WO2024042546A1 - Vitrage comprenant un empilement de couches minces ayant une couche fonctionnelle à base d'argent et de multiples couches fonctionnelles à base de nitrure de titane - Google Patents

Vitrage comprenant un empilement de couches minces ayant une couche fonctionnelle à base d'argent et de multiples couches fonctionnelles à base de nitrure de titane Download PDF

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Publication number
WO2024042546A1
WO2024042546A1 PCT/IN2023/050797 IN2023050797W WO2024042546A1 WO 2024042546 A1 WO2024042546 A1 WO 2024042546A1 IN 2023050797 W IN2023050797 W IN 2023050797W WO 2024042546 A1 WO2024042546 A1 WO 2024042546A1
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Prior art keywords
glazing
silver
layers
functional layer
layer
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PCT/IN2023/050797
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English (en)
Inventor
Priyesh DHANDHARIA
Uditendu MUKHOPADHYAY
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Saint-Gobain Glass France
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Publication of WO2024042546A1 publication Critical patent/WO2024042546A1/fr

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    • 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
    • B32B17/1022—Metallic coatings
    • B32B17/10229—Metallic layers sandwiched by dielectric layers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • C03C17/36—Surface 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
    • C03C17/3602—Surface 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
    • C03C17/3626—Surface 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
    • 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
    • C03C17/36—Surface 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
    • C03C17/3602—Surface 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
    • C03C17/3639—Multilayers containing at least two functional metal layers
    • 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
    • C03C17/36—Surface 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
    • C03C17/3602—Surface 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
    • C03C17/3644—Surface 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 metal being silver
    • 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
    • C03C17/36—Surface 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
    • C03C17/3602—Surface 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
    • C03C17/3657—Surface 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
    • C03C17/366—Low-emissivity or solar control 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the present disclosure relates, in general to a glazing comprising a transparent substrate, on the surface of which a stack of thin layers is deposited which comprises one functional layer based on silver and multiple other functional layers based on titanium nitride making the substrate possible to act on the solar and/or infrared radiation likely to strike said surface. More specifically the invention relates to a glazing comprising a monolayer silver stack that achieves high selectivity equivalent to that of bilayer silver stack.
  • VLT visual light transmission
  • a glass substrate provided with a single silver layer in the coating generally achieves selectivity between 1.2 and 1.4.
  • a glass substrate provided with double and triple silver layers in the coating generally achieve selectivity up to 1.8 and 2.2, respectively.
  • Such solar control products are now commonly available in the market. It should be quite clear that increasing the amount of silver improves the selectivity of a coating. However, this results in an increase in light reflection to levels considered aesthetically undesirable especially greater than 25% or even 27%, for a visible transmission between 20% – 55%, particularly for stacks comprising a monolayer of silver. And further makes these coatings largely expensive owing to the increased cost associated with the increased silver content.
  • Other highly conducting metals such as gold, copper, etc.
  • Titanium nitride when deposited close to working point, shows excellent IR reflectivity while keeping visual light transmission reasonably high. This makes TiN a good candidate to substitute silver layers in a coating. Unfortunately, TiN has a much higher emissivity in comparison to silver. This means replacing all silver layers of a coating by TiN will not result in comparable performances.
  • the present invention proposes TiN as a material to be used alongside a monolayer of silver in a coating to achieve high selectivity (>1.5).
  • JP2006143525A is particularly referenced for disclosing a thermal barrier film including a silver layer and a titanium nitride or oxynitride layer as the main components for achieving high visible light transmittance, low visible light reflectance, and high heat shielding performance.
  • the invention proposes a glass plate having an antireflection film on the outdoor side and a thermal barrier film on the indoor side surface.
  • positioning of the TiN layer over the silver functional layer in the stack configuration compromises the U-value.
  • WO2019/097192, WO2010072973, WO2010072974 and WO2014/044984 disclose thin film stacks comprising a single silver functional layer and one or more absorbent layers based on titanium or titanium nitride material to reduce light reflection. Solutions proposed in these prior art references show low selectivity (>1.4), high visible light transmission values (>55%) and do not particularly optimize achieving low emissivity, high selectivity alongside low internal and external reflection.
  • the objective of the invention is to overcome the drawbacks of the prior art, by developing a new type of stack with a single silver based functional layer positioned atop another functional layers based on TiN in order to achieve a low emissivity and high selectivity with visible light transmission values ranging between 20% to 55%.
  • the titanium nitride functional layer was found to be deposited as significantly thick layer.
  • deposition of thick titanium nitride layer leads to building up of stress in the coating layer which in turn leads to cracking in the coating stack, in few instances.
  • the present invention achieves the desired solar performance and aesthetic characteristics by splitting the thick titanium nitride functional layer into multiple thin layers to overcome the abovementioned problems.
  • Such a deposition of thin titanium nitride layers allows for flexibility in the coating line and as well contributes to the coating durability.
  • a glazing comprising a transparent substrate with a stack of thin layers.
  • Two functional layers are provided to have reflection properties in the infrared and/or solar radiation range.
  • Dielectric coatings each comprising one or more dielectric layers are provided such as to sandwich each of the functional layers.
  • Each dielectric layer independently comprises a dielectric material.
  • the functional layers based on titanium nitride has an extinction coefficient k>3 in the wavelength ranging between 1000 nm to 2500 nm and are all positioned below the functional layer based on silver or silver-containing metal alloy.
  • a glazing comprising a transparent substrate with a stack of thin layers comprising starting from the substrate: a first dielectric coating; a first functional layer based on titanium nitride having reflection properties in the infrared and/or solar radiation range, wherein the first functional layer has an extinction coefficient k>3 in the wavelength ranging between 1000 nm to 2500 nm; a second dielectric coating; a second functional layer based on silver or silver-containing metal alloy having reflection properties in the infrared and/or solar radiation range; and a third dielectric coating is disclosed.
  • the first functional layer based on titanium nitride is spilt by dielectric coatings into two layers, each interposed between two dielectric coatings.
  • a glazing comprising a transparent substrate with a stack of thin layers comprising starting from the substrate: a first dielectric coating; a first functional layer based on titanium nitride having reflection properties in the infrared and/or solar radiation range, wherein the first functional layer has an extinction coefficient k>3 in the wavelength ranging between 1000 nm to 2500 nm; a second dielectric coating; a second functional layer based on silver or silver-containing metal alloy having reflection properties in the infrared and/or solar radiation range; and a third dielectric coating is disclosed.
  • the first functional layer based on titanium nitride is spilt by dielectric coatings into three layers, each interposed between two dielectric coatings.
  • the glazing is characterized in that when said transparent substrate is mounted in a double glazing with the stack of thin layers on face 2, the double glazing has visible light transmission ranging between 20% to 55%; and high selectivity greater than 1.5.
  • a glazing comprising a transparent substrate with a stack of thin layers comprising starting from the substrate: a first dielectric coating; a first functional layer based on titanium nitride having reflection properties in the infrared and/or solar radiation range, wherein the first functional layer has an extinction coefficient k>3 in the wavelength ranging between 1000 nm to 2500 nm; a second dielectric coating; a second functional layer based on silver or silver-containing metal alloy having reflection properties in the infrared and/or solar radiation range; and a third dielectric coating is disclosed.
  • the first functional layer based on titanium nitride is spilt by dielectric coatings into four layers, each interposed between two dielectric coatings.
  • FIG. 1 illustrates a stack of thin layers deposited on a transparent glass substrate, according to one embodiment of the present disclosure
  • FIG. 2 illustrates a stack of thin layers deposited on a transparent glass substrate, according to one other embodiment of the present disclosure
  • FIG.3A, 3B, 3C illustrate a stack of thin layers deposited on a transparent glass substrate, according to three exemplary embodiments of the present disclosure, respectively.
  • Skilled artisans appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. Detailed Description Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or similar parts.
  • Embodiments disclosed herein are related to a solar control glazing comprising a single silver based functional layer positioned atop multiple functional layers based on TiN, having reflection properties in the infrared and/or solar radiation.
  • the proposed glazing achieves higher selectivity (>1.5, even >1.6) as compared to conventional glazing comprising stacks having a single silver based functional layer and conventional stacks mentioned in prior art that does not comprise any absorbing layers having selectivity close to 1.4 or even 1.45.
  • the proposed glazing stack is a cost effective alternative to coating stack comprising bilayer silver functional layers as it provides for replacing one of the silver functional layer with a less expensive material such as TiN and yet achieves high selectivity as that of the bilayer silver functional layer stack.
  • the solar factor "FS" corresponds to the ratio in% between the total energy entering the room through the glazing and the incident solar energy.
  • luminous characteristics described herein are obtained according to the principles and methods of the European standard EN 410 relating to the determination of the luminous and solar characteristics of glazing used in glass for construction.
  • Properties such as selectivity, outer or inner light reflection and color properties are calculated with: materials comprising a substrate coated with a stack of layers according to the present invention mounted in a double glazing unit, the double glazing having a configuration: 6-15 (Ar-90%) -6, that is to say a configuration consisting of a material comprising a substrate and another 6 mm glass substrate; two substrates are separated by a lamina of intermediate gas with 90% of argon and 10% of air with a thickness of 15 mm with the stack positioned in face 2.
  • FIG. 1 illustrates a structure of a stack of thin layer having two functional layers 50, 100 deposited on a transparent substrate 10.
  • Each of the functional layers 50, 100 is positioned between dielectric coatings 20 (first dielectric coating), 40 (second dielectric coating), 60 (third dielectric coating) such that: the first functional layer 50, starting from the substrate, is positioned between the dielectric coatings 20, 40 and the second functional layer 100 is positioned between the dielectric coatings 40, 60.
  • the dielectric coatings 20, 40, 60 each include at least one dielectric layer viz., 21; 41; 61.
  • Each dielectric layer includes a dielectric material.
  • the functional layer 50 is based on titanium nitride having reflection properties in the infrared and/or solar radiation range and has an extinction coefficient k>3 in the wavelength ranging between 1000 nm to 2500 nm.
  • the functional layer 50 according to several embodiments of the present invention can be spilt into multiple thin layers (not more than four) viz., 50a, 50b, 50c, and 50d. When spilt each of these thin layers 50a, 50b, 50c, and 50d is sandwiched between dielectric coatings 41a, 41b, 41c, 41d.
  • the dielectric coatings 41a, 41b, 41c, 41d each include at least one dielectric layer. Each dielectric layer includes a dielectric material.
  • the dielectric coating 40 placed above the functional layer 50 comprising at least one dielectric layer 41 is spilt into layers 41a, 41b, 41c, 41d such as to sandwich each of the thin functional layers 50a, 50b, 50c, and 50d.
  • the functional layer 100 is based on silver or silver-containing metal alloy having reflection properties in the infrared and/or solar radiation range.
  • the stack of thin layer comprises no more than one functional layer based on silver or silver-containing metal alloy.
  • the invention relates to a material comprising a transparent substrate coated with a stack of thin layers comprising, starting from the substrate: - a first dielectric coating; - a first functional layer based on titanium nitride having reflection properties in the infrared and/or solar radiation range, - a second dielectric coating; - a second functional layer based on silver or silver-containing metal alloy having reflection properties in the infrared and/or solar radiation range; and - a third dielectric coating, wherein the titanium nitride functional layer is deposited as multiple thin layers each sandwiched by dielectric layers of the second dielectric coating.
  • All the functional layers based on titanium nitride is positioned below the functional layer based on silver or silver containing metal alloys to provide low emissivity and high selectivity.
  • the total optical thickness (nd, calculated at 480 nm wavelength) of the dielectric coating interposed between the titanium nitride functional layer closest to the substrate and the functional layer based on silver or silver-containing metal alloy ranges between 40 to 300 nm.
  • total optical thickness (nd, calculated at 480 nm wavelength) of the dielectric coating 40 that is interposed between the titanium nitride functional layer 50a closest to the substrate and the functional layer 100 based on silver or silver-containing metal alloy ranges between 40 to 300 nm.
  • the invention also relates to a multiple glazing comprising at least one material according to the invention and at least one second substrate, the material and the second substrate are separated by at least one interlayer of gas.
  • the stack is positioned in face 2.
  • the double glazing presents: - a selectivity greater than 1.5 or 1.6, - visible light transmission ranging between 20% to 55% - glass side reflection (Rg) less than 25%, - coating side reflection (Rc) less than 20%,
  • the high selectivity of the stack of thin layers, attributable to the presence of titanium nitride layers in combination with silver both reflecting infrared and/or solar radiation, depends on its position and thickness and also its extinction coefficient k>3 in the wavelength ranging between 1000 nm to 2500 nm that maximizes the reflection property.
  • Titanium nitride layers when deposited close to working point (herein ‘working point’ refers to the stack position of TiN layer that is optimally nitrided whose nitrogen content is optimal enough to nitride the layer as well as retain high deposition rate), shows excellent IR reflectivity while keeping visual light transmission reasonably high.
  • working point refers to the stack position of TiN layer that is optimally nitrided whose nitrogen content is optimal enough to nitride the layer as well as retain high deposition rate
  • titanium nitride has much higher emissivity as compared to silver.
  • the silver layer can then be used as a top functional layer to achieve low emissivity and high selectivity.
  • the lower silver layer can be replaced with a less expensive yet IR reflective material such as titanium nitride to achieve a product which is far less expensive but performs (selectivity) better than a monolayer silver stack.
  • a monolayer silver stack have a selectivity of ⁇ 1.5
  • the stack of thin layers of the present invention can achieve selectivity >1.5 or even >1.6 using a combination of functional layers: one based on silver or silver containing metal alloys and more than one other functional layer based on titanium nitride.
  • the stack Surprisingly, by configuring the stack to: - provide low emissivity in spite of employing TiN layers by placing a silver layer atop it; - optimizing the thickness of the dielectric coatings (especially those that are lying there between the titanium nitride layer closest to the substrate and the functional layer based on silver) to maximally reflect IR while at the same time allowing visible light as much as possible, - achieving desired thickness of titanium nitride by depositing multiple thin layers of titanium nitride, each sandwiched by dielectric layers we obtain a material that satisfies: - high selectivity, - desirable visible light transmission between 20% to 55%, - less than 25% glass side reflection, - less than 20% coating side reflection, - low emissivity ⁇ 0.12, - solar factor in order of increasing preference less than 37%, 34%, 30%
  • the preferred features which appear in the remainder of the description are applicable both to the material according to the invention and, where appropriate, to the glazing or to the process according to the invention
  • the thicknesses discussed herein are optical thicknesses (nd) at 480 nm wavelength, wherein ‘n’ denotes the actual refractive index of a dielectric layer at the given wavelength and ‘d’ is the physical thickness of the dielectric layer.
  • the layers are thin layers. By thin film is meant a layer having a thickness of between 0.1 nm and 100 micrometers.
  • the phrase "reflection properties in the infrared and/or solar radiation" with particular reference to the material titanium nitride means a layer made of a material having an extinction coefficient k>3 in the wavelength ranging between 1000 nm to 2500 nm.
  • IR reflection the reflection of infrared radiation in the solar spectrum, between 1000 nm to 2500 nm, due to the reflecting layer, measured by depositing only this reflecting layer (30 nm of TiN layer) on plain clear glass of 4 mm.
  • the reflection, measured on the coating side, is greater than 50%.
  • the stack comprises two or three or four functional layers based on titanium nitride (TiN x ), wherein x ranges between 0.7 and 1.3.
  • the titanium nitride based functional layers comprises less than 10.0% by weight of oxygen.
  • One or all titanium nitride based functional layers may also include elements selected from, for example, Mo or Nb.
  • each of these elements represents less than 10%, less than 5%, less than 2%, less than 1%, less than 0.5% by weight of the functional titanium nitride layer.
  • the maximum proportions of these element depend on the nature of these element.
  • the total physical thickness of all titanium nitride functional layers present in the layer stack ranges between 4 nm and 60 nm.
  • the multiple TiN x layers according to various embodiments of the present invention can have identical or non-identical thickness, their individual thicknesses totaling to thickness ranging between 4 nm and 60 nm.
  • the stack comprises a single functional metallic layer based on silver. This type of stack is also called "functional monolayer stacking".
  • a silver-based functional layer comprises at least 85.0%, preferably at least 90%, and most preferably at least 95%, by weight of silver relative to the weight of the functional layer.
  • the silver-based functional metal layer comprises less than 1.0% by weight of non-silver metals relative to the weight of the silver functional metal layer.
  • the silver-based functional metal layer may also include elements selected from, for example, copper, palladium, gold or aluminum or their combinations thereof. Preferably, each of these elements represents less than 15%, less than 10%, less than 5%, less than 1%, less than 0.5% by weight of the functional silver-based metal layer.
  • the maximum proportions of these element depend on the nature of these element.
  • the physical thickness of the silver-based functional layer ranges between 8 nm and 20 nm.
  • the silver-based functional layer may be protected by a layer known as a blocking layer.
  • the stack of thin layers further comprises at least one blocking layer 90, 91 located in direct contact with below and above the silver-based functional layer (as shown in FIG.2).
  • the blocking layers are chosen from metal layers based on a metal or a metal alloy or metal nitride layers of one or more elements chosen from titanium, nickel, chromium, niobium, zirconium, silica and aluminum such as Ti, Nb, NbN, NiCr, Zr, SiAl, NbZr.
  • these blocking layers When these blocking layers are deposited in metallic or nitrided form, these layers may undergo partial or total oxidation according to their thickness and the nature of the layers which surround them, for example, at the time of deposition of the next layer or by oxidation in contact with the underlying layer.
  • the blocking layers are preferably chosen from metal layers, especially of a nickel-chromium (NiCr) alloy. Each blocking layer has a physical thickness ranging between 0.4 nm and 3.0 nm.
  • the blocking layers although deposited in metallic form and presented as being metal layers, are in practice oxidized layers because their primary function is to oxidize during the deposition of the stack in order to protect the functional layer.
  • a blocking layer is however sometimes interposed between one or each dielectric coating and the functional silver layer, the blocking layer disposed under the functional layer towards the substrate protects it during a possible heat treatment at high temperature, the bending type and and/ or quenching and the blocking layer disposed on the functional layer opposite the substrate protects this layer from possible degradation during the deposition of the upper dielectric coating and during a possible heat treatment at high temperature, such as bending and/ or quenching.
  • the blocking layers are provided below and/or above the titanium nitride functional layer.
  • the blocking layer provided above and/or below the titanium nitride functional layer are chosen from metal layers based on a metal or a metal alloy or metal nitride layers of one or more elements chosen from titanium, nickel, chromium, niobium, zirconium, silica and aluminum such as Ti, Nb, NbN, NiCr, Zr, SiAl, NbZr.
  • the functional layer based on titanium nitride and the functional layer based on silver or silver containing metal alloy are each arranged between two dielectric coatings.
  • the stack of thin layer of the invention is provided on at least one of the faces of the transparent substrate.
  • the thickness of the dielectric coating corresponds to the sum of the individual thicknesses of the layer(s) constituting the coating.
  • the total optical thickness (nd, calculated @ 480nm) of the dielectric coating 40 separating the functional layer based on titanium nitride closest of the substrate and the functional layer based on silver or silver containing metal alloys ranges between 40 to 300 nm.
  • the dielectric coating 20 closest to the transparent substrate 10 and the dielectric coating 60 farthest from the transparent substrate each have a total optical thickness (nd, calculated @480nm) ranging between 40 nm and 200 nm.
  • dielectric layer in the sense of the present invention, it should be understood that from the point of view of its nature, the material is “non-metallic", that is to say is not a metal. In the context of the invention, this term designates a material having an n / k ratio over the entire visible wavelength range (from 380 nm to 780 nm) equal to or greater than 5.
  • the dielectric layers of the coatings have the following characteristics alone or in combination: - they are deposited by magnetic field assisted sputtering, - they are chosen from oxides or nitrides or oxynitrides of one or more elements chosen from titanium, silicon, aluminum, zirconium, tin, niobium and zinc or their combinations thereof, - they have a physical thickness of up to 150 nm, preferably between 1 nm and 150 nm and most preferably between 20 nm and 150 nm.
  • the dielectric layers may have a barrier function.
  • barrier layer is understood to mean a layer made of a material capable of impeding the diffusion of oxygen and water at high temperature, originating from the ambient atmosphere or from the substrate. transparent, towards the functional layer.
  • Such dielectric layers are chosen from the layers: - based on silicon and / or aluminum compounds chosen from oxides such as SiO 2 , nitrides such as silicon nitride Si 3 N 4 and aluminum nitrides AIN, and oxynitrides SiOxNy, optionally doped with at least one other element, - based on zinc oxide and tin, - based on titanium oxide.
  • the dielectric layers may also be so-called layers of wetting layers.
  • wetting layer is meant a layer of a material capable of stabilizing the interface with the functional layer.
  • These wetting layers are generally based on zinc oxide.
  • the zinc oxide layer may be optionally doped with at least one other element, such as aluminum.
  • the dielectric coating in few embodiments of the present invention comprise of at least one dielectric layer with barrier function and at least one dielectric layer as wetting layer.
  • the dielectric layers can also be chosen according to their refractive index.
  • One or more dielectric coatings, according to a few embodiments of the present invention further comprise a layer of absorber material. In such embodiments, the layer having the absorber material is in contact and in between two dielectric layers of one or more dielectric coatings.
  • Such an absorber layer may comprise Nb, Zr, NbZr, NiCr, Ni, Cr, Si, Mn, Mo, Pd, Ta, W, In, Sn, InSn, Cu, Al, Zn, V, stainless steel, or their nitrides, oxides or oxynitrides. Thickness of such absorbent layer is in the range of 0.5 nm and 5 nm.
  • the position of the absorber layer sandwiched between the dielectric layers of a dielectric coating provides for a better control over reflection values both in the external glass side and the internal coating side. Further this configuration of the absorber layer provides for achieving a wide range of reflection colors while maintaining the desired levels of reflection.
  • the dielectric coating 20 comprising the dielectric layer 21 based on silicon nitride is located directly in contact with the transparent substrate below the functional layer 50 based on titanium nitride; the dielectric coating 40 comprising the dielectric layer 41 based on silicon nitride is located directly above and in contact with the functional layer 50 based on titanium nitride; the functional layer 50 based on titanium nitride is spilt into 50a and/or 50b and/or 50c and/or 50d and sandwiched by dielectric layer 41a and/or 41b and/or 41c and/or 41d; the dielectric coating 60 comprising the dielectric layer 61 based on silicon nitride is located above the functional layer 100 based on silver or silver containing metal alloy.
  • the stack of thin layers may optionally comprise an overcoat layer 80, as shown in FIG. 2.
  • the overcoat layer is preferably the last layer of the stack, that is to say the layer furthest from the substrate coated with the stack (before heat treatment). These layers generally have a thickness of between 0.5 and 10 nm, preferably 1 and 5 nm.
  • This overcoat layer may be chosen from a layer comprising titanium or zirconium, or these metals being in metallic, oxidized or nitrided form (partially or wholly). According to one embodiment, the overcoat layer is based on titanium zirconium oxide and / or nitride, preferably based on titanium zirconium nitride.
  • the transparent substrates according to the invention are preferably in a mineral rigid material, such as glass, or organic based on polymers (or polymer).
  • the substrate is preferably glass or glass-ceramic sheet.
  • the substrate is preferably transparent, colorless (it is then a clear or extra-clear glass) or colored, for example blue, gray or bronze.
  • the glass is preferably of the silico-soda-lime type, but it may also be of borosilicate or alumino- borosilicate type glass.
  • the substrate is made of glass, in particular silico-soda-lime or polymeric organic material.
  • the substrate advantageously has at least one dimension greater than or equal to 1 m, or even 2 m and even 3 m.
  • the thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, especially between 2 and 8 mm, or even between 4 and 6 mm.
  • the substrate may be flat or curved, or even flexible.
  • the invention also relates to a method for preparing a material comprising a transparent substrate coated with a thin film stack deposited by cathodic sputtering possibly assisted by a magnetic field, the method comprises the following sequence of steps: (i) first dielectric coating comprising at least one dielectric layer is deposited on the transparent substrate, (ii) a first functional layer based on titanium nitride is then deposited, (iii) a second dielectric coating comprising at least one dielectric layer is deposited on titanium nitride layer, (iv) steps (ii) and (iii) are repeated twice or thrice or four times according to multiple embodiments of the present invention, (v) one another functional layer based on silver or silver- containing metal alloy is then deposited followed
  • the label “first”, “second”, “third” for the functional layers and/ or dielectric coatings are defined starting from the substrate bearing the stack and with reference to the layers or coatings having the same function.
  • the functional layer closest to the substrate is the first functional layer
  • the next one moving away from the substrate is the second functional layer.
  • the dielectric coating closest to the substrate is the first dielectric coating
  • the next one moving away from the substrate is the second dielectric coating etc.
  • the solar control glass article 101 is provided with a temporary protective coating conventionally known in the art in order as the furthest layer from the substrate to protect the underlying stack of thin layers during heat treatment. As is known from the conventional processes this temporary protective layer is burned off during the heat treatment.
  • the invention also relates to a glazing unit comprising at least one material according to the invention.
  • the glazing may be in the form of monolithic glazing or single glazing, laminated glazing or multiple glazing.
  • a monolithic glazing has 2 faces, the face 1 is outside the building and therefore constitutes the outer wall of the glazing, the face 2 is inside the building and therefore constitutes the inner wall of the glazing.
  • a double glazing has 4 faces, the face 1 is outside the building and therefore constitutes the outer wall of the glazing, the face 4 is inside the building and therefore constitutes the inner wall of the glazing, the faces 2 and 3 being inside the double glazing.
  • the stack is preferably positioned in the glazing so that the incident light coming from outside passes through the first dielectric coating before passing through the first functional metallic layer.
  • the stack is not deposited on the face of the substrate that defines the external wall of the glazing but on the inner face of this substrate.
  • the stack is therefore advantageously positioned on face 2, face 3 of the glazing being the outermost face of the glazing, as is customary.
  • the glazing is preferably chosen from multiple glazings, in particular a double- glazing unit or a triple-glazing unit, comprising at least one material according to the invention and at least one second substrate, the material and the second substrate being separated by at least one intermediate gas, said glazing providing a separation between an outer space and an interior space.
  • These double glazings advantageously have: - visible light transmission ranging between 20% to 55%, and / or - high selectivity greater than 1.5, more preferably greater than 1.6, and / or - glass side reflection (Rg) less than 25%, and / or - coating side reflection (Rc) less than 20%.
  • These windows are mounted on a building or a vehicle.
  • the material that is to say the substrate coated with the stack, may undergo a high-temperature heat treatment such as an annealing, for example a flash annealing such as a laser or flame annealing, a tempering and/or a bending.
  • the temperature of the heat treatment is greater than 500° C, preferably greater than 550° C, and better still greater than 600° C.
  • the substrate coated with the stack may therefore be curved and/or tempered.
  • the stack is preferably deposited on face 2, that is to say that it is on the substrate that defines the external wall of the glazing and more specifically on the inner face of this substrate.
  • a monolithic glazing comprises 2 faces; face 1 is on the outside of the building and therefore constitutes the external wall of the glazing, face 2 is on the inside of the building and therefore constitutes the internal wall of the glazing.
  • a multiple glazing comprises at least two substrates kept at a distance so as to delimit a cavity filled by an insulating gas (e.g., dry air, Ar, Kr or their mixture).
  • an insulating gas e.g., dry air, Ar, Kr or their mixture.
  • the materials according to the invention are very particularly suitable when they are used in double glazings with enhanced thermal insulation (ETI).
  • a double glazing comprises 4 faces; face 1 is outside of the building and therefore constitutes the external wall of the glazing, face 4 is inside the building and therefore constitutes the internal wall of the glazing, faces 2 and 3 being on the inside of the double glazing.
  • a triple glazing comprises 6 faces; face 1 is outside of the building (external wall of the glazing), face 6 is inside the building (internal wall of the glazing) and faces 2 to 5 are on the inside of the triple glazing.
  • a laminated glazing comprises at least one structure of first substrate/sheet(s)/second substrate type. The stack of thin layers is positioned on at least one of the faces of one of the substrates. The stack may be on the face of the second substrate not in contact with the, preferably polymer, sheet.
  • This embodiment is advantageous when the laminated glazing is assembled as double glazing with a third substrate.
  • the glazing according to the invention used in a multiple glazing e.g., a double glazing unit, has internal and external reflection colors that is not too dull at the same time is not too reflective. These two features aid in visual comfort for people facing the interior and exterior of the glazing. Furthermore, these visual appearances change minimally irrespective of the angle of incidence with which the glazing is observed (normal incidence and under an angle). This means that an observer does not have the impression of a significant lack of uniformity in color or in appearance.
  • a coated solar control glass article 101 having the stack of thin layers comprises starting from the glass substrate 10, as illustrated in FIG.3A: a first dielectric coating 20 consisting of a dielectric layer 21 made of silicon nitride; a functional layer 50 based on TiN x spilt into two layers 50a, 50b; a second dielectric coating 40 consisting of a dielectric layer 41 spilt into two layers 41a, 41b each made of silicon nitride; a blocking layer 90 made of Ni and Cr; a second functional layer 100 based on silver; a blocking layer 91 made of Ni and Cr; a third dielectric coating 60 consisting of a dielectric layer 61 made of silicon nitride; and optionally one overcoat layer 80 made of TiZrN x .
  • a coated solar control glass article 101 having the stack of thin layers comprises starting from the glass substrate 10, as illustrated in FIG.3B: a first dielectric coating 20 consisting of a dielectric layer 21 made of silicon nitride; a functional layer 50 based on TiN x spilt into three layers 50a, 50b, 50c; a second dielectric coating 40 consisting of a dielectric layer 41 spilt into three layers 41a, 41b, 41c each made of silicon nitride; a blocking layer 90 made of Ni and Cr; a second functional layer 100 based on silver; a blocking layer 91 made of Ni and Cr; a third dielectric coating 60 consisting of a dielectric layer 61 made of silicon nitride; and optionally one overcoat layer 80 made of TiZrN x .
  • a coated solar control glass article 101 having the stack of thin layers comprises starting from the glass substrate 10, as illustrated in FIG.3C: a first dielectric coating 20 consisting of a dielectric layer 21 made of silicon nitride; a functional layer 50 based on TiN x spilt into four layers 50a, 50b, 50c, 50d; a second dielectric coating 40 consisting of a dielectric layer 41 spilt into four layers 41a, 41b, 41c, 41d each made of silicon nitride; a blocking layer 90 made of Ni and Cr; a second functional layer 100 based on silver; a blocking layer 91 made of Ni and Cr; a third dielectric coating 60 consisting of a dielectric layer 61 made of silicon nitride; and optionally one overcoat layer 80 made of TiZrN x .
  • Example 1 The following example illustrate the present invention. Preparation of the Substrates: Stack of thin layers and Heat Treatments Stack of thin layers, defined below, are deposited on substrates made of clear soda-lime glass with a thickness of 6 mm.
  • one functional layer is a layer of silver (Ag)
  • two or more other functional layers are layers of titanium nitride (TiN x )
  • the blocking layers are metallic layers made of nickel-chromium alloy (NiCr)
  • the dielectric barrier layers are based on silicon nitride (Si 3 N 4 )
  • the overcoat layer is made of titanium zirconium oxide (TiZrNx).
  • Table 1 lists the materials and thicknesses in nanometers for each layer or coating that forms the stacks as a function of their position with respect to the substrate bearing the stack (final line at the bottom of the table).
  • the “Ref.” numbers correspond to the references from FIG.3A.
  • Example 2 Comparative samples 1, 2, 3 were also prepared using solar control product available in the market place comprising a single layer of silver that exhibit a selectivity of ⁇ 1.5.
  • T L indicates: the light transmission in the visible region in %, measured according to the illuminant D65 Obs 2; a*T and b*T indicate the a* and b* colors in transmission in the L*a*b* system measured according to the illuminant D65 Obs 2 and measured perpendicularly to the glazing;
  • R ext indicates: the light reflection in the visible region in %, measured according to the illuminant D65 Obs 2 on the side of the outermost face, face 1; a*R ext and b*R ext indicate the a* and b* colors in reflection in the L*a*b* system measured according to the illuminant D65 Obs 2 on the side of the outermost face and thus measured perpendicularly to the glazing;
  • R int indicates: the light reflection in the visible region in %, measured according to the illuminant D65 Obs 2 on the side of the internal face, face 4; a*R int and b*R int
  • the colorimetric values at an angle a*g60° and b*g60° are measured on single glazing under an incidence of 60° is shown in Table 4. This takes into account the stability of the colors at an angle.
  • the samples according to the present invention all achieve high selectivity values >1.6, more particularly >1.65.
  • the inventive samples are particularly advantageous since they have, in addition to a high selectivity, low external reflection, particularly less than 20%, low internal reflection, particularly less than 15%.
  • the proposed invention therefore makes it possible to achieve combined desired solar performance, optical and aesthetic properties.
  • Comparative samples 1, 2, 3 are particularly useful to demonstrate how the inventive samples prepared according to the teachings of the present invention have improved performance (selectivity) as compared to conventional coated products having a single layer of silver.
  • the inventive sample is able to achieve a high selectivity without any additional silver layers.
  • Industrial Applicability The glazing described in the present disclosure finds application as a glazed element in building.
  • the glazing may form a double or triple glazing with the coating side of the glass arranged facing the closed space inside the multiple glazing.
  • the glazing may also form a laminated glazing whose stack of layers may be in contact with the thermoplastic adhesive material connecting the substrates, in general PVB.
  • the glazing according to the invention is, however, particularly useful when the multilayer stack is facing the outer environment, whether it is an insulated glazing or laminated glazing, but also optionally a multiple glazing.
  • the glazing may also be enameled.
  • the glazing of the present disclosure can also be annealed, strengthened, toughened, tempered or curved and/or bent.
  • the tempered glazing can also be used in building wall cladding panel of curtain walling for interior applications. Further an also be used as a side window, rear window or sunroof for an automobile or other vehicle. Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described.
  • a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • A is true (or present) and B is false (or not present)
  • A is false (or not present) and B is true (or present)
  • both A and B are true (or present).
  • the use of "a” or “an” is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural, or vice versa, unless it is clear that it is meant otherwise. For example, when a single item is described herein, more than one item may be used in place of a single item.

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Abstract

Un empilement de couches minces sur un substrat transparent comprend n couches fonctionnelles ayant des propriétés de réflexion dans la plage de rayonnement infrarouge et/ou solaire à base d'argent ou d'alliage métallique contenant de l'argent, n = 1 ; une autre couche fonctionnelle ayant des propriétés de réflexion dans la plage de rayonnement infrarouge et/ou solaire à base de nitrure de titane et de revêtements diélectriques placés de manière à prendre en sandwich chacune des couches fonctionnelles. La couche fonctionnelle à base de nitrure de titane peut être répandue par des revêtements diélectriques jusqu'à quatre couches, chacune interposée entre deux revêtements diélectriques. Les couches fonctionnelles à base de nitrure de titane ont un coefficient d'extinction k > 3 dans la longueur d'onde allant de 1000 nm à 2500 nm et sont toutes situées au-dessous de la couche fonctionnelle à base d'argent ou d'alliage métallique contenant de l'argent. Ce nouveau type d'empilement ayant une combinaison de couches fonctionnelles : l'une à base d'argent et l'autre à base d'étain présente une performance (sélectivité) améliorée par comparaison avec des empilements de revêtement comprenant une seule couche fonctionnelle d'argent existant dans l'état de la technique.
PCT/IN2023/050797 2022-08-26 2023-08-24 Vitrage comprenant un empilement de couches minces ayant une couche fonctionnelle à base d'argent et de multiples couches fonctionnelles à base de nitrure de titane WO2024042546A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7166360B2 (en) * 2000-12-15 2007-01-23 Saint-Gobain Glass France Glazing provided with a stack of thin layers for solar protection and/or heat insulation
WO2020083873A1 (fr) * 2018-10-22 2020-04-30 Mimsi Materials Ab Vitrification et procédé destiné à sa production
WO2021214109A1 (fr) * 2020-04-21 2021-10-28 Mimsi Materials Ab Vitrage à commande solaire et procédé de production associé

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7166360B2 (en) * 2000-12-15 2007-01-23 Saint-Gobain Glass France Glazing provided with a stack of thin layers for solar protection and/or heat insulation
WO2020083873A1 (fr) * 2018-10-22 2020-04-30 Mimsi Materials Ab Vitrification et procédé destiné à sa production
WO2021214109A1 (fr) * 2020-04-21 2021-10-28 Mimsi Materials Ab Vitrage à commande solaire et procédé de production associé

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