Materials including a functional coating used in the form of laminated and multiple glazing

Abstract

The invention relates to a material comprising a transparent substrate coated with a functional coating successively comprising, from the substrate, an alternation of three silver-based functional metallic layers and four dielectric coatings (Di1, Di2, Di3, and Di4), each having an optical thickness Eo1, Eo2, Eo3, and Eo4. Each dielectric coating comprises at least one dielectric layer, such that each functional metallic layer is arranged between two dielectric coatings with: - the dielectric coating Di1 having an optical thickness Eo1 of less than 80 nm, - the dielectric coating Di2 having an optical thickness Eo2 of less than 160 nm, - the dielectric coating Di3 having an optical thickness Eo3 of less than 160 nm, - the dielectric coating Di4 having an optical thickness Eo4 of less than 60 nm, - Eo2 / Eo1 greater than 1.70 including this value, - the thickness of the second functional metallic layer being less than 12 nm,- the ratio of the thickness of the third functional metallic layer to the thickness of the first functional metallic layer Ag3 / Ag1 is greater than or equal to 1.20.

Description

Title of the invention: Materials comprising a functional coating used in the form of laminated and multiple glazing

[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. The invention also relates to glazing comprising these materials and to the use of such materials for manufacturing thermal insulation and / or solar protection glazing.

[0002] In the following description, the term "functional" qualifying "functional coating" means "capable of acting on solar radiation and / or infrared radiation".

[0003] These glazing units can be used to equip both buildings and vehicles, in particular for:

[0004] - reduce the air conditioning effort and / or prevent excessive overheating, so-called "solar control" glazing and / or

[0005] - reduce the amount of energy dissipated to the outside, so-called "low" glazing emissives.

[0006] The selectivity “S” allows for the evaluation of the performance of these glazings. It corresponds to 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” corresponds to the ratio, expressed as a percentage, between the total energy entering the room through the glazing and the incident solar energy.

[0007] Selectivity is a key parameter of solar control glazing.

[0008] Known selective glazing comprises transparent substrates coated with a functional coating comprising a stack of one or more metallic functional layers, each arranged between two dielectric coatings. Such glazing improves solar protection while maintaining high light transmission. These functional coatings are generally obtained by a series of deposits made by sputtering, possibly assisted by a magnetic field.

[0009] Depending on the applications intended and in particular on the properties sought, these glazings can be in the form of monolithic glazing, multiple glazing, laminated glazing or multiple and laminated glazing.

[0010] Conventionally, 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 inside of the dwelling or room it equips. This means that sunlight incident light crosses the faces in ascending order of their number.

[0011] The best performing known selective glazings are generally double glazings comprising a functional coating with at least three silver-based metallic functional layers located on face 2, i.e. on the outermost substrate of the building; on its face turned towards the intercalated gas layer.

[0012] There is currently a growing demand for laminated solar control glazing. This laminated glazing makes it possible, in particular, to improve safety or to comply with the requirements of certain standards such as hurricane-resistant standards.

[0013] Currently, the two most commonly used configurations are double-glazed units without lamination and with a functional coating on surface 2, and single-glazed units with a functional coating on surface 2. In the "double-glazed unit without lamination" configuration, the functional coating is located opposite the interlayer gas. In the "laminated unit" configuration, the functional coating is located opposite the lamination interlayer.

[0014] Functional coatings developed for double glazing applications are not suitable for laminated glass because their aesthetic appearance is generally unacceptable when the functional coating is in contact with the laminate interlayer. Very red or turquoise colors at angles and a strong angular variation of colors are often observed. Except in specific cases, these colors are unsuitable because the aim is to obtain neutral or sometimes blue-green colors.

[0015] When it is desired to have laminated glazing with defined colorimetric properties, it is therefore not possible to use substrates coated with functional coatings developed for double glazing applications with these properties.

[0016] In any case, we cannot expect to have the same aesthetics in laminated glass as in double glazing if we take the existing functional coatings.

[0017] Indeed, the optical and colorimetric properties differ depending on whether the functional coating is in contact with the interlayer gas sheet or the laminate interlayer. This is due to the differences in refractive index between the interlayer gas sheet (1.0) and the interlayer (1.5). The "functional coating / gas sheet" and "functional coating / interlayer" interfaces behave optically differently.

[0018] For laminated applications, it is therefore necessary to modify known functional coatings in order to obtain acceptable optics and the desired optical performance.

[0019] The processor or end user wishing to be able to supply multiple glazing and laminated glazing with equivalent optical properties must have two different ranges of materials in stock.

[0020] It would be particularly advantageous to have materials with equivalent optical properties, whether in the form of laminated or double glazing. Indeed, having such materials greatly simplifies inventory management for the processor or the end user.

[0021] The object of the invention is therefore to overcome the disadvantages of the prior art by developing a glazing having equivalent optical properties, whether in the form of a multiple glazing when the functional coating is in contact with the interlayer gas layer or of a laminated glazing when the functional coating is in contact with the lamination interlayer.

[0022] According to the invention, "optical properties" means the light transmission and reflection properties in the visible range as well as the colorimetric properties.

[0023] Regarding energy properties, it is impossible to obtain the same performance with laminated and non-laminated double glazing. The solar factor will always be lower with non-laminated double glazing than with laminated glazing. This is because laminated glazing does not benefit from the thermal insulation of the interlayer gas present in multi-pane glazing.

[0024] According to the invention, the term "laminated material" means a material optimized to exhibit the desired optical properties and energy performance after the lamination step.

[0025] According to the invention, the term "laminateable material" means an optimized material exhibiting the desired optical properties: - when it is in laminated form, after the lamination stage, - when it is in the form of non-laminated double glazing.

[0026] The invention relates to a selective laminated material with high light transmission having a similar aesthetic whether in the form of non-laminated double glazing or laminated glazing.

[0027] The applicant has surprisingly discovered a combination of features that yields high light-transmitting materials which, when mounted as double glazing or laminated glazing, exhibit similar optical properties. The materials include three-layer silver functional coatings. The combination of features relates to the thicknesses of the silver layers and the dielectric coatings.

[0028] The invention relates in particular 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, designated from the substrate first, second and third functional layers, and four dielectric coatings designated from the substrate D1, Di2, Di3 and Di4 which each have an optical thickness E0, 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 dielectric coating Dil has an optical thickness Eol of less than 80 nm, - the dielectric coating Di2 has an optical thickness Eo2 of less than 160 nm, - the dielectric coating Di3 has an optical thickness Eo3 of less than 160 nm, - the dielectric coating Di4 has an optical thickness Eo4 of less than 60 nm, - the ratio of optical thicknesses Eo2 / Eol is greater than 1.70 including this value, - the thickness of the second functional metallic layer is less than 12 nm, - the ratio of the thickness of the third functional metallic layer to the thickness of the first functional metallic layer Ag3 / Agl is greater than or equal to 1.20.

[0029] The invention also relates to: - a glazing comprising a material according to the invention, - glazing comprising a material according to the invention, mounted on a vehicle or building - the process for preparing a material or glazing according to the invention, - the use of glazing according to the invention as solar control and / or low-emissivity glazing for buildings or vehicles, - a building, a vehicle or a device comprising glazing according to the invention.

[0030] The invention therefore relates to glazing comprising at least one material according to the invention in the form of monolithic, laminated or multiple glazing, in particular double glazing or triple glazing.

[0031] The coating is advantageously positioned in the glazing so that the incident light from the outside passes through the first dielectric coating before passing through the first functional metallic layer.

[0032] The invention relates to a multiple glazing comprising a material and at least one additional substrate, the material and the additional substrate are separated by at least one layer of intercalated gas.

[0033] The invention relates to a laminated glazing comprising a material and at least one additional substrate, the material and the additional substrate are separated by at least one lamination interlayer.

[0034] 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.

[0035] All the described luminous characteristics 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.

[0036] Conventionally, refractive indices are measured at a wavelength of 550 nm.

[0037] 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.

[0038] 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).

[0039] 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.

[0040] 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.

[0041] The thicknesses of the blocking layers are not taken into account for the calculation of the optical thickness of the dielectric coating.

[0042] 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.

[0043] The luminous characteristics are measured with respect to illuminant D65 at 2° perpendicular to the material mounted in a double glazing unit (unless otherwise specified): - TL corresponds to the light transmission in the visible spectrum as a percentage - Rext corresponds to the external light reflection in the visible spectrum as a percentage, from the observer's perspective on the exterior space. - Rint corresponds to the internal light reflection in the visible spectrum as a percentage, from the observer's perspective on the interior space side. - a*T and b*T correspond to the colors in transmission a* and b* in the L*a*b* system, - a*Rext and b*Rext correspond to the reflected colors a* and b* in the L*a*b* system, observer on the outside space side. - a*Rint and b*Rint correspond to the reflected colors a* and b* in the L*a*b* system, observer on the interior space side. - a*Rext 60° and b*Rext 60° correspond to the colors in reflection a* and b* in the L*a*b* system at an angle of 60° with respect to the normal to the plane of the glazing, observer on the outside space side.

[0044] In double-glazed configurations (hereinafter referred to as DGU), colorimetric properties such as L*, a* and b* values ​​and all values ​​and ranges of values ​​of optical and thermal characteristics such as selectivity, external or internal light reflection, light transmission are calculated with: - materials comprising a substrate coated with a functional coating, mounted in double glazing, - the double glazing has a configuration: 4-16(Ar-90%)-4, that is to say a configuration consisting of a material comprising a substrate of ordinary soda-lime glass of 4 mm and another substrate of soda-lime glass of 4 mm, the two substrates are separated by an interlayer of gas of 90% argon and 10% air with a thickness of 16 mm, - the functional coating is preferably positioned on face 2, that is to say on the substrate furthest outside the building; on its face turned towards the intercalated gas layer.

[0045] In configurations in the form of laminated glazing (hereinafter Lam.), the colorimetric properties such as the L*, a* and b* values ​​and all the values ​​and ranges of values ​​of the optical and thermal characteristics such as selectivity, external or internal light reflection, light transmission are calculated with: - materials comprising a substrate coated with a functional coating mounted in laminated glazing, - Laminated glazing comprises a material including a 4 mm ordinary soda-lime glass substrate and another 4 mm soda-lime glass substrate, the two substrates being separated by a 0.76 mm PVB lamination interlayer, - the functional coating is preferably positioned on face 2 on its face turned towards the laminate interlayer.

[0046] According to the invention, a material is said to be "laminated" when it has similar colors in a non-laminated double glazing configuration and in a laminated glazing configuration.

[0047] This can result in maximum permissible deviations between the following configurations: - in light transmission - ATL (%) = | TLDGU-TLLam | <4 - Aa*T (%) = | a*TDGU-a*TLam | < 3 - Ab*T (%) = | b*TDGU-b*TLam | < 3 - in external light reflection: - ARLext (%) = | RLextDGU- RLextLam | <4 - Aa* Rext (%) = | a* RextDGU-a* RextLam | < 3 - Ab* Rext (%) = | b* RextDGU-b* Rext, ,,m | < 3 - in external light reflection at an angle (60°): - Aa* Rext 60° (%) = | a* Rext60°DGU-a* Rext60°Lam | < 3 - Ab* Rext 60° (%) = | b* Rext60°DGU-b* Rext 60°Lam | <3.

[0048] These gaps ensure that two panes of glass separated by these maximum gaps are visually close.

[0049] The Delta C* representing the variation between the colors obtained in double glazing and in laminated glazing defined by (a*DGU, b*DGU) and (a*Lam, b*Lam) in transmission or in reflection is calculated by the following formula: Delta C* = V((a*DGU - a*Lam)2 + (b*DGU - b*Lam)2)

[0050] The flaky character can also be expressed by the following Delta C* (color difference) values: - in transmission: Delta C* max = 4.2, - in external reflection: Delta C* max = 4.2, - in internal reflection: Delta C* max = 8.5, - in external reflection at 60°: Delta C* max = 4.2.

[0051] The permissible difference between double glazing and laminated glass is more restricted in transmission and external reflection than in internal reflection, the latter being less visible.

[0052] The invention therefore also relates to glazing in the form of double glazing or laminated glazing, the color variations of which between a material mounted as double glazing with the functional coating positioned on surface 2 and a material mounted as laminated glazing with the functional coating positioned on surface 2, defined by Delta C* with Delta C* = ^((a*DGU-a*Lam)2-(b*DGU-b*Lam)2), satisfy: - in transmission: Delta C* < 4.2, - in external reflection: Delta C* < 4.2, - in internal reflection: Delta C* < 8.5, - in external reflection at 60°: Delta C* < 4.2,

[0053] with a*DGU and b*DGU being the colorimetric coordinates of the material mounted as double glazing and a*Lam and b*Lam being the colorimetric coordinates of the material mounted in the form of laminated glazing in transmission, external reflection, internal reflection.

[0054] The material according to the invention has the following characteristics: - an internal and external light reflection of less than 20%, and / or - a light transmission greater than 50%, greater than 55%, greater than 60%, between 50% and 70%, between 60% and 70% or between 65% and 69%.

[0055] These values ​​are obtained for the material alone. A single material corresponds to a monolithic glazing.

[0056] The material according to the invention, in the form of multiple and / or laminated glazing, also provides the following advantageous properties: - a light transmission greater than 50%, greater than 55%, greater than 60%, between 50% and 70%, between 55% and 65%, or between 58% and 62% and / or - an external reflection of less than 20%.

[0057] Preferably, the material gives neutral colors to the glazing incorporating it. According to the invention, neutral colors in transmission and external or internal reflection are defined by: - values ​​of a* between, in increasing order of preference, -10 and 0, -4 and 0, -3 and 0, -2 and 0, -1 and 0 and / or - values ​​of b* between, in increasing order of preference, -10 and +5, -5 and 0, -3 and 0, -2 and 0, -1 and 0.

[0058] According to advantageous embodiments, the glazing of the invention in the form of double glazing comprising the functional coating positioned on surface 2 has, in particular: - a high selectivity, in ascending order of preference, of at least 1.7, greater than 1.8, of at least 1.9, of at least 2.0, of at least 2.1, and / or - a solar factor g less than or equal to 40%, less than or equal to 35%, less than or equal to 30%, between 25 and 35% and / or - a solar factor g greater than or equal to 26%, and / or - an internal and external light reflection of less than 20%, and / or - a light transmission greater than 50%, greater than 55%, greater than 60%, between 40% and 70%, between 50% and 70%, between 50% and 65%, between 55% and 65%, or between 58% and 62% and / or - values ​​of a* in external reflection at 0 and 60° and in transmission between, in increasing order of preference, -10 and +0, between -5 and +0, and / or - values ​​of b* in external reflection at 0 and 60° and in transmission included, in order of increasing preference, between -10 and +5, between -5 and +0.

[0059] According to advantageous embodiments, the glazing of the invention in the form of laminated glazing comprising the functional coating positioned on face 2 makes it possible to achieve, in particular, the following performances: - a light transmission greater than 50%, greater than 55%, greater than 60%, between 50% and 70%, between 55% and 65% or between 58% and 62% and / or - an external reflection of less than 25%, less than 22%, less than 20% and / or - Neutral colors in transmission and external reflection at 0° and 60°: a* between -10 and 0; b* between -10 and 5, and / or - an aesthetic in transmission and external reflection (at 0° and at an angle) close to that of double glazing.

[0060] The glazing according to the invention is mounted on a building or a vehicle.

[0061] The invention therefore also relates to: - glazing mounted on a vehicle or building, and - a vehicle or a building comprising glazing according to the invention.

[0062] Glazing for a building generally delimits two spaces, a space described as "exterior" and a space described as "interior". Sunlight entering a building is considered to travel from the outside to the inside.

[0063] According to the invention, glazing used as a constituent element of balustrades, balconies and / or railings is also included in the "building" applications.

[0064] The invention also relates to: - the process for obtaining a material or glazing according to the invention, - the use of glazing according to the invention as solar control and / or low emissivity glazing for buildings or vehicles.

[0065] The functional coating is deposited by magnetic field-assisted sputtering (magnetron process). According to this advantageous embodiment, all the coating layers are deposited by magnetic field-assisted sputtering.

[0066] The invention also relates to the method of obtaining a material and glazing according to the invention, in which the coating layers are deposited by magnetron sputtering.

[0067] Unless otherwise specified, the expressions "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).

[0068] 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%.

[0069] 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.

[0070] An ordinary clear glass 4 to 6 mm thick has the following luminous characteristics: - a light transmission between 87.5 and 91.5% - a light reflection between 7 and 9.5% - a light absorption of between 0.3 and 5%.

[0071] 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).

[0072] The 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% by mass of metals other than silver relative to the mass of the silver-based metallic functional layer.

[0073] The three functional metallic layers can satisfy the following characteristics: - the first functional silver-based metallic layer has a thickness between 7 and 11 nm, preferably between 7 and 10 nm, and / or - the second functional silver-based metallic layer has a thickness between 9 and 12 nm excluding the terminal, preferably between 9 and 10 nm, and / or - the third functional silver-based metallic layer has a thickness between 12 and 18 nm, preferably between 13 and 17 nm, 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 between 1.05 and 2.00, between 1.10 and 1.80 or between 1.10 and 1.50 including these values, and / or - the ratio of the thickness of the third functional metallic layer to the thickness of the second functional metallic layer Ag3 / Ag2 is between 1.05 and 2.00, between 1.10 and 1.80 or between 1.20 and 1.7, including these values, and / or - the ratio of the thickness of the third functional metallic layer to the thickness of the first functional metallic layer Ag3 / Agl is between 1.20 and 3.00 or between 1.50 and 2.50, including these values.

[0074] The thicknesses of the functional metal layers starting from the substrate can increase. In this case, the increase in thickness between two successive functional layers is greater than 0.8 nm, greater than 1 nm, greater than 1.5 nm.

[0075] The ratio of the thickness between two successive functional layers is between 1.05 and 2.30 or between 1.1 and 2.30 including these values.

[0076] The stack may further include at least one blocking layer located in contact with a functional metallic layer.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] The dielectric layers of the coatings have the following characteristics, alone or in combination: - they are deposited by magnetic field-assisted sputtering, and / or - they are chosen from the oxides or nitrides of one or more elements chosen from titanium, silicon, aluminum, zirconium, tin and zinc, and / or - they are chosen from

[0084] oxide layers of one or more elements selected from titanium, silicon, aluminium, 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 - they have a thickness greater than 2 nm, preferably between 4 and 100 nm.

[0085] 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 can be based on oxide or nitride of one or more elements chosen from silicon, zirconium, titanium, aluminum, tin, zinc, 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 - 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 barrier layers are based on silicon and / or aluminum compounds and may include at least one other element, such as aluminum, hafnium and zirconium, 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.

[0086] 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.

[0087] 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 the following: - based on silicon and / or aluminium 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.

[0088] Preferably, each coating comprises at least one dielectric layer consisting of: - of an aluminum and / or silicon nitride or oxynitride or - of a mixed oxide of zinc and tin, or - of titanium oxide.

[0089] 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.

[0090] 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.

[0091] The dielectric layer(s) with stabilizing function may be in direct contact with a functional layer or separated by a blocking layer.

[0092] 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.

[0093] It is also advantageous to have a stabilizing functional layer, for example, based on zinc oxide above a functional layer, to increase its adhesion and optimally oppose diffusion on the side of the stack opposite the substrate.

[0094] 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.

[0095] Advantageously, each barrier dielectric layer is separated from a functional layer by at least one stabilizing dielectric layer.

[0096] 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.

[0097] Preferably, the dielectric coatings of the functional coatings comprise a zinc oxide-based dielectric layer located below the silver-based metallic layer.

[0098] The zinc oxide layers have, in increasing order of preference, a thickness: - of at least 3.0 nm, of at least 4.0 nm, of at least 5.0 nm, and / or - of at most 25 nm, of at most 10 nm, of at most 8.0 nm.

[0099] According to advantageous embodiments of the invention, the dielectric coatings satisfy one or more of the following conditions in terms of thickness: - the dielectric coatings Dil, Di2, Di3 and Di4 each have an optical thickness Eol, Eo2, Eo3 and Eo4 satisfying one or more of the following relationships: Eo4 < Eol, Eo4 < Eo2, Eol < Eo3, and / or - the Dil dielectric coating has an optical thickness between 20 and 80 nm, between 30 and 80 nm, between 57 and 80 nm, and / or - the Di2 dielectric coating has an optical thickness between 80 and 160 nm, between 90 and 150 nm, between 100 and 150 nm, between 110 and 145 nm, between 124 and 144 nm and / or - the Di4 dielectric coating has an optical thickness between 80 and 160 nm, between 90 and 150 nm, between 100 and 150 nm, between 124 and 160 nm, between 144 and 160 nm and / or - the Di4 dielectric coating has an optical thickness of between 30 and 60 nm, from 30 to 55 nm.

[0100] The functional coating may optionally include a protective top layer. The protective top layer is preferably the last layer of the stack, that is, the layer furthest from the coated substrate of 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.

[0101] The protective layer may 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.

[0102] 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 stabilizing dielectric layer, - possibly a blocking layer, - a first functional layer, - possibly a blocking layer, - a second dielectric coating comprising at least one lower stabilizing dielectric layer, one barrier layer and one upper stabilizing dielectric layer, - possibly 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.

[0103] 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, - 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.

[0104] The transparent substrates according to the invention are preferably made of a rigid mineral material, such as glass, or organic polymer-based (or polymer).

[0105] The transparent organic substrates according to the invention may also be made of polymer, rigid or flexible. Examples of suitable polymers according to the invention include, in particular: - polyethylene, - polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN); - polyacrylates such as polymethyl methacrylate (PMMA); - polycarbonates; - polyurethanes; - polyamides; - polyimides; - fluorinated polymers such as fluoroesters like 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 resins and - polythiourethanes.

[0106] The substrate is preferably a sheet of glass or glass-ceramic.

[0107] The substrate is preferably transparent, colorless (in which case it is clear glass or extra clear) or colored, for example in blue, gray or bronze. The glass is preferably of the soda-lime silicate type, but it can also be of the borosilicate or aluminoborosilicate type.

[0108] According to a preferred embodiment, the substrate is made of glass, in particular soda-lime silico-glass or of polymeric organic matter.

[0109] The substrate advantageously has at least one dimension greater than or equal to 1 m, or even 2 m and 3 m. The substrate thickness generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, particularly between 2 and 8 mm, or even between 4 and 6 mm. The substrate can be flat or domed, or even flexible.

[0110] The material according to the invention can be in the form of monolithic, laminated and / or multiple glazing, in particular double glazing or triple glazing.

[0111] A monolithic glazing unit comprises a material according to the invention. Face 1 is on the outside of the building and therefore constitutes the outer wall of the glazing unit, face 2 is on the inside of the building and therefore constitutes the inner wall of the glazing unit.

[0112] A multiple glazing unit comprises a material and at least one additional substrate; the material and the additional substrate are separated by at least one layer of intercalated gas. The glazing unit provides a separation between an exterior space and an interior space.

[0113] A double glazing, for example, has 4 faces, face 1 is outside the building and therefore constitutes the outer wall of the glazing, face 4 is inside the building and therefore constitutes the inner wall of the glazing, faces 2 and 3 being inside the double glazing.

[0114] Laminated glazing comprises a material and at least one additional substrate, the material and the additional substrate being separated by at least one lamination interlayer. Laminated glazing therefore has at least one material / lamination interlayer / additional substrate structure. In the case of laminated glazing, all faces of the materials and additional substrates are numbered, but the faces of the lamination interlayers are not. Face 1 is on the exterior of the building and therefore constitutes the outer surface of the glazing, face 4 is on the interior of the building and therefore constitutes the inner surface of the glazing, and faces 2 and 3 are in contact with the lamination interlayer.

[0115] A laminated and multiple glazing comprises a material and at least two additional substrates corresponding to a second substrate and a third substrate, the material and the third substrate being separated by at least one layer of intercalated gas, and - the material and the second substrate or - the second substrate and the third substrate, are separated by at least one layer of puff pastry.

[0116] The laminate interlayers can be chosen from sheets of thermoplastic material, for example polyurethane (PU), polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), ethylene copolymer (ionomer) or be made of multi- or single-component resin that is thermally crosslinkable (epoxy, PU) or ultraviolet crosslinkable (epoxy, acrylic resin).

[0117] Typically, the dividers have a thickness between 0.20 and 3.00 mm.

[0118] An interleaf may be composed of one or more polymer sheets. The range The given thicknesses are the total thicknesses of the interlayer.

[0119] 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 better still above 500 °C. The substrate coated with the functional coating can therefore be bent and / or quenched.

[0120] The advantageous details and features of the invention will become apparent from the following non-limiting examples. Examples I. Nature of layers and coatings

[0121] Functional coatings defined below are deposited on clear soda-lime glass substrates with a thickness of 4 mm. The functional metallic layers (F) are silver (Ag) layers. The blocking layers are nickel-chromium alloy metallic layers. (NiCr). The dielectric coatings of functional coatings include barrier layers and stabilizing layers. The barrier layers are based on aluminum-doped silicon nitride (Si3N4:Al) or on mixed zinc-tin oxide (SnZnOx). The stabilizing layers are made of zinc oxide (ZnO).

[0122] The deposition conditions of the layers, which were deposited by sputtering (so-called "magnetron cathode sputtering"), are summarized in Table 1.

[0123] [Tables 1] Table 1 Target Used Deposition Pressure Gas Si3N4 Si:Al 92:8 wt% 3.2 x 10⁻³ mbar Ar / (Ar + N2) 55% ZnO Zn:Al 98:2 wt% 1.8 x 10⁻³ mbar Ar / (Ar + O2) 63% SnZnOx Sn:Zn (60:40 wt%) 1.5 x 10³ mbar Ar / (Ar + O2) 39% NiCr Ni (80 att.) : Cr (20 att.) 2-3 x 10³ mbar Ar 100% Ag Ag 3 x 10⁻³ mbar Ar 100%

[0124] At. = atomic. III. Functional Coatings

[0125] 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).

[0126] [Tables2] Tab. 2 Ml M2 CM1 CM2 CM3 RD: M4 - Si3N4 17 17 31 23 -ZnO 8 8 8 8 CB: NiCr 0.1 0.3 0.1 0.1 CF: Ag3 16 14 20 19 RD: M3 -ZnO 8 8 8 8 -SnZnO 8 8 8 8 - Si3N4 50 50 57 15 54 -ZnO 10 10 10 10 10 CB: NiCr 0.3 0.1 0.3 2 0.3 CF: Ag2 10 11 12 9 12 CB: NiCr 0.1 0.3 0.1 0.1 0.1 RD: M2 -ZnO 8 8 8 8 8 - Si3N4 48 53 57 55 53 -ZnO 8 8 8 8 8 CB: NiCr 0.4 0.3 0.4 0.1 0.1 CF: Agi 8 9 9 7 7 CB: NiCr 0.1 0.1 0.1 0.5 0.1 RD: Ml -ZnO 4 4 4 4 4 - Si3N4 26 28 42 27 31 Substrate (mm) 4 4 4 4 4

[0127] RD: Dielectric coating; CB: Blocking layer; CF: Functional layer.

[0128] [Tables3] Tab.3 Targets Ml M2 CM1 CM2 CM3 Eo4 <60 50 50 79 - 62 Eo3 < 160 152 152 166 50 160 Eol <80 61 65 94 63 71 Eo2 / Eol >1.7 2 2 2 2 2 Ag2 <12 10 11 12 9 12 Ag3 / Agl > 1.2 2 2 2 - 3

[0129] IV. Configuration of double glazing and laminated glazing

[0130] Materials comprising a transparent substrate, one face of which is coated with a functional coating, have been assembled in the form of double glazing or in the form of laminated glazing. The double glazing, hereinafter referred to as the “DGU” configuration, has a 4 / 16 / 4 structure: 4 mm glass / 16 mm space between panes filled with 90% argon and 10% air / 4 mm glass, with the functional coating positioned on face 2. Laminated glass panes, hereinafter referred to as the "Lam." configuration, have a structure of the type: first substrate 4 mm / sheet(s) / second substrate 4 mm. The functional coating is positioned on surface 2.

[0131] V. "Solar control" performance and colorimetry

[0132] [Tables4] Tab.4 Ml Ml M2 M2 CM1 CM1 CM2 CM2 CM3 CM3 Targets Property DGU In DGU In DGU In DGU In DGU In DGU In TL (%) 55-65 % 58.9 60.7 58.5 61.0 60.2 a 69 60 60 57 [−10;0] -3.6 -5.9 -4.0 -5.7 -4.2 -3.7 -4.2 -5.5 -5.5 -4 b*T [-10;5] -1.1 1.1 -1.1 0.0 -0.3 1.4 - 6 % -2.4, 12.8 11.8 11.8 10.6 12 15.7 9 8.5 14.5 16.7 a*Rext [−10;0] −4.1 −4.6 −1.1 −3.1 −2.3 −5.3* [5.1−1 [Re] 1.5−1 0.7 -2.0 -1.9 -1.3 -7 -8.2 -0.5 -4.3 -9 -14 RLint (%) 17.9 14.9 17.2 13.2 16 21.3 15.8 11.1 17 .20 -0.4 a-Rint -2.4 -4.6 -1.3 2.2 -4.5 -10 b*Rint 1.1 -3.2 -0.7 -1.9 -0.8 -2.4 1.9 3.6 -7 -15 a*Rext 60° [-10;0-8] -1.7-7 -0.1 0.7 5.8 -5.7 1 b*Rext 60° [-10;5] -2.3 -0.3 -1.5 1.3 -3.1 -5 -1.8 -2 -1.2 -7.6 g 25-35 % 83.3.9 35.7 37.7 43.8 28 38

[0133] [Tables5] Tab.5: Target Properties Ml M2 CM1 CM2 CM3 ATL (%) <4 1.8 2.5 4.4 3 3 Aa*T <3 2.4 1.7 0.6 1.3 1.5 Ab*T <3 2.2 1.2 1.7 0.5 3.5 ARLext (%) <4 0.9 1.1 3.7 0.5 2.2 Aa*Rext <3 0.5 2.0 3 6.6 7.5 Ab*Rext <3 2.7 0.6 1.2 3.8 5 ARLint (%) - 3.0 4.0 5.3 4.7 3 Aa*Rint - 5.8 3.8 2.2 3.5 5.5 Ab*Rint - 4.3 1.2 1.6 1.7 8 Aa*Rext 60° <3 3.0 2.7 5.5 5.1 6.7 Ab*Rext 60° <3 2.0 2.8 1.9 0.2 6.4 Ag - 4.9 5.8 5.1 4.7 10 Delta C* T <4.2 3.2 2.0 1.8 1.4 3.8 Delta C* Rext <4.2 2.7 2.1 3.2 7.7 9.0 Delta C* Rint <8.5 7.1 4.0 2.7 3.9 9.7 Delta C* Rext 60° <4.2 3.6 3.9 5.7 5.0 9.3

[0134] Materials CM1, CM2, and CM3 do not all meet the conditions regarding the claimed layer thicknesses. The aesthetics of double glazing and laminated glass are too different for the DGU and laminated glass configurations to be considered visually similar.

[0135] The CM2 material has 2 silver-based functional layers instead of 3. The gap between DGU and laminate is too large on some parameters and the aesthetics of DGU and laminate are not visually close.

[0136] The materials according to the invention, when mounted in the form of laminated glazing or in the form of laminated glazing, have sufficiently small color deviations.

Claims

Demands

1. 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, E12, E13, and E14, each dielectric coating comprising at least one dielectric layer, such that each functional metallic layer is arranged between two dielectric coatings, characterized in that: - the dielectric coating D1 has an optical thickness E10 of less than 80 nm, - the dielectric coating Di2 has an optical thickness E12 of less than 160 nm, - the dielectric coating Di3 has an optical thickness E13 of less than 160 nm, - the dielectric coating Di4 has an optical thickness E14 of less than 60 nm,- the ratio of optical thicknesses Eo2 / Eol is greater than 1.70 including this value, - the thickness of the second functional metallic layer is less than 12 nm, - the ratio of the thickness of the third functional metallic layer to the thickness of the first functional metallic layer Ag3 / Agl is greater than or equal to 1.

20.

2. 2. Material according to any one of the preceding claims characterized in that: - the first functional silver-based metal layer has a thickness of between 7 and 11 nm, preferably between 7 and 10 nm, - the second functional silver-based metal layer has a thickness of between 9 and 12 nm excluding the endpoint, preferably between 9 and 10 nm, - the third functional silver-based metal layer has a thickness of between 12 and 18 nm, preferably between 13 and 17 nm.

3. 3. Material according to any one of the preceding claims ca- characterized in that: - the dielectric coating Dil has an optical thickness between 57 and 80 nm, - the dielectric coating Di2 has an optical thickness between 124 and 144 nm, - the dielectric coating Di3 has an optical thickness between 144 and 160 nm, - the dielectric coating Di4 has an optical thickness between 30 and 55 nm.

4. Material according to any one of the preceding claims, characterized in that the three functional metallic layers satisfy the following characteristics: - the ratio of the thickness of the second functional metallic layer to the thickness of the first functional metallic layer Ag2 / Agl is between 1.05 and 2.00, between 1.10 and 1.80, or between 1.10 and 1.50 inclusive, and / or - the ratio of the thickness of the third functional metallic layer to the thickness of the second functional metallic layer Ag3 / Ag2 is between 1.05 and 2.00, between 1.10 and 1.80, or between 1.20 and 1.7 inclusive, - the ratio of the thickness of the third functional metallic layer to the thickness of the first functional metallic layer Ag3 / Agl is between 1.20 and 3.00, or between 1.50 and 2.50 inclusive. values.

5. Material according to any one of the preceding claims, characterized in that the dielectric layers are selected from: - oxide layers of one or more elements selected from titanium, silicon, zirconium, iron, chromium, cobalt, manganese, tungsten, niobium, bismuth, tantalum, zinc and / or tin - nitride layers of one or more elements selected from silicon, zirconium and aluminium, - oxynitride layers of one or more elements selected from silicon, zirconium and aluminium, - metallic sulfide layers such as zinc sulfide.

6. Material according to any one of the preceding claims, characterized in that each functional silver-based metallic layer is located below and / or above and in contact with a blocking layer based on at least one element selected from nickel, chromium, niobium, the Tantalum and titanium.

7. 7. Material according to any one of the preceding claims characterized in that the stack comprises, starting from the substrate: - a first dielectric coating comprising at least one silicon nitride-based layer and one zinc oxide-based layer, - optionally a blocking layer, - a first functional layer, - optionally 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, - optionally a blocking layer, - a second functional layer, - optionally 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, - optionally a blocking layer,- a third functional layer, - a blocking layer, - a fourth dielectric coating comprising at least one zinc oxide-based layer, one silicon nitride-based layer and - optionally a protective layer.

8. Material according to any one of the preceding claims characterized in that it has: - an internal and external light reflection of less than 20%, and - a light transmission of between 50 and 70%.

9. 9. Glazing comprising at least one material according to any one of claims 1 to 8 characterized in that it is in the form of monolithic, laminated or multiple glazing, in particular double glazing or triple glazing.

10. Glazing according to claim 9 characterized in that the coating is positioned in the glazing so that the incident light from the outside passes through the first dielectric coating before passing through the first functional metallic layer.

11. Multiple glazing according to claim 9 or 10 comprising the material and at least one additional substrate, the material and the additional substrate are separated by at least one layer of intercalated gas.

12. 12. Multiple glazing according to claim 11, characterized in that the glazing is a double glazing comprising the functional coating positioned on face 2: - a selectivity greater than 1.8, - a solar factor greater than 26%, - an internal and external light reflection less than 20%, - a light transmission between 40 and 70%, - values ​​of a* in external reflection at 0 and 60° and in transmission between, in increasing order of preference, -10 and +0, between -5 and +0, - values ​​of b* in external reflection at 0 and 60° and in transmission between, in increasing order of preference, -10 and +5, between -5 and +0.

13. Laminated glazing according to claim 9 comprising the material and at least one additional substrate, the material and the additional substrate are separated by at least one lamination interlayer.