• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The invention relates to a material comprising a transparent substrate coated with a stack of thin layers successively comprising from the substrate an alternation of three functional metallic layers based on silver and four dielectric coatings, so that each metal layer functional is arranged between two dielectric coatings. The thicknesses of the three functional layers and the thicknesses of the dielectric coatings are chosen so as to give the materials solar factor values of less than 20% for a light transmission of the order of 40%.
    公开号:FR3038596A1
    申请号:FR1556476
    申请日:2015-07-08
    公开日:2017-01-13
    发明作者:Jean Carlos Lorenzzi；Thierry Kauffmann
    申请人:Saint Gobain Glass France SAS；
    IPC主号:
    专利说明:

    At. = atomique
    Le tableau 2 liste les matériaux et les épaisseurs physiques en nanomètres (sauf autre indication) de chaque couche ou revêtement qui constitue les empilements en fonction de leur position vis-à-vis du substrat porteur de l’empilement (dernière ligne en bas du tableau). Les numéros « Réf. » correspondent aux références de la figure 1.
    Chaque revêtement diélectrique 20, 60, 100 en-dessous d’une couche fonctionnelle 40, 80, 120 comporte une dernière couche stabilisante 28, 68, 108 à base d’oxyde de zinc cristallisé, et qui est au contact de la couche fonctionnelle 40, 80, 120 déposée juste au-dessus.
    Chaque revêtement diélectrique 60, 100, 140 au-dessus d’une couche fonctionnelle 40, 80, 120 comporte une première couche stabilisante 62, 102, 142 à base d’oxyde de zinc cristallisé, et qui est au contact de la couche fonctionnelle 40, 80, 120 déposée juste au-dessus.
    Chaque revêtement diélectrique 20, 60, 100, 140 comporte une couche diélectrique à fonction barrière 24, 64, 104, 144, à base de nitrure de silicium, dopé à l’aluminium appelée ici S13N4.
    Le revêtement diélectrique 100 comporte en outre une couche de lissage à base d’oxyde mixte de zinc et d’étain 106.
    Chaque couche fonctionnelle métallique 40, 80, 120 est au-dessus d’une couche de blocage 30, 70 et 110 (non représentées sur la figure 1) et en-dessous et au contact d’une couche de blocage 50, 90 et 130. L’empilement comprend en outre une couche de protection en oxyde de titane et de zirconium 160 (non représentée sur la figure 1).
    Le tableau 3 suivant résume les caractéristiques liées aux épaisseurs des couches fonctionnelles et des revêtements diélectriques.
    RD : Revêtement diélectrique ; CB : Couche de blocage ; Ep : Epaisseur physique ; Eo : Epaisseur optique. II. Performances « contrôle solaire » et colorimétrie
    Le tableau 4 liste les principales caractéristiques optiques mesurées lorsque les vitrages font parties de double vitrage de structure 6/16/4 : verre de 6 mm / espace intercalaire de 16 mm rempli de 90% d’argon et 10% d’air / verre de 4 mm, l’empilement étant positionné en face 2 (la face 1 du vitrage étant la face la plus à l’extérieur du vitrage, comme habituellement).
    Pour ces doubles vitrages : - TL indique : la transmission lumineuse dans le visible en %, mesurée selon l’illuminant D65 à 2° Observateur ; - a*T et b*T indiquent les couleurs en transmission a* et b* dans le système L*a*b* mesurées selon l’illuminant D65 à 2° Observateur et mesurées perpendiculairement au vitrage ; - RLext indique : la réflexion lumineuse dans le visible en %, mesurée selon l’illuminant D65 à 2° Observateur du côté de la face la plus à l’extérieur, la face 1 ; - a*Rext et b*Rext indiquent les couleurs en réflexion a* et b* dans le système L*a*b* mesurées selon l’illuminant D65 à 2° Observateur du côté de la face la plus à l’extérieur et mesurées ainsi perpendiculairement au vitrage, - RLint indique : la réflexion lumineuse dans le visible en %, mesurée selon l’illuminant D65 à 2° Observateur du côté de la face intérieur, la face 4 ; - a*Rint et b*Rint indiquent les couleurs en réflexion a* et b* dans le système L*a*b* mesurées selon l’illuminant D65 à 2° Observateur du côté de la face intérieur et mesurées ainsi perpendiculairement au vitrage.
    Les valeurs colorimétriques en angle a*g60° et b*g60° sont mesurées sur simple vitrage sous incidence de 60°. Cela rend compte de la neutralité des couleurs en angle.
    Les exemples selon l’invention présentent tous une coloration en transmission agréable et douce, de préférence dans la gamme des bleus ou bleus-verts.
    Les vitrages selon l’invention présentent à la fois un facteur solaire inférieur ou égal à 20 % et une sélectivité supérieure à 2,0. Ces vitrages présentent en plus une réflexion extérieure au moins inférieure à 20 %.
    La solution proposée permet donc d'avoir un facteur solaire inférieur à 20% en gardant une sélectivité supérieure à 2,0 et une esthétique favorable.
    Les exemples selon l’invention 3 et 4 sont particulièrement avantageux car il présente en plus d’un facteur solaire bas et d’une sélectivité élevée, des valeurs de réflexion lumineuse côté extérieure extrêmement faibles notamment inférieures à 15 %.
    The invention relates to a material, such as a glazing unit, comprising a transparent substrate coated with a stack of thin layers comprising a plurality of functional layers that can act on solar radiation and / or infrared radiation. . The invention also relates to glazing comprising these materials as well as the use of such materials to manufacture thermal insulation glazing and / or sun protection.
    These glazings can be intended both to equip buildings and vehicles, especially to reduce the air conditioning effort and / or to prevent excessive overheating, so-called "solar control" glazing and / or reduce the amount of energy dissipated to the outside, so-called "low emissivity" glazing driven by the ever increasing importance of glazed surfaces in buildings and vehicle interiors.
    Depending on the climates of the countries where these windows are installed, the desired performance in terms of light transmission and solar factor may vary within a certain range. The light transmission shall be sufficiently small to suppress glare and sufficiently high that the reduction in the amount of light entering the space defined by the glazing shall not make the use of artificial light mandatory. For example, in countries where sunlight levels are high, there is a strong demand for glazing with a light transmission of about 40% and solar factor values sufficiently low.
    Glazing comprising transparent substrates coated with a stack of thin layers comprising three metal functional layers, each disposed between two dielectric coatings have been proposed to improve the sun protection while maintaining a sufficient light transmission. These stacks are generally obtained by a succession of deposits made by cathodic sputtering possibly assisted by magnetic field. These windows are qualified as selective because they make it possible: - to reduce the amount of solar energy penetrating inside the buildings by presenting a weak solar factor (FS or g), - to guarantee a sufficient light transmission, - to present a low emissivity to reduce heat loss by long-wave infrared radiation.
    According to the invention, we mean: - solar factor "g", the ratio in percentage between the total energy entering the room through the glazing and the incident solar energy, - selectivity "s", the ratio between the transmission light and solar factor TL / g.
    The prior art stack-based materials comprising three most selective functional layers make it possible to obtain solar factor values of up to 22%. However, this value is still too high for some countries, where Γόη looks for solar factor values below 20%.
    The materials currently on the market do not allow to combine a low solar factor, especially less than 20%, for a light transmission of about 40%, good selectivity (> 2.0) and a low reflection on the outside. The object of the invention is therefore to develop a material having exceptional solar control properties and in particular solar factor values less than 20% for a light transmission of the order of 40%. According to the invention, it is therefore sought to minimize the solar factor and increase the selectivity, while keeping a light transmission adapted to allow good insulation and good vision.
    The complexity of the stacks comprising three silver-based functional layers makes it difficult to improve the thermal performance and properties in reflection without affecting the other properties of the stack.
    The Applicant has surprisingly discovered that by optimizing the thicknesses of the three functional layers and the thicknesses of the dielectric coatings, a material is obtained which may have the desired properties.
    The solution of the invention represents an excellent compromise between optical performance, thermal, transparency and aesthetic appearance. The subject of the invention is a material comprising a transparent substrate coated with a stack of thin layers successively comprising, from the substrate, an alternation of three functional silver-based metal layers, named starting from the first, second and third functional layers substrate. and four dielectric coatings referred to starting from the substrate M1, M2, M3 and M4, each dielectric coating comprising at least one dielectric layer, so that each functional metal layer is arranged between two dielectric coatings, characterized in that: the thickness of the first functional layer is less than the thickness of the second functional layer, - the thickness of the first functional layer is less than the thickness of the third functional layer, - the ratio of the thickness of the third functional metallic layer on the thickness of the second the functional layer is between 0.90 and 1.10 including these values, preferably between 0.95 and 1.05, the dielectric coatings M1, M2, M3 and M4 each have an optical thickness Eo1, Eo2, Eo3 and Eo4 satisfying the following relation: Eo4 <Eo1 <Eo2 <Eo3, the optical thickness Eo1 of the dielectric coating M1 is greater than 80 nm, the optical thickness Eo2 of the dielectric coating M2 is greater than 100 nm, the optical thickness Eo3 of the dielectric coating M3 is greater than 120 nm. the optical thickness Eo4 of the dielectric coating M4 is greater than 60 nm. The invention also relates to: the process for obtaining a material according to the invention, the glazing comprising at least one material according to the invention, the use of a glazing unit according to the invention as glazing. solar control system for the building or vehicles, - a building or a vehicle comprising a glazing unit according to the invention.
    By modulating the thicknesses of the functional layers and the dielectric coatings, the transparency of the glazing can be controlled so as to obtain TL values of light transmission of the order of 40%, a range which is particularly suitable for glazing intended to be used in regions with strong sunshine. But the major advantage of the invention is that obtaining the satisfactory visual appearance including particular colors in external reflection and sufficiently low outside reflection values do not operate at the expense of sunscreen performance. The excellent energy performances are maintained without requiring substantial modifications of the other parameters of the stack such as the nature, the thickness and the sequence of the layers constituting it.
    The preferred features which appear in the remainder of the description are applicable both to the process according to the invention and, where appropriate, to the products, that is to say the materials or glazings comprising the material.
    All the luminous characteristics presented in the description are obtained according to the principles and methods described in the European standard EN 410 relating to the determination of the luminous and solar characteristics of glazing used in glass for construction.
    Conventionally, the refractive indices are measured at a wavelength of 550 nm. TL light transmittance and RL light reflection factors are measured under illuminant D65 with a 2 ° field of view.
    Unless otherwise indicated, all values and ranges of values for optical and thermal characteristics are given for a double glazing consisting of a 6 mm ordinary soda-lime glass type substrate carrying the thin film stack, a spacer space 16 mm filled with argon at a rate of 90% and air at a rate of 10% and another substrate type soda-lime glass, uncoated, a thickness of 4 mm. The coated substrate is placed so that the stack of thin layers is on the face 2 of the glazing. The external reflection Rext. is observed on the side of the substrate comprising the stack, while the reflection observed on the substrate side not comprising the stack is designated as the internal reflection. The light transmission (TL) of standard soda-lime glass substrates without stacking is greater than 89%, preferably 90%.
    Unless otherwise mentioned, the thicknesses mentioned in this document without further details are physical, real or geometrical thicknesses called Ep and are expressed in nanometers (and not optical thicknesses). The optical thickness Eo is defined as the physical thickness of the layer considered multiplied by its refractive index at the wavelength of 550 nm: Eo = n * Ep. The refractive index being a dimensionless value, it can be considered that the unit of the optical thickness is that chosen for the physical thickness.
    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.
    Throughout the description the substrate according to the invention is considered laid horizontally. The stack of thin layers is deposited above the substrate. The meaning of the terms "above" and "below" and "below" and "above" should be considered in relation to this orientation. In the absence of specific stipulation, the terms "above" and "below" do not necessarily mean that two layers and / or coatings are arranged in contact with each other. When it is specified that a layer is deposited "in contact" with another layer or coating, this means that there can not be one (or more) layer (s) interposed between these layers. two layers (or layer and coating).
    Within the meaning of the present invention, the "first", "second", "third" and "fourth" qualifications for the functional layers or the dielectric coatings are defined starting from the carrier substrate of the stack and referring to the layers or coatings of the same function. 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.
    Preferably, the stack is deposited by sputtering assisted by a magnetic field (magnetron process). According to this advantageous embodiment, all the layers of the stack are deposited by sputtering assisted by a magnetic field. The invention also relates to the process for obtaining a material according to the invention, in which the layers of the stack are deposited by magnetron sputtering.
    Silver-based metal functional layers comprise at least 95.0%, preferably at least 96.5% and most preferably at least 98.0% by weight of silver based on the weight of the functional layer. Preferably, the silver-based functional metal layer comprises less than 1.0 mass% of non-silver metals relative to the weight of the silver-based functional metal layer.
    According to advantageous embodiments of the invention, the functional metal layers satisfy one or more of the following conditions: the three functional metal layers correspond to the first, second and third functional metal layers defined starting from the substrate, the ratio of the thickness of the third functional metal layer to the thickness of the second functional layer is between 0.90 and 1.10, including these values, preferably 0.95 and 1.05, and / or the thickness of the first functional metal layer is, in order of increasing preference, between 6 and 12 nm, between 7 and 11 nm, between 8 and 10 nm, and / or the thickness of the second functional layer is greater than 15 nm, and / or - the thickness of the second functional metal layer is, in order of increasing preference, between 15 and 20 nm, between 16 and 18 nm, and / or - the thickness of the third The second functional metal layer is, in order of increasing preference, between 15 and 20 nm, between 16 and 18 nm.
    These thickness ranges for the functional metal layers are the ranges for which the best results are obtained for a double glazing light transmission of about 40%, a light reflection and a low solar factor. This gives a high selectivity and reflective colors of the neutral exterior. The stack may further comprise at least one blocking layer in contact with a functional layer.
    The blocking layers have traditionally function to protect the functional layers from possible degradation during the deposition of the upper dielectric coating and during a possible heat treatment at high temperature, of the annealing, bending and / or quenching type.
    The blocking layers are chosen from metal layers based on a metal or a metal alloy, metal nitride layers, metal oxide layers and metal oxynitride layers of one or more elements chosen from titanium, nickel, chromium and niobium such as Ti, TiN, TiOx, Nb, NbN, Ni, NiN, Cr, CrN, NiCr, NiCrN. When these blocking layers are deposited in metallic, nitrided or oxynitrided form, these layers may undergo partial or total oxidation according to their thickness and the nature of the layers which surround them, for example, at the time of deposition of the next layer or by oxidation in contact with the underlying layer.
    According to advantageous embodiments of the invention, the blocking layer or layers satisfy one or more of the following conditions: each functional metal layer is in contact with at least one blocking layer chosen from a blocking underlayer and a blocking overlay, and / or - each functional metal layer is in contact with a blocking underlayer and a blocking overlay, and / or - the thickness of each blocking layer is at least 0 , 1 nm, preferably between 0.5 and 2.0 nm, and / or - the total thickness of all the blocking layers in contact with the functional layers is between 3 and 8 nm including these values, preferably between 4 and 7 nm, or even 5 and 6 nm.
    According to advantageous embodiments of the invention, the dielectric coatings satisfy one or more of the following conditions in terms of thicknesses: the optical thickness of the first dielectric coating M1 is, in order of increasing preference, from 80 to 140; nm, from 90 to 130 nm, from 95 to 125 nm, and / or - the physical thickness of the first dielectric coating M1 is, in order of increasing preference, from 30 to 80 nm, from 40 to 70 nm, from 45 to at 65 nm, and / or the optical thickness of the second dielectric coating M2 is, in order of increasing preference, from 100 to 170 nm, from 130 to 160 nm, from 140 to 150 nm, and / or The physical thickness of the second dielectric coating M2 is, in order of preference, increasing from 40 to 100 nm, from 50 to 80 nm, from 65 to 75 nm, and / or - the optical thickness of the third dielectric coating M3 is, for example, order of increasing preference, ranging from 120 to 240 nm, 220 nm, from 155 to 210 nm, from 180 to 200 nm, and / or - the physical thickness of the third dielectric coating M3 is, in order of increasing preference, from 60 to 120 nm, from 80 to 110 nm, 90 to 100 nm, and / or - the optical thickness of the fourth dielectric coating M4 is, in order of increasing preference, between 60 to 120 nm, 70 to 110 nm, 80 to 100 nm, and / or - The physical thickness of the fourth dielectric coating M4 is, in order of increasing preference, from 20 to 60 nm, from 30 to 55 nm, from 40 to 50 nm.
    According to advantageous embodiments of the invention, the dielectric coatings satisfy one or more of the following conditions: the dielectric coatings comprise at least one dielectric layer based on oxide or nitride of one or more elements chosen from silicon , titanium, zirconium, aluminum, tin, zinc, and / or - at least one dielectric coating comprises at least one dielectric layer with a barrier function, and / or - each dielectric coating comprises at least one dielectric layer with barrier function, and / or - the barrier-based dielectric layers based on silicon and / or aluminum compounds chosen from oxides such as SiO 2 and Al 2 O 3, silicon nitrides Si 3 N 4 and AlN and the oxides SiO x N y and Al O x N y. and / or - the barrier-function dielectric layers are based on silicon and / or aluminum compounds optionally comprise at least one other element, such as aluminum, hafnium and zirconium, and / or - at least one coating dielectric material comprises at least one dielectric layer with a stabilizing function, and / or - each dielectric coating comprises at least one dielectric layer with a stabilizing function, and / or - the dielectric layers with a 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, the dielectric layers with a stabilizing function are preferably based on crystalline oxide, in particular based on zinc oxide, optionally doped with at least one other element, such as aluminum, and / or - each functional layer is above a dielectric coating whose upper layer is a dielectric layer electric 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, - at least a dielectric coating situated below a functional metal layer comprises at least one dielectric layer with a smoothing function, and / or - each dielectric coating situated below a functional metal layer comprises at least one dielectric layer with a smoothing function, and / or - the smoothing function dielectric layers are preferably based on a mixed oxide of at least two metals chosen from Sn, Zn, In, Ga, and / or - the smoothing function dielectric layers are preferably layers of mixed zinc oxide and optionally doped tin.
    Preferably, each dielectric coating consists solely of one or more dielectric layers. Preferably, there is therefore no absorbing layer in the dielectric coatings in order not to reduce the light transmission.
    The stacks of the invention may comprise dielectric layers with a barrier function. The term barrier dielectric layers means a layer of a material capable of barrier to the diffusion of oxygen and water at high temperature, from the ambient atmosphere or the transparent substrate, to the functional layer. The materials constituting the dielectric barrier layer must therefore not undergo chemical or structural modification at high temperature which would cause a change in their optical properties. The barrier layer or layers are preferably also chosen from a material capable of forming a barrier to the constituent material of the functional layer. The dielectric layers with barrier function thus allow the stack to undergo without significant optical evolution heat treatments of the annealing, quenching or bending type.
    The stacks of the invention may comprise dielectric layers with 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 reinforcing the adhesion of the functional layer to the layers that surround it, and in fact it will oppose the migration of its constituent material.
    The dielectric layer (s) with a stabilizing function can be directly in contact with a functional layer or separated by a blocking layer.
    Preferably, the last dielectric layer of each dielectric coating located below a functional layer is a dielectric layer with a stabilizing function. Indeed, it is advantageous to have a stabilizing function layer, for example, based on zinc oxide below a functional layer, because it facilitates the adhesion and crystallization of the functional layer based on and increases its quality and stability at high temperatures.
    It is also advantageous to have a stabilizing function layer, for example, based on zinc oxide over a functional layer, to increase its adhesion and oppose optimally to the diffusion of the the stack opposite the substrate.
    The stabilizing function dielectric layer or layers can therefore be above and / or below at least one functional layer or each functional layer, either directly in contact with it or separated by a blocking layer.
    Advantageously, each barrier-function dielectric layer is separated from a functional layer by at least one dielectric layer with a stabilizing function.
    This dielectric layer with a stabilizing function may have a thickness of at least 4 nm, in particular a thickness of between 4 and 10 nm and better still of 8 to 10 nm. The stack of thin layers may optionally comprise a smoothing layer. Smoothing layers are understood to mean a layer whose function is to promote the growth of the stabilizing layer in a preferential crystallographic orientation, which favors the crystallization of the silver layer by epitaxial phenomena. The smoothing layer is located below and preferably in contact with a stabilizing layer.
    The mixed oxide smoothing layer can be described as "non-crystallized" in the sense that it can be completely amorphous or partially amorphous and thus partially crystallized, but can not be completely crystallized throughout its thickness. . It can not be metallic in nature because it is based on mixed oxide (a mixed oxide is an oxide of at least two elements). The stack of thin layers may optionally comprise a protective layer. The protective layer is preferably the last layer of the stack, that is to say the layer furthest from the substrate coated with the stack. These upper layers of protection are considered to be included in the fourth dielectric coating. These layers generally have a thickness of between 2 and 10 nm, preferably 2 and 5 nm. This protective layer may be chosen from a layer of titanium, zirconium, hafnium, zinc and / or tin, or these metals being in metallic, oxidized or nitrided form.
    The protective layer may for example be selected from a layer of titanium oxide, a layer of zinc oxide and tin or a layer of titanium oxide and zirconium.
    A particularly advantageous embodiment relates to a substrate coated with a stack defined on the basis of the transparent substrate, comprising: a first dielectric coating comprising at least one dielectric layer with a barrier function and a dielectric layer with stabilizing function, optionally a blocking layer; a first functional layer, optionally a blocking layer, a second dielectric coating comprising at least one dielectric layer with a lower stabilizing function, a barrier-type dielectric layer and a dielectric layer with a higher stabilizing function; blocking, - a second functional layer, - optionally a blocking layer, - a third dielectric coating comprising at least one dielectric layer with a lower stabilizing function, a barrier-type dielectric layer and a functional dielectric layer upper stabilizer, - optionally a blocking layer, - a third functional layer, - optionally a blocking layer, - a fourth dielectric coating comprising at least one dielectric layer with a stabilizing function, a dielectric barrier layer and optionally a protective layer .
    The transparent substrates according to the invention are preferably in a mineral rigid material, such as glass, or organic based on polymers (or polymer).
    The transparent organic substrates according to the invention can also be made of polymer, rigid or flexible. 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 such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP); photocurable and / or photopolymerizable resins, such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate resins and polythiourethanes.
    The substrate is preferably a glass or glass-ceramic sheet.
    The substrate is preferably transparent, colorless (it is then a clear or extra-clear glass) or colored, for example blue, gray or bronze. The glass is preferably of the silico-soda-lime type, but it may also be of borosilicate or alumino-borosilicate type glass.
    The substrate advantageously has at least one dimension greater than or equal to 1 m, or even 2 m and even 3 m. The thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, especially between 2 and 8 mm, or even between 4 and 6 mm. The substrate may be flat or curved, or even flexible.
    The material, that is to say the substrate coated with the stack, can undergo a heat treatment at high temperature such as annealing, for example by flash annealing such as laser or flame annealing, quenching and / or bending. The temperature of the heat treatment is greater than 400 ° C, preferably greater than 450 ° C, and more preferably greater than 500 ° C. The substrate coated with the stack can therefore be curved and / or tempered. The invention also relates to a glazing unit comprising a material according to the invention. 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 interior of the passenger compartment or the room it equips. This means that incident sunlight passes through the faces in increasing order of their number. The stack is preferably positioned in the glazing so that incident light from outside passes through the first dielectric coating before passing through the first functional metal layer. The stack is not deposited on the face of the substrate defining the outer wall of the glazing but on the inner face of this substrate. The stack is therefore advantageously positioned in face 2, the face 1 of the glazing being the outermost face of the glazing, as usual.
    The material may be for applications requiring that the stack-coated substrate has been heat-treated at a high temperature such as quenching, annealing, or bending.
    The glazing of the invention may be in the form of monolithic glazing, laminated or multiple, in particular double glazing or triple glazing.
    In the case of monolithic or multiple glazing, the stack is preferably deposited in face 2, that is to say, it is on the substrate defining the outer wall of the glazing and more specifically on the inner face of this substrate.
    A monolithic glazing has 2 faces, the face 1 is outside the building and therefore constitutes the outer wall of the glazing, the face 2 is inside the building and therefore constitutes the inner wall of the glazing.
    Multiple glazing comprises at least two substrates held at a distance so as to define a cavity filled with an insulating gas. The materials according to the invention are particularly suitable when they are used in double-glazing with reinforced thermal insulation (ITR).
    A double glazing has 4 faces, the face 1 is outside the building and therefore constitutes the outer wall of the glazing, the face 4 is inside the building and therefore constitutes the inner wall of the glazing, the faces 2 and 3 being inside the double glazing.
    In the same way, a triple glazing has 6 faces, the face 1 is outside the building (outer wall of the glazing), the face 6 inside the building (inner wall of the glazing) and the faces 2 to 5 are inside the triple glazing.
    A laminated glazing unit comprises at least one structure of the first substrate / sheet (s) / second substrate type. The stack of thin layers is positioned on at least one of the faces of one of the substrates. The stack may be on the face of the second substrate not in contact with the sheet, preferably a polymer. This embodiment is advantageous when the laminated glazing is mounted in double glazing with a third substrate.
    The glazing according to the invention, used as monolithic glazing or in a multiple glazing type double glazing, has neutral, pleasant and soft colors in external reflection, in the range of blue or blue-green (values of wavelength dominant on the order of 470 to 500 nanometers). In addition, this visual appearance remains almost unchanged regardless of the angle of incidence with which the glazing is observed (normal incidence and sub angle). This means that an observer does not have the impression of a significant inhomogeneity of hue or aspect.
    By "color in blue-green" in the sense of the present invention, it should be understood that in the color measurement system L * a * b *, a * is between -10.0 and 0.0, preferably between -5.0 and 0.0 and b * is between -10.0 and 0.0, preferably between -5.0 and 0.0.
    The glazing of the invention has colors in transmission in the color measurement system L * a * b *: - a * is between -6.0 and 0.0, preferably between -5.0 and -1 , 0, - b * is between -6.0 and 3.0, preferably between -5.0 and 0.0.
    The glazing unit of the invention has colors in reflection on the outside in the color measurement system L * a * b *: - a * between -5.0 and 0.0, preferably between -4.0 and - 1.0 and / or - b * is between -10.0 and 0.0, preferably between -9.0 and -5.0.
    According to advantageous embodiments, the glazing of the invention in the form of a double glazing comprising the stack positioned in face 2 makes it possible to achieve in particular the following performances: a solar factor less than or equal to 20%, or even less or equal to 19%, and / or a light transmission of less than 50%, preferably of between 30% and 50%, and even between 35% and 45%, and / or a high selectivity, in order of increasing preference, of at least 1.8, at least 1.9, at least 2.0, at least 2.1 and / or - a low emissivity, especially less than 1%, and / or - a reflection bright outer side less than or equal to 25%, preferably less than or equal to 22.5%, or even less than or equal to 20%, and / or - neutral colors in external reflection.
    The details and advantageous features of the invention emerge from the following nonlimiting examples, illustrated with the aid of the attached figure.
    The proportions between the different elements are not respected in order to facilitate the reading of the figures.
    FIG. 1 illustrates a stacking structure with three functional metal layers 40, 80, 120, this structure being deposited on a transparent glass substrate 10. Each functional layer 40, 80, 120 is arranged between two dielectric coatings 20, 60, 100, 140 so that: the first functional layer 40 starting from the substrate is disposed between the dielectric coatings 20, 60, the second layer The functional layer 80 is disposed between the dielectric coatings 60, 100 and the third functional layer 120 is disposed between the dielectric coatings 100, 140.
    These dielectric coatings 20, 60, 100, 140 each comprise at least one dielectric layer 24, 28; 62, 64, 68; 102, 104, 106, 108; 142, 144. The stack may also comprise: blocking sub-layers 30, 70, and 110 (not shown), 50, 90 and 130 in contact with a functional layer, blocking overlay layers 50, 90 and 130 in contact with a functional layer, - a protective layer 160 (not shown).
    Examples I. Preparation of the substrates: Stacks, deposition conditions and heat treatments
    Stacks of thin layers defined below are deposited on substrates of clear soda-lime glass with a thickness of 6 mm.
    In the examples of the invention: the functional layers are silver layers (Ag); the blocking layers are metal layers made of nickel and chromium alloy (NiCr); the barrier layers are based on silicon nitride, doped with aluminum (Si3N4: Al), - the stabilizing layers are made of zinc oxide (ZnO), - the smoothing layers are based on mixed oxide of zinc and étaon (SnZnOx), - The protective layers are made of titanium oxide and zirconium (TiZrOx).
    The deposition conditions of the layers, which have been deposited by sputtering ("cathodic magnetron" sputtering), are summarized in Table 1.
    At. = Atomic
    Table 2 lists the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating that constitutes the stacks as a function of their position vis-à-vis the carrier substrate of the stack (last line at the bottom of the table). ). The numbers "Ref. Correspond to the references of Figure 1.
    Each dielectric coating 20, 60, 100 below a functional layer 40, 80, 120 comprises a last stabilizing layer 28, 68, 108 based on crystallized zinc oxide, and which is in contact with the functional layer 40 , 80, 120 deposited just above.
    Each dielectric coating 60, 100, 140 above a functional layer 40, 80, 120 comprises a first stabilizing layer 62, 102, 142 based on crystallized zinc oxide, and which is in contact with the functional layer 40 , 80, 120 deposited just above.
    Each dielectric coating 20, 60, 100, 140 comprises a barrier-doped dielectric layer 24, 64, 104, 144, based on aluminum nitride, doped with aluminum, here called S13N4.
    The dielectric coating 100 further comprises a smoothing layer based on a mixed oxide of zinc and tin 106.
    Each metal functional layer 40, 80, 120 is above a blocking layer 30, 70 and 110 (not shown in FIG. 1) and below and in contact with a blocking layer 50, 90 and 130 The stack further comprises a protective layer of titanium oxide and zirconium 160 (not shown in Figure 1).
    The following table 3 summarizes the characteristics related to the thicknesses of the functional layers and dielectric coatings.
    RD: dielectric coating; CB: blocking layer; Ep: Physical thickness; Eo: Optical thickness. II. "Solar control" performance and colorimetry
    Table 4 lists the main optical characteristics measured when the glazing is part of 6/16/4 double glazing: 6 mm glass / 16 mm spacer filled with 90% argon and 10% air / glass 4 mm, the stack being positioned in face 2 (the face 1 of the glazing being the outermost face of the glazing, as usual).
    For these double glazings: - TL indicates: the light transmission in the visible in%, measured according to the illuminant D65 at 2 ° Observer; - a * T and b * T indicate the colors in transmission a * and b * in the system L * a * b * measured according to the illuminant D65 at 2 ° Observer and measured perpendicular to the glazing; - RLext indicates: the luminous reflection in the visible in%, measured according to the illuminant D65 at 2 ° Observer on the side of the outermost face, the face 1; - a * Rext and b * Rext indicate the colors in reflection a * and b * in the system L * a * b * measured according to the illuminant D65 at 2 ° Observer on the side of the outermost face and measured thus perpendicular to the glazing, - RLint indicates: the luminous reflection in the visible in%, measured according to the illuminant D65 at 2 ° Observer on the side of the inner face, the face 4; - a * Rint and b * Rint indicate the colors in reflection a * and b * in the system L * a * b * measured according to the illuminant D65 at 2 ° Observer on the inner side and thus measured perpendicular to the glazing.
    The color values at angles a * g60 ° and b * g60 ° are measured on single glazing with a 60 ° incidence. This accounts for the color neutrality angle.
    The examples according to the invention all have a pleasant and soft transmission coloration, preferably in the range of blue or blue-green.
    The glazings according to the invention have both a solar factor less than or equal to 20% and a selectivity greater than 2.0. These glazings also have an external reflection of at least less than 20%.
    The proposed solution therefore makes it possible to have a solar factor of less than 20% while maintaining a selectivity greater than 2.0 and a favorable aesthetic.
    The examples according to the invention 3 and 4 are particularly advantageous because it has, in addition to a low solar factor and a high selectivity, extremely small values of light reflection on the outer side, in particular of less than 15%.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Material comprising a transparent substrate coated with a stack of thin layers successively comprising from the substrate an alternation of three silver-based functional metal layers denoted starting from the first substrate, second and third functional layers and four dielectric coatings referred to starting from the substrate M1, M2, M3 and M4, each dielectric coating comprising at least one dielectric layer, so that each functional metal layer is arranged between two dielectric coatings, characterized in that: - the thickness of the first functional layer is less than the thickness of the second functional layer, - the thickness of the first functional layer is less than the thickness of the third functional layer, - the ratio of the thickness of the third functional metal layer to the thickness of the second couc it is functional between 0.90 and 1.10 including these values, - the dielectric coatings M1, M2, M3 and M4 each have an optical thickness Eo1, Eo2, Eo3 and Eo4 satisfying the following relation: Eo4 <Eo1 <Eo2 <Eo3, the optical thickness Eo1 of the dielectric coating M1 is greater than 80 nm, the optical thickness Eo2 of the dielectric coating M2 is greater than 100 nm, the optical thickness Eo3 of the dielectric coating M3 is greater than 120 nm. the optical thickness Eo4 of the dielectric coating M4 is greater than 60 nm.
    [2" id="c-fr-0002]
    2. Material according to claim 1 characterized in that the thickness of the second functional layer is greater than 15 nm.
    [3" id="c-fr-0003]
    3. Materials according to one of the preceding claims, characterized in that the three functional metal layers satisfy the following characteristics: - the thickness of the first functional metal layer is between 6 and 12 nm, - the thickness of the second functional metal layer is between 15 and 20 nm, the thickness of the third functional metal layer is between 15 and 20 nm.
    [4" id="c-fr-0004]
    4. Material according to any one of the preceding claims, characterized in that the stack further comprises at least one blocking layer in contact with a functional metal layer selected from metal layers based on a metal or metal. a metal alloy, the metal nitride layers, the metal oxide layers and the metal oxynitride layers of one or more elements selected from titanium, nickel, chromium and niobium such as a Ti layer, TiN, TiOx, Nb, NbN, Ni, NiN, Cr, CrN, NiCr, NiCrN.
    [5" id="c-fr-0005]
    5. Material according to the preceding claim, characterized in that the total thickness of all the blocking layers in contact with the functional layers is between 4 and 7 nm including these values.
    [6" id="c-fr-0006]
    6. Materials according to one of the preceding claims, characterized in that the dielectric coatings satisfy the following characteristics: - the optical thickness of the first dielectric coating M1 is from 80 to 140 nm, - the optical thickness of the second dielectric coating M2 is from 100 to 170 nm, the optical thickness of the third dielectric coating M3 is from 120 to 240 nm, the optical thickness of the fourth dielectric coating M4 is from 60 to 120 nm.
    [7" id="c-fr-0007]
    7. Material according to any one of the preceding claims, characterized in that each dielectric coating comprises at least one barrier-based dielectric layer based on silicon and / or aluminum compounds chosen from oxides such as SiO 2 and Al 2 O 3, silicon nitrides Si3N4 and AlN and oxynitrides SiOxNy and AlIOxNy.
    [8" id="c-fr-0008]
    8. Material according to any one of the preceding claims, characterized in that each dielectric coating comprises at least one dielectric layer stabilizing function based on crystalline oxide, in particular based on zinc oxide, optionally doped using at least one other element, such as aluminum.
    [9" id="c-fr-0009]
    9. Material according to any one of the preceding claims, characterized in that 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.
    [10" id="c-fr-0010]
    10. Material according to any one of the preceding claims, characterized in that it comprises a stack defined starting from the transparent substrate comprising: a first dielectric coating comprising at least one dielectric layer with a barrier function and a dielectric layer with a stabilizing function; optionally a blocking layer, a first functional layer, optionally a blocking layer, a second dielectric coating comprising at least one dielectric layer with a lower stabilizing function, a barrier-type dielectric layer and a dielectric layer with a higher stabilizing function. - optionally a blocking layer, - a second functional layer, - optionally a blocking layer, - a third dielectric coating comprising at least a dielectric layer with a lower stabilizing function, a dielectric barrier layer and a layer dielectric with higher stabilizing function, - optionally a blocking layer, - a third functional layer, - optionally a blocking layer, - a fourth dielectric coating comprising at least one dielectric layer with a stabilizing function, a dielectric barrier layer and optionally a protective layer.
    [11" id="c-fr-0011]
    11. Material according to any one of the preceding claims, characterized in that it has a light transmission of less than 50% and / or an outside light reflection less than 20%.
    [12" id="c-fr-0012]
    12. Process for obtaining a material according to one of the preceding claims, in which the layers of the stack are deposited by magnetron sputtering.
    [13" id="c-fr-0013]
    13. Glazing comprising at least one material according to any one of claims 1 to 12.
    [14" id="c-fr-0014]
    14. Glazing according to the preceding claim characterized in that the stack is positioned in the glazing so that the incident light from outside passes through the first dielectric coating before passing through the first functional metal layer.
    [15" id="c-fr-0015]
    15. Glazing according to any one of claims 13 or 14, characterized in that it is in the form of monolithic glazing, laminated or multiple, in particular double glazing or triple glazing.
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    同族专利:
    公开号 | 公开日
    WO2017006027A1|2017-01-12|
    RU2720336C2|2020-04-29|
    HUE055180T2|2021-11-29|
    EP3319919A1|2018-05-16|
    CN107709263A|2018-02-16|
    EP3319919B1|2021-06-16|
    PL3319919T3|2021-09-27|
    MX2017016710A|2018-03-09|
    US10843962B2|2020-11-24|
    KR20180028436A|2018-03-16|
    JP6951317B2|2021-10-20|
    PT3319919T|2021-09-02|
    CN107709263B|2022-02-22|
    FR3038596B1|2021-12-10|
    US20180194676A1|2018-07-12|
    ES2884111T3|2021-12-10|
    RU2018103405A|2019-08-08|
    CO2017012948A2|2018-03-09|
    RU2018103405A3|2019-10-22|
    JP2018519238A|2018-07-19|
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    法律状态:
    2016-07-25| PLFP| Fee payment|Year of fee payment: 2 |
    2017-01-13| PLSC| Publication of the preliminary search report|Effective date: 20170113 |
    2017-07-25| PLFP| Fee payment|Year of fee payment: 3 |
    2018-07-26| PLFP| Fee payment|Year of fee payment: 4 |
    2020-07-24| PLFP| Fee payment|Year of fee payment: 6 |
    2021-07-29| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1556476A|FR3038596B1|2015-07-08|2015-07-08|MATERIAL EQUIPPED WITH A THERMAL PROPERTIES STACK|FR1556476A| FR3038596B1|2015-07-08|2015-07-08|MATERIAL EQUIPPED WITH A THERMAL PROPERTIES STACK|
    PCT/FR2016/051645| WO2017006027A1|2015-07-08|2016-06-30|Substrate provided with a stack having thermal properties|
    MX2017016710A| MX2017016710A|2015-07-08|2016-06-30|Substrate provided with a stack having thermal properties.|
    CN201680039871.1A| CN107709263B|2015-07-08|2016-06-30|Substrate provided with a stack having thermal properties|
    US15/742,310| US10843962B2|2015-07-08|2016-06-30|Substrate provided with a stack having thermal properties|
    PL16750913T| PL3319919T3|2015-07-08|2016-06-30|Substrate provided with a stack having thermal properties|
    RU2018103405A| RU2720336C2|2015-07-08|2016-06-30|Substrate equipped with stack of layers with heat engineering properties|
    HUE16750913A| HUE055180T2|2015-07-08|2016-06-30|Substrate provided with a stack having thermal properties|
    PT167509132T| PT3319919T|2015-07-08|2016-06-30|Substrate provided with a stack having thermal properties|
    ES16750913T| ES2884111T3|2015-07-08|2016-06-30|Substrate provided with a pile that has thermal properties|
    EP16750913.2A| EP3319919B1|2015-07-08|2016-06-30|Substrate provided with a stack having thermal properties|
    JP2018500298A| JP6951317B2|2015-07-08|2016-06-30|Base material with a laminate with thermal properties|
    KR1020187000105A| KR20180028436A|2015-07-08|2016-06-30|A substrate provided with a stack having thermal properties|
    CONC2017/0012948A| CO2017012948A2|2015-07-08|2017-12-15|Material comprising a transparent substrate provided with a laminate that has thermal properties and its manufacturing process|
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