EP4118043A1 - Feuille de verre revetue d'un empilement de couches minces et d'une couche d'email - Google Patents

Feuille de verre revetue d'un empilement de couches minces et d'une couche d'email

Info

Publication number
EP4118043A1
EP4118043A1 EP21709718.7A EP21709718A EP4118043A1 EP 4118043 A1 EP4118043 A1 EP 4118043A1 EP 21709718 A EP21709718 A EP 21709718A EP 4118043 A1 EP4118043 A1 EP 4118043A1
Authority
EP
European Patent Office
Prior art keywords
layer
enamel
stack
glass sheet
thin layers
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.)
Pending
Application number
EP21709718.7A
Other languages
German (de)
English (en)
French (fr)
Inventor
Juliette JAMART
Marion LALLEMENT
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 EP4118043A1 publication Critical patent/EP4118043A1/fr
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
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    • 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165Functional features of the laminated safety glass or glazing
    • B32B17/10247Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
    • B32B17/10256Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
    • B32B17/10284Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on intermediate layer
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    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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    • C03C17/3429Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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    • C03C17/3626Surface 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 one layer at least containing a nitride, oxynitride, boronitride or carbonitride
    • CCHEMISTRY; METALLURGY
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
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    • 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
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    • 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
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    • 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
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    • 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
    • C03C17/3639Multilayers containing at least two functional metal layers
    • 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
    • C03C17/3657Surface 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 optical properties
    • 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
    • C03C2218/10Deposition methods
    • C03C2218/11Deposition methods from solutions or suspensions
    • C03C2218/119Deposition methods from solutions or suspensions by printing
    • 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
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/154Deposition methods from the vapour phase by sputtering
    • 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
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/154Deposition methods from the vapour phase by sputtering
    • C03C2218/156Deposition methods from the vapour phase by sputtering by magnetron sputtering

Definitions

  • the invention relates to the field of materials comprising a glass sheet coated with a stack of thin layers and with a layer of enamel.
  • Such materials are in particular intended to be incorporated into curved laminated glazing for motor vehicles, for example for roofs or windshields.
  • Laminated glazing is glazing in which two sheets of glass are adhesively bonded by means of a lamination interlayer. The latter makes it possible in particular to retain shards of glass in the event of breakage, but also provides other functionalities, in particular in terms of resistance to burglary or improvement of acoustic properties.
  • These glazings often include coatings of various types, intended to impart different properties.
  • Enamel layers generally black and opaque, are often deposited on part of the glazing, generally in the form of a peripheral strip intended to conceal and protect against ultraviolet radiation the polymeric seals used for fixing and positioning the glazing on the bodywork bay. Enamelled areas also conceal the fixing areas of the interior mirror and various connectors and sensors.
  • SUBSTITUTE SHEET (RULE 26) the exterior of the vehicle is of particular importance to vehicle manufacturers.
  • the enamel is generally obtained by firing above 500 ° C. of a composition comprising a glass frit and pigments.
  • a glass frit consists of fine particles of a low-melting point glass, which under the effect of a heat-firing treatment softens and adheres to the glass sheet.
  • a generally opaque mineral layer is thus formed, with high chemical and mechanical resistance, adhering perfectly to the glass while maintaining the pigment particles.
  • the baking step is generally carried out simultaneously with the bending of the glass sheet.
  • the two sheets of glass of the glazing are bent together, the sheet of glass intended to be positioned inside the vehicle being generally disposed above the other sheet of glass, which wears enamel. It is then necessary for the enamel to have non-stick properties in order to prevent any sticking between the two sheets of glass during bending.
  • enamels containing bismuth that is to say obtained from glass frits containing bismuth oxide.
  • Coatings can also be present on one of the glass sheets of the laminated glazing. They can in particular be electrically conductive layers, which can provide two types of functionalities.
  • the electrically conductive layers can on the one hand, when current leads are provided, dissipate heat by the Joule effect. These are then heating layers, useful for example for defrosting or demisting. These layers have on the other hand, by their reflection of infrared radiation, properties of solar control or low emissivity. Layers are then appreciated for improving thermal comfort or for the energy savings they provide, by reducing consumption intended for heating or air conditioning.
  • These stacks of layers are generally placed on face 3 of the laminated glazing, therefore also in contact with the lamination interlayer.
  • the aim of the invention is to propose a simpler and less expensive solution to the aforementioned problem.
  • the invention relates to a material comprising a sheet of glass 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 not comprising bismuth, said enamel layer being coated with an anti-adhesion layer.
  • the subject of the invention is also a process for obtaining a material according to the invention, comprising the following steps:
  • the subject of the invention is also a curved laminated glazing, in particular for a vehicle windshield or roof. automobile, comprising a material according to the invention, adhesively bonded to an additional sheet of glass by means of a lamination interlayer, so that the enamel layer and the stack of thin layers face towards said interlayer, in particular either opposite 2 of the glazing.
  • a subject of the invention is a process for obtaining a curved laminated glazing as defined above, comprising the following steps:
  • the stack of thin layers is not degraded by the deposition of the enamel.
  • the material according to the invention therefore has, superposed, a stack of thin layers then a layer of enamel, the latter not being in contact with the glass sheet.
  • an enamel layer not containing bismuth makes it possible to avoid any undesirable interaction during bending, in particular with stacks of thin layers comprising at least one layer based on a nitride.
  • an anti-adhesion layer is placed on the enamel layer.
  • anti-adhesion layer is understood to mean a layer capable of preventing the sticking of the two sheets of glass during bending.
  • the glass sheet can be flat or curved.
  • the glass sheet is generally flat at the time of deposition of the stack of thin layers and then of the enamel layer, and is then curved.
  • the glass sheet is therefore normally flat in the material according to the invention (intermediate product) and curved in the curved laminated glazing according to the invention (final product).
  • the glass is typically a soda-lime 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 may be clear glass or tinted glass, preferably tinted glass, for example green, gray or blue.
  • the chemical composition of the glass sheet advantageously comprises iron oxide, in a weight content ranging from 0.5 to 2%. It can also comprise other coloring agents, such as cobalt oxide, chromium oxide, nickel oxide, erbium oxide, or else selenium.
  • the glass sheet preferably has a thickness within a range ranging 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 lateral dimensions of the glass sheet are to be adapted as a function of those of the laminated glazing in which it is intended to be integrated.
  • the glass sheet preferably has a surface area of at least 1 m 2 .
  • the glass sheet is preferably coated with the stack of thin layers over at least 70%, in particular over at least 90%, or even over the entire surface of the face of the glass sheet. Some areas may indeed not to be coated in order in particular to provide communication windows allowing waves to pass.
  • the stack is preferably coated with the enamel layer over 2 to 25%, in particular 3 to 20%, or even 5 to 15% of its surface.
  • the enamel layer preferably comprises a peripheral strip, that is to say a strip closed on itself which, from each point of the periphery of the glass sheet, extends towards the interior of the sheet. of glass over a certain width, typically between 1 and 20 cm.
  • the anti-stick layer preferably coats the entire enamel layer.
  • the anti-adhesion layer only coats the enamel layer; it is then not present in the uncoated areas of the enamel layer.
  • the stack of thin layers is preferably in contact with the glass sheet.
  • the enamel layer is preferably in contact with the stack of thin layers.
  • the anti-adhesion layer is preferably in contact with the enamel layer.
  • the stack of thin layers, the enamel layer and the anti-stick layer are collectively referred to as "the coatings".
  • the material according to the invention preferably consists of these coatings.
  • contact is meant in the present text a 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%, or even 70% and even 80% or 90%.
  • the layer may even essentially consist of or consist of this material.
  • essentially consist it should be understood that the layer can comprise impurities without influence on its properties.
  • oxide or “nitride” do not necessarily mean that the oxides or nitrides are stoichiometric. They can in fact be substoichiometric, superstoichiometric or stoichiometric.
  • the stack preferably comprises at least one layer based on a nitride.
  • the nitride is in particular a nitride of at least one element chosen from aluminum, silicon, zirconium and titanium. It can comprise a nitride of at least two or three of these elements, for example a nitride of silicon and zirconium, or a nitride of silicon and aluminum.
  • the layer based on a nitride is a layer based on silicon nitride, more particularly a layer consisting essentially of a silicon nitride.
  • the layer based on a nitride preferably has a physical thickness in a range ranging from 2 to 100 nm, in particular from 5 to 80 nm.
  • Nitride-based layers are commonly used in a number of stacks of thin layers because they have advantageous blocking properties, in the sense that they prevent the oxidation of other layers present in the stack, in particular functional layers. which will be described below.
  • 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:
  • a transparent conductive oxide in particular chosen from indium tin oxide, doped tin oxides (for example with fluorine or with antimony), doped zinc oxides (for example aluminum or gallium).
  • low-emissive glazing makes it possible in hot weather to reflect part of the solar radiation to the outside, and therefore to limit the heating of the interior of said vehicles, and where appropriate reduce air conditioning expenses.
  • these glazings make it possible to conserve heat within the passenger compartment, and consequently to reduce the heating energy effort. It is the same in the case of glazing equipping buildings.
  • the stack of thin layers comprises at least one layer of silver, in particular one, two or three, or even four layers of silver.
  • the physical thickness of the silver layer or, where appropriate, the sum of the thicknesses of the silver layers is preferably between 2 and 20 nm, in particular between 3 and 15 nm.
  • the stack of thin layers 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.
  • each of these layers is preferably surrounded by at least two dielectric layers.
  • the dielectric layers are preferably based on the oxide, nitride and / or oxynitride of at least one element chosen from silicon, aluminum, titanium, zinc, zirconium and tin.
  • 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 cathodic sputtering, in particular assisted by a magnetic field (magnetron process).
  • CVD chemical vapor deposition
  • cathodic sputtering in particular assisted by a magnetic field (magnetron process).
  • the stack of thin layers is preferably deposited by cathode sputtering, in particular assisted by a magnetic field.
  • a plasma is created under a high vacuum in the vicinity of a target comprising the chemical elements to be deposited.
  • the active species of the plasma 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 the same line a very complex stack of layers by successively making the glass sheet scroll under different targets, generally in one and the same device.
  • the aforementioned stacks have properties of electricity conduction and infrared reflection useful for providing a heating function (defrosting, demisting) and / or a thermal insulation function.
  • current leads When the stack of thin layers is intended to provide a heating function, current leads must be planned. They may in particular be strips of silver paste deposited by screen printing on the stack of thin layers, at two opposite edges of the glass sheet.
  • the enamel layer is preferably formed from a composition comprising at least one pigment and at least one glass frit.
  • 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, diluents, oils and / or resins.
  • enamel composition is used to describe the liquid composition which is used to deposit, on the glass sheet, a layer of wet enamel.
  • enamel layer is used to describe the final layer, after firing, while the term “wet enamel layer” is used to describe the enamel layer before firing.
  • the enamel layer is preferably deposited by screen printing.
  • a silkscreen screen is placed on the sheet of glass, which comprises meshes, some of which are sealed, then the enamel composition is deposited on the screen, then a doctor blade is applied in order to force the composition of enamel to pass through the screen in areas where the mesh of the screen is not sealed, 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 subsequent bending treatment of the glass sheet.
  • the pigments preferably comprise one or more oxides chosen from oxides of chromium, copper, iron, manganese, cobalt and nickel. It may be, for example, chromates of copper and / or iron.
  • the enamel layer is based on zinc borosilicate.
  • the enamel layer advantageously has a chemical composition comprising the following oxides, in weight contents varying within the limits mentioned below: B2O3 2-20%, in particular 4-10% S1O2 20-45%, in particular 25 -40% B12O3 0
  • the composition advantageously comprises at least one alkali metal oxide, in particular of potassium, in contents of at most 5% and / or sodium, in contents ranging from 2 to 15%, in particular from 5 to 13%.
  • the composition preferably contains titanium oxide (T1O2), 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 Cr0 3 and CuO contents range from 8 to 20% and from 3 to 12% respectively.
  • the chemical composition of the enamel can be determined by conventional chemical analysis methods, especially from baked enamel. It is therefore indeed the chemical composition of the baked enamel layer, and not the glass frit which was used to form the enamel.
  • the enamel layer is opaque, black in color. Its clarity L * measured in reflection on the glass side is preferably less than 5. As indicated above, 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 seals, connection elements, or sensors.
  • the anti-adhesion layer is preferably a layer based on refractory particles (in particular pigments) or a sol-gel layer.
  • the anti-adhesion layer preferably does not contain bismuth because it has been observed that the presence of bismuth could generate defects, even when the anti-adhesion layer is not in contact with the stack of thin layers.
  • refractory particles is understood to mean particles which do not undergo transformation during bending.
  • the refractory particles can be for example alumina particles.
  • the refractory particles can advantageously be pigments.
  • the pigments preferably comprise one or more oxides of transition metals, in particular chosen from oxides of chromium, copper, iron, manganese, cobalt, nickel and titanium.
  • the pigments are titanium oxide pigments, which exhibit excellent non-stick properties. Although these pigments are white (while the enamel is generally black) these pigments do not change the appearance of the enamel when viewed from the exterior of the vehicle. When, in the final laminated glazing, the additional glass sheet or the lamination interlayer is tinted, the color imparted by these pigments is not detrimental to the aesthetics seen from the interior of the passenger compartment either.
  • the pigment-based layer preferably comprises at least 40%, in particular at least 60%, or even at least 80% by weight, of pigments.
  • the anti-adhesion layer consists of pigments. These pigments are attached to the glass sheet thanks to the underlying enamel layer: its softening during bending makes it possible to fix the pigments deposited above it.
  • the layer anti ⁇ adhesion includes pigments and a vitreous binder.
  • the vitreous binder does not include bismuth, and can be based on the same glass frit as the underlying enamel.
  • the mass proportion of pigment in the anti-stick layer should be at least 40% by weight.
  • a very simple way to obtain this type of layer consists in adding a certain proportion of pigments to an enamel composition identical to that which was used to deposit the underlying enamel layer.
  • the anti-adhesion layer is a sol-gel layer.
  • sol-gel layer is understood to mean a layer obtained by a sol-gel process.
  • the sol-gel layer is preferably based on silica.
  • a sol-gel process is a process in which a sol containing precursors of the layer to be produced is deposited on the glass sheet by various means, such as spraying, curtain, laminar coating, roller, screen printing etc. .... Deposition by screen printing is preferred here since it easily makes it possible to deposit the sol-gel layer only on a part of the glass sheet, in this case only on the area covered with enamel (and advantageously on this whole area).
  • the sol preferably contains organometallic precursors of the layer to be produced, for example tetraethyl orthosilicate (TEOS).
  • TEOS tetraethyl orthosilicate
  • the layer is then generally dried and then annealed in order to densify it. The annealing preferably takes place during the same step as the baking of the enamel, therefore generally during the bending of the glass sheet.
  • the anti-adhesion layer preferably has a thickness (in particular in the wet state) of between 5 and 100 ⁇ m. When the layer is based on refractory particles, its thickness is preferably between 10 and 100 ⁇ m, in particular between 12 and 30 ⁇ m. When the layer is a sol-gel layer, its thickness is preferably between 5 and 20 ⁇ m.
  • the step of depositing the enamel layer and the step of depositing the anti-adhesion layer are carried out by screen printing.
  • the anti-adhesion layer consists of pigments
  • the pigments are mixed with an organic medium, which is then removed during bending or during a possible pre-baking.
  • the step of depositing the enamel layer is preferably followed by a drying step, typically at a temperature between 100 and 200 ° C., before depositing the anti-adhesion layer.
  • the latter In the case of deposition by screen printing of an anti-adhesion layer based on refractory particles, the latter must have a size compatible with the screen printing screen used.
  • the particles preferably have an D90 of between 5 and 40 ⁇ m.
  • the particle size distribution is here a volume distribution, determined for example by laser particle size distribution.
  • the step of depositing the anti-adhesion layer is preferably followed by a pre-curing step, preferably at a temperature between 150 and 600 ° C.
  • a pre-curing step preferably at a temperature between 150 and 600 ° C.
  • a pre-baking step is usually carried out in the case of the use of bismuth-based enamels, in order to to develop the non-stick properties of such an enamel by causing its partial crystallization.
  • This step must however be carried out at high temperature, typically at least 500 ° C., while the pre-cooking carried out in the context of the present process can advantageously be carried out at lower temperatures.
  • the material according to the invention is adhesively bonded to an additional sheet of glass by means of a lamination interlayer, so that the coatings are facing said interlayer.
  • the coatings are preferably positioned on face 2 of the glazing, that is to say on the face of the glass sheet intended to be positioned on the outside of the vehicle facing the laminating insert.
  • the bending can in particular be carried out by gravity (the glass deforming under its own weight) or by pressing, at temperatures typically ranging from 550 to 650 ° C.
  • the glass sheets are preferably kept at a distance by placing between them an intermediate powder ensuring a space of a few tens of micrometers, typically 20 to 50 ⁇ m.
  • the intermediate powder is for example based on calcium carbonate and / or magnesium.
  • the inner sheet of glass (intended to be positioned inside the passenger compartment) is normally placed above the outer sheet of glass.
  • the additional glass sheet is placed on top of the material according to the invention.
  • the laminating step can be carried out by treatment in an autoclave, for example at temperatures of 110 to 160 ° C. and under a pressure ranging from 10 to 15 bars.
  • the air trapped between the glass sheets and the lamination interlayer can be removed by calendering or by vacuum.
  • the additional sheet is preferably the inner sheet of the laminated glazing, that is to say the sheet located on the concave side of the glazing, intended to be positioned inside the passenger compartment of the vehicle. In this way, the coatings are placed on face 2 of the laminated glazing.
  • the additional glass sheet may be soda-lime-silicate glass, or else of borosilicate or aluminosilicate glass. It can be in clear or tinted glass. Its thickness is preferably between 0.5 and 4 mm, in particular between 1 and 3 mm.
  • the additional glass sheet has a thickness of between 0.5 and 1.2 mm.
  • the additional glass sheet is in particular made of sodium aluminosilicate glass, preferably chemically reinforced.
  • the additional glass sheet is preferably the inner sheet of the laminated glazing.
  • the invention is particularly useful for this type of configuration, for which it is difficult to place the stack of thin layers on the face 3.
  • Chemical reinforcement also called “ion exchange” consists in bringing the surface of the glass into contact with it. a molten potassium salt (for example potassium nitrate), so as to strengthen the surface of the glass by exchanging ions of the glass (here sodium ions) with ions of greater ionic radius (here potassium ions).
  • the surface stress is at least 300 MPa, in particular 400 and even 500 MPa, and at most 700 MPa
  • the thickness of the zone in compression is at least 20 ⁇ m, typically between 20 ⁇ m. and 50 pm.
  • the stress profile can be determined in a known manner using a polarizing microscope equipped with a Babinet compensator.
  • Step of Chemical quenching is preferably carried out at a temperature ranging from 380 to 550 ° C, and for a period ranging from 30 minutes to 3 hours.
  • the chemical reinforcement is preferably carried out after the bending step but before the laminating step.
  • the glazing obtained is preferably a motor vehicle windshield, in particular a heated windshield.
  • the additional sheet of glass carries on the face opposite to the face facing the laminating insert (preferably face 4, the additional sheet being the inner sheet) a stack of additional thin layers, in particular a low emissivity stack, comprising a transparent conductive oxide, in particular indium tin oxide (ITO).
  • ITO indium tin oxide
  • the lamination interlayer and / or the additional glass sheet is preferably tinted, the glass sheet carrying the coatings possibly being of clear glass.
  • the glazing obtained is preferably a motor vehicle roof.
  • a laminated curved roof comprising, from the outside of the vehicle, a sheet of clear glass coated on the face 2 with a stack of thin layers comprising at least one layer of silver. then a layer of enamel then a non-stick layer, a tinted PVB lamination interlayer, and an additional sheet of tinted glass, bearing on face 4 a stack of thin layers with low emissivity, in particular at ITO base.
  • 1 / laminating interlayer preferably comprises at least one sheet of polyvinylacetal, in particular of polyvinylbutyral (PVB).
  • the lamination interlayer can be tinted or non-tinted in order, if necessary, to regulate the optical or thermal properties of the glazing.
  • 1 / laminating interlayer can advantageously have sound absorption properties in order to absorb sounds of aerial or solidary origin.
  • it may in particular consist of three polymeric sheets, including two so-called external PVB sheets flanking an internal polymeric sheet, optionally made of PVB, of lower hardness than that of the external sheets.
  • the lamination interlayer can also have thermal insulation properties, in particular reflection of infrared radiation.
  • it may comprise a coating of thin low emissivity layers, for example a coating comprising a thin layer of silver or a coating of alternating dielectric layers of different refractive indices, deposited on an internal PET sheet framed by two external PVB sheets.
  • the thickness of the lamination interlayer is generally within a range ranging from 0.3 to 1.5 mm, in particular from 0.5 to 1 mm.
  • the lamination interlayer may have a lower thickness on one edge of the glazing than in the center of the glazing in order to avoid the formation of a double image when using a head-up vision system, called HUD ( head-up display).
  • HUD head-up display
  • the enamel layer “El” (enamel marketed by the company Ferro under the reference 144011) was based on a zinc borosilicate frit (without bismuth) and black pigments based on D. oxides of chromium and copper.
  • the enamel layer “E2” (enamel sold by the company Prince under the reference DV173770 / N) was based on a frit of bismuth and zinc borosilicate and on black pigments based on oxides. of chromium and copper.
  • an anti-adhesion layer of the following composition according to the examples:
  • Al TiCp pigments, wet thickness approximately 10 ⁇ m, having an D50 of the order of 3 to 5 ⁇ m and a D90 of the order of 10 ⁇ m.
  • A2 sol-gel silica, wet thickness approximately 7 ⁇ m, deposited from a solution marketed under the reference TLU0059B01 by the company Ferro
  • A3 enamel layer E2, wet thickness 25 ⁇ m
  • A4 mixture of 80% by weight of E1 enamel with 20% by weight of TiCp pigments, wet thickness of 10 ⁇ m.
  • the glass sheet thus coated was then subjected to a pre-baking treatment at 570 ° C. for 120 seconds.
  • An additional glass sheet of 2.1 mm thick tinted glass covered on face 4 with a low-emissive stack based on ITO was then placed on the glass sheet, on the coating side.
  • An intermediate powder providing a space of a few tens of micrometers based on calcium carbonate was interposed between the two sheets of glass.
  • the assembly then underwent a bending heat treatment at 600 ° C. for 480 seconds.
  • Table 1 summarizes the results obtained, indicating for each example (comparative examples C1 to C3 and examples according to the invention 1 to 3), the nature of the enamel layer and of the anti-adhesion layer (when 'she was present), as well as the results in terms of aesthetics and bonding.
  • Aesthetics more particularly the black color seen from face 1, is evaluated by measuring the clarity L * in reflection (illuminant D65, reference observer 10 °).
  • the collage is qualitatively assessed by visual observation.
  • Comparative Examples C1 and C2 do not use an anti-adhesion layer.
  • Example C1 shows that enamels at bismuth, if they do not cause sticking, do not make it possible to obtain the desired black shade, due to interactions between the enamel and the stack of thin layers during bending.
  • the bismuth-free enamel of Comparative Example C2 makes it possible to achieve the desired shade, but a bond between the two sheets of glass is observed.
  • Comparative Example C3 uses a bismuth-free enamel in contact with the stack, topped with a bismuth enamel in contact with the additional glass sheet. Bonding is then avoided, but the presence of the bismuth enamel, even if it is not in contact with the stack of thin layers, degrades the aesthetics.
  • Examples 1 to 3 according to the invention show that the use of an anti-adhesion layer in combination with an enamel without bismuth makes it possible to obtain both an absence of sticking and a satisfactory aesthetic appearance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Glass Compositions (AREA)
  • Structures Of Non-Positive Displacement Pumps (AREA)
EP21709718.7A 2020-03-13 2021-03-10 Feuille de verre revetue d'un empilement de couches minces et d'une couche d'email Pending EP4118043A1 (fr)

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EP21709718.7A Pending EP4118043A1 (fr) 2020-03-13 2021-03-10 Feuille de verre revetue d'un empilement de couches minces et d'une couche d'email

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US (1) US20230134399A1 (es)
EP (1) EP4118043A1 (es)
JP (1) JP2023516987A (es)
KR (1) KR20220155569A (es)
CN (1) CN113692396B (es)
BR (1) BR112022010007A2 (es)
FR (1) FR3108114B1 (es)
MX (1) MX2022011337A (es)
WO (1) WO2021180749A1 (es)

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Publication number Priority date Publication date Assignee Title
FR3116021B1 (fr) * 2020-11-12 2023-12-29 Saint Gobain Vitrage feuilleté pour véhicule, notamment automobile

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
FR2652037B1 (fr) * 1989-09-18 1992-04-03 Saint Gobain Vitrage Int Vitrage feuillete chauffant.
US20090053534A1 (en) * 2007-08-21 2009-02-26 Robert Prunchak Coating compositions
FR2976576B1 (fr) * 2011-06-17 2014-08-08 Saint Gobain Procede de fabrication d'un substrat en verre comportant des motifs imprimes en email.
MX2015007463A (es) * 2012-12-14 2015-09-16 Ferro Corp Metodo de fabricacion de estructura de vidrio de multiples capas.
EP2961710A2 (en) 2013-02-28 2016-01-06 Guardian Industries Corp. Window units made using ceramic frit that dissolves physical vapor deposition (pvd) deposited coatings, and/or associated methods
FR3074167B1 (fr) 2017-11-30 2019-11-15 Saint-Gobain Glass France Feuille de verre revetue d'un empilement de couches minces et d'une couche d'email.
FR3082840B1 (fr) * 2018-06-22 2021-04-02 Saint Gobain Feuille de verre revetue d'un empilement de couches minces et d'une couche d'email

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JP2023516987A (ja) 2023-04-21
FR3108114A1 (fr) 2021-09-17
US20230134399A1 (en) 2023-05-04
MX2022011337A (es) 2022-10-07
CN113692396B (zh) 2024-01-30
BR112022010007A2 (pt) 2022-08-16
FR3108114B1 (fr) 2022-07-22
WO2021180749A1 (fr) 2021-09-16
CN113692396A (zh) 2021-11-23
KR20220155569A (ko) 2022-11-23

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