Laminated glazing including a functional silver-based coating

Abstract

The invention relates to a material comprising a transparent substrate coated with a functional coating comprising successively, from the substrate, an alternation of three silver-based functional metallic layers, named from the substrate first, second and third functional layers, and four dielectric coatings named from the substrate Di1, Di2, Di3 and Di4, each having an optical thickness Eo1, Eo2, Eo3 and Eo4, each dielectric coating comprising at least one dielectric layer, such that each functional metallic layer is disposed between two dielectric coatings, characterized in that: - the ratio of the thickness of the first functional metallic layer to the thickness of the third functional metallic layer Ag1 / Ag3 is greater than 1,05 or the ratio of the thickness of the second functional metallic layer to the thickness of the third functional metallic layer Ag2 / Ag3 is greater than 1.05 and - the ratio of the optical thicknesses Eo2 / Eo3 is greater than 1.00.,

Description

Title of the invention: Laminated glazing comprising a functional silver-based coating

[0001] The invention relates to a material comprising a transparent substrate coated with a functional coating capable of acting on solar radiation and / or infrared radiation. In the following description, the term "functional" qualifying a coating or layer means "capable of acting on solar radiation and / or infrared radiation." The invention also relates to glazing comprising these materials and the use of such materials for manufacturing thermal insulation and / or solar protection glazing.

[0002] These glazings can be intended to equip vehicles or buildings, in particular to prevent excessive overheating, so-called "solar control" glazings, caused by the ever-increasing importance of glazed surfaces in vehicle interiors and buildings.

[0003] The function or property "solar control" corresponds to the ability of glazing to allow visible light to enter while blocking infrared radiation. This property is evaluated using selectivity "s", the solar factor (FS or g), and the total solar transmission (TTS). Selectivity is the ratio of the visible light transmission TLvis of the glazing to the solar factor FS of the glazing (s = TLvis / FS). The solar factor "FS or g" and the total solar transmission (TTS) correspond to the amount of heat transmitted by the glass. The solar factor and the total solar transmission therefore measure the contribution of glazing to the heating of the room. The lower the solar factor or the total solar transmission, the lower the solar heat gain.The solar control function therefore corresponds to a significant reduction in the total energy transmission and the solar factor (g) of the glazing, combined with a slight reduction in light transmission (TL).

[0004] The invention relates particularly to glazing for automotive applications, especially for automotive windshields. Glazing intended for these applications must necessarily exhibit the following properties: high light transmission, solar control properties, a neutral or bluish aesthetic appearance upon reflection, and the ability to withstand high-temperature heat treatment. Other functionalities may be added to these properties to improve driver comfort.

[0005] Among these features, compatibility with so-called head-up display (HUD) systems is particularly sought after. To obtain clear images, a birefringent film or coating is often applied to the part of the laminated glass where the images are intended to be projected. This part of the glass must therefore reflect the projected images while maintaining good visibility.

[0006] Applying any additional film or coating to laminated windshield glass, whether for HUD compatibility or to acquire other functions, necessarily results in a loss of light transmission. This is particularly detrimental in windshield applications because light transmission must remain high, specifically above 70%, for legal and safety reasons.

[0007] Materials comprising a substrate coated with a functional coating comprising several silver-based functional metallic layers are used to give the glazing solar control properties.

[0008] The objective of the invention is to propose a new improved material with ultra-high light transmission comprising a substrate coated with a functional coating which makes it possible to obtain in combination good solar control performance, a satisfactory aesthetic appearance and a capacity to be thermally treated (“heatability”).

[0009] According to the invention, a material exhibiting good heat-treatable properties is understood to be a material which, following heat treatment: - retains its aesthetic properties or solar control performance or - acquires its aesthetic properties or solar control performance.

[0010] According to the invention, "good solar control performance" means a material that gives the glazing incorporating it: - low total energy transmission, in particular less than 48.5%, and / or - high selectivity, - low external reflection, in particular less than 20%, preferably less than 15%.

[0011] According to the invention, a material or glazing with a satisfactory aesthetic appearance is understood to mean a material or glazing that reflects uniform and pleasant colors, preferably blue or neutral, whether the material is flat or curved.

[0012] In order to identify functional coatings capable of exhibiting these properties, the applicant focused on finding combinations of characteristics specific to functional coatings that could lead to the required properties. Extensive explorations were carried out using optical simulation. These explorations revealed a family of solutions meeting these criteria. Indeed, only specific combinations of thickness characteristics for the layers Functional properties and dielectric coatings make it possible to obtain the desired combination of characteristics.

[0013] The invention relates to a material comprising a transparent substrate coated with a functional coating comprising successively, from the substrate, an alternation of three silver-based functional metallic layers, named from the substrate first, second and third functional layers, and four dielectric coatings named from the substrate D1, Di2, Di3 and Di4, each having an optical thickness E10, E02, E03 and E04, each dielectric coating comprising at least one dielectric layer, such that each functional metallic layer is disposed between two dielectric coatings, characterized in that: - the ratio of the thickness of the first functional metallic layer to the thickness of the third functional metallic layer Agl / Ag3 is greater than 1.05 and / or the ratio of the thickness of the second functional metallic layer to the thickness of the third functional metallic layer Ag2 / Ag3 is greater than 1.05 and - the ratio of optical thicknesses Eo2 / Eo3 is greater than 1.00.

[0014] The invention relates to materials comprising a substrate coated with a functional coating used in laminated glazing for automotive applications with ultra-high light transmission, in particular exceeding 70%, or even 75% or 77%. The functional coating is preferably applied to face 3 or face 2 of the laminated glazing. The coated material is preferably heat-treated. The functional coating can be combined with other functionalities. This means that the functional coating can be located on a portion of the glazing surface comprising another film or coating, for example, a birefringent film or coating.

[0015] The material makes it possible to obtain a light transmission of more than 77% in a conventional laminated glazing configuration, a low light reflection on the outside, while maintaining high selectivity with low energy transmission (TTS < 48.5%) and stable external reflection colors.

[0016] The material of the invention has the following advantages compared to previous solutions.

[0017] It makes it possible to obtain laminated glazing with very high light transmission while maintaining high-quality aesthetic and thermal properties. This means that the coating can be applied in combination with other films, such as a birefringent coating, for HUD applications, without risk of reducing the light transmission below legal and safety requirements.

[0018] It retains excellent energy, thermal, and aesthetic properties. The thermal properties of the functional coating correspond to a TTS (Total Thermal Strength) of 48.5% or less when the functional coating is used in conventional laminated glazing. Conventional laminated glazing is defined as a material comprising a clear glass substrate coated with the functional coating laminated to another clear glass substrate via a PVB lamination interlayer. The functional coating is positioned on surface 2 or 3 of the laminated glazing.

[0019] The material of the invention advantageously exhibits low-intensity reflected colors over a wide range of angles of incidence. The material of the invention advantageously exhibits the following external reflections: - a bluish or neutral color from all viewing angles, and / or - a stable color between 8° and 60°, and / or - limited light reflectance RLext, in particular less than or equal to 15%.

[0020] Color stability is characterized by measuring the color variation between the two observation angles 8° and 60° of Aa*Rext = | a*Rext 60°-a*Rext 0° | and Ab*Rext = | a*Rext 60°-a*Rext 0° | . According to the invention, colors are considered stable if Aa*Rext < 4 and Ab*Rext < 5.

[0021] The functional coating of the invention is particularly suitable for use in laminated glazing, to improve thermal comfort and the aesthetic appearance seen from the outside.

[0022] The invention therefore relates to a laminated glazing comprising a material according to the invention and at least one second substrate, the material and the second substrate are linked together by means of a lamination interlayer.

[0023] Conventionally, the faces of a glazing unit are designated from the outside by numbering the faces of the substrates from the outside towards the inside of the passenger compartment or room it equips. This means that incident sunlight passes through the faces in ascending numerical order. In the case of laminated glazing, all the faces of the substrates are numbered, but the faces of the lamination interlayers are not.

[0024] The laminated glazing according to the invention comprises a face 1 located on the outside of the building or vehicle it equips, faces 2 and 3 in contact with the lamination interlayer, and a face 4 on the inside of the building or vehicle. The silver-based functional coating is then positioned on face 2 or 3, that is to say, on the inner face of the substrate located furthest from the outside (face 2) or on the inner face of the substrate located furthest from the inside (face 3).

[0025] The laminated glazing according to the invention may include curved substrates.

[0026] The invention also relates to: - laminated glazing according to the invention mounted on a vehicle or building, and -1. The use of laminated glazing according to the invention as glazing for buildings or vehicles, - a building, a vehicle comprising glazing according to the invention.

[0027] The preferred characteristics which appear in the following description are applicable both to the material according to the invention and, where applicable, to the glazing, the process, the use, the building or the vehicle according to the invention.

[0028] All the luminous characteristics described are obtained according to the principles and methods of ISO 9050, EN 410 and ISO 13837 relating to the determination of the luminous and solar characteristics of glazing used in glass for construction.

[0029] According to the invention: - Light reflection corresponds to the reflection of solar radiation in the visible part of the spectrum. - Light transmission corresponds to the transmission of solar radiation in the visible part of the spectrum. - Light absorption corresponds to the absorption of solar radiation in the visible part of the spectrum.

[0030] The luminous and energy characteristics are measured with respect to illuminant A at 2°, perpendicular to the material mounted in laminated glazing with the functional coating positioned on face 3 (unless otherwise specified): - TL corresponds to the visible light transmission in %, - Rext corresponds to the external visible light reflection in %, observer on the functional coating side. - TTS corresponds to the total energy transmission, it is measured according to convention A with a wind speed of 4 m / s.

[0031] The colorimetric characteristics are measured according to illuminant D65, observer at 10°, perpendicular to the material mounted in a laminated glazing with the functional coating positioned on face 2 (unless otherwise indicated): - a*Rext 8° and b* Rext 8° correspond to the colors in reflection a* and b* in the L*a*b* system observer on the functional coating side measured at an angle of 8°, - a*Rext 60° and b* Rext 60° correspond to the colors in reflection a* and b* in the L*a*b* system observer on the functional coating side measured at an angle of 60°.

[0032] The material exhibits excellent energy and thermal properties. This results in total energy transmission values ​​of less than 48.5%, measured on a laminated glazing comprising the functional coating on face 3 deposited on a clear glass substrate and laminated to a second clear glass substrate via a clear PVB polymer interlayer.

[0033] These properties are measured on ordinary clear glass. Ordinary clear glass 4 to 6 mm thick has the following luminous characteristics: - a light transmission between 87 and 91.5%, - a light reflection between 7 and 9.5%, - a light absorption between 0.3 and 5%.

[0034] A clear PVB laminate interlayer has a light transmission greater than 80%.

[0035] Conventionally, refractive indices are measured at a wavelength of 550 nm.

[0036] Unless otherwise stated, the thicknesses referred to in this document without further specification are physical, real, or geometric thicknesses denoted Ep and are expressed in nanometers (and not optical thicknesses). The optical thickness Eo is defined as the physical thickness of the layer in question multiplied by its refractive index at a wavelength of 550 nm: Eo = n*Ep. Since the refractive index is a dimensionless value, the unit of the optical thickness can be considered to be the same as that chosen for the physical thickness.

[0037] According to the invention, a dielectric coating corresponds to a sequence of layers comprising at least one dielectric layer, located between the substrate and the first functional layer (Dil), between two functional layers (Di2 or Di3) or above the last functional layer (Di4).

[0038] 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.

[0039] If a dielectric coating includes an absorbing layer for which the refractive index at 550 nm includes an imaginary part of the non-zero (or non-negligible) dielectric function, for example a metallic layer, the thickness of this layer is not taken into account for the calculation of the optical thickness of the dielectric coating.

[0040] The thicknesses of the blocking layers are not taken into account for the calculation of the optical thickness of the dielectric coating.

[0041] For the purposes of the present invention, the terms "first", "second", "third" and "fourth" for functional layers or dielectric coatings are defined starting from the substrate carrying the stack and referring to the layers or coatings with the same function. For example, 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.

[0042] The functional coating is deposited by magnetic field-assisted sputtering (magnetron process). According to this advantageous embodiment, All coating layers are deposited by magnetic field-assisted sputtering. Unless otherwise specified, the terms "above" and "below" do not necessarily mean that two layers and / or coatings are 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 cannot be one (or more) layer(s) interposed between these two layers (or layer and coating).

[0043] In this description, unless otherwise indicated, the expression "based on", used to describe a material or layer as to what it contains, means that the mass fraction of the constituent it comprises is at least 50%, in particular at least 70%, preferably at least 90%.

[0044] The functional coating comprises at least three silver-based metallic functional layers (Fl, F2 and F3), each arranged between two dielectric coatings (Dil, Di2, Di3, Di4).

[0045] Silver-based metallic functional layers comprise at least 95.0%, preferably at least 96.5%, and more preferably at least 98.0% by mass of silver relative to the mass of the functional layer. Preferably, a silver-based metallic functional layer comprises less than 1.0% or less than 0.5% by mass of metals other than silver relative to the mass of the silver-based metallic functional layer.

[0046] According to the invention, the third functional layer has a thinner profile than the first functional layer, or the second functional layer, or both the first and second functional layers. The functional layers may have the following characteristics: - the ratio of the thickness of the first functional metallic layer to the thickness of the third functional metallic layer Agl / Ag3 is greater than 1.10 and / or - the ratio of the thickness of the first functional metallic layer to the thickness of the third functional metallic layer Agl / Ag3 is greater than 1.15 and / or - the ratio of the thickness of the first functional metallic layer to the thickness of the third functional metallic layer Agl / Ag3 is greater than 1.20 and / or - the ratio of the thickness of the first functional metallic layer to the thickness of the third functional metallic layer Agl / Ag3 is less than 1.60 and / or - the ratio of the thickness of the second functional metallic layer to the thickness of the third functional metallic layer Ag2 / Ag3 is greater than 1.10, and / or - the ratio of the thickness of the second functional metallic layer to the thickness of the third functional metallic layer Ag2 / Ag3 is greater than 1.15, and / or - the ratio of the thickness of the second functional metallic layer to the thickness of the third functional metallic layer Ag2 / Ag3 is greater than 1.20 and / or - the ratio of the thickness of the second functional metallic layer to the thickness of the third functional metallic layer Ag2 / Ag3 is less than 1.40 and / or - the ratio of the thickness of the second functional metallic layer to the thickness of the first functional metallic layer Ag2 / Agl is less than or equal to 1.30, 1.20, 1.10, 1.05, 1.00, or 1.10, and / or - the ratio of the thickness of the second functional metallic layer to the thickness of the first functional metallic layer Ag2 / Agl is greater than or equal to 0.60 or 0.70, and / or, - the first functional silver-based metallic layer has a thickness of between 6 and 15 nm, between 8 and 14 nm or between 9 and 13 nm, and / or between 9 and 12 nm, and / or - the second functional silver-based metallic layer has a thickness between 6 and 16 nm, between 8 and 14 nm, between 8 and 12 nm, and / or - the third functional silver-based metallic layer has a thickness between 6 and 15 nm, between 6 and 11 nm, between 6 and 10 nm or between 6 and 9 nm, and / or - the sum of the thicknesses of all the functional silver-based layers of the functional coating is less than 30 nm.

[0047] The stack may further include at least one blocking layer located in contact with a functional metallic layer.

[0048] The blocking layers traditionally serve to protect the functional layers from possible degradation during the deposition of the upper anti-reflective coating and during possible high-temperature heat treatment, such as annealing, bending and / or quenching.

[0049] The blocking layers are chosen from: - metallic coatings based on a metal or metallic alloy, metallic nitride coatings, and metallic oxynitride coatings of one or more elements selected from titanium, zinc, tin, nickel, chromium, and niobium, - the metallic oxide layers of one or more elements chosen from titanium, nickel, chromium and niobium.

[0050] The blocking layers may in particular be layers of Ti, TiN, TiOx, Nb, NbN, Ni, NiN, Cr, CrN, NiCr, NiCrN, SnZnN. When these blocking layers are deposited in metallic, nitrided or oxynitrided form, these layers may undergo partial or total oxidation depending on their thickness and the nature of the layers surrounding them, for example, at the time of deposition of the next layer or by oxidation in contact with the underlying layer.

[0051] According to advantageous embodiments of the invention, the blocking layer(s) satisfy one or more of the following conditions: - each functional silver-based metallic layer can be located below and / or above, and possibly in contact with, a blocking layer selected from a blocking sublayer and a blocking overlayer, and / or - the blocking layer may be based on at least one element chosen from nickel, chromium, niobium, tantalum and titanium, and / or - each functional metallic layer is in contact with a blocking overlayer, and / or - the thickness of each blocking layer is at least 0.1 nm, preferably between 0.2 and 2.0 nm.

[0052] According to the invention, the blocking layers are considered not to be part of a dielectric coating. This means that their thickness is not taken into account in the calculation of the optical or geometric thickness of the dielectric coating in contact with them.

[0053] According to advantageous embodiments of the invention, the dielectric coatings of the functional coatings satisfy one or more of the following conditions: - the dielectric coating Dil has an optical thickness Eol between 50 and 90 nm or between 50 and 80 nm, and / or - the dielectric coating Di2 has an optical thickness Eo2 between 120 and 190 nm, and / or - the dielectric coating Di3 has an optical thickness Eo3 between 110 and 160 nm, and / or - the dielectric coating Di4 has an optical thickness Eo4 between 60 and 100 nm and / or - the ratio of optical thicknesses Eo2 / Eo3 is greater than 1.10, and / or - the ratio of optical thicknesses Eo2 / Eol is greater than 1.5, and / or - the ratio of optical thicknesses Eo2 / Eol is less than 3.0, and / or - the ratio of optical thicknesses Eo2 / Eo4 is greater than 1.5, and / or - the ratio of optical thicknesses Eo2 / Eo4 is less than 3.0, and / or - the ratio of optical thicknesses Eol / Eo3 is greater than 0.30, and / or - the ratio of optical thicknesses Eol / Eo3 is less than 0.80, and / or - the ratio of optical thicknesses Eol / Eo2 is less than 0.60, and / or - the optical thickness ratio Eol / Eo4 is greater than 0.80 and / or - the optical thickness ratio Eol / Eo4 is less than 1.00.

[0054] For the purposes of this invention, "dielectric layer" means a material that is "non-metallic" in nature, i.e., not a metal. In the context of this invention, this term refers to 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.

[0055] According to advantageous embodiments of the invention, the dielectric coatings of the functional coatings satisfy one or more of the following conditions: - the dielectric layers are deposited by magnetic field-assisted sputtering, and / or - the dielectric layers can be based on oxide or nitride of one or more elements chosen from silicon, zirconium, titanium, aluminum, tin, zinc, and / or - the dielectric layers are chosen from: oxide layers of one or more elements chosen from titanium, silicon, aluminum, zirconium, iron, chromium, cobalt, manganese, tungsten, niobium, bismuth, tantalum, zinc and / or tin, nitride layers of one or more elements chosen from silicon, zirconium and aluminum, Oxynitride layers of one or more elements chosen from silicon, zirconium and aluminium, metallic sulfide layers such as zinc sulfide, and / or - the dielectric layers have a thickness greater than 2 nm, preferably between 4 and 100 nm, and / or - at least one dielectric coating comprises at least one barrier dielectric layer, and / or - each dielectric coating comprises at least one barrier dielectric layer, and / or - each dielectric coating comprises a layer including silicon selected from silicon nitride-based layers and / or - The dielectric barrier layers are based on silicon and / or aluminum compounds chosen from oxides such as SiO2 and Al2O3, and nitrides Si3N4 and AIN and the oxynitrides SiOxNy and A10xNy, based on zinc and tin oxide or titanium oxide, - the dielectric layers with barrier function are based on silicon and / or aluminum compounds and may include at least one other element, such as aluminum, hafnium and zirconium, and / or - each dielectric coating comprises a layer including silicon selected from silicon nitride-based layers, and / or - the sum of the physical thicknesses of all layers containing silicon in each dielectric coating is greater than 25% of the total thickness of the dielectric coating, and / or - at least one dielectric coating includes at least one dielectric layer with a stabilizing function, and / or - each dielectric coating includes at least one dielectric layer with a stabilizing function, and / or - the dielectric layers with stabilizing function are preferably based on an oxide chosen from zinc oxide, tin oxide, zirconium oxide or a mixture of at least two of them, and / or - the dielectric layers with stabilizing function are preferably based on crystalline oxide, in particular zinc oxide, possibly doped with at least one other element, such as aluminium, 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, and / or - each dielectric coating located beneath a functional layer comprises a zinc oxide-based layer situated below, in contact with, or separated by a blocking layer from, the functional layer, and / or - each dielectric coating located above a functional layer comprises a zinc oxide-based layer situated above, in contact with, or separated by a blocking layer from, the functional layer, and / or - each dielectric coating located below a functional layer comprises a zinc oxide and tin oxide-based layer located below and in contact with a zinc oxide-based layer.

[0056] Preferably, each dielectric coating consists solely of one or more dielectric layers. Preferably, there is therefore no absorbing layer in the dielectric coatings so as not to reduce light transmission.

[0057] Dielectric layers may have a barrier function. A barrier dielectric layer (hereinafter referred to as a barrier layer) is defined as a layer made of a material capable of blocking the diffusion of oxygen and water at high temperatures, from the ambient atmosphere or the transparent substrate, towards the functional layer. Such dielectric layers are selected from layers: - based on silicon, aluminum and / or zirconium compounds selected from oxides such as SiO2 and Al2O3, nitrides such as Si3N4 and AlN, and oxynitrides such as SiOxNy, AlOxNy, possibly doped with at least one other element, - based on zinc and tin oxide, - based on titanium oxide.

[0058] Preferably, each coating comprises at least one dielectric layer consisting of: - of an aluminium and / or silicon nitride or oxynitride or - of a mixed zinc and tin oxide, or - of a titanium oxide.

[0059] These dielectric layers have a thickness: - less than or equal to 80 nm, less than or equal to 60 nm, or less than or equal to 25 nm, and / or - greater than or equal to 5 nm, greater than or equal to 10 nm or greater than or equal to 15 nm.

[0060] The functional coatings of the invention may include dielectric layers with a stabilizing function. For the purposes of the invention, "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 increased adhesion of the functional layer to the surrounding layers, and in fact, it will prevent the migration of its constituent material.

[0061] The dielectric layer(s) with stabilizing function may be in direct contact with a functional layer or separated by a blocking layer.

[0062] Preferably, the last dielectric layer of each dielectric coating located below a functional layer is a stabilizing dielectric layer. Indeed, it is advantageous to have a stabilizing layer, for example, based on zinc oxide, below a functional layer, because it facilitates the adhesion and crystallization of the silver-based functional layer and increases its quality and stability at high temperatures.

[0063] It is also advantageous to have a stabilizing functional layer, for example, based on zinc oxide, above a functional layer, in order to increase adhesion and optimally oppose diffusion on the side of the stack opposite the substrate.

[0064] The dielectric layer(s) with stabilizing function can therefore be located 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.

[0065] Advantageously, each barrier dielectric layer is separated from a functional layer by at least one stabilizing dielectric layer.

[0066] The zinc oxide layer may optionally be doped with at least one other element, such as aluminum. The zinc oxide is crystalline. The zinc oxide-based layer comprises, in increasing order of preference, at least 90.0%, at least 92%, at least 95%, at least 98.0% by mass of zinc relative to the mass of elements other than oxygen in the zinc oxide-based layer.

[0067] Preferably, the dielectric coatings of the functional coatings comprise a zinc oxide-based dielectric layer located below the silver-based metallic layer.

[0068] The zinc oxide layers have, in order of increasing preference, a thickness of: - at least 3.0 nm, at least 4.0 nm, at least 5.0 nm, and / or - at most 25 nm, at most 10 nm, at most 8.0 nm.

[0069] The functional coating may optionally include a protective top layer. The protective top layer is preferably the last layer in the stack, that is, the layer furthest from the coated substrate in the stack. These protective top layers are considered to be included in the last dielectric coating. These layers generally have a thickness of between 2 and 10 nm, preferably between 2 and 5 nm.

[0070] The protective layer can be selected from a layer of titanium, zirconium, hafnium, zinc and / or tin, this or these metals being in metallic, oxidized or nitrided form. Advantageously, the protective layer is a layer of titanium oxide, a layer of zinc and tin oxide or a layer based on titanium and zirconium oxide.

[0071] Another particularly advantageous embodiment relates to a substrate coated with a defined stack starting from the transparent substrate comprising: - a first dielectric coating comprising at least one barrier layer and one dielectric stabilizing layer, - optionally a blocking layer, - a first functional layer, - optionally a blocking layer, - a second dielectric coating comprising at least one lower stabilizing dielectric layer, one barrier layer and one upper stabilizing dielectric layer, - optionally a blocking layer, - a second functional layer, - possibly a blocking layer, - a third dielectric coating comprising at least one lower stabilizing dielectric layer, one barrier layer, and one upper stabilizing dielectric layer, - possibly a blocking layer, - a third functional layer, - possibly a blocking layer, - a fourth dielectric coating comprising at least one dielectric layer with a stabilizing function, one layer with a barrier function, - possibly a protective layer.

[0072] Another particularly advantageous embodiment includes a stacking which comprises, starting from the substrate: - a first dielectric coating comprising at least one silicon nitride-based layer and one zinc oxide-based layer, - possibly a blocking layer, - a first functional layer, - possibly a blocking layer, - a second dielectric coating comprising at least three successive layers: a zinc oxide-based layer, a silicon nitride-based layer, and a zinc oxide-based layer, - possibly a blocking layer, - a second functional layer, - possibly a blocking layer, - a third dielectric coating comprising at least three successive layers: a zinc oxide-based layer, a silicon nitride-based layer, and a zinc oxide-based layer, - possibly a blocking layer, - a third functional layer, - possibly a blocking layer, - a fourth dielectric coating comprising at least one zinc oxide-based layer, one silicon nitride-based layer and - possibly a protective layer.

[0073] The invention also relates to glazing comprising at least one material as defined above in the form of monolithic, laminated or multiple glazing, in particular double glazing or triple glazing.

[0074] Laminated glazing comprises the material as defined above and at least one second substrate. The material and the second substrate are bonded together by means of a lamination interlayer. It has a face 1 located on the exterior of the building or vehicle it equips, faces 2 and 3 in contact with the lamination interlayer, and a face 4 on the interior of the building or vehicle. The functional coating is positioned on face 2 or 3. It has: - a light transmission greater than 70%, preferably greater than 75%, and / or - a total energy transmission less than 50%, preferably less than 48.5%, and / or - an external light reflection of less than 15%.

[0075] In configurations using laminated glazing, the colorimetric properties are calculated using: - materials comprising a substrate coated with a functional coating mounted in laminated glazing, - laminated glazing comprises a material including an ordinary soda-lime glass substrate of 1 to 2.1 mm and another soda-lime glass substrate of 1 to 2.1 mm, the two substrates are separated by a 0.76 mm Polyvinyl Butyral (PVB) lamination interlayer, - The silver-based functional coating is preferably positioned on surface 3.

[0076] The laminated glazing may further comprise a conductive oxide-based functional coating. It is preferably positioned on surface 4. The conductive oxide layer is selected from fluorine-doped tin oxide, antimony-doped tin oxide, and / or indium tin oxide.

[0077] The substrates may be mineral glass or transparent polymer material. The substrates are preferably mineral glass.

[0078] The mineral glass substrates that constitute the glazing can be made of soda-lime glass, aluminosilicate or borosilicate.

[0079] The substrates may be made of transparent polymer material which include poly(methyl methacrylate) (PMMA), polycarbonate (PC), polyurethane or polyurea (PU) substrates.

[0080] The substrate is preferably transparent, colorless (in which case it is clear or extra-clear glass) or colored, for example in blue, grey or bronze.

[0081] The substrate can be an ultrathin glass, for example, with a thickness of less than 0.7 mm.

[0082] The substrate can be tempered (thermally).

[0083] The silver-based functional coating can advantageously be deposited on a clear glass substrate to allow maximum reflection of infrared radiation and thus obtain low total energy transmission.

[0084] The silver-based functional coating can be deposited on a tinted substrate to neutralize the external reflective appearance. However, in this case, a compromise must be found between color neutralization and energy performance.

[0085] Preferably, the lamination interlayers comprise one or more sheets of organic polymers.Organic polymers are selected from polyvinyl butyral (PVB), polyurethanes (PU), polyureas, ethylene vinyl acetate (EVA), polyolefins (including polyethylene (PE), polypropylene (PP) or polyisobutylene (P-IB)), polyvinyl chloride and its derivatives (e.g. poly(vinyl dichloride) (PVDC)), styrenic polymers (e.g. polystyrene (PS), acrylostyrene butadiene (ABS), styrene acrylonitrile (SAN)), polyacrylics (including polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA)), polyesters (including poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT)), polyoxymethylene (POM), polyamides (PA), fluoropolymers such as polychlorotrifluoroethylene (PCTFE), Polycarbonates (PC), aromatic polysulfones including polysulfone (PSU), polyphenylene ether (PPE), epoxies (EP) alone or in mixtures and / or copolymers of several of them. The lamination interlayer may be tinted.

[0086] Typically, interleaves have a thickness between 0.20 and 3.00 mm. An interleave can be composed of one or more polymer sheets. The thickness ranges given are the total thicknesses of the interleave.

[0087] The material, i.e., the substrate coated with the functional coating, can undergo high-temperature heat treatment such as annealing, for example by flash annealing such as laser or flame annealing, quenching, and / or bending. The heat treatment temperature is above 400 °C, preferably above 450 °C, and even better above 500 °C. The substrate coated with the functional coating can therefore be bent and / or quenched.

[0088] The material of the invention is particularly suitable for use in laminated automotive glazing, especially curved glazing such as roofs or windshields. The laminated glazing according to the invention is therefore preferably automotive glazing such as a car roof window or a windshield.

[0089] Laminated glazing may also have a light transmission greater than 70%, greater than 75%, or greater than 77%. Laminated glazing according to the invention, when used in particular as a windshield or side window, preferably has a light transmission TL of at least 70% and even at least 75% or even at least 77%.

[0090] Laminated glazing can be used as a windscreen to provide in combination a solar control function and another function, for example a HUD function with advantageous reflective optical properties.

[0091] Finally, the glazing of the invention is suitable for building applications, particularly when the glazing is used as a partition with the outside. The glazing may then be in the form of single glazing, multiple glazing, or laminated glazing. Multiple glazing comprises a material according to the invention and a second substrate separated by a layer of gas.

[0092] The advantageous details and features of the invention will become apparent from the following non-limiting examples. Examples I. Nature of layers and coatings

[0093] Functional coatings defined below are deposited on clear soda-lime glass substrates with a thickness of 1.6 mm. The functional metallic layers (F) are silver (Ag) layers. The blocking layers are nickel-chromium alloy (NiCr) metallic layers. The dielectric coatings of the functional coatings include barrier and stabilizing layers. The barrier layers are based on aluminum-doped silicon nitride (Si3N4:Al), aluminum-doped silicon-zirconium nitride (SiZrl7Nx), or mixed zinc-tin oxide (SnZnOx). The stabilizing layers are zinc oxide (ZnO). The deposition conditions of the layers, which were deposited by sputtering (so-called "magnetron cathode sputtering"), are summarized in Table 1.

[0094] [Table 1] Table 1 Target Used Deposition Pressure Gas Si3N4 Si:Al at 92:8 wt% 3.2 x 10⁻³ mbar Ar / (Ar + N₂) at 55% SiZr(17)Nx Si:Zr:Al at 78:17:5 wt% 2 x 10⁻³ mbar Ar / (Ar + N₂) at 45% ZnO Zn:Al at 98:2 wt% 1.8 x 10⁻³ mbar Ar / (Ar + O₂) at 63% SnZnOx Sn:Zn (60:40 wt%) 1.5 x 10³ mbar Ar / (Ar + O₂) at 39% Ag Ag 3 x 10⁻³ mbar Ar at 100%

[0095] At. = atomic.

[0096] Table 2 lists the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating that constitutes the coatings according to their position with respect to the substrate carrying the stack (last line at the bottom of the table).

[0097] [Tables2] Material RFI RF2 RF4 CT RFX RF5 RF6 RF7 Di4 SiZr(17)NX - - - - - 20.7 27 20.8 Si3N4 29.2 21.6 27.3 19 5-30 - - - ZnO 14.8 14.8 14.8 14.8 4 -17 14 14 CF3 Ag 7.9 7.7 8.6 6.8 6-15 7.3 7.7 8.9 Di3 ZnO 12.8 12.8 12.8 12.8 12-17 15 15 15 ZnSnOx 6.9 6.96 6.15 15-15 11.5 11.5 SiZr(17)NX 20.1 16.4 15.3 17.6 5-30 11 20.6 14.3 Si3N4 9.1 11.8 23.6 12 5-30 10.6 10.3 10.3 Zn O 12.8 10-17 14 14 14 CF2 Ag 8.8 10 11.5 8.5 8-15 8.9 10.6 9.5 Di2 ZnO 12.3 12.3 12.3 12.3 10-15 15 15 15 Zn Ox 8.6.68 8.6 6-15 11.5 11.5 11.5 SiZr(17)NX 15.2 15.2 18.7 12.5 5-30 11 20.6 14.3 Si3N4 11.5 9.6 13.9 14.4 5-30 17.1.19.8 SiZr(17)NX 11.4 13.2 12.7 11 5-30 10.6 10.3 10.3 ZnO 11.1 9.5 Dil ZnO 10.8 10.8 10.8 10.8 10-15 12 12 12 ZnSnOx 7.7 7.7 7.7 7.7 6-10 9 9 9 SiZr(17)NX 18.1 9.9 -2 - Si - - 5-30 12.5 17.6 10.9 Glass Substrate

[0098] Di: Dielectric coating; CF: Functional layer.

[0099] Table 3 shows the optical thicknesses and thickness ratios of the functional layers and dielectric coatings.

[0100] [Tables3] Material RFI RF2 RF4 CT RF5 RF6 RF7 Eo Dil 79.0 60.2 67.1 88.0 67.5 77.7 64.3 Eo Di2 152.8 153.2 168.7 151.5 168.1 176.8 159.8 Eo Di3 129.8 126.7 147.7 129.8 128.1 147.7 136.1 Eo Di4 88.0 72.8 84.2 67.6 75.6 90.1 75.8 Ag2 / Agl 0.74 1.06 1.16 0.76 0.81 0.95 1.00 Ag2 / Ag3 1.11 1.30 1.34 1.25 1.22 1.38 1.07 Agl / Ag3 1.51 1.22 1.15 1.65 1.51 1.44 1.07 Eo2 / Eol 1.93 2.55 2.52 1.72 2.49 2.28 2.49 Eo2 / Eo3 1.18 1.21 1.14 1.17 1.31 1.20 1.17 Eo2 / Eo4 1.74 2.10 2.00 2.24 2.22 1.96 2.11

[0101] The substrates undergo heat treatment for several minutes at a temperature of at least 550°C II. Laminated glass configuration

[0102] Materials comprising a transparent substrate, one face of which is coated with a functional coating, have been assembled in the form of laminated glazing. Laminated glazing, hereinafter configuration “L.”, has a structure of type first substrate 2.1 mm / lamination interlayer / second substrate 1.6 mm. The silver-based functional coating is positioned on face 3. The interlayer is a clear PVB. The second substrate is chosen from clear glass. III. Exploratory Research

[0103] Extensive explorations were carried out using optical simulation to determine the functional coatings likely to confer the desired properties. In these simulations, all layer thicknesses were varied. The thickness ranges within which the layers varied are defined in Table 2 using RFX. The results of these Brownian explorations are shown in Figures 1, 2, and 3.

[0104] Figures 1 and 2 represent the distribution of functional coatings exhibiting the following properties: - The points correspond to functional coatings exhibiting: a TL > 77% and a TTS < 48.5%, - the squares correspond to functional coatings exhibiting: a TL > 77%, a TTS < 48.5% and values ​​of a*Rext and b*Rext < 0, - the stars correspond to functional coatings exhibiting: a TL > 77%, a TTS < 48.5%, values ​​of a*Rext and b*Rext < 0 and values ​​of a*60Rext and b*60Rext < 0.

[0105] Fig. 1 represents the thickness of Agi on the abscissa and the thickness of Ag2 on the ordinate. Figure [Fig.2] represents the thickness of Agi on the x-axis and the thickness of Ag3 on the y-axis.

[0106] These figures highlight that: - high light transmission values ​​can only be obtained for certain Ag2 / Agl and Ag3 / Agl thickness ratios. Figure 2 highlights a high concentration of functional coatings exhibiting all the desired properties, represented by stars with Agl thicknesses both greater than 10 nm and greater than the Ag3 thicknesses. Figure 1 highlights a high concentration of functional coatings exhibiting all the desired properties, represented by stars with Agl and Ag2 thicknesses such that the Ag2 / Agl ratio is less than or equal to 1.30.

[0107] Figure 1[3] represents the distribution of functional coatings exhibiting the combination of all the desired properties: a TL > 77%, a TTS < 48.5%, values ​​of a*Rext and b*Rext < 0 and values ​​of a*60Rext and b*60Rext < 0, as a function of the thickness of the following elements of the functional coatings: - thicknesses of the functional layers Agi, Ag2 and Ag3, - thicknesses of all the nitride layers present in a dielectric coating Dil, Di2, Di3, Di4, respectively called NDil, NDi2, NDi3, NDi4.

[0108] For example, NDi2 comprises the sum of the thicknesses of the Si3N4 and SiZrN layers in the dielectric coating Di2. This figure highlights that the advantageous property combination is obtained with silver layers satisfying Agl>Ag2 and / or Ag2>Ag3 and Eo2>Eo3.

[0109] III. "Solar control" performance and colorimetry

[0110] The colorimetric performance and properties were determined by simulation. [YES] [Tables 4] Target Glazing L.RF1 L.RF2 L.RF4 L.CT RF5 RF6 RF7 TL >77% 77.5 77.7 77 78.6 77 77.5 77.7 RL 8° <20% 8.9 8.6 9.3 8.5 10.6 10.1 9.3 a Rext*8° [-10;0] -4.3 -2.6 -2.6 -3.5 -3.1 -2.7 -2.4 b Rext*8° [-10;5] -8.4 -4.9 -4.8 3.9 -8.2 -11.8 -1.1 a Rext*60° [-10;0] -1.1 -0.2 -1.7 3.1 -3 -1.4 -3.6 b Rext*60° [-10;5] -4.4 -2.7 -2.5 -6.6 -5.2 -7 -0.7 A a*Rext (8° vs., 60°) < 5 3.2 2.4 0.9 6.6 0.1 1.3 -1.2 A b*Rext (8° vs., 6 0°) < 5 4 2.2 2.3 -10.5 3 4.8 0.4 TTS <48.5% 47.9 48.5 48.4 50 48 47.7 48.2

Claims

Demands

1. Laminated glazing comprising a material and at least one second substrate, the material and the second substrate being bonded together by means of a lamination interlayer, the material comprising a transparent substrate coated with a functional coating comprising successively, from the substrate, an alternation of three silver-based functional metallic layers, named from the substrate first, second and third functional layers, and four dielectric coatings named from the substrate D1, Di2, Di3 and Di4, each having an optical thickness E10, E02, E03 and E04, each dielectric coating comprising at least one dielectric layer, such that each functional metallic layer is disposed between two dielectric coatings,characterized in that: - the ratio of the thickness of the first functional metallic layer to the thickness of the third functional metallic layer Agl / Ag3 is greater than 1.05 and the ratio of the thickness of the second functional metallic layer to the thickness of the third functional metallic layer Ag2 / Ag3 is greater than 1.05 and - the ratio of the optical thicknesses Eo2 / Eo3 is greater than 1.10, and - the first silver-based functional metallic layer has a thickness between 6 and 15 nm, and / or - the second silver-based functional metallic layer has a thickness between 6 and 16 nm, and / or - the third silver-based functional metallic layer has a thickness between 6 and 15 nm, - the sum of the thicknesses of all the silver-based functional layers of the functional coating is less than 30 nm,- Laminated glazing has a light transmission greater than 70% as measured according to standard EN 410.

2. Laminated glazing according to claim 1 characterized in that the ratio of the thickness of the second functional metallic layer to the thickness of the first functional metallic layer Ag2 / Agl is less than or equal to 1.

30.

3. Laminated glazing according to any one of the preceding claims, characterized in that: - The dielectric coating Dil has an optical thickness Eol between 50 and 90 nm, - The dielectric coating Di2 has an optical thickness Eo2 between 120 and 190 nm, - The dielectric coating Di3 has an optical thickness Eo3 between 110 and 160 nm, - The dielectric coating Di4 has an optical thickness Eo4 between 60 and 100 nm.

4. Laminated glazing according to the preceding claim characterized in that: - the ratio of optical thicknesses Eo2 / Eol is greater than 1.5 and less than 3.0, - the ratio of optical thicknesses Eo2 / Eo4 is greater than 1.5 and less than 3.0, - the ratio of optical thicknesses Eol / Eo3 is greater than 0.30 and less than 0.80, - the ratio of optical thicknesses Eol / Eo4 is greater than 0.80 and less than 1.

00.

5. Laminated glazing according to any one of the preceding claims characterized in that each dielectric coating comprises a layer comprising silicon selected from silicon nitride-based layers.

6. Laminated glazing according to any one of the preceding claims characterized in that the sum of the physical thicknesses of all the layers comprising silicon in each dielectric coating is greater than 25% of the total thickness of the dielectric coating.

7. Laminated glazing according to any one of the preceding claims characterized in that each dielectric coating located below a functional layer comprises a zinc oxide-based layer located below, in contact with, or separated by a blocking layer from the functional layer.

8. Laminated glazing according to any one of the preceding claims characterized in that each dielectric coating situated above a functional layer comprises a zinc oxide-based layer situated above, in contact with, or separated by a blocking layer from, the functional layer.

9. Laminated glazing according to any one of the preceding claims characterized in that each dielectric coating situated below a functional layer comprises a zinc tin oxide-based layer situated below and in contact with a zinc oxide-based layer.

10. Laminated glazing according to any one of the preceding claims characterized in that it comprises a face 1 located outside the building or vehicle it equips, faces 2 and 3 in contact with the lamination interlayer and a face 4 inside the building or vehicle, the functional coating is positioned on face 2 or 3.

11. Laminated glazing according to any one of the preceding claims characterized in that it has: - a light transmission greater than 75%, and / or - a total energy transmission less than 50%, preferably less than 48.5%, and / or - an external light reflection less than 15%.

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