• 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 part of one of its faces with a stack of thin layers, said stack being coated on at least part of its surface with a layer of enamel comprising zinc and less than 5% by weight of bismuth oxide, said stack further comprising, in contact with the enamel layer, a layer, called contact layer, which is based on an oxide, the physical thickness of said contact layer being at least 5 nm.
    公开号:FR3082840A1
    申请号:FR1855568
    申请日:2018-06-22
    公开日:2019-12-27
    发明作者:Juliette MARIA；Yann COHIN；Arnaud Huignard
    申请人:Saint Gobain Glass France SAS；Compagnie de Saint Gobain SA；
    IPC主号:
    专利说明:

    GLASS SHEET COATED WITH A STACK OF THIN LAYERS AND AN ENAMEL LAYER
    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 in building glazing or in parts of household appliances, such as oven doors.
    Stacks of thin layers give various properties to materials, for example optical properties (reflective or anti-reflective layers), energy (solar control and / or low emissivity layers) or electrical conduction (used for example for glazing 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 glass sheets used in oven doors to camouflage certain areas of the oven. Low-emissivity stacks are sometimes placed under the enamel layer to reduce heat exchange with the outside of the oven. There are also in the building sector glazing 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. Solar control stacks are sometimes placed under the enamel layer to limit the heating of the building under the effect of solar radiation. The enamel layers can also be used to create a certain design, by depositing the enamel in the form of any patterns, for example in applications on the facade, in partitions, in shower walls, etc.
    The inventors have been able to demonstrate that in the case of the use of enamels containing zinc and less than 5% by weight of bismuth oxide deposited on stacks of thin layers, the visual appearance of the enamel could strongly depend on the cooking temperature. Typically, whether it is in the enamelling of bare glass or of a glass coated with a stack of thin layers, there is a minimum baking temperature necessary to obtain good baking of the enamel and a good appearance. visual in reflection. For bare glass, the range of possible baking temperatures is wide, in the sense that an increase in the baking temperature of 50 or 100 ° C above this minimum baking temperature does not substantially alter the appearance. enamel reflection. On the other hand, in the case of a glass coated with a stack of thin layers, a sometimes minimal increase in the baking temperature relative to the minimum baking temperature can lead to a change in the appearance in reflection. The range of possible cooking temperatures, called ΔΤ, is then reduced. Thus, it has been observed that for stacks whose last layer (or one of the last layers) was based on silicon nitride, the range ΔΤ could be as low as 5 or 10 ° C.
    Low ranges ΔΤ are detrimental from the point of view of industrial production since obtaining products of homogeneous color requires the use of cooking equipment capable of heating the glass sheet very homogeneously. Even in the case of high-performance equipment, the edges of the glass sheet often experience temperatures slightly higher than the center, which can lead to color heterogeneities. Finally, in the case of layers of layers having a low emissivity, the areas lacking enamel are essentially heated by convection while the areas covered with enamel are heated by convection and radiation. Areas near enamel-free areas therefore experience lower temperatures than the others. It is therefore very difficult in the case of low ranges ΔΤ to obtain industrially perfectly homogeneous glass sheets in terms of visual appearance.
    The invention aims to solve these problems by proposing stacks for which the range Δ plage is high, making it possible to reduce the costs of industrial production.
    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 with a stack of thin layers, said stack being coated on at least part of its surface d '' an enamel layer comprising zinc and less than 5% by weight of bismuth oxide, said stack further comprising, in contact with the enamel layer, a layer, called contact layer, which is based on 'An oxide, the physical thickness of said contact layer being at least 5 nm.
    The subject of the invention is also a method of manufacturing a material according to the invention, comprising depositing a stack of thin layers on at least part of one face of a glass sheet, then depositing it, on at least part of the surface of said stack of an enamel layer comprising zinc and less than 5% by weight of bismuth oxide.
    The material according to the invention has, in a superimposed manner, a stack of thin layers 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 increase the range ΔΤ and therefore the visual uniformity of the material.
    The glass sheet is preferably flat, in particular when the material is intended for glazing for the building or oven doors, but it can also be curved. In the latter case, 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, 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. Depending on the applications, the stack can be coated with the enamel layer on at least 80%, or even 90% of its surface (case of lighters), or on at most 40%, in particular 30% and even 20%, even 15 % of its surface, often at the periphery of the glass sheet (case of oven doors, or even glazing incorporating a Marie-Louise). In the case of enamelled patterns intended to confer a certain design, this figure is typically between 5 and 80%.
    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.
    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 is preferably obtained by sputtering or by a sol-gel process. More than
    details on these processes are given in the following of text.The layer of contact present preferably a thickness physical at minus 10 nm, including 20 nm, 30 nm, 40 nm, even 50 nm and even 8 0 or 100 nm, or
    150 or 200 nm. This thickness is preferably at most
    2 pm, especially 1 pm or even 500 nm and even 100 nm. The increase of The thickness of the layer of contact East favorable to obtaining beaches ΔΤ high • stacking includes of preference at less a
    nitride-based layer.
    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, or even from 20 to 50 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, in particular near the enamel layer, was detrimental to obtaining high ΔΤ ranges. The invention is therefore particularly useful for stacks containing this type of layer.
    Preferably, at least one layer based on a nitride is in contact with at a distance of less than 5 nm from the advantages of the invention are the contact layer, or the contact layer. The most obvious for these stacks.
    The stack preferably comprises at least one functional layer, in particular an electrically conductive, solar control, or low emissivity 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 functional layer is advantageously chosen from:
    - metallic layers, in particular silver or niobium, layers of a transparent conductive oxide, in particular chosen from indium and tin oxide, doped tin oxides (for example fluorine or antimony) and doped zinc oxides (e.g. aluminum or gallium), and
    - layers based on niobium nitride.
    These layers are particularly appreciated for their low emissivity or their ability to filter solar radiation, which gives glazing excellent thermal insulation properties. Low-emissivity glazing makes it possible, in hot weather, to reflect some of the solar radiation towards the outside, and therefore to limit the heating of the interior of the dwellings, and if necessary to reduce the air conditioning expenses. Conversely, in cold weather, these glazings make it possible to conserve heat within the dwelling, and consequently to reduce the energy effort of heating. In the case of oven doors, the low-emissivity layers make it possible to reduce the heat emissions outside the oven, thus increasing the efficiency of the latter while limiting the risk of burns for users.
    According to one embodiment of the invention, 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.
    According to another embodiment of the invention, the stack of thin layers comprises at least one layer of silver, in particular one, two or three layers of silver. The total physical thickness in silver is preferably between 3 and 30 nm, in particular between 5 and 20 nm. The or each silver layer is preferably surrounded by dielectric layers, some of which are based on nitride, in particular silicon nitride.
    According to another embodiment of the invention, the stack of thin layers comprises a layer of niobium or niobium nitride. The functional layer is preferably surrounded by dielectric layers, some of which are based on nitride, in particular silicon nitride.
    Alternatively, the stack may not include a functional layer. The stack can thus, for example, comprise a succession of thin layers, none of which, individually, confers a particular function, but which together make it possible to obtain optical effects, in particular by means of multiple interference. For example, they may be anti-reflective stacks or, on the contrary, reflective stacks.
    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 (including the contact layer) 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 preferably deposited by the sol-gel process. In this latter process, a soil containing precursors of the layer to be produced is deposited on the glass sheet by various means, such as spraying, the curtain, the laminar coating, the roller, the screen printing, etc. soil preferably contains organometallic precursors of the layer to be produced, for example tetraethyl orthosilicate (TEOS). The layer is then dried and 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 nm, in particular 200 nm and even 500 nm, or even 1 μm and more.
    The enamel layer is preferably formed from a composition comprising at least one pigment and at least one glass borosilicate zinc frit. The enamel layer preferably does not include lead oxide. The weight content of bismuth oxide in the enamel layer is advantageously at most 4%, in particular 3%, even 2%, and even 1%. It is preferably zero.
    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 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. They may, for example, be copper and / or iron chromates.
    Preferably the enamel layer is opaque, black or gray in color. Any other color is possible, however: white, red, blue, green, yellow, etc. The enamel layer can cover the entire surface of the glass sheet, or even be placed on the periphery of the glass sheet.
    The invention also relates to glazing, in particular a sill, or a door for an appliance comprising at least one material as described above.
    The glazing is preferably a glazing for building. It may in particular be a sill, a part of the facade, a partition, a shower wall, comprising a stack of thin layers conferring properties of low emissivity and / or solar control or special optical effects. The enamel can cover the entire glazing (case of the lighter) or only a part, either to hide and / or protect elements behind the glazing, or to create a design.
    The material according to the invention can be laminated to another glass sheet by means of a laminating interlayer, in particular made of polyvinlybutyral (PVB). The stack of thin layers is then preferably on the side of the interlayer. In this case, the use of a silica-based contact layer is particularly advantageous because the silica has the same refractive index as the PVB, so that it has no impact on the optics of the final material.
    The appliance door is preferably an oven door or a cooling device door (positive or negative cold).
    The oven door preferably comprises at least one exterior glass, close to the user, and an interior glass, close to the interior of the oven. In this case, the material according to the invention can be an interior glass, in particular coated with a low-emissivity stack, or an exterior glass, in particular coated with a stack conferring optical effects, for example a reflective stack.
    The cooling device door can in particular be single glazing or multiple glazing, in particular double glazing. The material according to the invention, integrated into this door, is preferably coated with a low-emissivity stack.
    The exemplary embodiments which follow illustrate the invention without limitation.
    Comparative example 1
    In this comparative example, a sheet of clear soda-lime glass was coated by screen printing with a layer of black enamel. The enamel, based on zinc borosilicate, comprises (by weight) 8% of B2O3, 32% of S1O2, 17% of ZnO, 4% of T1O2, 2% of A ^ Ch, 22% of C ^ Ch and 12% CuO. The composition of the enamel is free of bismuth oxide.
    The range ΔΤ was then evaluated in the following manner. A sample is placed in a gradient oven to cook the enamel at a different temperature depending on the area of the sample. A measurement of the clarity L * in non-specular reflection as a function of the zone makes it possible to evaluate the amplitude of the range ΔΤ.
    The range ΔΤ is greater than 50 ° C. A value of L * less than 5 (characteristic of a black color) is obtained.
    Comparative example 2
    Comparative example 2 differs from the previous one in that the soda lime clear glass sheet was previously coated by magnetron cathode sputtering with a stack of thin layers with low emissivity consisting, from the glass, of the following layers: S1N X ( 40 nm) / NiCr (1 nm) / Ag (7 nm) / NiCr (0.5 nm) / S1N X (40 nm) / TiZrO x (3 nm).
    The enamel layer was therefore deposited in contact with this stack of thin layers.
    In this case the range ΔΤ was only 5 ° C. L * values of 7 were obtained, characteristic of a shallower black than in the case of Comparative Example 1.
    Example 1
    Example 1 differs from Comparative Example 2 in that a silica contact layer deposited by a sol-gel process was deposited on the stack of thin layers. The contact layer was deposited by screen printing and its thickness was 100 nm.
    The range ΔΤ was at least 15 ° C. L * values of 5 were obtained.
    Example 2
    Unlike Example 1, the silica contact layer was deposited by magnetron sputtering of a silicon target doped with aluminum in a reactive plasma containing argon and oxygen. The thickness of the contact layer was 30 nm.
    The range ΔΤ was at least 20 ° C.
    L * values were obtained.
    Similar results have been obtained with contact layer thicknesses of 50 and 70 nm.
    Example 3
    In this example, the soda lime clear glass sheet was previously coated by magnetron sputtering with a stack of thin solar control layers consisting, from the glass, of the following layers: S1N X (10 nm) / Nb (30 nm ) / S1N X (30 nm).
    The silica contact layer was deposited by magnetron sputtering of an aluminum doped silicon target in a reactive plasma containing argon and oxygen. The thickness of the contact layer was 10 or 30 nm according to the tests.
    The range ΔΤ was at least 20 ° C in all cases.
    L * values of 5 were obtained.
    The use of a contact layer has therefore made it possible to increase the range of usable baking temperatures and to achieve deeper black tones.
    权利要求:
    Claims (14)
    [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, said stack being coated on at least part of its surface with an enamel layer comprising zinc and less than 5% by weight of bismuth oxide, said stack further comprising, in contact with the enamel layer, a layer, called contact layer, which is based on an oxide, the physical thickness of said contact layer being at least 5 nm.
    [2" id="c-fr-0002]
    2. Material according to claim 1, wherein the contact layer comprises an oxide of at least one element chosen from aluminum, silicon, titanium, zinc, zirconium, tin, in particular is a layer with silicon oxide base.
    [3" id="c-fr-0003]
    3. Material according to one of the preceding claims, in which the contact layer is obtained by sputtering or by a sol-gel process.
    [4" id="c-fr-0004]
    4. Material according to one of the preceding claims, wherein the stack of thin layers comprises at least one layer based on a nitride, in particular a nitride of at least one element chosen from aluminum, silicon , zirconium, titanium.
    [5" id="c-fr-0005]
    5. Material according to the preceding claim, wherein at least one layer based on a nitride is in contact with the contact layer or spaced less than 5 nm from the contact layer.
    [6" id="c-fr-0006]
    6. Material according to one of the preceding claims, in which the contact layer has a physical thickness of at least 10 nm, in particular at least 20 nm.
    [7" id="c-fr-0007]
    7. Material according to one of the preceding claims, such that the stack comprises at least one functional layer, said functional layer being an electrically conductive, solar control, or low emissivity functional layer.
    [8" id="c-fr-0008]
    8. Material according to the preceding claim, wherein at least one functional layer is chosen from metal layers, in particular silver or niobium, the layers of a transparent conductive oxide, in particular chosen from indium oxide and tin, doped tin oxides and doped zinc oxides, and niobium nitride layers.
    [9" id="c-fr-0009]
    9. Material according to one of the preceding claims, such that the enamel layer is formed from a composition comprising at least one pigment and at least one glass frit of zinc borosilicate.
    [10" id="c-fr-0010]
    10. Material according to one of the preceding claims, such that the enamel layer is opaque, in particular of black or gray tint, and covers the entire surface of the glass sheet, or is arranged at the periphery of the sheet of glass. glass.
    [11" id="c-fr-0011]
    11. Glazing, in particular lighter, or door of household appliance comprising at least one material according to one of the preceding claims.
    [12" id="c-fr-0012]
    12. A method of manufacturing a material according to one of claims 1 to 10, comprising depositing a stack of thin layers on at least part of one face of a glass sheet, then depositing it on at least part of the surface of said stack of an enamel layer comprising zinc and less than 5% by weight of bismuth oxide.
    [13" id="c-fr-0013]
    13. Method according to the preceding claim, wherein at least part of the stack of thin layers is deposited by sputtering.
    [14" id="c-fr-0014]
    14. Method according to one of claims 12 and 13, wherein the deposition of the enamel layer comprises a firing step at a temperature of at least 600 ° C, in particular during a bending treatment and / or tempering of the glass sheet.
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    同族专利:
    公开号 | 公开日
    EP3810557A1|2021-04-28|
    FR3082840B1|2021-04-02|
    CO2020015708A2|2021-05-20|
    WO2019243755A1|2019-12-26|
    US20210155537A1|2021-05-27|
    BR112020025360A2|2021-03-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1996041773A1|1995-06-08|1996-12-27|Saint-Gobain Vitrage|Curable squeegee paste for printing on glass surfaces, and method for making same|
    WO2001021540A1|1999-09-23|2001-03-29|Saint-Gobain Glass France|Glazing provided with a stack of thin layers acting on solar radiation|
    WO2007028913A1|2005-07-29|2007-03-15|Saint-Gobain Glass France|Glazing provided with a stack of thin films acting on the sunlight|
    WO2015145073A1|2014-03-28|2015-10-01|Saint-Gobain Glass France|Glazing provided with a thin-layer stack for solar protection|
    FR3074167B1|2017-11-30|2019-11-15|Saint-Gobain Glass France|GLASS SHEET COATED WITH A STACK OF THIN LAYERS AND AN ENAMEL LAYER.|FR3108114A1|2020-03-13|2021-09-17|Saint-Gobain Glass France|glass sheet coated with a stack of thin layers and a layer of enamel|
    EP3909925A4|2020-05-14|2021-11-17|Saint Gobain|Method for producing a glass product|
    法律状态:
    2019-06-21| PLFP| Fee payment|Year of fee payment: 2 |
    2019-12-27| PLSC| Search report ready|Effective date: 20191227 |
    2020-06-29| PLFP| Fee payment|Year of fee payment: 3 |
    2021-06-30| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1855568A|FR3082840B1|2018-06-22|2018-06-22|SHEET OF GLASS COATED WITH A STACK OF THIN LAYERS AND A LAYER OF ENAMEL|
    FR1855568|2018-06-22|FR1855568A| FR3082840B1|2018-06-22|2018-06-22|SHEET OF GLASS COATED WITH A STACK OF THIN LAYERS AND A LAYER OF ENAMEL|
    PCT/FR2019/051527| WO2019243755A1|2018-06-22|2019-06-21|Glass sheet coated with a stack of thin layers and with an enamel layer|
    BR112020025360-0A| BR112020025360A2|2018-06-22|2019-06-21|GLASS SHEET COATED WITH A STACK OF FINE LAYERS AND WITH AN ENAMEL LAYER|
    US17/254,678| US20210155537A1|2018-06-22|2019-06-21|Glass sheet coated with a stack of thin layers and an with an enamel layer|
    EP19745703.9A| EP3810557A1|2018-06-22|2019-06-21|Glass sheet coated with a stack of thin layers and with an enamel layer|
    CONC2020/0015708A| CO2020015708A2|2018-06-22|2020-12-15|Glass sheet coated with a stack of thin layers and with a layer of enamel|
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