EP2488462A1 - Enameled reflective glass panel - Google Patents

Enameled reflective glass panel

Info

Publication number
EP2488462A1
EP2488462A1 EP10771696A EP10771696A EP2488462A1 EP 2488462 A1 EP2488462 A1 EP 2488462A1 EP 10771696 A EP10771696 A EP 10771696A EP 10771696 A EP10771696 A EP 10771696A EP 2488462 A1 EP2488462 A1 EP 2488462A1
Authority
EP
European Patent Office
Prior art keywords
layer
oxide
enamel
glazing according
tzo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10771696A
Other languages
German (de)
French (fr)
Inventor
Laurent Dusoulier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Glass Europe SA
Original Assignee
AGC Glass Europe SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AGC Glass Europe SA filed Critical AGC Glass Europe SA
Priority to EP10771696A priority Critical patent/EP2488462A1/en
Publication of EP2488462A1 publication Critical patent/EP2488462A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3423—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings comprising a suboxide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/72—Decorative coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/13—Deposition methods from melts
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer

Definitions

  • the present invention relates to glazings comprising a vacuum deposited layer system and an enamel layer in at least partial contact with this layer system.
  • the combination envisaged is typically those found on some glazing used for example in the building to build lighters.
  • the lighters it being understood that this is only a simplification, the invention covering all the products in which the combination of a dielectric layer system is present with at least one enamel in contact with this system and covering it at least in part.
  • glazing More specifically, an important application of glazing according to the invention concerns buildings coated with glass.
  • the glazing used normally include layer systems with radiated energy control properties to limit the need for air conditioning (solar control) and reduction of the energy emitted by the building ( insulation). Buildings are frequently almost completely covered. Also the glazing covers both the parts that must offer a significant light transmission, and those whose transmission is virtually zero. These last correspond in particular to the elements of structure. For this purpose it is usual to use opaque enamel layers to hide these elements.
  • the glazings used seen from outside the buildings preferably offer an improved aesthetics. For this reason it is traditional to maintain the layer system even in the enamel-coated parts, which can lead to the superposition of a layer system and enamel.
  • Sunscreen or low emissive coatings can be applied in different ways depending on the nature of the layers. For pyrolytic type deposits, the layers formed are generally very strong. But even on these layers the application of the enamel layer can cause the appearance of defects. Vacuum deposits offer a variety of properties that can not always be achieved with pyrolytically deposited layers. Nevertheless, the vacuum deposition layer systems, of the sputtering type, are generally much more fragile and give rise to visible defects after deposition of the enamel.
  • the enamels used for these applications typically consist of a composition comprising a glass frit for forming the vitreous matrix, and coloring pigments.
  • the composition further comprises a medium allowing the application of the sintered mixture / pigments, which ensures a good suspension of the solid particles and is eliminated during the cooking of the enamel.
  • This medium includes solvents, resins oils etc ...
  • the inventors have sought a way to prevent the occurrence of defects in this type of products.
  • the invention provides glazings comprising a system of vacuum deposited dielectric layers, system having solar radiation filter properties, the layer system being at least partly coated with enamel.
  • the inventors have established that it is possible to choose the components of the layer system so that it is not altered by contact with the enamel composition.
  • the glazings according to the invention comprise a system of layers deposited under vacuum, having solar radiation filter properties in the absence of the enamelled coating, the layer system comprising at least one surface resistant layer, this layer being based on titanium oxide, niobium oxide, tantalum oxide, or mixed oxides of the foregoing, or with other metal oxides.
  • those of the group consisting of Al, Zr, Hf, V, Mn, Fe, Co, Ni, Cu, Si, Cr, Ta and Nb are advantageous.
  • the surface layer may also contain in a very small proportion, in general less than 8% by weight and most often less than 5%, additional elements.
  • additional elements include dopants whose role is primarily to improve the manufacture and / or implementation of cathodes in the production of layers in vacuum deposition techniques.
  • These elements are traditionally intended in particular to improve the conductivity of materials constituting cathodes such as: Ti, Al. It can also be compounds stabilizing certain constituents such as Ca, Mg, or elements that appear as inseparable from others during preparation. This is the case of lanthanides such as yttrium or hafnium oxide.
  • titanium oxide When titanium oxide is chosen as the base of the surface resistant layer, it is necessarily combined with at least one other metal oxide which strengthens its resistance. It appears in fact that titanium oxide, which has good optical properties, is insufficiently resistant to mechanical or chemical stresses. Conversely, oxides of tantalum or niobium can be used alone (apart from the possible doping elements present).
  • titanium oxide layer When a titanium oxide layer is chosen, it contains at least 40% and at most 95% by weight of titanium oxide.
  • the glazing comprising the layer system when coated with enamel is practically opaque.
  • the light transmittance of the enamelled glazing is in all cases less than 5%, and most often less than 2%.
  • the presence of the layer system under the enamel aims to maintain the properties, and especially the reflection properties that are those of the glazing does not include enamelled coating.
  • the important thing is to maintain a similar external appearance for the parties transparent glazing and those that are not. This necessity is all the more important because the reflection itself is higher.
  • the glazings according to the invention comprise a system of layers as applied to a clear float glass of 4 mm in thickness, the reflection on the opposite side of the glass sheet to the layer system would be at least 15% of the solar light incident, and the transmission of at least 60%.
  • the glazing according to the invention comprise a system of reflective layers which applied to a 4mm clear float glass sheet would lead to a reflection of between 20 and 40% of the incident solar light.
  • the system may comprise other layers between this reflective layer and the glass sheet.
  • Additional layers are used in particular to prevent the diffusion of alkaline ions from the glass substrate. These additional layers can also improve the mechanical strength or the optical properties of the layer system and in particular the reflectivity.
  • Preferred "barrier" sub-layers used to improve the protection against the diffusion of alkaline ions from the glass sheet consist for example of at least one of the silicon compounds: oxide (SiO 2 ), nitride (Si 3 N 4 ), oxynitride (SiON); or oxides of SnO 2 and oxides composed of tin and zinc (up to 50% by weight of zinc oxide), or even TiO 2 possibly substoichiometric or optionally in the form of oxynitride containing a low content nitrogen (N / O less than 10%).
  • the barrier sub-layers made of SiO 2 have an index of about 1.5 when that of TiO 2 is of the order of 2.5.
  • the additional layers have a low refractive index
  • their thickness is preferably chosen to be relatively smaller than that of the reflecting layer or layers in order not to alter the properties in question.
  • the optical path corresponding to this layer Low-index barrier advantageously does not represent more than a quarter of the optical path of all the layers of the system.
  • one or more sub-layers when used to contribute to the reflective properties of the system, they are chosen with a refractive index as high as possible and preferably greater than 2.2.
  • Different reflective layers are used in particular titanium oxide layers, niobium oxide, tantalum oxide, zirconium oxide optionally in oxidized form or in the form of oxynitrides.
  • a reflection enhancing underlayer In contrast to the surface layer, when a reflection enhancing underlayer is based on titanium oxide, it is not necessary to combine this oxide with elements that improve its strength. Being under the reflective layer by resistant principle, this underlayer, in itself may not offer the same qualities.
  • the utility of such a TiO 2 layer without the addition of another oxide lies in the high index that it has compared to that of the mixed oxides of titanium and at least one other metal. These mixed oxides, although forming a significant reflection layer of equal thickness, reflect less than titanium oxide alone.
  • the combination of a primary layer of titanium oxide in contact with the glass and a layer of mixed oxide of titanium and another metal combines the overall advantage of a high refractive index with a good surface resistance.
  • the use of a high index titanium oxide layer may not, however, have the best set of properties, particularly mechanical properties.
  • the relatively thick layers of TiO 2 are not necessarily the most appropriate. This can further lead to limiting the thickness of the underlying layer of TiO 2 (or TiOx, or TiOxNy), other relatively high index layers completing the system, including in particular another layer of mixed titanium oxide of which the other metal is of the same kind or different from that of the metal of the superficial layer.
  • a typical assembly comprises, for example, in addition to the very strong surface layer, one or more layers with a high index of refraction, and a barrier layer.
  • a set of reflective layers of this type is, for example, a succession of layers comprising a surface layer based on a mixed titanium / zirconium oxide composition, in contact therewith a titanium oxide layer advantageously deposited. from a ceramic cathode of optionally doped titanium oxide, and leading to a slightly substoichiometric oxide layer, under this layer another layer of mixed oxide of titanium and another oxide of the type of those which can intervene in the superficial layer.
  • Reflective layers deposited under vacuum under good conditions do not normally give rise to phenomena of light scattering.
  • a surface protective layer according to the invention alters the optical properties by formation of spots or less the appearance of sails ("haze") that alter the appearance of these windows.
  • An important veil gives the appearance of a white halo.
  • the presence of a veil in these windows is not homogeneous which adds to the lack of appearance.
  • the veil is defined by the expression:
  • R d is the scattered reflection under wide angle (scattered light), and the total reflection.
  • the reflective layers of which are resistant practically do not develop this type of defect.
  • the application and firing of the enamel that covers the reflective layers does not lead to the formation of a noticeable veil.
  • the glazings according to the invention do not exhibit a film greater than 3.5%, and preferably not greater than 2.5%. In the best conditions, the haze is advantageously kept below 2%.
  • glazing coated with enamel has no stain or noticeable veil, certain optical qualities are nevertheless modified by the presence of enamel.
  • the reflection of the whole may differ from that of the glazing which includes only the system of reflective layers. This variation is however acceptable as long as the color variation in reflection remains limited.
  • the layers of the reflecting system, but also the color of the enamel used are such that the reflection color variation ⁇ of glazing coated with enamel compared to that which does not include enamel, remains less than 3 and preferably less than 2.
  • E corresponds to the expression:
  • the variations of the reflection may be relatively large without leading to a detrimental difference in appearance.
  • this difference in reflection with and without the enamel layer can reach 25% of the value in the absence of enamel, but is preferably less than 20%.
  • the glazings according to the invention are made with sheets of clear glass but also and preferably with colored glass sheets.
  • the most common colors are gray, blue and green.
  • the colors of the enamel are generally as neutral as possible. Enamels are mostly black but can have shades.
  • Layering systems are formed in the following way starting from the glass, the thicknesses given in parentheses are expressed in nanometers:
  • TZO is a layer consisting of a mixed oxide of titanium and zirconium at 45% by weight of zirconium. It further comprises yttrium oxide (about 6%) which stabilizes zirconium. Optionally the layer also comprises oxides of aluminum, titanium or other elements that incorporated in the cathodes improve their conductivity and thereby the stability of the deposition operation.
  • TiOx denotes titanium oxide deposited from a ceramic cathode, and possibly having a slight substoichiometry.
  • TaNbO is a mixed oxide of tantalum and niobium.
  • Type 6 layer systems indicated above are applied by magnetron deposition to clear, gray, blue and green glass samples.
  • the glass sheets of the samples have a thickness of 6 mm.
  • a layer of black enamel composition comprising 15% by weight of pigments (iron oxides, chromium and cobalt), and 60% of frit based on borosilicates, the rest consisting of the medium of 'application.
  • the enamel is applied by screen printing over the entire surface of the sample previously coated with the layer system. The enamel is fired at 670 ° C for 45 seconds per millimeter of glass thickness.
  • Examples I and II show that the application of the enamel on the reflective layers does not substantially alter the reflection color.
  • the values a * and b * are virtually identical.
  • the presence of the enamel varies the luminance, in other words, the intensity of the reflected light.
  • Example III shows typical shades obtained with glasses simultaneously offering a significant reflection and a well-marked coloration.
  • the gray-glass application of Example V illustrates what can be achieved with a more "neutral" color glass.
  • a sample (C) is prepared which comprises a layer of titanium oxide obtained by gas pyrolysis (CVD) in principle stronger.
  • the thicknesses reported are in nanometers. The values correspond first to those of the sample with the layers, the last values are those of the same sample coated with enamel after cooking.
  • the first layer is deposited on the glass.
  • the superficial layer is the second layer for Examples 1 to 16.
  • the surface layer is the third layer.
  • TZO is the titanium / zirconium mixed oxide layer previously described consisting of a mixed oxide of 50% by weight of TiO 2 , 46% of ZrO 2 , the remainder coming from elements usually accompanying zirconium, especially from yttrium oxide.
  • ZSO50 is a mixed tin / zinc oxide layer in 50/50 weight ratio.
  • TaO denotes tantalum oxide (it is not a question of the chemical formula but of a generic designation, idem for NbO and TaNbO with regard respectively to niobium oxide or mixed oxide of niobium and tantalum (50/50 atomic proportion).
  • Metal targets of Ta, Nb and Ta-Nb are used and deposited in ⁇ 2 to obtain Tao, NbO and TaNbO.
  • TxO is titanium oxide deposited from ceramic cathodes.
  • TNO is the mixed oxide of titanium and niobium in mass proportion50 / 50.
  • the layer of titanium oxide alone even obtained by pyrolysis, has a substantial haze after application of the enamel layer.
  • the deposited layers under the conditions of the invention are substantially less affected.
  • the colors are a little modified but the overall color is not affected.
  • the brightness changes a bit which is not detrimental for lighters.
  • FIG. 1 shows the glazing arrangement in front of a building
  • FIG. 2 shows a glazing similar to that of Figure 1 comprising an enamelled portion
  • FIG. 3 illustrates a way of using a glazing unit according to the invention
  • FIG. 4 schematically shows a glazing comprising a layer system according to the invention with several reflective layers.
  • the facade of a glass-clad building has "vision" parts that allow significant transmission of external light. This part of vision is represented by a double glazing (1,2).
  • the two sheets of glass delimit an enclosed space with the unrepresented intermediate joints.
  • the sheet 1 is coated by a system of layers (3) filtering the radiation. This is for example a system reflecting a significant part of solar radiation.
  • the position of the layer system (3) in the space of the insulating glass protects it from possible alterations either mechanical or in contact with the atmosphere.
  • This arrangement is particularly desirable for sputtered vacuum deposited layers which are known to be relatively brittle compared to "hard" pyrolysis layers.
  • Figure 1 also shows part of the building structure (4). To preserve from the outside a uniform appearance it is usual to also have a glazing (5) having the same properties as those of the viewing part. In particular to maintain a similar reflection, this part is also covered with a reflective layer (6).
  • the building structure (4) is not concealed.
  • the sheet 5 has the same light transmission as the sheet (3).
  • the use of a masking enamel is therefore desired.
  • this enamel can not be arranged on the outer face of the sheet 5, the appearance in terms of color or reflection could not be maintained similar to that of the vision sheet.
  • the coating of the layer system (6) deposited under vacuum by an enamel was previously inapplicable because of the defects and color changes resulting from the interaction of the enamel with the layer system because of the fragility of the latter.
  • Figure 2 shows an earlier solution to meet the need to combine the concealment of the structure (4) and the maintenance of the external appearance.
  • the enamel (8) is applied to a sheet 7 distinct from that (5) carrying the reflective layer (6).
  • the set of sheets (5) and (7) does not form properly speak an "insulating" glazing insofar as it is not necessary that the space between these two sheets be closed, and the only function of the sheet (7) is first support of the enamelled layer.
  • Figure 3 illustrates a use of glazing according to the invention. This time because of the improved behavior of the reflective layer system (9), it is possible to coat it with enamel (10). As a result, a single sheet is likely to conceal the structure of the building and preserve the external appearance. An important simplification is thus made possible.
  • FIG. 4 schematically illustrates a coating according to the invention comprising a multilayer system.
  • the enamel layer (10) covers the resistant layer (9).
  • the resistant layer (9) covers the resistant layer (9).
  • other reflective layers with high refractive index (11a and 11b) are disposed under the latter. These layers complement the effect of the surface layer (9) and improve its performance.
  • a barrier layer (12) is also applied to prevent the migration of the alkaline ions from the glass sheet (5).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to a glass panel comprising a system of vacuum-deposited layers having solar radiation filtering properties, said system being at least partially coated with an enamel layer.

Description

Vitrage réfléchissant émaillé  Glazed reflective glazing
La présente invention concerne des vitrages comportant un système de couches déposées sous vide et une couche d'émail en contact au moins partiel avec ce système de couches. The present invention relates to glazings comprising a vacuum deposited layer system and an enamel layer in at least partial contact with this layer system.
La combinaison envisagée est typiquement de celles qui se trouvent sur certains vitrages utilisés par exemple dans le bâtiment pour constituer des allèges. Dans la suite de la description, parlant des produits visés par l'invention, il sera fait référence aux allèges étant entendu qu'il ne s'agit que d'une manière de simplification, l'invention couvrant l'ensemble des produits dans lesquels la combinaison d'un système de couches diélectriques est présent avec au moins un émail au contact de ce système et le recouvrant au moins en partie.  The combination envisaged is typically those found on some glazing used for example in the building to build lighters. In the remainder of the description, speaking of the products targeted by the invention, reference will be made to the lighters, it being understood that this is only a simplification, the invention covering all the products in which the combination of a dielectric layer system is present with at least one enamel in contact with this system and covering it at least in part.
De manière plus précise une application importante des vitrages selon l'invention concerne les immeubles revêtus de verre. Pour ces bâtiments, compte tenu des surfaces concernées, les vitrages utilisés comportent normalement des systèmes de couches présentant des propriétés de contrôle de l'énergie rayonnée pour limiter la nécessité de climatisation (contrôle solaire) et réduction de l'énergie émise par le bâtiment (isolation) . Les bâtiments sont fréquemment pratiquement entièrement revêtus. Aussi les vitrages couvrent à la fois les parties qui doivent offrir une transmission lumineuse significative, et celles dont la transmission est pratiquement nulle. Ces dernières correspondent notamment aux éléments de structure. A cet effet il est habituel d'utiliser des couches d'émail opaque pour masquer ces éléments.  More specifically, an important application of glazing according to the invention concerns buildings coated with glass. For these buildings, given the surfaces concerned, the glazing used normally include layer systems with radiated energy control properties to limit the need for air conditioning (solar control) and reduction of the energy emitted by the building ( insulation). Buildings are frequently almost completely covered. Also the glazing covers both the parts that must offer a significant light transmission, and those whose transmission is virtually zero. These last correspond in particular to the elements of structure. For this purpose it is usual to use opaque enamel layers to hide these elements.
Les vitrages utilisés vus de l'extérieur des bâtiments, offrent de préférence une esthétique améliorée. Pour cette raison il est traditionnel de conserver le système de couches même dans les parties revêtues d'émail, ce qui peut conduire à la superposition d'un système de couches et de l'émail. Les revêtements antisolaires ou bas émissifs peuvent être appliqués de différentes façons selon la nature des couches. Pour les dépôts de type pyrolytique, les couches constituées sont en règle générale bien résistantes. Mais même sur ces couches l'application de la couche d'émail peut occasionner l'apparition de défauts. Les dépôts sous vide offrent une variété de propriétés qui ne peuvent pas toujours être obtenues avec les couches déposées par pyrolyse. Néanmoins les systèmes de couches formés par dépôt sous vide, du type pulvérisation cathodique, sont en règle générale beaucoup plus fragiles et engendre des défauts visibles après dépôt de l'émail. The glazings used seen from outside the buildings, preferably offer an improved aesthetics. For this reason it is traditional to maintain the layer system even in the enamel-coated parts, which can lead to the superposition of a layer system and enamel. Sunscreen or low emissive coatings can be applied in different ways depending on the nature of the layers. For pyrolytic type deposits, the layers formed are generally very strong. But even on these layers the application of the enamel layer can cause the appearance of defects. Vacuum deposits offer a variety of properties that can not always be achieved with pyrolytically deposited layers. Nevertheless, the vacuum deposition layer systems, of the sputtering type, are generally much more fragile and give rise to visible defects after deposition of the enamel.
Les émaux utilisés pour ces applications sont constitués typiquement d'une composition comprenant une fritte de verre destinée à former la matrice vitreuse, et de pigments colorants. La composition comprend encore un médium permettant l'application du mélange fritte/pigments, lequel assure une bonne suspension des particules solides et s'élimine au cours de la cuisson de l'émail. Ce médium comprend des solvants, huiles résines etc...  The enamels used for these applications typically consist of a composition comprising a glass frit for forming the vitreous matrix, and coloring pigments. The composition further comprises a medium allowing the application of the sintered mixture / pigments, which ensures a good suspension of the solid particles and is eliminated during the cooking of the enamel. This medium includes solvents, resins oils etc ...
Dans la pratique, en particulier lors de la cuisson de l'émail, opération qui s'effectue à des températures de l'ordre de 550-700°C, des modifications peuvent intervenir dans les couches au contact de cet émail. Les réactions de nature indéfinie entraînent une altération de l'apparence du vitrage. Il se forme des tâches qui modifient leur aspect.  In practice, in particular when cooking enamel, which is carried out at temperatures of the order of 550-700 ° C, changes may occur in the layers in contact with this enamel. Reactions of an indefinite nature cause an alteration of the appearance of the glazing. Tasks that change their appearance are formed.
Les inventeurs ont recherché un moyen de prévenir l'apparition des défauts dans ce type de produits.  The inventors have sought a way to prevent the occurrence of defects in this type of products.
L'invention propose des vitrages comportant un système de couches diélectriques déposées sous vide, système présentant des propriétés de filtre du rayonnement solaire, le système de couches étant au moins en partie revêtu d'un émail. Les inventeurs ont établi qu'il était possible de choisir les composants du système de couches de telle sorte que celui-ci ne soit pas altéré par le contact avec la composition d'émail.  The invention provides glazings comprising a system of vacuum deposited dielectric layers, system having solar radiation filter properties, the layer system being at least partly coated with enamel. The inventors have established that it is possible to choose the components of the layer system so that it is not altered by contact with the enamel composition.
Les vitrages selon l'invention comprennent un système de couches déposé sous vide, présentant des propriétés de filtre du rayonnement solaire en l'absence du revêtement émaillé, le système de couches comprenant au moins une couche résistante superficielle, cette couche étant à base d'oxyde de titane, d'oxyde de niobium, d'oxyde de tantale, ou d'oxydes mixtes des précédents, ou avec d'autres oxydes métalliques. The glazings according to the invention comprise a system of layers deposited under vacuum, having solar radiation filter properties in the absence of the enamelled coating, the layer system comprising at least one surface resistant layer, this layer being based on titanium oxide, niobium oxide, tantalum oxide, or mixed oxides of the foregoing, or with other metal oxides.
Parmi les oxydes additionnels ceux des métaux du groupe comprenant Al, Zr, Hf, V, Mn, Fe, Co, Ni, Cu, Si, Cr, Ta et Nb sont avantageux.  Among the additional oxides, those of the group consisting of Al, Zr, Hf, V, Mn, Fe, Co, Ni, Cu, Si, Cr, Ta and Nb are advantageous.
La couche superficielle peut aussi renfermer en très faible proportion, en général moins de 8% en poids et le plus souvent moins de 5%, des éléments additionnels. Il s'agit notamment de dopants dont le rôle est principalement d'améliorer la fabrication et/ou la mise en oeuvre des cathodes dans la production des couches dans les techniques de dépôt sous vide. Ces éléments traditionnellement sont destinés notamment à améliorer la conductibilité des matériaux constituant des cathodes tels que : Ti, Al. Il peut aussi s'agir de composés stabilisant certains constituants tels que Ca, Mg, ou encore d'éléments qui apparaissent comme indissociables d'autres lors de la préparation. C'est le cas des lanthanides comme l'oxyde d'yttrium ou de celui de hafnium.  The surface layer may also contain in a very small proportion, in general less than 8% by weight and most often less than 5%, additional elements. These include dopants whose role is primarily to improve the manufacture and / or implementation of cathodes in the production of layers in vacuum deposition techniques. These elements are traditionally intended in particular to improve the conductivity of materials constituting cathodes such as: Ti, Al. It can also be compounds stabilizing certain constituents such as Ca, Mg, or elements that appear as inseparable from others during preparation. This is the case of lanthanides such as yttrium or hafnium oxide.
Lorsque l'oxyde de titane est choisi comme base de la couche résistante superficielle, il est nécessairement combiné à au moins un autre oxyde métallique qui renforce sa résistance. Il apparaît en effet que l'oxyde de titane qui offre de bonnes propriétés optiques, est insuffisamment résistant aux sollicitations mécaniques ou chimiques. A l'inverse les oxydes de tantale ou niobium peuvent être utilisés seuls (en dehors des possible éléments dopants présents).  When titanium oxide is chosen as the base of the surface resistant layer, it is necessarily combined with at least one other metal oxide which strengthens its resistance. It appears in fact that titanium oxide, which has good optical properties, is insufficiently resistant to mechanical or chemical stresses. Conversely, oxides of tantalum or niobium can be used alone (apart from the possible doping elements present).
Lorsqu'une couche à base d'oxyde de titane est choisie, elle renferme au moins 40% et au plus 95% en poids d'oxyde de titane.  When a titanium oxide layer is chosen, it contains at least 40% and at most 95% by weight of titanium oxide.
Il va de soi que le vitrage comportant le système de couches lorsqu'il est revêtu d'émail est pratiquement opaque. La transmission lumineuse du vitrage émaillé est dans tous les cas inférieure à 5%, et le plus souvent inférieure à 2%. La présence du système de couches sous l'émail à pour but de maintenir les propriétés, et surtout les propriétés de réflexion qui sont celles du vitrage ne comprenant pas de revêtement émaillé. L'important est en effet de maintenir une apparence externe similaire pour les parties transparentes des vitrages et celles qui ne le sont pas. Cette nécessité est d'autant plus importante que la réflexion est elle-même plus élevée. Avantageusement les vitrages selon l'invention comportent un système de couches tel qu'appliqué sur un verre float clair de 4mm d'épaisseur, la réflexion du côté de la feuille de verre opposé au système de couches serait d'au moins 15% de la lumière solaire incidente, et la transmission d'au moins 60%. It goes without saying that the glazing comprising the layer system when coated with enamel is practically opaque. The light transmittance of the enamelled glazing is in all cases less than 5%, and most often less than 2%. The presence of the layer system under the enamel aims to maintain the properties, and especially the reflection properties that are those of the glazing does not include enamelled coating. The important thing is to maintain a similar external appearance for the parties transparent glazing and those that are not. This necessity is all the more important because the reflection itself is higher. Advantageously, the glazings according to the invention comprise a system of layers as applied to a clear float glass of 4 mm in thickness, the reflection on the opposite side of the glass sheet to the layer system would be at least 15% of the solar light incident, and the transmission of at least 60%.
De préférence les vitrages selon l'invention comportent un système de couches réfléchissant qui appliqués sur une feuille de verre float clair de 4mm conduirait à une réflexion comprise entre 20 et 40% de la lumière solaire incidente.  Preferably the glazing according to the invention comprise a system of reflective layers which applied to a 4mm clear float glass sheet would lead to a reflection of between 20 and 40% of the incident solar light.
En dehors de la couche réfléchissante superficielle très résistante constituée comme indiqué ci-dessus, le système peut comprendre d'autres couches entre cette couche réfléchissante et la feuille de verre.  Apart from the highly resistant superficial reflective layer constituted as indicated above, the system may comprise other layers between this reflective layer and the glass sheet.
Des couches additionnelles sont utilisées notamment pour éviter la diffusion d'ions alcalins à partir du substrat verrier. Ces couches additionnelles peuvent aussi améliorer la résistance mécanique ou les propriétés optiques du système de couches et notamment le caractère réfléchissant.  Additional layers are used in particular to prevent the diffusion of alkaline ions from the glass substrate. These additional layers can also improve the mechanical strength or the optical properties of the layer system and in particular the reflectivity.
Des sous-couches "barrière" préférées utilisées pour améliorer la protection contre la diffusion d'ions alcalins depuis la feuille de verre sont par exemple constituées d'au moins un des composés du silicium : oxyde (SiO2), nitrure (Si3N4), oxynitrure (SiON); ou des oxydes de SnO2 et oxydes composés d'étain et de zinc (jusqu'à 50% en poids d'oxyde de zinc), ou encore le TiO2 éventuellement sous-stoechiométrique ou éventuellement sous forme d'oxynitrure contenant une faible teneur en azote (N/O inférieur à 10%). Preferred "barrier" sub-layers used to improve the protection against the diffusion of alkaline ions from the glass sheet consist for example of at least one of the silicon compounds: oxide (SiO 2 ), nitride (Si 3 N 4 ), oxynitride (SiON); or oxides of SnO 2 and oxides composed of tin and zinc (up to 50% by weight of zinc oxide), or even TiO 2 possibly substoichiometric or optionally in the form of oxynitride containing a low content nitrogen (N / O less than 10%).
A titre indicatif les sous-couches barrières constituées à base de SiO2 ont un indice de l'ordre de 1,5 quand celui du TiO2 est de l'ordre 2,5. As an indication, the barrier sub-layers made of SiO 2 have an index of about 1.5 when that of TiO 2 is of the order of 2.5.
Lorsque les couches additionnelles présentent un indice de réfraction peu élevé leur épaisseur est choisie de préférence relativement plus faible que celle de la ou des couches réfléchissantes pour ne pas altérer les propriétés en question. Le chemin optique correspondant à cette couche barrière de faible indice avantageusement ne représente pas plus du quart du chemin optique de l'ensemble des couches du système. When the additional layers have a low refractive index, their thickness is preferably chosen to be relatively smaller than that of the reflecting layer or layers in order not to alter the properties in question. The optical path corresponding to this layer Low-index barrier advantageously does not represent more than a quarter of the optical path of all the layers of the system.
Avantageusement lorsqu'une ou plusieurs sous-couches sont utilisées pour contribuer aux propriétés réfléchissantes du système, elles sont choisies avec un indice de réfraction aussi élevé que possible et de préférence supérieur à 2,2. Différentes couches réfléchissantes sont utilisables notamment les couches d'oxyde de titane, d'oxyde de niobium, oxyde de tantale, oxyde de zirconium éventuellement sous forme sous oxydée ou sous forme d'oxy- nitrures.  Advantageously, when one or more sub-layers are used to contribute to the reflective properties of the system, they are chosen with a refractive index as high as possible and preferably greater than 2.2. Different reflective layers are used in particular titanium oxide layers, niobium oxide, tantalum oxide, zirconium oxide optionally in oxidized form or in the form of oxynitrides.
Contrairement à la couche superficielle, lorsqu'une sous-couche améliorant la réflexion est à base d'oxyde de titane, il n'est pas nécessaire de combiner cet oxyde avec des éléments qui en améliorent la résistance. Etant sous la couche réfléchissante par principe résistante, cette sous-couche, en elle même peut ne pas offrir les mêmes qualités. L'utilité d'une telle couche TiO2 sans addition d'un autre oxyde réside dans l'indice élevé qu'il présente comparé à celui des oxydes mixtes de titane et d'au moins un autre métal. Ces oxydes mixtes, bien que formant une couche de réflexion significative, à épaisseur égale, réfléchissent moins que l'oxyde de titane seul. La combinaison d'une couche primaire d'oxyde de titane au contact du verre et d'une couche d'oxyde mixte de titane et d'un autre métal combine à la fois l'avantage globalement d'un indice de réfraction élevé et d'une bonne résistance superficielle. In contrast to the surface layer, when a reflection enhancing underlayer is based on titanium oxide, it is not necessary to combine this oxide with elements that improve its strength. Being under the reflective layer by resistant principle, this underlayer, in itself may not offer the same qualities. The utility of such a TiO 2 layer without the addition of another oxide lies in the high index that it has compared to that of the mixed oxides of titanium and at least one other metal. These mixed oxides, although forming a significant reflection layer of equal thickness, reflect less than titanium oxide alone. The combination of a primary layer of titanium oxide in contact with the glass and a layer of mixed oxide of titanium and another metal combines the overall advantage of a high refractive index with a good surface resistance.
L'utilisation d'une couche d'oxyde de titane d'indice élevé peut ne pas présenter cependant le meilleur ensemble de propriétés, en particulier de propriétés mécaniques. Les couches relativement épaisses de TiO2 ne sont pas nécessairement les plus appropriées. Ceci peut encore conduire à limiter l'épaisseur de la couche sous-jacente de TiO2 (ou TiOx, ou TiOxNy), d'autres couches à relativement fort indice complétant le système, y compris notamment une autre couche d'oxyde de titane mixte dont l'autre métal est de même nature ou différente de celle du métal de la couche superficielle. The use of a high index titanium oxide layer may not, however, have the best set of properties, particularly mechanical properties. The relatively thick layers of TiO 2 are not necessarily the most appropriate. This can further lead to limiting the thickness of the underlying layer of TiO 2 (or TiOx, or TiOxNy), other relatively high index layers completing the system, including in particular another layer of mixed titanium oxide of which the other metal is of the same kind or different from that of the metal of the superficial layer.
Un ensemble typique comprend par exemple en plus de la couche superficielle très résistante, une ou plusieurs couches à fort indice de réfraction, et une couche barrière. Un ensemble de couches réfléchissantes de ce type est par exemple une succession de couches comprenant une couche superficielle à base d'une composition d'oxyde mixte de titane et de zirconium, au contact de celle-ci une couche d'oxyde de titane avantageusement déposée à partir d'un cathode céramique d'oxyde de titane éventuellement dopé, et conduisant à une couche d'oxyde légèrement sous- stoechiométrique, sous cette couche une autre couche d'oxyde mixte de titane et d'un autre oxyde du type de ceux pouvant intervenir dans la couche superficielle. A typical assembly comprises, for example, in addition to the very strong surface layer, one or more layers with a high index of refraction, and a barrier layer. A set of reflective layers of this type is, for example, a succession of layers comprising a surface layer based on a mixed titanium / zirconium oxide composition, in contact therewith a titanium oxide layer advantageously deposited. from a ceramic cathode of optionally doped titanium oxide, and leading to a slightly substoichiometric oxide layer, under this layer another layer of mixed oxide of titanium and another oxide of the type of those which can intervene in the superficial layer.
Les couches réfléchissantes déposées sous vide dans de bonnes conditions ne donnent pas naissance normalement à des phénomènes de diffusion de la lumière. A l'inverse en l'absence d'une couche protectrice superficielle selon l'invention, l'application d'une couche d'émail, et la cuisson de celle-ci comme indiqué précédemment altèrent les propriétés optiques par formation de taches ou au moins l'apparition de voiles ("haze") qui altèrent l'aspect de ces vitrages. Un voile important donne l'apparence d'un halo blanc. De plus la présence d'un voile dans ces vitrages n'est pas homogène ce qui ajoute au défaut d'aspect.  Reflective layers deposited under vacuum under good conditions do not normally give rise to phenomena of light scattering. Conversely, in the absence of a surface protective layer according to the invention, the application of an enamel layer, and the firing thereof as indicated above, alter the optical properties by formation of spots or less the appearance of sails ("haze") that alter the appearance of these windows. An important veil gives the appearance of a white halo. In addition the presence of a veil in these windows is not homogeneous which adds to the lack of appearance.
Le voile est défini par l'expression :  The veil is defined by the expression:
H= Rd/Rl X 100 H = R d / R l X 100
dans laquelle Rd est la réflexion dispersée sous grand angle (lumière diffusée), et la réflexion totale. in which R d is the scattered reflection under wide angle (scattered light), and the total reflection.
Les vitrages selon l'invention dont les couches réfléchissantes sont résistantes ne développent pratiquement pas ce type de défaut. L'application et la cuisson de l'émail qui recouvre les couches réfléchissantes ne conduit pas à la formation d'un voile notable. De préférence les vitrages selon l'invention ne présentent pas de voile supérieur à 3,5%, et de préférence pas supérieur à 2 ,5% . Dans les meilleures conditions le voile est avantageusement maintenu en dessous de 2%.  Glazing according to the invention, the reflective layers of which are resistant, practically do not develop this type of defect. The application and firing of the enamel that covers the reflective layers does not lead to the formation of a noticeable veil. Preferably, the glazings according to the invention do not exhibit a film greater than 3.5%, and preferably not greater than 2.5%. In the best conditions, the haze is advantageously kept below 2%.
Si le vitrage revêtu d'émail ne présente ni tache, ni voile notable, certaines qualités optiques sont néanmoins modifiées par la présence de l'émail. En particulier la réflexion de l'ensemble peut différer des celle du vitrage qui ne comporte que le système de couches réfléchissant. Cette variation est cependant acceptable pour autant que la variation de couleur en réflexion reste limitée. If glazing coated with enamel has no stain or noticeable veil, certain optical qualities are nevertheless modified by the presence of enamel. In particular, the reflection of the whole may differ from that of the glazing which includes only the system of reflective layers. This variation is however acceptable as long as the color variation in reflection remains limited.
Pour les vitrages selon l'invention, les couches du système réfléchissant, mais aussi la couleur de l'émail utilisé, sont tels que la variation de couleur en réflexion ΔΕ, du vitrage revêtu d'émail par rapport à celui qui ne comporte pas d'émail, demeure inférieur à 3 et de préférence inférieur à 2. E correspond à l'expression :  For the glazings according to the invention, the layers of the reflecting system, but also the color of the enamel used, are such that the reflection color variation ΔΕ of glazing coated with enamel compared to that which does not include enamel, remains less than 3 and preferably less than 2. E corresponds to the expression:
E = (a*2+b*2)½ E = (a * 2 + b * 2 ) ½
dans laquelle a* et b* sont les coordonnées colorimétriques dans le système Hunter LAB. where a * and b * are the colorimetric coordinates in the Hunter LAB system.
La condition indiquée précédemment sur la variation ΔΕ est d'autant mieux satisfaite que l'émail utilisé est plus sombre.  The condition indicated above on the variation ΔΕ is all the better satisfied that the enamel used is darker.
Lorsque la condition précédente est remplie, les variations de la réflexion peuvent être relativement importantes sans pour autant conduire à une différence d'aspect préjudiciable. A titre indicatif cette différence de réflexion avec et sans la couche d'émail peut atteindre 25% de la valeur en l'absence d'émail, mais est de préférence inférieure à 20%.  When the preceding condition is fulfilled, the variations of the reflection may be relatively large without leading to a detrimental difference in appearance. As an indication, this difference in reflection with and without the enamel layer can reach 25% of the value in the absence of enamel, but is preferably less than 20%.
Les vitrages selon l'invention sont réalisés avec des feuilles de verre clair mais aussi et de préférence avec des feuilles de verre colorés. Dans les applications au verre de bâtiment les couleurs les plus usuelles sont le gris, le bleu et le vert. Les couleurs de l'émail sont généralement aussi neutres que possible. Les émaux sont essentiellement noirs mais peuvent présenter des nuances.  The glazings according to the invention are made with sheets of clear glass but also and preferably with colored glass sheets. In building glass applications the most common colors are gray, blue and green. The colors of the enamel are generally as neutral as possible. Enamels are mostly black but can have shades.
Dans la suite de la description sont reportés des exemples de systèmes de couches réfléchissants et leurs propriétés lorsque ces systèmes sont revêtus d'une couche d'émail.  In the remainder of the description are reported examples of reflective layer systems and their properties when these systems are coated with an enamel layer.
Des systèmes de couches sont notamment constitués de la façon suivante en partant du verre, les épaisseurs données entre parenthèses sont exprimées en nanomètres :  Layering systems are formed in the following way starting from the glass, the thicknesses given in parentheses are expressed in nanometers:
1. G/ SnO2 (15)/TZO (50) 1. G / SnO 2 (15) / TZO (50)
2. G/Si3N4 (17)/TZO (38) 3. G/SiO2 (10)/TZO (50) 2. G / Si 3 N 4 (17) / TZO (38) 3. G / SiO 2 (10) / TZO (50)
4. G/SnO2 (10)/TaO (20) 4. G / SnO 2 (10) / TaO (20)
5. G/SnO2 (10)/TaNbO (20) 5. G / SnO 2 (10) / TaNbO (20)
6. G/SnO2 (10)/TiOx (10)/TZO (30) 6. G / SnO 2 (10) / TiOx (10) / TZO (30)
7. G/SiO2 (40)/TiOx (10)/TZO (30) 7. G / SiO 2 (40) / TiOx (10) / TZO (30)
Dans ces systèmes TZO est une couche constituée d'un oxyde mixte de titane et de zirconium à 45% en poids de zirconium. Elle comprend en outre de l'oxyde d'yttrium (environ 6%) qui stabilise le zirconium. Eventuellement la couche comprend aussi des oxydes d'aluminium, de titane ou d'autres éléments qui incorporés aux cathodes améliorent leur conductibilité et par là, la stabilité de l'opération de dépôt. TiOx désigne l'oxyde de titane déposé à partir d'une cathode céramique, et présentant éventuellement une légère sous- stoechiométrie. TaNbO est oxyde mixte de tantale et de niobium.  In these systems TZO is a layer consisting of a mixed oxide of titanium and zirconium at 45% by weight of zirconium. It further comprises yttrium oxide (about 6%) which stabilizes zirconium. Optionally the layer also comprises oxides of aluminum, titanium or other elements that incorporated in the cathodes improve their conductivity and thereby the stability of the deposition operation. TiOx denotes titanium oxide deposited from a ceramic cathode, and possibly having a slight substoichiometry. TaNbO is a mixed oxide of tantalum and niobium.
Dans ce qui précède, il est question du revêtement du système de couches par une composition d'émail. Ce revêtement peut être uniforme sur l'ensemble de la feuille de verre, il peut aussi ne viser qu'une partie de celle-ci. De la même façon l'application de l'émail peut correspondre à un motif déterminé appliqué sur la feuille notamment à des fins décoratives.  In the foregoing, it is a question of the coating of the layer system by an enamel composition. This coating can be uniform over the entire glass sheet, it can also aim only a part of it. In the same way the application of the enamel may correspond to a particular pattern applied to the sheet, in particular for decorative purposes.
Des systèmes de couches du type 6 indiqué ci-dessus sont appliqués par dépôt magnétron sur des échantillons de verre clair, gris, bleu et vert. Les feuilles de verre des échantillons ont une épaisseur de 6 mm.  Type 6 layer systems indicated above are applied by magnetron deposition to clear, gray, blue and green glass samples. The glass sheets of the samples have a thickness of 6 mm.
Sur le système en question on dépose une couche de composition d'émail noir comprenant 15% en poids de pigments (oxydes de fer, de chrome et cobalt), et 60% de fritte à base de borosilicates, le reste étant constitué du médium d'application. L'émail est appliqué par sérigraphie sur la totalité de la surface de l'échantillon revêtu préalablement du système de couches. L'émail est cuit à 670 °C durant 45 seconde par millimètre d'épaisseur de verre.  On the system in question is deposited a layer of black enamel composition comprising 15% by weight of pigments (iron oxides, chromium and cobalt), and 60% of frit based on borosilicates, the rest consisting of the medium of 'application. The enamel is applied by screen printing over the entire surface of the sample previously coated with the layer system. The enamel is fired at 670 ° C for 45 seconds per millimeter of glass thickness.
Le tableau suivant donne en coordonnées Hunter (illuminant D65, 10°) les qualités colorimétriques en réflexion des différents échantillons. Aucun de ces échantillons ne montre de voile significatif (reste inférieur à 1%). Le premier échantillon n'est pas revêtu d'émail pour établir une comparaison avec les autres échantillons. The following table gives in Hunter coordinates (illuminant D65, 10 °) the colorimetric qualities in reflection of the different samples. None of these samples show significant haze (remains less than 1%). The first sample is not enameled to compare with other samples.
Les exemples I et II montrent que l'application de l'émail sur les couches réfléchissantes ne modifie pas sensiblement la couleur en réflexion. Les valeurs a* et b* sont pratiquement identiques. La présence de l'émail fait varier la luminance, autrement dit, l'intensité de la lumière réfléchie. Examples I and II show that the application of the enamel on the reflective layers does not substantially alter the reflection color. The values a * and b * are virtually identical. The presence of the enamel varies the luminance, in other words, the intensity of the reflected light.
Cette constatation est mise à profit dans l'utilisation de vitrages dont la coloration est assurée par celle de la feuille de verre. Les exemples III et IV, montrent des nuances types obtenues avec des verres offrant simultanément une réflexion significative et une coloration bien marquée. L'application sur verre gris de l'exemple V, illustre ce qui peut être obtenu avec un verre de coloration plus «neutre».  This observation is used in the use of glazing whose color is ensured by that of the glass sheet. Examples III and IV show typical shades obtained with glasses simultaneously offering a significant reflection and a well-marked coloration. The gray-glass application of Example V illustrates what can be achieved with a more "neutral" color glass.
D'autres essais sont réalisés avec des systèmes de couches variées toutes déposées sur verre clair de 6 d'épaisseur. Le tableau suivant indique la nature et l'épaisseur des couches de ces systèmes et les caractéristiques colorimétriques avant et après application de l'émail (comme aux exemples précédents) ainsi que la mesure du voile après cuisson de l'émail.  Other tests are carried out with various layer systems all deposited on clear glass of 6 of thickness. The following table indicates the nature and the thickness of the layers of these systems and the colorimetric characteristics before and after application of the enamel (as in the previous examples) as well as the measurement of the fog after enamel firing.
A titre comparatif un échantillon (C) est préparé qui comporte une couche d'oxyde de titane obtenue par pyrolyse gazeuse (CVD) en principe plus résistante.  For comparison, a sample (C) is prepared which comprises a layer of titanium oxide obtained by gas pyrolysis (CVD) in principle stronger.
Les épaisseurs reportées sont en nanomètres. Les valeurs correspondent d'abord à celles de l'échantillon avec les couches, les dernières valeurs sont celles du même échantillon revêtu d'émail après cuisson. La première couche est déposée sur le verre. La couche superficielle est la seconde couche pour les exemples 1 à 16. Pour les exemples 17 à 23 la couche superficielle est la troisième couche. The thicknesses reported are in nanometers. The values correspond first to those of the sample with the layers, the last values are those of the same sample coated with enamel after cooking. The first layer is deposited on the glass. The superficial layer is the second layer for Examples 1 to 16. For Examples 17 to 23 the surface layer is the third layer.
lere oème . Oth the era.
couche L. couche L* a* b* L* a* b* voile  layer L. layer L * a * b * L * a * b * sail
et 3eme couche sans émail avec émailand 3rd layer without enamel with enamel
C. Ti02 (45) 60 - 3,2 -6,0 52,2 -2,8 -5,4 9,8C. Ti0 2 (45) 60 - 3.2 -6.0 52.2 -2.8 -5.4 9.8
1 TZO (30) 53,4 -1,5 -9,4 40,4 -2,1 -6,6 3,11 TZO (30) 53.4 -1.5 -9.4 40.4 -2.1 -6.6 3.1
2 ZSO50 (30) TZO (30) 58,0 -1,9 -0,4 41,6 -2,3 2,1 1,22 ZSO50 (30) TZO (30) 58.0 -1.9 -0.4 41.6 -2.3 2.1 1.2
3 Sn02 (10) TaO (50) 57,9 -2,1 -0,2 40,5 -1,6 4,0 2,73 Sn0 2 (10) TaO (50) 57.9 -2.1 -0.2 40.5 -1.6 4.0 2.7
4 Sn02 (25) TaO (25) 55,8 -2,2 -4,8 46,9 -2,2 0,7 2,24 Sn0 2 (25) TaO (25) 55.8 -2.2 -4.8 46.9 -2.2 0.7 2.2
5 Sn02 (25) TaNbO(25) 57,6 -2,3 -5,1 45,2 -2,2 -1,8 1,85 Sn0 2 (25) TaNbO (25) 57.6 -2.3 -5.1 45.2 -2.2 -1.8 1.8
6 Sn02 (30) TaNbO(20) 56,8 -2,2 -5,1 44,2 -2,1 -1,6 1,66 Sn0 2 (30) TaNbO (20) 56.8 -2.2 -5.1 44.2 -2.1 -1.6 1.6
7 Sn02 (25) NbO (25) 58,2 -2,2 -6,2 45,7 -2,3 -2,9 1,97 Sn0 2 (25) NbO (25) 58.2 -2.2 -6.2 45.7 -2.3 -2.9 1.9
8 Si3N4 (10) TZO (50) 61,7 -2,1 -1,7 47,4 -2,4 0,2 3,28 If 3 N 4 (10) TZO (50) 61.7 -2.1 -1.7 47.4 -2.4 0.2 3.2
9 Si3N4 (17) TZO (38) 60,0 -1,9 -4,7 46,1 -2,2 -2,0 2,29 If 3 N 4 (17) TZO (38) 60.0 -1.9 -4.7 46.1 -2.2 -2.0 2.2
10 Si02 (10) TZO (50) 61,4 -2,1 -5,4 46,7 -2,6 -2,5 1,810 Si0 2 (10) TZO (50) 61.4 -2.1 -5.4 46.7 -2.6 -2.5 1.8
11 Si02 (30) TZO (50) 61,3 -2,1 -5,8 46,5 -2,6 -3,0 1,511 Si0 2 (30) TZO (50) 61.3 -2.1 -5.8 46.5 -2.6 -3.0 1.5
12 TiOx (20) TZO (20) 61,7 -1,9 -8,2 45,1 -2,1 -5,8 2,212 TiOx (20) TZO (20) 61.7 -1.9 -8.2 45.1 -2.1 -5.8 2.2
13 TiOx (30) TZO (20) 64,6 -2,5 2,5 46,6 -2,4 2,4 2,213 TiOx (30) TZO (20) 64.6 -2.5 2.5 46.6 -2.4 2.4 2.2
14 Sn02 (30) TNO (30) 61,8 -2,4 -2,4 49,1 -2,4 -0,8 1,314 Sn0 2 (30) TNO (30) 61.8 -2.4 -2.4 49.1 -2.4 -0.8 1.3
15 TiOx (30) TNO (25) 65,3 -2,3 -2,9 52,3 -3,1 1,8 2,1TiOx (30) TNO (25) 65.3 -2.3 -2.9 52.3 -3.1 1.8 2.1
16 TiOx (20) TNO (30) 65,1 -2,2 -6,0 51,8 -3,1 -0,8 2,416 TiOx (20) TNO (30) 65.1 -2.2 -6.0 51.8 -3.1 -0.8 2.4
17 Si02 (40) TiOx (10)/ 59,59 -1,98 -9,09 46,3 -2,2 -6,4 1,49 Si0 2 (40) TiOx (10) / 59.59 -1.98 -9.09 46.3 -2.2 -6.4 1.49
TZO (30)  TZO (30)
18 TZO (10) TiOx (20)/ 62,24 -2,33 1 1 ,74 46 -0,6 1 1 ,5 1 , 17  18 TZO (10) TiOx (20) / 62.24 -2.33 1 1, 74 46 -0.6 1 1, 5 1, 17
TZO (40)  TZO (40)
19 TZO (5) TiOx (10)/ 58,81 -1 ,99 -8,48 44,7 -2 -5,9 1 ,66  19 TZO (5) TiOx (10) / 58.81 -1.99 -8.48 44.7 -2 -5.9 1, 66
TZO (20)  TZO (20)
20 TZO (20) TiOx (5)/ 63,36 -2,26 3,3 46,2 -1 ,3 9,44 1 ,33  TZO (20) TiOx (5) / 63.36 -2.26 3.3 46.2 -1, 3 9.44 1, 33
TZO (40)  TZO (40)
21 Sn02 (40 ) TiOx (10 )/ 59,5 -1 ,25 7,05 42,4 -0,2 9,71 1 ,64 Sn0 2 (40) TiOx (10) / 59.5 -1, 7.05 42.4 -0.2 9.71 1, 64
TZO (30 )  TZO (30)
22 Sn02 (10) TiOx (30)/ 64, 1 1 -2,52 9,03 46,9 -1 , 1 7,8 1 ,66 Sn0 2 (10) TiOx (30) / 64, 1 1 -2.52 9.03 46.9 -1, 1 7.8 1, 66
TZO (30)  TZO (30)
23 Sn02 (5) TiOx (10)/ 61 ,55 -2, 14 -6,47 46,8 -2,4 -2,4 1 ,88 23 Sn0 2 (5) TiOx (10) / 61, 55 -2, 14 -6.47 46.8 -2.4 -2.4 1, 88
TZO (30) TZO est la couche d'oxyde mixte de titane et de zirconium décrite précédemment constituée d'un oxyde mixte de 50% en poids de TiO2, 46% de ZrO2, le reste venant d'éléments accompagnant habituellement le zirconium, notamment d'oxyde d'yttrium. TZO (30) TZO is the titanium / zirconium mixed oxide layer previously described consisting of a mixed oxide of 50% by weight of TiO 2 , 46% of ZrO 2 , the remainder coming from elements usually accompanying zirconium, especially from yttrium oxide.
ZSO50 est une couche d'oxyde mixte d'étain et de zinc en proportion en poids 50/50. ZSO50 is a mixed tin / zinc oxide layer in 50/50 weight ratio.
TaO désigne l'oxyde de tantale (il ne s'agit pas de la formule chimique mais d'une désignation générique, idem pour NbO et TaNbO en ce qui concerne respectivement l'oxyde de niobium ou l'oxyde mixte de niobium et de tantale (proportion atomique 50/50).  TaO denotes tantalum oxide (it is not a question of the chemical formula but of a generic designation, idem for NbO and TaNbO with regard respectively to niobium oxide or mixed oxide of niobium and tantalum (50/50 atomic proportion).
On utilise de cibles métallique de Ta, Nb et Ta-Nb et on dépose dans Ο2 afin d'obtenir Tao, NbO et TaNbO.  Metal targets of Ta, Nb and Ta-Nb are used and deposited in Ο2 to obtain Tao, NbO and TaNbO.
TxO est l'oxyde de titane déposé à partir des cathodes céramiques.  TxO is titanium oxide deposited from ceramic cathodes.
TNO est l'oxyde mixte de titane et de niobium en proportion massique50/50.  TNO is the mixed oxide of titanium and niobium in mass proportion50 / 50.
Dans les exemples on remarque que la couche d'oxyde de titane seul, même obtenue par pyrolyse présente un voile conséquent après application de la couche d'émail. Les couches déposées dans les conditions de l'invention sont sensiblement moins affectées.  In the examples, it is noted that the layer of titanium oxide alone, even obtained by pyrolysis, has a substantial haze after application of the enamel layer. The deposited layers under the conditions of the invention are substantially less affected.
Toujours dans les exemples selon l'invention les couleurs sont un peu modifiées mais la teinte générale est peu affectée. La luminosité change un peu ce qui n'est pas préjudiciable pour des allèges.  Still in the examples according to the invention the colors are a little modified but the overall color is not affected. The brightness changes a bit which is not detrimental for lighters.
Les figures annexées présentent les avantages liés à l'utilisation des vitrages selon l'invention comme allèges. Dans ces figures :  The attached figures show the advantages associated with the use of glazing according to the invention as lighters. In these figures:
- la figure 1 représente la disposition de vitrage en façade d'un bâtiment ;  - Figure 1 shows the glazing arrangement in front of a building;
- la figure 2, représente un vitrage analogue à celui de la figure 1 comprenant une partie émaillée ;  - Figure 2 shows a glazing similar to that of Figure 1 comprising an enamelled portion;
- la figure 3 illustre une manière d'utilisation d'un vitrage selon l'invention  FIG. 3 illustrates a way of using a glazing unit according to the invention
- la figure 4 représente de façon schématique un vitrage comportant un système de couche selon l'invention avec plusieurs couches réfléchissantes. La façade d'un bâtiment revêtue de verre comporte de parties de "vision" permettant une transmission significative de la lumière extérieure. Cette partie de vision est représentée par un vitrage double (1,2). S' agissant de vitrage isolant les deux feuilles de verre délimitent un espace clos avec les joints intercalaires non représentés. La feuille 1 est revêtue par un système de couches (3) filtrant les rayonnements. Il s'agit par exemple d'un système réfléchissant une part significative du rayonnement solaire. - Figure 4 schematically shows a glazing comprising a layer system according to the invention with several reflective layers. The facade of a glass-clad building has "vision" parts that allow significant transmission of external light. This part of vision is represented by a double glazing (1,2). In the case of insulating glass, the two sheets of glass delimit an enclosed space with the unrepresented intermediate joints. The sheet 1 is coated by a system of layers (3) filtering the radiation. This is for example a system reflecting a significant part of solar radiation.
La position du système de couches (3) dans l'espace du vitrage isolant, le protège des altérations possibles soit mécaniques soit au contact de l'atmosphère. Cette disposition est particulièrement souhaitable pour les couches déposées sous vide par pulvérisation cathodique qui sont connues pour être relativement fragiles par comparaison aux couches "dures" formées par pyrolyse.  The position of the layer system (3) in the space of the insulating glass, protects it from possible alterations either mechanical or in contact with the atmosphere. This arrangement is particularly desirable for sputtered vacuum deposited layers which are known to be relatively brittle compared to "hard" pyrolysis layers.
La figure 1 présente aussi une partie de la structure du bâtiment (4). Pour conserver de l'extérieur une apparence uniforme il est usuel de disposer également un vitrage (5) présentant les mêmes propriétés que celles de la partie de vision. En particulier pour maintenir une réflexion analogue, cette partie est également couverte d'une couche réfléchissante (6).  Figure 1 also shows part of the building structure (4). To preserve from the outside a uniform appearance it is usual to also have a glazing (5) having the same properties as those of the viewing part. In particular to maintain a similar reflection, this part is also covered with a reflective layer (6).
Dans la configuration de la figure 1 la structure du bâtiment (4) n'est pas dissimulée. La feuille 5 présente la même transmission lumineuse que la feuille (3). L'utilisation d'un émail de masquage est donc souhaitée. Néanmoins cet émail ne peut être disposé sur la face externe de la feuille 5, l'apparence en termes de couleur ou de réflexion ne pourrait être maintenue analogue à celle de la feuille de vision. Le recouvrement du système de couches (6) déposé sous vide par un émail était antérieurement inapplicable en raison des défauts et des changements de teintes résultant de l'interaction de l'émail avec le système de couches du fait de la fragilité de ce dernier.  In the configuration of Figure 1 the building structure (4) is not concealed. The sheet 5 has the same light transmission as the sheet (3). The use of a masking enamel is therefore desired. However, this enamel can not be arranged on the outer face of the sheet 5, the appearance in terms of color or reflection could not be maintained similar to that of the vision sheet. The coating of the layer system (6) deposited under vacuum by an enamel was previously inapplicable because of the defects and color changes resulting from the interaction of the enamel with the layer system because of the fragility of the latter.
La figure 2 présente une solution antérieure destinée à répondre à la nécessité de combiner la dissimulation de la structure (4) et le maintien de l'apparence externe. Pour parvenir à ce résultat l'émail (8) est appliqué sur une feuille 7 distincte de celle (5) portant la couche réfléchissante (6). Dans cette configuration l'ensemble des feuilles (5) et (7) ne forme pas à proprement parler un vitrage "isolant" dans la mesure où il n'est pas nécessaire que l'espace entre ces deux feuilles soit clos, et la seule fonction de la feuille (7) est d'abord de support de la couche émaillée. Figure 2 shows an earlier solution to meet the need to combine the concealment of the structure (4) and the maintenance of the external appearance. To achieve this result the enamel (8) is applied to a sheet 7 distinct from that (5) carrying the reflective layer (6). In this configuration the set of sheets (5) and (7) does not form properly speak an "insulating" glazing insofar as it is not necessary that the space between these two sheets be closed, and the only function of the sheet (7) is first support of the enamelled layer.
La figure 3 illustre une utilisation des vitrages selon l'invention. Cette fois en raison du comportement amélioré du système de couches réfléchissant (9), il est possible de le revêtir de l'émail (10). De ce fait une feuille unique est susceptible de dissimuler la structure du bâtiment et de conserver l'apparence externe. Une simplification importante est donc rendue possible.  Figure 3 illustrates a use of glazing according to the invention. This time because of the improved behavior of the reflective layer system (9), it is possible to coat it with enamel (10). As a result, a single sheet is likely to conceal the structure of the building and preserve the external appearance. An important simplification is thus made possible.
La figure 4 illustre schématiquement un revêtement selon l'invention comprenant un système à couches multiples. Dans cette représentation, comme précédemment la couche d'émail (10) recouvre la couche résistante (9). Sous cette dernière sont disposées d'autres couches réfléchissantes à fort indice de réfraction (lia et 11b). Ces couches complètent l'effet de la couche superficielle (9) et en améliorent les performances. Le cas échéant une couche barrière (12) est aussi appliquée pour prévenir la migration des ions alcalins depuis la feuille de verre (5).  Figure 4 schematically illustrates a coating according to the invention comprising a multilayer system. In this representation, as previously the enamel layer (10) covers the resistant layer (9). Under the latter are disposed other reflective layers with high refractive index (11a and 11b). These layers complement the effect of the surface layer (9) and improve its performance. If necessary, a barrier layer (12) is also applied to prevent the migration of the alkaline ions from the glass sheet (5).

Claims

REVENDICATIONS
1. Vitrage comportant un système de couches déposées sous vide présentant des propriétés de filtre du rayonnement solaire, ce système étant revêtu au moins en partie par une couche d'émail. 1. Glazing comprising a system of vacuum deposited layers having solar radiation filter properties, this system being coated at least in part by a layer of enamel.
2. Vitrage selon la revendication 1 dans lequel le système de couches comporte en contact avec la couche d'émail une couche superficielle à base d'oxyde de titane, d'oxyde de niobium, d'oxyde de tantale ou d'oxydes mixtes des précédents, l'oxyde de titane étant nécessairement combiné à au moins un oxyde métallique du groupe comprenant Ta, Nb, Al, Zr, Hf, V, Mn, Fe, Co, Ni, Cu, Si, Cr. 2. Glazing according to claim 1 wherein the layer system comprises in contact with the enamel layer a surface layer based on titanium oxide, niobium oxide, tantalum oxide or mixed oxides of preceding, the titanium oxide being necessarily combined with at least one metal oxide of the group comprising Ta, Nb, Al, Zr, Hf, V, Mn, Fe, Co, Ni, Cu, Si, Cr.
3. Vitrage selon la revendication 2 dans laquelle la couche en contact avec l'émail est à base d'oxyde de titane lequel représente au moins 40% en poids de cette couche et au plus 95%. 3. Glazing according to claim 2 wherein the layer in contact with the enamel is based on titanium oxide which is at least 40% by weight of this layer and at most 95%.
4. Vitrage selon l'une des revendications précédentes dans lequel le système de couches est tel qu'appliqué sur une feuille de verre clair de 4mm d'épaisseur, il conduirait à une réflexion du coté de la feuille ne comportant pas le système, d'au moins 15% et une transmission d'au moins 60%. 4. Glazing according to one of the preceding claims wherein the layer system is as applied to a clear glass sheet of 4mm thick, it would lead to a reflection on the side of the sheet without the system, d at least 15% and a transmission of at least 60%.
5. Vitrage selon la revendication 4 dans lequel le système de couches est tel qu'appliqué sur une feuille de verre clair de 4mm d'épaisseur il conduirait à une réflexion du coté de la feuille ne comportant pas le système, compris entre 20% et 40%. 5. Glazing according to claim 4 wherein the layer system is as applied to a clear glass sheet 4mm thick it would lead to a reflection on the side of the sheet not comprising the system, between 20% and 40%.
6. Vitrage selon l'une des revendications précédentes dans lequel le système de couches comporte au contact du verre au moins une couche protégeant contre la diffusion des alcalins constituée d'au moins un des composés suivants : oxyde de silicium (SiO2), oxynitrure de silicium (SiON), nitrure de silicium, (Si3N4), oxyde d'étain éventuellement en combinaison avec de l'oxyde de zinc (jusqu'à 50% en poids de zinc), l'oxyde de titane TiO2 éventuellement sous- stoechiométrique, les oxynitrures de titane. 6. Glazing according to one of the preceding claims wherein the layer system comprises in contact with the glass at least one layer protecting against the diffusion of alkali consisting of at least one of the following compounds: silicon oxide (SiO 2 ), silicon oxynitride (SiON), silicon nitride, (Si 3 N 4 ), tin oxide optionally in combination with zinc oxide (up to 50% by weight of zinc), titanium oxide TiO 2 optionally substoichiometric, titanium oxynitrides.
7. Vitrage selon la revendication 6 dans lequel la couche barrière présente un chemin optique qui n'est pas supérieur au quart de celui de l'ensemble du système. 7. Glazing according to claim 6 wherein the barrier layer has an optical path that is not greater than one quarter of that of the entire system.
8. Vitrage selon l'une des revendications précédentes comprenant une ou plusieurs couches d'indice de réfraction supérieur à8. Glazing according to one of the preceding claims comprising one or more layers of refractive index greater than
2,2 sous la couche superficielle au contact de l'émail. 2.2 under the superficial layer in contact with the enamel.
9. Vitrage selon l'une des revendications précédentes ne présentant pas un voile supérieur à 3,5 %, et de préférence pas supérieur à 2,5 %. 9. Glazing according to one of the preceding claims not having a web greater than 3.5%, and preferably not more than 2.5%.
10. Vitrage selon l'une des revendications précédentes tel que la réflexion du côté de la feuille non revêtu, conduise à une différence de coloration avant et après application de la couche d'émail ΔΕ qui est inférieure à 3 et de préférence à 2, E étant défini par l'expression E = (a*2+b*2)½ dans le système colorimétrique Hunter. 10. Glazing according to one of the preceding claims such that the reflection on the side of the uncoated sheet, lead to a difference in color before and after application of the enamel layer ΔΕ which is less than 3 and preferably 2, E being defined by the expression E = (a * 2 + b * 2 ) ½ in the Hunter color system.
11. Vitrage selon l'une des revendications précédentes comportant un des systèmes de couches : 11. Glazing according to one of the preceding claims comprising one of the layer systems:
G/ SnO2/TZO; G / SnO 2 / TZO;
G/Si3N4 /TZO; G / Si 3 N 4 / TZO;
G/SiO2 /TZO; G / SiO 2 / TZO;
G/SnO2 /TaO; G / SnO 2 / TaO;
G/SnO2/TaNbO; G / SnO 2 / TaNbO;
G/SnO2/TiOx/TZO; G / SnO 2 / TiOx / TZO;
G/SiO2/TiOx/TZO dans lesquelles G désigne le verre, TZO est un oxyde mixte de titane et de zirconium à 45% en poids de zirconium comprenant 6% d'yttrium, TaO est l'oxyde de tantale désigné de façon générique de même que TaNbO est un oxyde mixte de tantale et de niobium (pourcentage 50/50 en poids), TiOx est l'oxyde de titane déposé à partir de cathodes céramiques G / SiO 2 / TiOx / TZO wherein G denotes glass, TZO is a mixed oxide of titanium and zirconium at 45% by weight of zirconium comprising 6% yttrium, TaO is tantalum oxide generically referred to as TaNbO is a mixed oxide of tantalum and niobium (50/50 by weight), TiOx is titanium oxide deposited from ceramic cathodes
12. Utilisation d'un vitrage selon l'une des revendications précédentes comme allège. 12. Use of a glazing according to one of the preceding claims as a spandrel.
13. Utilisation d'un vitrage selon l'une des revendications 1 à 11 pour constituer une feuille revêtue de motifs décoratifs émaillés. 13. Use of a glazing according to one of claims 1 to 11 to form a sheet coated with enamelled decorative patterns.
EP10771696A 2009-10-16 2010-10-15 Enameled reflective glass panel Withdrawn EP2488462A1 (en)

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PCT/EP2010/065516 WO2011045412A1 (en) 2009-10-16 2010-10-15 Enameled reflective glass panel

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WO2021122856A1 (en) 2019-12-20 2021-06-24 Agc Glass Europe Enameled glazing

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BE1019638A3 (en) * 2010-03-10 2012-09-04 Agc Glass Europe GLAZING WITH HIGH REFLECTION.
FR3019173B1 (en) 2014-03-28 2016-03-25 Saint Gobain GLAZING PROVIDED WITH A STACK OF THIN LAYERS FOR SOLAR PROTECTION
FR3052769B1 (en) 2016-06-15 2018-07-13 Saint-Gobain Glass France GLASS SHEET WITH EMAIL REFLECTING INFRARED RADIATION
FR3083228B1 (en) * 2018-06-27 2020-06-26 Saint-Gobain Glass France GLAZING HAVING A STACK OF THIN FILMS ACTING ON THE SOLAR RADIATION AND OF A BARRIER LAYER
FR3086590B1 (en) 2018-09-27 2021-01-01 Saint Gobain PROCESS FOR OBTAINING A MATERIAL INCLUDING A SHEET OF GLASS.

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302503A (en) * 1978-05-17 1981-11-24 Libbey-Owens-Ford Company Architectural spandrel
DE3716860A1 (en) * 1987-03-13 1988-09-22 Flachglas Ag METHOD FOR PRODUCING A TENSILE AND / OR CURVED GLASS DISC WITH A SILVER LAYER, THE GLASS DISC PRODUCED THEREOF, AND THE USE THEREOF
GB8900166D0 (en) * 1989-01-05 1989-03-01 Glaverbel Glass coating
EP1183912B2 (en) * 1999-05-20 2013-11-06 AGC Flat Glass Europe SA Automotive glazing panel having an electrically heatable solar control coating layer
FR2799005B1 (en) * 1999-09-23 2003-01-17 Saint Gobain Vitrage GLAZING PROVIDED WITH A STACK OF THIN FILMS ACTING ON THE SOLAR RADIATION
FR2856627B1 (en) * 2003-06-26 2006-08-11 Saint Gobain TRANSPARENT SUBSTRATE WITH COATING WITH MECHANICAL STRENGTH PROPERTIES
US20090258222A1 (en) * 2004-11-08 2009-10-15 Agc Flat Glass Europe S.A. Glazing panel
FR2878844B1 (en) * 2004-12-06 2007-07-13 Saint Gobain DECORATED AND LAYERED STRUCTURE
KR20070087079A (en) * 2004-12-17 2007-08-27 에이에프지 인더스트리즈, 인크. Air oxidizable scratch resistant protective layer for optical coatings
FR2889182B1 (en) * 2005-07-29 2007-10-26 Saint Gobain GLAZING PROVIDED WITH A STACK OF THIN LAYERS ACTING ON SOLAR RADIATION
DE102006027029B4 (en) * 2006-06-09 2010-09-30 W.C. Heraeus Gmbh Sputtering target with a sputtering material based on TiO2 and manufacturing process
EP1980539A1 (en) * 2007-03-19 2008-10-15 AGC Flat Glass Europe SA Glazing with low emissivity
FR2927897B1 (en) * 2008-02-27 2011-04-01 Saint Gobain ANTISOLAR GLAZING HAVING IMPROVED LUMINOUS TRANSMISSION COEFFICIENT.
EA021185B1 (en) * 2008-03-20 2015-04-30 Агк Гласс Юроп Glazing coated with thin layers
EP3702337B1 (en) * 2008-03-20 2023-10-04 AGC Glass Europe Window coated with fine layers
BRPI0911918A2 (en) * 2008-04-30 2015-10-06 Agc Glass Europe solar control glazing
FR2931147B1 (en) * 2008-05-19 2010-11-19 Saint Gobain GLAZING PROVIDED WITH A STACK OF THIN LAYERS
FR2949774B1 (en) * 2009-09-08 2011-08-26 Saint Gobain MATERIAL COMPRISING A GLASS SUBSTRATE COATED WITH A THIN FILM STACK

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011045412A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021122856A1 (en) 2019-12-20 2021-06-24 Agc Glass Europe Enameled glazing

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EP2314553A1 (en) 2011-04-27
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US20120202023A1 (en) 2012-08-09
WO2011045412A1 (en) 2011-04-21

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