,
    15 in particular during a bending and / or tempering treatment of the glass sheet.
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    同族专利:
    公开号 | 公开日
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    WO2019106264A1|2019-06-06|
    EP3717421A1|2020-10-07|
    BR112020010109A2|2020-10-13|
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    KR20200088407A|2020-07-22|
    MA51209A|2020-10-07|
    RU2020121405A3|2021-12-30|
    FR3074167B1|2019-11-15|
    JP2021504282A|2021-02-15|
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    法律状态:
    2018-11-20| PLFP| Fee payment|Year of fee payment: 2 |
    2019-05-31| PLSC| Publication of the preliminary search report|Effective date: 20190531 |
    2019-11-28| PLFP| Fee payment|Year of fee payment: 3 |
    2020-11-30| PLFP| Fee payment|Year of fee payment: 4 |
    2021-11-30| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1761391A|FR3074167B1|2017-11-30|2017-11-30|GLASS SHEET COATED WITH A STACK OF THIN LAYERS AND AN ENAMEL LAYER.|
    FR1761391|2017-11-30|FR1761391A| FR3074167B1|2017-11-30|2017-11-30|GLASS SHEET COATED WITH A STACK OF THIN LAYERS AND AN ENAMEL LAYER.|
    CN201880003967.1A| CN110099873A|2017-11-30|2018-11-23|Coated with stack of thin and with the glass plate of glaze layer|
    EP18819542.4A| EP3717421A1|2017-11-30|2018-11-23|Glass sheet coated with a stack of thin layers and with an enamel layer|
    PCT/FR2018/052965| WO2019106264A1|2017-11-30|2018-11-23|Glass sheet coated with a stack of thin layers and with an enamel layer|
    RU2020121405A| RU2020121405A3|2017-11-30|2018-11-23|
    BR112020010109-5A| BR112020010109A2|2017-11-30|2018-11-23|glass sheet coated with a stack of thin layers and with a layer of enamel|
    JP2020529348A| JP2021504282A|2017-11-30|2018-11-23|Glass sheet coated with thin stack and enamel layer|
    CA3082049A| CA3082049A1|2017-11-30|2018-11-23|Glass sheet coated with a stack of thin layers and with an enamel layer|
    US16/767,453| US11192821B2|2017-11-30|2018-11-23|Glass sheet coated with a stack of thin layers and with an enamel layer|
    KR1020207017139A| KR20200088407A|2017-11-30|2018-11-23|Glass sheet coated with a stack of thin layers and an enamel layer|
    MA051209A| MA51209A|2017-11-30|2018-11-23|SHEET OF GLASS COATED WITH A STACK OF THIN LAYERS AND A LAYER OF ENAMEL.|
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