EP3762342A1 - Material provided with a stack having thermal properties - Google Patents
Material provided with a stack having thermal propertiesInfo
- Publication number
- EP3762342A1 EP3762342A1 EP19713108.9A EP19713108A EP3762342A1 EP 3762342 A1 EP3762342 A1 EP 3762342A1 EP 19713108 A EP19713108 A EP 19713108A EP 3762342 A1 EP3762342 A1 EP 3762342A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- thickness
- dielectric
- layers
- functional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C03C17/36—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
- C03C17/3613—Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
-
- 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
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
-
- 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
-
- 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
- C03C17/3652—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 coating stack containing at least one sacrificial layer to protect the metal from oxidation
-
- 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
-
- 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
- C03C17/3668—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 electrical 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
- C03C17/3681—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 being used in glazing, e.g. windows or windscreens
-
- 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
- C03C2217/25—Metals
- C03C2217/251—Al, Cu, Mg or noble metals
- C03C2217/254—Noble metals
- C03C2217/256—Ag
-
- 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
Definitions
- the invention relates to a material comprising a transparent substrate coated with a stack of thin layers comprising a plurality of functional layers that can act on solar radiation and / or infrared radiation.
- the invention also relates to glazing comprising these materials as well as the use of such materials to manufacture thermal insulation glazing and / or sun protection.
- glazings can be intended both to equip buildings and vehicles, especially to reduce the air conditioning effort and / or to prevent excessive overheating, so-called “solar control” glazing and / or reduce the amount of energy dissipated to the outside, so-called “low emissivity” glazing driven by the ever increasing importance of glazed surfaces in buildings and vehicle interiors.
- One of the objectives of the invention is to develop a material that is both "low emissive” and “solar control".
- the material or glazing must be selective.
- the solar factor "FS or g” corresponds to the ratio in% between the total energy entering the room through the glazing and the incident solar energy.
- Known selective glazings comprise transparent substrates coated with a stack of thin layers comprising three metal functional layers, each disposed between two dielectric coatings. Such glazing can improve the sun protection while maintaining a high light transmission. These stacks are generally obtained by a succession of deposits made by cathodic sputtering possibly assisted by magnetic field.
- Another object of the invention is to obtain an exceptionally neutral aesthetic in exterior reflection, interior and transmission.
- the known stacks are colors in external reflection in the range of blue or blue-green.
- Blue-green colors correspond to negative values for a * and b * in the L * a * b * color measurement system.
- a * is between -10.0 and 0.0, preferably between -5.0 and 0.0 and
- b * is between -10.0 and 0.0, preferably between -5.0 and 0.0.
- neutral hues in external reflection, internal reflection or transmission are defined by:
- Stacks comprising three metal functional layers are complex stacks. They include many layers of different types and thicknesses deposited by sputtering on large substrates.
- These large substrates are especially flat glass substrates manufactured in the form of a continuous ribbon, for example a continuous ribbon of float glass or cast glass.
- These so-called "PLF” glass substrates are obtained directly by transverse cutting in the glass ribbon. These glass substrates therefore have at least one dimension, generally the width, corresponding to the width of the glass ribbon from which they are derived. The other dimension, generally the length, corresponds to the length of cut tape.
- the so-called "PLF” glass substrates typically have dimensions of 3.21 m by about 6 m.
- thicknesses are sometimes observed for certain layers of the stack perpendicular to the direction of travel of the substrates (transverse uniformity). These variations can reach 5 to 10% of the desired thickness.
- the same stacks are sometimes manufactured on two different production sites. For this, we try to better adapt the sputter deposition parameters to obtain equivalent stacks. However, the adjustment of these parameters can also lead to certain layers of the stack, depending on the production site, thickness variations of up to 5 to 10% of the thickness.
- the object of the invention is to propose a material having a low optical sensitivity in external reflection.
- Low optical sensitivity is understood to mean a slight variation of the color in external reflection for a variation of the thicknesses of the layers composing the stack of the order of 5%. All the luminous characteristics described 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.
- colorimetric properties such as L * , a * and b * values and all values and ranges of optical and thermal characteristics such as selectivity, external or internal light reflection, light transmission and are calculated with :
- the double glazing has a configuration: 6-16 (Ar-90%) -4, that is to say a configuration consisting of a material comprising a 6 mm ordinary soda-lime glass type substrate optionally coated with a stack and another glass substrate of 4 mm soda-lime glass type (uncoated), the two substrates are separated by an interlayer gas blade with 90% argon and 10% air. a thickness of 16 mm,
- the stack is positioned in face 2.
- optical sensitivity AC in external reflection of a layer following a thickness variation of 5% is defined as follows:
- the colorimetric values a * and b * are determined in external reflection.
- the thickness of the layer i is increased by 5% so as to form the layer (i + 5%) with a thickness e (i + 5%).
- the thickness e (i + 5%) is 21 nm.
- the colorimetric values a * (i + 5%) and b * (i + 5%) in external reflection are determined.
- optical sensitivity (ACi) of a layer i is defined by the following equation:
- the optical sensitivity is measured at about 2 °, that is to say with values a * and b * measured perpendicularly to the glazing.
- a low optical sensitivity ACi in external reflection of a layer i results in a value ACi of less than 5, preferably less than 4, and better still less than 3.
- the stack comprising layers has a low optical sensitivity in external reflection. This results in AC.sub.50 values of less than 5, preferably less than 4, and better still less than 3, for all the layers comprising the stack having a thickness of greater than 10 nm, preferably for all the component layers. stacking.
- the ones most likely to generate high ACi values are the thickest layers in the range 10 to 100 nm, especially the layers of 50 to 80 nm.
- a stack with low optical sensitivity is easily adjustable and can improve the quality of production.
- the optical sensitivity of the stack reaches values that are too high, it is considered impossible to produce homogeneously with a constant quality over the width of the substrate, especially in the case of PLF substrate.
- the object of the invention is therefore to overcome these disadvantages by developing a substrate comprising a stack comprising at least three silver-based layers which has a high selectivity, ie a ratio TL / g on higher possible for a given TL value, while ensuring excellent neutrality and low optical sensitivity.
- the Applicant has surprisingly discovered that by combining the use of three silver-based layers of increasing thickness and the choice of similar optical thicknesses for the two dielectric coatings closest to the substrate, and the use of blocking layers all of thin, we get a material, which mounted in double glazing, has high selectivity, excellent neutrality in color but above all low optical sensitivity.
- WO201 1/020974 disclose substrates coated with a stack of thin layers having 3 silver-based functional layers arranged between dielectric coatings.
- the stacks described in document FR 3005048 comprise at least one thick blocking layer of more than 1.8 nm.
- the stacks described in WO2017 / 006027 comprise at least one blocking layer thicker than 1, 8 nm and / or comprise first and second dielectric coatings of very different optical thickness.
- the stacks described in WO2017 / 006029 comprise first and second dielectric coatings of very different optical thickness.
- the document FR2985724 describes substrates coated with a thin film stack comprising 4 silver-based functional layers arranged between dielectric coatings.
- Comparative Example 2 comprises first and second dielectric coatings of very different optical thickness.
- the document WO 201 1/147864 describes substrates coated with a stack of thin layers comprising 3 silver-based functional layers arranged between dielectric coatings.
- the stacks further include absorbent layers.
- the first and second dielectric coatings have very different optical thicknesses.
- the subject of the invention is a material as defined in claim 1.
- This material comprises a transparent substrate coated with a stack of thin layers comprising successively from the substrate an alternation of three functional silver-based metallic layers denoted by starting from the first substrate, second and third functional layers, the thicknesses of the functional metal layers starting from the substrate increase as a function of the distance of the substrate, and four dielectric coatings called starting from the substrate M1, M2, M3 and M4 which have each having an optical thickness Eo1, Eo2, Eo3 and Eo4, each dielectric coating comprising at least one dielectric layer when the dielectric coatings comprise a plurality of dielectric layers, the optical thicknesses Eo1, Eo2, Eo3 and Eo4 are measured in summing the optical thickness of each dielectric layer constituting the dielectric coating.
- Each functional metal layer is disposed between two dielectric coatings.
- the invention is remarkable in that:
- the ratio of the thickness of the second functional metal layer to the thickness of the first functional metal layer Ag 2 / Ag 1 is greater than or equal to 1.05
- the ratio of the thickness of the third functional metal layer to the thickness of the second functional metal layer Ag 3 / Ag 2 is greater than or equal to 1.05
- the dielectric coatings M1 and M2 have optical thicknesses Eo1 and Eo2 of between 50 and 140 nm, the ratio of the optical thicknesses of the first and second dielectric coating Eo1 / Eo2 is between 0.80 and 1, including these values; , preferably between 0.90 and 1, 15, including these values
- the stack comprising at least one blocking layer in contact with a functional metal layer, the thickness of which is between 0.1 and 1.8 nm.
- each blocking layer is between 0.1 and 1, 8 nm.
- the at least one blocking layer is preferably located on a functional metal layer.
- the stack of thin layers comprises successively from the substrate an alternation of only three functional metal layers based on silver.
- the presence of at least one blocking layer while limiting the blocking layer thickness in the stack allows, in the configuration of the invention, to obtain a material, which is mounted in double glazing, has a selectivity high, excellent neutrality in color and a light transmission in the desired range.
- the dielectric coatings M1 and M2 have, in order of increasing preference, an optical thickness of from 60 to 135 nm, from 70 to 130 nm, from 80 to 130 nm.
- the choice of a fourth dielectric coating M4 of low optical thickness also contributes to obtaining the advantageous properties of the invention.
- the optical thickness of the fourth dielectric coating M4 is advantageously less than that of the first dielectric coating M1.
- the ratio of the optical thicknesses of M4 / M1 is, in order of increasing preference, less than or equal to 0.95, less than or equal to 0.90, less than 0.85.
- the optical thickness of the fourth dielectric coating M4 is, in order of increasing preference, from 50 to 120 nm, from 60 to 100 nm, from 70 to 90 nm.
- a high selectivity especially greater than 1, 8 or even greater than 2, and / or
- an interior and exterior light reflection of less than or equal to 20%, preferably of between 10 and 20%, and / or
- a light transmission between 40 and 70%, preferably between 42 and 68%, even between 45 and 60%, or between 50 and 60%, and / or
- the material according to the invention once mounted in double glazing, with the stack positioned in face 2, provides a double glazing having:
- thin film is meant a layer having a (physical) thickness of between 0.1 nm and 100 micrometers.
- the refractive indices are measured at a wavelength of 550 nm.
- the thicknesses mentioned in this document without further details are physical, real or geometrical thicknesses called Ep and are expressed in nanometers (and not optical thicknesses).
- the refractive index being a dimensionless value, it is possible to consider that the unit of the optical thickness is that chosen for the physical thickness.
- a dielectric coating corresponds to a sequence of layers comprising at least one dielectric layer, located between the substrate and the first functional layer (M1), between two functional layers (M2 or M3) or above the last one functional layer (M4). If a dielectric coating is composed of several dielectric layers, the optical thickness of the dielectric coating corresponds to the sum of the optical thicknesses of the different dielectric layers constituting the dielectric coating.
- a dielectric coating comprises an absorbing layer for which the refractive index at 550 nm comprises an imaginary part of the non-zero (or non-negligible) dielectric function, for example a metal layer, the thickness of this layer is not taken into account for the calculation of the optical thickness of the dielectric coating.
- the light transmission (TL) of standard soda-lime glass substrates without stacking is greater than 89%, preferably 90%.
- a glazing for the building generally defines two spaces, a space qualified as "outside” and a space qualified as “interior”. Solar light entering a building is considered to go from the outside to the inside.
- the faces of a glazing are designated from the outside of the building and by numbering the faces of the substrates from the outside towards the interior of the passenger compartment or the room it equips. This means that incident sunlight passes through the faces in increasing order of their number.
- the stack is either located:
- the luminous characteristics are measured according to the illuminant D65 at 2 ° perpendicular to the material mounted in a double glazing unit (unless otherwise indicated):
- the invention also relates to:
- the glazing comprising at least one material according to the invention, the process for preparing a material according to the invention,
- glazing according to the invention as solar control glazing and / or low emissivity for the building or vehicles
- a building or a vehicle comprising a glazing unit according to the invention.
- 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 gas strip.
- the stack is positioned in face 2.
- the present invention makes it possible to obtain a high selectivity S in particular greater than 1, 8 or even greater than 2, a solar factor (FS) of less than 30%, neutral colors in transmission and reflection. outside and inside.
- a solar factor (FS) of less than 30%
- the stack is deposited by sputtering assisted by a magnetic field (magnetron process). According to this advantageous embodiment, all the layers of the stack are deposited by sputtering assisted by a magnetic field.
- the invention also relates to the process for obtaining a material according to the invention, in which the layers of the stack are deposited by magnetron sputtering.
- the terms “above” and “below” do not necessarily mean that two layers and / or coatings are arranged in contact with each other. When it is specified that a layer is deposited "in contact” with another layer or coating, this means that there can not be one (or more) layer (s) interposed between these layers. two layers (or layer and coating).
- the "first”, “second”, “third” and “fourth” qualifications for the functional layers or the dielectric coatings are defined starting from the carrier substrate of the stack and referring to the layers or coatings of 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, and so on.
- the invention also relates to a glazing unit comprising a material according to the invention.
- the silver-based metal functional layers comprise at least 95.0%, preferably at least 96.5% and better still at least 98.0% by weight of silver. relative to the mass 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 thicknesses of the functional metal layers starting from the substrate increase.
- the thickness of the third functional metal layer is greater than that of the second functional metal layer.
- the thickness of the second functional metal layer is greater than that of the first functional metal layer.
- the increase in thickness between two successive functional layers is greater than 0.8 nm, greater than 1 nm, greater than 2 nm, greater than 3 nm or greater than 4 nm.
- the functional metal layers satisfy one or more of the following conditions:
- the ratio of the thickness of the second functional metal layer to the thickness of the first functional metal layer Ag2 / Ag1 is between 1.05 and 2.30 by including these values, between 1.06 and 2.10; or between 1, 07 and 2.00 including these values, and / or
- the ratio of the thickness of the third functional metal layer to the thickness of the second functional metal layer Ag 3 / Ag 2 is between 1.05 and 1.50, including these values, between 1.06 and 1.40; or between 1, 07 and 1, 30 including these values, and / or
- the ratio of the thickness of the third functional metal layer to the thickness of the first functional metal layer Ag 3 / Ag 1 is between 1.15 and 2.50, between 1.20 and 2.30, or between 1, 30 and 2.20, including these values, including these values, and / or
- the thickness of the first functional metal layer is between 6 and 14 nm, between 7 and 13 nm or between 8 and 12 nm, and / or
- the thickness of the second functional metal layer is between 10 and 20 nm, between 11 and 18 nm or between 12 and 15 nm, and / or
- the thickness of the third functional metal layer is between 12 and 20 nm, between 13 and 18 nm or between 15 and 17 nm, and / or
- the total thickness of the functional metal layers is between 30 and 50 nm, including these values, preferably between 35 and 45 nm.
- the stack may further comprise blocking layers located beneath the functional metal layers.
- the blocking layers have traditionally function to protect the functional layers from possible degradation during the deposition of the upper antireflection coating and during a possible high temperature heat treatment, such as annealing, bending and / or quenching.
- the blocking layers are chosen from metal layers based on a metal or a metal alloy, metal nitride layers, metal oxide layers and metal oxynitride layers of one or more elements chosen from titanium, nickel, chromium and niobium such as a layer of Ti, TiN, TiOx, Nb, NbN, Ni, NiN, Cr, CrN, NiCr, NiCrN.
- these blocking layers When these blocking layers are deposited in metallic, nitrided or oxynitrided 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 layer or layers satisfy one or more of the following conditions:
- each functional metal layer is in contact with at least one blocking layer chosen from a blocking underlayer and a blocking overlay, and / or
- each functional metal layer is in contact with a blocking overlay, and / or
- each blocking layer is preferably between 0.2 and 1.0 nm and / or
- the total thickness of all the blocking layers in contact with the functional layers is between 0.5 and 5 nm, including these values, preferably between 1 and 3 nm and / or
- the total thickness of all blocking overlays is less than 2.5, preferably less than 2.0, more preferably less than 1.4 nm, and / or
- the total thickness of all blocking sub-layers is between 0.1 and
- the blocking layers are considered as not forming part of a dielectric coating. This means that their thickness is not taken in calculating the optical thickness of the dielectric coating on contact.
- the dielectric coatings satisfy one or more of the following conditions in terms of thicknesses:
- the dielectric coatings M1, M2, M3 and M4 each have an optical thickness Eo1, Eo2, Eo3 and Eo4 satisfying one or more of the following relations: Eo4 ⁇ Eo1, Eo4 ⁇ Eo2, Eo1 ⁇ Eo3, Eo2 ⁇ Eo3, and / or
- the optical thickness of the first dielectric coating M1 is 50 to 140 nm, 60 to 135 nm, 70 to 130 nm, 80 to 130 nm, 80 to 125 nm, 90 and 120 nm, and / or
- the physical thickness of the first dielectric coating M1 is 25 to 65 nm, 30 to 60 nm or 35 to 55 nm, and / or
- the optical thickness of the second dielectric coating M2 is from 50 to 140 nm, from 55 to 125 nm, from 60 to 135 nm, from 70 to 130 nm, from 80 to 130 nm, from 80 to 125 nm, or from 90 to 125 nm, and / or
- the physical thickness of the second dielectric coating M2 is from 25 to 65 nm, from 30 to 60 nm or from 35 to 55 nm, and / or
- the optical thickness of the third dielectric coating M3 is from 140 to 200 nm, from 150 to 190 nm or from 160 to 180 nm, and / or
- the physical thickness of the third dielectric coating M3 is from 50 to 100 nm, from 55 to 90 nm, from 60 to 80 nm, and / or
- the optical thickness of the fourth dielectric coating M4 is from 50 to 120 nm, from 60 to 100 nm or from 70 to 90 nm, and / or
- the physical thickness of the fourth dielectric coating M4 is from 20 to 50 nm, from 25 to 45 nm, from 30 to 40 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 coatings satisfy one or more of the following conditions:
- the dielectric layers may be based on oxide or nitride of one or more elements chosen from silicon, zirconium, titanium, aluminum, tin, zinc, and / or
- the refractive indices of the dielectric layers are less than 2.30, preferably less than 2.20 and / or
- At least one dielectric coating comprises at least one dielectric layer with a barrier function, and / or
- each dielectric coating comprises at least one dielectric layer with a barrier function, and / or
- the barrier-type dielectric layers are based on silicon and / or aluminum compounds chosen from oxides such as SiO 2 and Al 2 O 3 , silicon nitrides Si 3 N 4 and AlN and oxynitrides SiO x N y and AIO x N y , based on zinc oxide and tin oxide or on titanium oxide,
- the barrier-type dielectric layers are based on silicon and / or aluminum compounds and optionally comprise at least one other element, such as aluminum, hafnium and zirconium, and / or
- At least one dielectric coating comprises at least one dielectric layer with a stabilizing function, and / or
- each dielectric coating comprises at least one dielectric layer with a stabilizing function, and / or
- the stabilizing functional dielectric layers are preferably based on an oxide chosen from zinc oxide, tin oxide, zirconium oxide or a mixture of at least two of them,
- the dielectric layers with a stabilizing function are preferably based on crystalline oxide, in particular based on zinc oxide, optionally doped with at least one other element, such as aluminum, and / or
- each functional layer is above a dielectric coating whose upper layer is a dielectric layer with a stabilizing function, preferably based on zinc oxide and / or below a dielectric coating whose lower layer is a dielectric layer with a stabilizing function, preferably based on zinc oxide.
- each dielectric coating consists solely of one or more dielectric layers.
- the dielectric layers may have a barrier function.
- barrier dielectric layers (hereinafter 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:
- oxides such as SiO 2 and Al 2 O 3 , nitrides such as nitrides such as Si 3 N 4 and AlN, and oxynitrides such as SiO x N y, AlOxNy optionally doped with at least one other element,
- each coating comprises at least one dielectric layer consisting of:
- These dielectric layers have a thickness:
- the stacks of the invention may comprise dielectric layers with stabilizing function.
- stabilizing means that the nature of the layer is selected so as to stabilize the interface between the functional layer and this layer. This stabilization leads to reinforcing the adhesion of the functional layer to the layers that surround it, and in fact it will oppose the migration of its constituent material.
- the dielectric layer (s) with a stabilizing function can be directly in contact with a functional layer or separated by a blocking layer.
- the last dielectric layer of each dielectric coating located below a functional layer is a dielectric layer with a stabilizing function.
- a stabilizing function layer for example, based on zinc oxide below a functional layer, because it facilitates the adhesion and crystallization of the functional layer based on and increases its quality and stability at high temperatures.
- a stabilizing function layer for example, based on zinc oxide over a functional layer, in order to increase the adhesion and oppose optimally to the diffusion side of the stack opposite the substrate.
- the stabilizing function dielectric layer or layers can therefore be above and / or below at least one functional layer or each functional layer, either directly in contact with it or separated by a blocking layer.
- each barrier-function dielectric layer is separated from a functional layer by at least one dielectric layer with a stabilizing function.
- the zinc oxide layer may be optionally doped with at least one other element, such as aluminum.
- Zinc oxide is crystallized.
- the zinc oxide-based layer comprises, in order of preference increasing at least 90.0%, at least 92%, at least 95%, at least 98.0% by weight zinc relative to the mass of elements other than oxygen in the zinc oxide layer.
- the dielectric coatings M1, M2 and M3 comprise a dielectric layer based on zinc oxide situated underneath and directly in contact with the silver-based metal layer.
- the layers of zinc oxide have, in order of increasing preference, a thickness:
- the stack of thin layers may optionally comprise a protective layer.
- the protective layer is preferably the last layer of the stack, that is to say the layer furthest from the substrate coated with the stack. These upper layers of protection are considered to be included in the fourth dielectric coating. These layers generally have a thickness of between 2 and 10 nm, preferably 2 and 5 nm.
- This protective layer may be chosen from a layer of titanium, zirconium, hafnium, zinc and / or tin, or these metals being in metallic, oxidized or nitrided form.
- the protective layer may for example be selected from a layer of titanium oxide, a layer of zinc oxide and tin or a layer of titanium oxide and zirconium.
- a first dielectric coating comprising at least one barrier layer and a stabilizing function dielectric layer
- a first functional layer possibly a blocking layer
- a second dielectric coating comprising at least one dielectric layer with a lower stabilizing function, a dielectric layer with a barrier function and a dielectric layer with a higher stabilizing function
- a third dielectric coating comprising at least one dielectric layer with a lower stabilizing function, a barrier-function layer, a dielectric layer with a higher stabilizing function,
- a fourth dielectric coating comprising at least one dielectric layer with a stabilizing function, a dielectric layer with a barrier function, and
- 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 transparent organic substrates according to the invention can also be made of polymer, rigid or flexible.
- suitable polymers according to the invention include, in particular:
- polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN);
- polyacrylates such as polymethyl methacrylate (PMMA);
- fluorinated polymers such as fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
- fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
- photocurable and / or photopolymerizable resins such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate and
- the substrate is preferably a 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 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 material that is to say the substrate coated with the stack, can undergo a heat treatment at high temperature such as annealing, for example by flash annealing such as laser or flame annealing, quenching and / or bending.
- the temperature of the heat treatment is greater than 400 ° C, preferably greater than 450 ° C, and more preferably greater than 500 ° C.
- the substrate coated with the stack can therefore be curved and / or tempered.
- the invention also relates to a glazing unit comprising at least one material according to the invention.
- the glazing of the invention may be in the form of monolithic glazing, laminated or multiple, in particular double glazing or triple glazing.
- the stack is preferably deposited in face 2, that is to say, it is on the substrate defining the outer wall of the glazing and more specifically on the inner face of this substrate.
- 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.
- a triple glazing has 6 faces, the face 1 is outside the building (outer wall of the glazing), the face 6 inside the building (inner wall of the glazing) and the faces 2 to 5 are inside the triple glazing.
- 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 blade intermediate gas, said glazing providing a separation between an outer space and an interior space.
- the glazing of the invention in the form of a double glazing comprising the stack positioned in face 2 makes it possible to achieve in particular the following performances:
- a solar factor g less than or equal to 30%, preferably less than or equal to 29% and / or
- a light transmission in order of increasing preference, between 40% and 70%, preferably between 42% and 68%, and even between 50% and 60%, and / or
- a high selectivity in order of increasing preference, greater than 1.8, of at least 1.9, of at least 2.0 and / or
- an external light reflection less than or equal to 20%, preferably less than or equal to 18%, and / or
- each layer i of the stack having a thickness greater than equal to 10 nm has an optical sensitivity ACi in external reflection less than 5, preferably less than 4, and better still less than 3.
- a laminated glazing unit comprises at least one structure of the 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 sheet, preferably a polymer. This embodiment is advantageous when the laminated glazing is mounted in double glazing with a third substrate.
- These windows are mounted on a building or a vehicle.
- the applications of this invention relate to very selective solar control stacks with excellent color neutrality and low external optical reflection sensitivity. This ensures a neutral color in reflection and transmission. This solution is preferably intended for countries with hot climates.
- FIG. 1 illustrates a stacking structure with three functional metal layers 40, 80, 120, this structure being deposited on a transparent glass substrate 10.
- Each functional layer 40, 80, 120 is disposed between two dielectric coatings 20, 60, 100, 140 so that:
- the first functional layer 40 starting from the substrate is placed between the dielectric coatings 20, 60,
- the second functional layer 80 is disposed between the dielectric coatings 60, 100 and
- the third functional layer 120 is disposed between the dielectric coatings 100, 140.
- These dielectric coatings 20, 60, 100, 140 each comprise at least one dielectric layer 24, 28; 62, 64, 68; 102, 104, 106, 108; 142, 144.
- Each dielectric coating 20, 60, 100 below a functional layer 40, 80, 120 comprises a last stabilizing layer 28, 68, 108 based on crystalline zinc oxide.
- Each dielectric coating 60, 100, 140 above a functional layer 40, 80, 120 comprises a first stabilizing layer 62, 102, 142 based on crystalline zinc oxide.
- Each dielectric coating 20, 60, 100, 140 comprises a dielectric barrier layer based on silicon nitride, doped with aluminum, here called Si 3 N 4 24, 64, 104, 144, or based on mixed oxide of zinc and tin 106.
- Stacking can also include:
- Stacks of thin layers defined below are deposited on substrates of clear soda-lime glass with a thickness of 6 mm.
- the functional layers are layers of silver (Ag)
- the blocking layers are metal layers made of nickel-chromium alloy (NiCr)
- the barrier layers are based on silicon nitride, doped with aluminum (Si 3 N 4 : Al) or based on mixed oxide of zinc and tin (SnZnOx),
- the stabilizing layers are made of zinc oxide (ZnO).
- Table 2 lists the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating that constitutes the stacks as a function of their position vis-à-vis the carrier substrate of the stack (last line at the bottom of the table). ).
- the numbers "Ref. Correspond to the references of Figure 1.
- the following table 3 summarizes the characteristics related to the thicknesses of the functional layers and dielectric coatings.
- RD dielectric coating
- CB blocking layer
- Ep Physical thickness
- Eo Optical thickness.
- Table 4 lists the main optical characteristics measured when the glazing is part of 6/16/4 double glazing: 6 mm glass / 16 mm spacer filled with 90% argon and 10% air / glass 4 mm, the stack being positioned in face 2 (the face 1 of the glazing being the outermost face of the glazing,
- the glazings according to the invention have both a solar factor of less than or equal to 30% and a selectivity greater than 2.0. These glazings have in addition an external and internal reflection at least less than 20%.
- the value of a * in transmission and the value of b * in external reflection are less than -4.
- the selectivity too low.
- the proposed solution therefore allows to have a solar factor of less than 30% keeping a selectivity greater than 2.0 and an extremely neutral aesthetics.
- the table below summarizes the optical sensitivity values in external reflection of each layer of the stacks having a geometric thickness greater than 10 nm.
- a low optical sensitivity in external reflection of a stack comprising i layers results in AC.sub.50 values of less than 5, preferably less than 4, and better still less than 3, for all the i layers comprising the stack having a thickness greater than equal to 10 nm.
- the comp.3 example is not satisfactory because two ACi values are greater than or equal to 4. To this is added the too low selectivity of this example.
- the example comp.4 is not satisfactory because two values ACi are greater than or equal to 4, one of which is equal to 7. To this is added the too low selectivity of this example.
- the proposed solution therefore makes it possible to have both high selectivity, excellent color neutrality and low optical sensitivity.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1852033A FR3078653B1 (en) | 2018-03-08 | 2018-03-08 | MATERIAL PROVIDED WITH A STACK WITH THERMAL PROPERTIES |
PCT/FR2019/050499 WO2019171002A1 (en) | 2018-03-08 | 2019-03-06 | Material provided with a stack having thermal properties |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3762342A1 true EP3762342A1 (en) | 2021-01-13 |
Family
ID=63557535
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19713108.9A Pending EP3762342A1 (en) | 2018-03-08 | 2019-03-06 | Material provided with a stack having thermal properties |
Country Status (6)
Country | Link |
---|---|
US (1) | US11208349B2 (en) |
EP (1) | EP3762342A1 (en) |
CA (1) | CA3091699A1 (en) |
FR (1) | FR3078653B1 (en) |
MX (1) | MX2020009315A (en) |
WO (1) | WO2019171002A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3114315B1 (en) | 2020-09-21 | 2023-03-24 | Saint Gobain | MATERIAL COMPRISING A SUBSTRATE PROVIDED WITH A STACK OF THIN LAYERS WITH THERMAL PROPERTIES |
FR3121675B1 (en) | 2021-04-12 | 2023-12-29 | Saint Gobain | SUBSTRATE PROVIDED WITH A STACK WITH THERMAL PROPERTIES |
EP4092571A1 (en) | 2021-05-20 | 2022-11-23 | Saint-Gobain Glass France | Method to classify quench patterns of heat-treated coated mineral glasses and predict the optical visibility thereof |
EP4328570A1 (en) | 2022-08-25 | 2024-02-28 | Saint-Gobain Glass France | Method to classify quench patterns of insulating glazing units and predict the optical visibility thereof |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2949226B1 (en) * | 2009-08-21 | 2011-09-09 | Saint Gobain | SUBSTRATE PROVIDED WITH A STACK WITH THERMAL PROPERTIES, ESPECIALLY FOR REALIZING A HEATED GLAZING. |
BE1019345A3 (en) * | 2010-05-25 | 2012-06-05 | Agc Glass Europe | SOLAR CONTROL GLAZING WITH LOW SOLAR FACTOR. |
FR2985724B1 (en) * | 2012-01-16 | 2014-03-07 | Saint Gobain | SUBSTRATE PROVIDED WITH A STACK WITH THERMAL PROPERTIES COMPRISING FOUR METAL FUNCTIONAL LAYERS. |
FR3005048B1 (en) * | 2013-04-30 | 2020-09-25 | Saint Gobain | SUBSTRATE EQUIPPED WITH A STACKING WITH THERMAL PROPERTIES |
FR3038598B1 (en) * | 2015-07-08 | 2017-07-21 | Saint Gobain | SUBSTRATE PROVIDED WITH A STACK WITH THERMAL PROPERTIES |
FR3038596B1 (en) * | 2015-07-08 | 2021-12-10 | Saint Gobain | MATERIAL EQUIPPED WITH A THERMAL PROPERTIES STACK |
FR3038597B1 (en) * | 2015-07-08 | 2021-12-10 | Saint Gobain | MATERIAL EQUIPPED WITH A THERMAL PROPERTIES STACK |
FR3072957B1 (en) * | 2017-10-30 | 2019-10-18 | Saint-Gobain Glass France | SUBSTRATE PROVIDED WITH A STACK WITH THERMAL PROPERTIES |
-
2018
- 2018-03-08 FR FR1852033A patent/FR3078653B1/en active Active
-
2019
- 2019-03-06 WO PCT/FR2019/050499 patent/WO2019171002A1/en active Application Filing
- 2019-03-06 CA CA3091699A patent/CA3091699A1/en active Pending
- 2019-03-06 MX MX2020009315A patent/MX2020009315A/en unknown
- 2019-03-06 US US16/978,548 patent/US11208349B2/en active Active
- 2019-03-06 EP EP19713108.9A patent/EP3762342A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US20210017071A1 (en) | 2021-01-21 |
US11208349B2 (en) | 2021-12-28 |
WO2019171002A1 (en) | 2019-09-12 |
FR3078653B1 (en) | 2023-10-27 |
FR3078653A1 (en) | 2019-09-13 |
MX2020009315A (en) | 2020-10-07 |
CA3091699A1 (en) | 2019-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3319916B1 (en) | Material provided with a stack having thermal properties | |
EP3319919B1 (en) | Substrate provided with a stack having thermal properties | |
EP2991944B1 (en) | Substrate provided with a stack having thermal properties | |
WO2017006030A1 (en) | Substrate provided with a stack having thermal properties | |
EP3129329B1 (en) | Substrate having a stack with thermal properties | |
EP3704071B1 (en) | Substrate provided with a stack having thermal properties | |
EP3762342A1 (en) | Material provided with a stack having thermal properties | |
EP3713890A1 (en) | Material comprising a single functional layer containing silver and an absorbent layer | |
WO2020079373A1 (en) | Glazing comprising a functional coating and a color adjustment coating | |
EP3867060B1 (en) | Glazing comprising a functional coating and an absorbing coating having a colorimetric adjustment | |
EP3826973B1 (en) | Material comprising a substrate provided with a stack having thermal properties | |
EP3917895B1 (en) | Substrate provided with a stack having thermal properties and an absorbent layer | |
WO2021018861A1 (en) | Material comprising a substrate provided with a stack having thermal properties for head-up display | |
EP3873863A1 (en) | Material comprising a substrate provided with a stack of thin layers with thermal properties | |
CA3125787A1 (en) | Substrate provided with a stack having thermal properties and an absorbent layer | |
EP3319920B1 (en) | Material comprising a stack of thin layers | |
WO2021063879A1 (en) | Laminated glazing having low light transmission and high selectivity | |
EP4367074A1 (en) | Materials comprising a functional coating used in the form of laminated and multiple glazing |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20201008 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20230504 |