Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/3411—Surface 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
  • C03C17/3429—Surface 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
  • C03C17/3435—Surface 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered 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
  • B32B17/10—Layered 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
  • B32B17/10005—Layered 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
  • B32B17/10009—Layered 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
  • B32B17/10036—Layered 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered 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
  • B32B17/10—Layered 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
  • B32B17/10005—Layered 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
  • B32B17/10165—Functional features of the laminated safety glass or glazing
  • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
  • B32B17/10201—Dielectric coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered 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
  • B32B17/10—Layered 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
  • B32B17/10005—Layered 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
  • B32B17/10165—Functional features of the laminated safety glass or glazing
  • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
  • B32B17/10201—Dielectric coatings
  • B32B17/10211—Doped dielectric layer, electrically conductive, e.g. SnO2:F
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered 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
  • B32B17/10—Layered 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
  • B32B17/10005—Layered 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
  • B32B17/10165—Functional features of the laminated safety glass or glazing
  • B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered 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
  • B32B17/10—Layered 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
  • B32B17/10005—Layered 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
  • B32B17/1055—Layered 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 resin layer, i.e. interlayer
  • B32B17/10761—Layered 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 resin layer, i.e. interlayer containing vinyl acetal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/0641—Nitrides
  • C23C14/0652—Silicon nitride
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/08—Oxides
  • C23C14/083—Oxides of refractory metals or yttrium
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/219—CrOx, MoOx, WOx
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/24—Doped oxides
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/28—Other inorganic materials
  • C03C2217/281—Nitrides
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/74—UV-absorbing coatings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/154—Deposition methods from the vapour phase by sputtering
  • C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering

Definitions

• the invention to a transparent substrate provided with a stack of thin layers conferring properties of "solar control" and transparency to radio frequencies.
• a “solar control” glazing is a glazing having the property of limiting the flow of energy, in particular infrared radiation (IR), passing through it from the outside to the inside without prejudice to the light transmission in the visible spectrum.
• IR infrared radiation
• a glazing which comprises a stack of layers comprising metallic functional layers can cause an attenuation of more than 30dB of telecommunication signals.
• JP H0812378 A [NISSAN MOTOR] 16.01.1996 describes a "solar control" functional stack comprising a layer of tungsten oxide placed between two dielectric layers based on oxide.
• the stack makes it possible to reduce the electrical surface resistance and to increase the transparency to radio waves compared to stacks comprising a metallic functional layer, in particular based on silver.
• the layer has a “solar control” function thanks to its strong absorption of near infrared radiation.
• WO 2012/020189 A1 [SAINT GOBAIN [FR]] 16.02.2012 describes a stack of thin layers comprising a layer that selectively absorbs infrared radiation with a wavelength greater than 800 nm.
• the absorbent layer consists of a titanium oxide substituted by a doping element X chosen from Nb or Ta.
• a glazing For current motor vehicles, a glazing must meet a triple requirement: a low solar factor, a high light transmission and transparency to radio frequencies. This triple requirement can also be expressed as a double requirement: high selectivity and transparency at radio frequencies.
• a first aspect of the invention relates to a transparent substrate as described in claim 1, the dependent claims being advantageous embodiments.
• a second aspect of the invention relates to laminated glazing comprising a transparent substrate according to the first aspect of the invention.
• a remarkable advantage of the substrate according to the first aspect of the invention is a gain of up to more than 30% on solar selectivity.
• a remarkable advantage of the glazing according to the second aspect of the invention is a gain of up to more than 10% in selectivity while maintaining a sufficient level of light transmission, approximately 70%.
• FIG. 1 is a schematic representation of a third embodiment of the first aspect of the invention.
• FIG. 1 is a schematic representation of a laminated glazing according to the second aspect of the invention.
• the term “thickness” used for a layer corresponds to the physical, real or geometric thickness, e, of said layer. It is expressed in nanometers.
• dielectric module designates one or more layers in contact with each other forming a set of globally dielectric layers, that is to say that it does not have the functions of a metallic functional layer. If the dielectric module comprises several layers, these can themselves be dielectric.
• the physical thickness, real or geometric, of a dielectric module of layers corresponds to the sum of the physical thicknesses, real or geometric, of each of the layers which constitute it.
• a layer of or "a layer based on”, used to qualify a material or a layer as to what it or it contains, are used in an equivalent manner. They mean that the mass fraction of the constituent that he or she comprises is at least 50%, in particular at least 70%, preferably at least 90%. In particular, the presence of minority or doping elements is not excluded.
• transparent used to qualify a substrate, means that the substrate is preferably colorless, non-opaque and non-translucent in order to minimize light absorption and thus maintain maximum light transmission in the visible electromagnetic spectrum.
• Direct solar transmittance means solar direct solar transmittance as defined and calculated according to ISO 13837:2021.
• TTS solar factor
• T TS the solar factor as defined according to the ISO 13837:2021 standard. It is equal to the sum of the direct solar transmittance, TE, and the secondary heat flux, qi.
• SE solar selectivity
• s is meant the ratio of light transmission, TL, to solar factor TTS.
• group 1 of chemical elements includes hydrogen and alkali elements i.e. lithium, sodium, potassium, rubidium, cesium and francium.
• a transparent substrate 1000 is provided provided on one of its main surfaces with a stack 1001 of thin layers, said stack 1001 of layers consists of the following layers starting from the substrate 1000: - A first dielectric module 1002 of one or more thin layers; - an absorbent layer 1003 of tungsten oxide; - A second dielectric module 1004 of one or more thin layers;
• Tungsten oxide comprises at least one doping element selected from the group 1 chemical elements according to the IUPAC nomenclature.
• the absorbing layer 1003 of tungsten oxide is an absorbing layer of infrared radiation, preferably absorbing infrared radiation whose wavelength is greater than 780 nm.
• an absorbent layer 1003 of tungsten oxide comprising a doping element chosen from the elements of group 1 according to the IUPAC nomenclature encapsulated between two dielectric modules makes it possible to increase the selectivity.
• the absorbent layer 1003 of tungsten oxide can comprise the doping element X or the doping elements X1, X2, etc. in proportions such as the molar ratio, X/W of said element to tungsten, W, or the sum of the molar ratios of each element on tungsten (X1+X2+...)/W is between 0.01 and 1, preferably between 0.01 and 0.6, or even between 0.02 and 0, 3.
• the absorbent layer 1003 of tungsten oxide can comprise at least one doping element selected from hydrogen, lithium, sodium, potassium and cesium.
• the absorbent layer 1003 of tungsten oxide may comprise cesium as a doping element, and the molar ratio of cesium to tungsten is between 0.01 and 1, preferably between 0.1 and 0, 4.
• the thickness of the absorbent layer 1003 of tungsten oxide can be between 6 and 350 nm, preferably between 20 and 250 nm, or even between 40 and 200 nm.
• the transparent substrate 1000 can preferably be planar. It can be organic or inorganic, rigid or flexible. In particular, it may be a mineral glass, for example a silico-sodo-lime glass.
• organic substrates that can be advantageously used for the implementation of the invention can be polymer materials such as polyethylenes, polyesters, polyacrylates, polycarbonates, polyurethanes, polyamides. These polymers can be fluorinated polymers.
• Examples of mineral substrates that can be advantageously implemented in the invention may be sheets of mineral glass or glass-ceramic.
• the glass can preferably be a glass of the silico-sodo-lime, borosilicate, aluminosilicate or even alumino-boro-silicate type.
• the transparent substrate 1000 is a sheet of silico-sodo-lime mineral glass.
• the first dielectric module 1002 and/or the second dielectric module 1004 can comprise one or more layers based on nitride and/or oxide, preferably based on zinc oxide and tin, zinc oxide, titanium oxide, zirconium oxide, aluminum nitride, silicon nitride and zirconium or silicon nitride optionally doped with aluminium, zirconium and/or boron.
• the first layer 1002a of the first dielectric module 1002 and the last layer 1004z of the second dielectric mode 1004 can be nitride-based layers, preferably based on aluminum nitride, silicon nitride and zirconium or silicon nitride possibly doped with aluminium, zirconium and/or boron.
• first layer 1002a of the first dielectric module 1002 and the last layer 1004z of the second dielectric mode 1004 are nitride-based, they make it possible to encapsulate the absorbent layer based on tungsten oxide.
• This encapsulation allows double protection of the absorbent layer 1003 based on tungsten oxide. On the one hand, it warns of possible contamination by elements likely to diffuse into the stack 1001 from the substrate 1000, such as in particular alkaline ions or oxygen in the case of mineral glass substrate. On the other hand, it makes it possible to limit, in particular during an annealing heat treatment step, the diffusion of oxygen in the stack 1001 towards the absorbent layer 1003 based on tungsten oxide from the atmosphere and/or the substrate.
• the encapsulation makes it possible to ensure a correct level of selectivity.
• the substrate 1000 according to the first aspect of the invention is more durable, in particular its performance is preserved over the long term.
• the first dielectric module 1002, the second dielectric module 1004 and, more generally the stack 1001 can comprise additional thin layers.
• these additional layers may have chemical compositions making it possible to confer particular optical properties, for example in terms of colors or filtering of certain wavelengths of the electromagnetic spectrum, to the substrate 1000. They may also confer certain mechanical properties and/or chemicals, such as resistance to abrasion, delamination and/or chemical attack.
• These layers are generally based on oxides or oxynitrides of metals or metal alloys.
• these additional layers can be sources of contamination of the absorbent layer 1003 based on tungsten oxide.
• These sources of contamination can be a diffusion of certain metal or doping ions or a diffusion of oxygen. They can take place during the deposition of additional layers, during any heat treatment of the stack, or during use.
• Such contaminations can alter the absorbent layer based on tungsten oxide and are detrimental to the performance of the substrate according to the first aspect of the invention.
• the last layer 1002z of the first dielectric module 1002 located under and in contact with the absorbent layer 1003 based on tungsten oxide and the first layer 1004a of the second dielectric module 1004 located on and in contact with the absorbent layer 1003 based on tungsten oxide are based on nitride, preferably based on aluminum nitride, silicon nitride and zirconium or silicon nitride optionally doped with aluminum, zirconium and/or boron.
• the absorbent layer 1003 of tungsten oxide is encapsulated by the layers 1002z, 1004 has dielectric modules 1002, 1004.
• This type of encapsulation makes it possible to use any type of additional layers capable of conferring optical, mechanical and/or chemical properties. while preserving any contamination by these additional layers adjacent to the absorbent layer 1003 based on tungsten oxide. The performances of the substrate according to the first aspect of the invention are thus preserved in use.
• the first dielectric module 1002 and/or the second dielectric module 1004 can consist of layers based on nitride, preferably based on aluminum nitride, silicon nitride and zirconium or silicon nitride optionally doped with aluminum, zirconium and/or boron.
• first dielectric module 1002 and/or the second dielectric module 1004 consist of nitride-based layers, that is to say they only comprise nitride-based layers.
• the risk of altering the absorbent layer based on tungsten oxide by a possible diffusion of oxygen is then limited, or even eliminated.
• the durability of the substrate according to the first aspect of the invention can then be maximal with regard to the desired "solar control" performance and transparency to radio frequencies.
• a second aspect of the invention relates to a laminated glazing comprising a transparent substrate according to the first aspect of the invention.
• the laminated glazing 4000 comprises a first transparent substrate 1000 according to any one embodiment of the first aspect of the invention, a lamination insert 4001 and a second transparent substrate 4002, such as the first transparent substrate 1000 and the second transparent substrate 4002 are in adhesive contact with the interlayer 4001 of lamination and the stack 4001 of thin layers of the first transparent substrate 1000 is in contact with the interlayer 4001 of lamination.
• the lamination insert may consist of one or more layers of thermoplastic material.
• thermoplastic material are polyurethane, polycarbonate, polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), ethylene vinyl acetate (EA) or an ionomer resin.
• the lamination insert can be in the form of a multilayer film. It may also have special functionalities such as, for example, acoustic or even anti-UV properties.
• the lamination insert comprises at least one layer of PVB. Its thickness is between 50 ⁇ m and 4 mm. In general, it is less than 1mm.
• the laminated glazing when it is used as glazing for a motor vehicle, for example as a windshield, is such that the substrate according to the first aspect of the invention is located inside the vehicle.
• the stack 1001 is placed on face 2 of the glazing from the substrate oriented towards the interior of the vehicle, face 1 being the face oriented towards the interior; or even on face 3 of the glazing from the substrate facing the outside of the vehicle, face 1 being the face facing outwards.
• one of the two substrates 1000, 4002 can be a mass-tinted mineral glass.
• the tinting or coloring in the mass of a mineral glass is known and abundantly detailed in the technical literature. Coloring can usually be achieved by adding oxide dyes to the glass chemistry.
• oxides can be iron II oxide, copper oxide, chromium oxide, nickel oxide, gold oxide, manganese oxide, cobalt oxide , uranium oxide, neodymium oxide and erbium oxide.
• Mixtures of oxides such as copper and tin oxide, or ionic complexes, such as iron-sulfur or cadmium-sulfur complex, can also be used.
• the processes for depositing thin layers on substrates are processes that are well known in industry.
• the deposition of a stack of thin layers on a glass substrate is carried out by the successive depositions of each thin layer of said stack by causing the glass substrate to pass through a succession of deposition cells suitable for depositing a given thin layer.
• Deposition cells can use deposition methods such as magnetic field assisted sputtering (also called magnetron sputtering), ion beam assisted deposition (IBAD), evaporation, chemical vapor deposition (CVD) , plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), etc.
• deposition methods such as magnetic field assisted sputtering (also called magnetron sputtering), ion beam assisted deposition (IBAD), evaporation, chemical vapor deposition (CVD) , plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), etc.
• the magnetic field-assisted sputter deposition process is particularly used.
• the layer deposition conditions are widely documented in the literature, for example in patent applications WO2012/093238 A1 and WO2017/00602 A1.
• a method of manufacturing a transparent substrate according to the first aspect of the invention such that the absorbent layer of tungsten oxide is deposited by a magnetron sputtering method at using a tungsten oxide target doped with a chemical element chosen from the chemical elements of group 1 according to the IUPAC nomenclature.
• the tungsten oxide target may in particular contain one or more doping elements in the proportions as described for the layer of doped tungsten oxide in certain embodiments of the first aspect of the invention.
• the tungsten oxide absorber layer can be deposited by sputtering using the aforementioned target under a deposition atmosphere of 60-100% argon and 0-40% oxygen, preferably 70-85 % argon and 15 to 30% oxygen.
• the absorbent layer of tungsten oxide can be deposited under a pressure of between 1 to 15 mTorr, preferably 3 to 10 mTorr.
• the deposition can be carried out cold, that is to say at a temperature below 100° C., in particular between 20° C. and 60° C., for the substrate.
• the deposition can also be carried out hot, in particular at a temperature between 100° C. and 400° C.
• the substrate 1000 after deposition of the stack 1001, can undergo an annealing heat treatment.
• the annealing temperature may be between 450°C and 800°C, in particular between 550°C and 750°C, or even between 600°C and 700°C.
• the annealing time can be between 5min and 30min, in particular between 5min and 20min, or even between 5min and 10min.
• the transparent substrate according to the first aspect of the invention and the laminated glazing according to the second aspect are particularly suitable for glazing applications for motor vehicles. They can also be adapted to certain building glazing applications, in particular as laminated glazing.
• a first example Ex1 of substrate according to the first aspect of the invention and three counter-examples CEx1, CEx2 and CEx3 not in accordance with the invention are described in table 1 which indicates the composition and the thickness expressed in nanometers of the different layers .
• the numbers in the first column correspond to the references of the figures.
• the transparent substrate is a silico-soda-lime glass with a thickness of 4mm marketed under the Planiclear® brand.
• the tungsten oxide (CWO) absorber layer includes the doping element cesium (Cs).
• the molar ratio of cesium to tungsten is around 0.05-0.1.
• the absorbent layer deposited by magnetron sputtering using a tungsten oxide target doped with cesium under an atmosphere comprising between 10% and 20% oxygen at a pressure of 4mTorr.
• the layer(s) of silicon nitride, Si3N4, are deposited using an 8 wt% Si:Al target at 5 ⁇ bar under an oxygen-free atmosphere and under a nitrogen flow at 14 sccm.
• the substrates After deposition of the thin layers, the substrates underwent an annealing heat treatment at 650° C. in air for 10 min.
• optical transmission spectra of example E1 and of the three examples CE1, CE2 and CE3 were measured and/or calculated in accordance with standard ISO 13837:2021. They are represented on the .
• the three counter-examples CE1, CE2 and CE3 present a high light transmission both in the visible and in the infrared.
• the layer based on tungsten oxide doped with cesium shows little absorption in the infrared range. All three counterexamples do not exhibit any "solar control" properties.
• example E1 of substrate according to the invention has a high light transmission in the visible range, and reduced in the infrared range.
• the layer based on cesium-doped tungsten oxide exhibits high absorption in the infrared range.
• Example E1 shows a "solar control" property.
• the transparent substrate is a 1.6 mm silico-soda-lime glass marketed under the Planiclear® brand.
• the tungsten oxide (CWO) absorber layer includes the doping element cesium (Cs). The molar ratio of cesium to tungsten is around 0.05-0.1.
• the absorbent layer was deposited by magnetron sputtering using a cesium-doped tungsten oxide target under an atmosphere comprising 20% oxygen at a pressure of 4 mTorr for examples E2, E4 and E6, and under atmosphere comprising 10% oxygen at a pressure of 4mTorr for E3, E5, and E7
• the layer(s) of silicon nitride, Si3N4, are deposited using an 8 wt% Si:Al target at 5 ⁇ bar under an oxygen-free atmosphere and under a nitrogen flow at 14 sccm.
• the substrates After deposition of the thin layers, the substrates underwent an annealing heat treatment at 650° C. in air for 10 min.
• Luminous transmittance, TL, and "direct solar transmittance", TE were measured and/or calculated according to ISO 13837:2021.
• the "solar selectivity”, SE defined as the ratio, TL/TE, of the light transmission TL to the direct solar transmittance TE, was also calculated.
• SE solar selectivity
• the results for examples E4 and E5 are described in table 4 and represented on the .
• Table 4 and also group the values of light transmission, TL, of solar transmittance, TE and of solar selectivity, SE, for the counter-examples CE4, CE5, CE6, CE7, CE8 corresponding respectively to examples 1, 2, 3, 8 and 9 of the substrates described in application JP H0812378 A [NISSAN MOTOR] 16.01.1996.
• the characteristics of the counter-examples are given in table 3.
• the numbers in the first column correspond to the references of the figures.
• the substrate is a transparent mineral glass.
• the absorbent layer is a layer of tungsten oxide that does not include any dopant.
• the absorber layer is a tungsten oxide layer including silicon as a dopant with a Si:W ratio of 0.1:1 for counterexamples CE5 and CE6 and a Si ratio: W of 0.2:1 for the CE7 and CE8 counterexamples.
• the dielectric modules consist of a single layer of SiO2 for counterexamples CE4 to CE6, and a single layer of TiO2 for counterexamples CE7 to CE8.
• the 4001 lamination interlayer is a PVB interlayer with a thickness of 0.76mm.
• the second substrate 4002 is a silico-soda-lime mineral glass with a thickness of 2.1 mm marketed under the brand name Planiclear® (PLC 2.1) for the examples EV1, EV2 and the counter-example CEV1.
• PLC 2.1 Planiclear®
• the second substrates are respectively two silico-soda-lime mineral glasses tinted in the mass with a thickness of 2.1 mm and marketed under the name TSA3+, TSA5+ for examples EV3 and EV4.
• Table 5 also describes two counter-examples CEV2 and CEV3 which do not include any stack of thin layers. These two counterexamples are reference examples corresponding to laminated glazing commonly used in the automotive field.
• the light transmission, TL, the "direct solar transmittance", TE, and the “solar factor”, TTS (or T TS ) were measured and/or calculated according to the ISO 13837:2021 standard for each example and counter-example.
• Selectivity s, defined as the ratio, TL/TTS, of light transmittance, TL, to solar factor TTS, and "Solar Selectivity”, SE, defined as the ratio, TL/TE, of transmittance luminous TL on the direct solar transmittance, TE, were calculated for each example and counter-example from the parameters measured and/or calculated previously.
• the colorimetric parameters a* and b* were measured and/or calculated in transmission (a*T, b*T) and in external reflection (a*Rext, b*Rext) in the CIE 1976 L*a*b* color space according to ISO 11664-4:2019 with D65 illuminant and 2° or 10° visual field for the reference observer.
• Characteristic a* is the chromatic position on a green-red axis (between -500 and 500)
• b* is the chromatic position on a blue-yellow axis (between -200 and 200).
• Table 6 shows that the four examples EV1 to EV4 according to the second aspect of the invention allow a gain of up to more than 35% on solar selectivity, SE, compared to the counter-example CEV1.
• This gain illustrates the synergistic effect of the combination of the absorbent layer based on tungsten oxide with the two adjacent dielectric modules, in particular when they include and/or consist of thin layers based on silicon nitride.
• the light transmission, TL, and solar factor, TTS, values are shown on the for examples EV1 to EV4 (filled circles), counterexample CEV1 (empty circle), and counterexamples CEV2 and CEV3 (empty squares).
• the examples EV1 to EV4 and more particularly the examples EV2 to EV4 have parameters a*T and b*T comparable to those of the counter-examples CEV2 and CEV3 of reference laminated glazing.
• the counter-example CEV1 presents parameters a*T and b*T shifted towards red and yellow.
• examples EV1 to EV4, and more particularly examples EV2 to EV4 have parameters a*R and b*R comparable to those of counter-examples CEV2 and CEV3 of reference laminated glazing.
• the counter-example CEV1 presents parameters a*R and b*R shifted towards green and blue.

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• 2023
  • 2023-01-05 EP EP23700451.0A patent/EP4469412A1/de active Pending
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