Glazing panel
Abstract
A glazing panel supporting a coating stack comprising in sequence at least: a glass substrate a base anti-reflective layer an infrared reflective layer an upper anti-reflective layer an upper coating layer ren which the coating layer upper comprises at least two sub-layers: a first upper coating sub-layer that is essentially composed of at least one material selected from the assembly that is It consists of Ti, Zr, Hf, V, Nb, Ta, Cr or its mixtures or a mixture of at least one of these metals with Al and / or B or an oxide, a sub-stoichiometric oxides, a nitride or an oxynitride of Ti, Zr, Hf, V, Nb, Ta, Cr or mixtures thereof, or unoxide, a sub-stoichiometric oxide, a nitride or an oxynitride that is a mixture of at least one of these metals Al and / or B, and a second upper cladding sublayer, above the first upper cladding sublayer, which is essentially composed of a silicon oxide, sub-stoichiometric silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon carbide, silicon oxycarbide or silicon oxycarbonitride, the second coating sublayer having a geometric thickness located at the range of 15 to 30 Å.

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27 claims: 17 independent, 10 dependent
- 1ES 2 425 365 T3 REIVINDICACIONES 1. Un panel de acristalamiento que soporta a una pila de revestimiento que comprende en secuencia por lo menos:un substrato de vidrio una capa antirreflectora de base una capa reflectora de rayos infrarrojos una capa antirreflectora superior una capa de revestimiento superior en el que la capa de revestimiento superior comprende por lo menos dos subcapas: una primera subcapa de revestimiento superior que se compone esencialmente de por lo menos un material seleccionado entre el conjunto que se compone de Ti, Zr, Hf, V, Nb, Ta, Cr o sus mezclas o de una mezcla de por lo menos uno de estos metales con Al y/o B o un óxido, un óxido sub-estequiométrico, un nitruro o un oxinitruro de Ti, Zr, Hf, V, Nb, Ta, Cr o sus mezclas, o un óxido, un óxido sub-estequiométrico, un nitruro o un oxinitruro que es una mezcla de por lo menos uno de estos metales Al y/o B, y una segunda subcapa de revestimiento superior, por encima de la primera subcapa de revestimiento superior, que se compone esencialmente de un óxido de silicio, óxido de silicio subestequiométrico, nitruro de silicio, oxinitruro de silicio, carburo de silicio, carbonitruro de silicio, oxicarburo de silicio u oxicarbonitruro de silicio, teniendo la segunda subcapa de revestimiento superior un espesor geométrico situado en el intervalo de 15 a 30 A.
- 2Un panel de acristalamiento de acuerdo con la reivindicación 1, en el que la primera subcapa de revestimiento superior se compone esencialmente de por lo menos un material seleccionado entre el conjunto que se compone de titanio, óxido de titanio, óxido de titanio sub-estequiométrico, nitruro de titanio y oxinitruro de titanio.
- 3Un panel de acristalamiento de acuerdo con la reivindicación 2, en el que la primera subcapa de revestimiento superior se compone esencialmente de por lo menos un material seleccionado entre el conjunto que se compone de titanio, un óxido de titanio y un nitruro de titanio.
- 4Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que la segunda subcapa de revestimiento superior está en contacto directo con la primera subcapa de revestimiento superior.
- 5Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que la segunda subcapa de revestimiento superior está expuesta al aire.
- 6Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que la primera subcapa de revestimiento superior tiene un espesor geométrico situado en el intervalo de 20 a 100 A.
- 7Un panel de acristalamiento de acuerdo con la reivindicación 6, en el que la primera subcapa de revestimiento superior tiene un espesor geométrico situado en el intervalo de 20 a 80 A.
- 8Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que la capa de revestimiento superior comprende una primera subcapa de revestimiento superior que se compone esencialmente de un nitruro de titanio y una segunda subcapa de revestimiento superior que se compone esencialmente de un óxido de silicio.
- 9Un panel de acristalamiento de acuerdo con la reivindicación 8, en el que la subcapa que se compone esencialmente de un nitruro de titanio tiene un espesor geométrico situado en el intervalo de 20 a 40 A, y la subcapa que se compone esencialmente de un óxido de silicio tiene un espesor geométrico situado en el intervalo de 15 a 25 A.
- 10Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que el panel de acristalamiento es tratable térmicamente.
- 11Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que por lo menos una de las capas antirreflectoras comprende un óxido.
- 12Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que por lo menos una de las capas antirreflectoras comprende un óxido mixto de zinc y de uno o más de los elementos estaño, aluminio y titanio. ES 2 425 365 T3
- 13Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, que soporta una pila de revestimiento que comprende en secuencia por lo menos un substrato de vidrio una capa antirreflectora de base una capa reflectora de rayos infrarrojos una capa antirreflectora superior una capa de revestimiento superior
- 14Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, que comprende en secuencia por lo menos un substrato de vidrio;una capa antirreflectora de base que comprende por lo menos una capa que comprende un óxido mixto de zinc y estaño;una capa reflectora de rayos infrarrojos;una capa de barrera;una capa antirreflectora superior que comprende por lo menos una capa que comprende un óxido mixto de zinc y estaño;y una capa de revestimiento superior que comprende en secuencia una primera subcapa que se compone esencialmente de un nitruro de titanio y una segunda subcapa que se compone esencialmente de un óxido de silicio.
- 15Un panel de acristalamiento de acuerdo con la reivindicación 14, en el que la capa de barrera se selecciona entre el conjunto que se compone de una capa de barrera en forma sustancialmente metálica y una capa de barrera que comprende una primera capa de barrera en forma sustancialmente metálica y una segunda capa de barrera situada encima que tiene una composición diferente de la de la primera capa de barrera que está en una forma seleccionada entre el conjunto que se compone de óxidos, óxidos sub-estequiométricos, nitruros, nitruros subestequiométricos, oxinitruros y oxinitruros sub-estequiométricos.
- 16Un panel de acristalamiento de acuerdo con la reivindicación 14 o la reivindicación 15, en el que la capa de barrera se selecciona entre el conjunto que se compone de una capa de barrera que comprende titanio y una capa de barrera que comprende una primera capa de barrera que comprende níquel y cromo y una segunda capa de barrera situada encima que comprende titanio.
- 17Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que el panel de acristalamiento revestido tiene una transmitancia luminosa mayor que 70 %.
- 18Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que un tratamiento provoca un aumento en la transmitancia luminosa del panel de acristalamiento.
- 19Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, que está adaptado para su ensamble en una unidad de doble acristalamiento.
- 20Un panel de acristalamiento de acuerdo con la reivindicación 19, en el que el panel de acristalamiento está adaptado para ser tratado térmicamente antes del ensamble en una unidad de doble acristalamiento
- 21Un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes, que muestra una calificación AWRT de por lo menos 250.
- 22Una unidad de doble acristalamiento que comprende por lo menos un panel de acristalamiento de acuerdo con una cualquiera de las reivindicaciones precedentes.
- 23Una unidad de doble acristalamiento que comprende por lo menos un panel de acristalamiento tratado térmicamente de acuerdo con una cualquiera de las reivindicaciones precedentes.
- 24Una unidad de doble acristalamiento de acuerdo con la reivindicación 22 o la reivindicación 23, en el que la unidad de doble acristalamiento tiene una transmitancia luminosa mayor que 70 %.
- 25Un método de producir un panel de acristalamiento tratado térmicamente que comprende, en orden, las etapas de:a) depositar una pila de revestimiento sobre un substrato de vidrio para proporcionar un panel de acristalamiento intermedio de acuerdo con una cualquiera de las reivindicaciones 1 hasta 17 o 19 hasta 21, b) someter all panel de acristalamiento intermedio revestido, a un proceso de tratamiento térmico en aire a una temperatura mayor que 550°C. ES 2 425 365 T3
- 26Un método de acuerdo con la reivindicación 25, en el que la transmitancia luminosa del panel de acristalamiento tratado térmicamente a continuación de la etapa de tratamiento térmico es mayor en al menos un 6 % que la transmitancia luminosa del panel de acristalamiento intermedio.
- 27Uso de una capa de revestimiento superior que comprende por lo menos dos subcapas:una primera subcapa de revestimiento que se compone esencialmente de por lo menos un material seleccionado entre el conjunto que se compone de Ti, Zr, Hf, V, Nb, Ta, Cr o sus mezclas o una mezcla de por lo menos uno de estos metales con Al y/o B o un óxido, un óxido sub-estequiométrico, un nitruro o un oxinitruro de Ti, Zr, Hf, V, Nb, Ta, Cr o sus mezclas, o un óxido, un óxido sub-estequiométrico, un nitruro o un oxinitruro que es una mezcla de por lo menos uno de estos metales con Al y/o B, y una segunda subcapa de revestimiento superior, por encima de la primera subcapa de revestimiento superior, que tiene un espesor geométrico en el intervalo de 15 a 30 A, y que se compone esencialmente de un óxido de silicio, óxido de silicio sub-estequiométrico, nitruro de silicio, oxinitruro de silicio, carbonitruro de silicio, oxicarburo de silicio u oxicarbonitruro de silicio, para aumentar la resistencia mecánica antes del tratamiento térmico de un panel de acristalamiento revestido tratable térmicamente, que tiene por lo menos una capa de revestimiento reflectora de rayos infrarrojos metálica emparedada entre capas dieléctricas y para reducir el número de arañazos visibles en la superficie del panel de acristalamiento revestido después de un tratamiento térmico.
Independent claims27
101 paragraphs in 10 sections, as filed
ES 2 425 365 T3
DESCRIPTION
Glazing panel
This invention relates to glazing panels and particularly, but not exclusively, to solar control panels and / or low-emissivity glazing and / or to glazing panels that can be subjected to a heat treatment following application. to the glazing substrate of an optical filter in the form of a coating stack. The invention relates more particularly to cases where a coating stack is applied to the glazing by a vacuum deposition technique, for example by sputtering or magnetron sputtering.
Multiple factors must be considered when designing cladding stacks for glazing applications. These include not only the desired opto-energy performance of the coated glazing panel but also, for example, the abrasion resistance of the coating stack (in order to facilitate handling, transport and treatment), the chemical stability and durability of the coating stack (in order to facilitate storage under various conditions) and the tolerances of the production process control (in order to facilitate acceptable production yields and consistency between batches of products).
It is known to apply a top coat to a coating stack, particularly in an attempt to increase the abrasion resistance and / or chemical durability of a coating stack. British patent document GB 2,293,179 relates to an additional protective layer to improve the chemical and mechanical durability of coated substrates, while minimizing any consequential changes in optical properties. This protective layer is made up of silicon oxides or oxynitrides, or mixtures of one or more silicon oxides, nitrides and oxynitrides, and has a thickness of 10 to 100 A.
However, the inventors have found that said additional protective layer, such as that described in the aforementioned document GB 2,293,179, when deposited on some coating piles, for example on a coating stack of the type "base anti-reflective layer / infrared reflective layer / top anti-reflective layer / top coating layer that is essentially composed of at least one material selected from the set consisting of titanium, oxide Titanium and Titanium Nitride ”was not always offering good resistance during shipping and scratches may appear on the coating surface. The scratches turned out to be even more numerous and visible when the coated glazing panel was heat treated after transport. By the concept of "transport", it is understood in the present context a transfer for example with trucks, in stacks or boxes, from, for example, the coating industrialist to the wholesaler or to the transformer industrialist or to the tempering furnace.
The present invention provides glazing panels, a method of producing glazing panels and using a top skin layer as defined in the independent claims. Preferred embodiments are defined in the dependent claims.
The present invention can provide an advantageous combination of good mechanical strength, particularly good resistance to scratches during shipping, heat treatability, chemical durability, moisture resistance and stability of the parameters of production.
The topcoat layer is a combination of at least two sublayers: the first topcoat sublayer is believed to provide, among other things, a useful "reserve" when the glazing panel is to be heat treated in order to ensure a thermal protection to other parts of the coating pile during a heat treatment; and the second upper cladding sublayer is believed to provide, among other things, mechanical protection to the coated glazing panel.
It has been found to be advantageous for the topcoat layer to comprise a first topcoat sublayer, located below the second topcoat sublayer, which is essentially composed of at least one material selected from the set consisting of titanium. , titanium oxide and titanium nitride. An advantage of the first topcoat sublayer of the present invention is that it can provide the glazing panel with particularly good chemical durability during storage, for example prior to heat treatment and / or assembly, with a means to control production tolerances and the production process. These can be combined with an ability to provide thermal protection to other parts of the coating pile during a heat treatment. Preferably, the first and second sub-layers of top coat are in direct contact with each other, but in other embodiments, yet another sub-layer may be present between them. Even more preferably, the top coat layer is composed of two top coat sub-layers. However, in some embodiments the topcoat layer may comprise additional sublayers, for example located below the first topcoat sublayer.
ES 2 425 365 T3
The first topcoat sublayer may comprise a material other than those mentioned above, for example, it may be composed of, may comprise or be based on:
Ti, Zr, Hf, V, Nb, Ta, Cr or their mixtures or a mixture of at least one of these metals with Al and / or B or an oxide, a sub-stoichiometric oxide, a nitride or an oxynitride of Ti , Zr, Hf, V, Nb, Ta, Cr or their mixtures, or an oxide, a sub-stoichiometric oxide, a nitride or an oxynitride that is a mixture of at least one of these metals with Al and / or B.
The first upper cladding sublayer may have a geometric thickness in the range of 20 to 100 A, preferably in the range of 20 to 80 A or 20 to 50 A or 20 to 40 A or 20 to 30 A , and still more preferably in the range of 25 to 30 A. Thicknesses of at least 20 A can allow the avoidance of damage when the glazing panel is heat treated, and thicknesses of not more than 100 A, preferably 80 A or 50 A, can avoid too great a decrease in the luminous transmittance of the coated glazing panel.
The second upper coating sublayer may be composed essentially of a silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon carbonitride, silicon oxycarbide or silicon oxycarbonitride. Preferably, this layer is deposited by a vacuum deposition technique, particularly magnetron sputtering. The target used to deposit said layer can be made of pure Si or Si doped with, for example, one or more of the elements Al (for example 8% Al in the Si target), Zr, Ti, NiCr, Ni , B or Sb, as is well known in the art. The second topcoat sublayer can consequently incorporate relatively small amounts of said doping agent without departing from this invention. SiC targets can also be used, such as the Carborundum Company FG90 target.
The geometric thickness of the second upper cladding sublayer is in the range of 15 to 30 A. Below 10 A, the second upper cladding sublayer may not be thick enough to protect the cladding stack from scratches, for example during transportation. Furthermore, when the coated glazing panel is heat treated after formation or after formation and transportation, we have found that thicknesses of the second upper coating sublayer above 50 A can cause unacceptable scratches. These latter scratches, which appear after a heat treatment of the coated glazing panel, appear to be actually "dendrites" that reveal areas of fragility in the coating, that is, a weakness of the coating itself when it is being subjected to a heat treatment. It appears that said dendrites are formed along the paths where mechanical contact has been made before a heat treatment, showing, at the macroscopic level, some "scratches" that make the glazing panel unusable. When the first topcoat sublayer is composed of, comprises or is based on Ti or one of its compounds mentioned above, the geometric thickness of the second topcoat sublayer is preferably in the range of 15 to 25 A.
Preferably, when the second upper coating sublayer is essentially composed of an oxide of silicon, this oxide is fully oxidized; this can provide optical advantages to the coating stack, with a fully oxidized silicon oxide layer having a lower impact on color, for example, of the entire coating stack. Alternatively, the second overcoat sublayer may consist essentially of a sub-stoichiometric silicon oxide.
Preferably, the second upper cladding sublayer is exposed to air, ie it is the outermost layer of the cladding stack. This can provide particularly good results in terms of strength and heat treatability.
In a preferred embodiment, the topcoat layer comprises a first topcoat sublayer consisting essentially of a titanium nitride, having a geometric thickness in the range of 20 to 40A, and a second topcoat sublayer upper that is essentially composed of an oxide of silicon, having a geometric thickness in the range of 15 to 25 A.
The combination of properties that can be provided by the present invention has particular advantages over heat treatable and heat treated glazing panels. However, the invention can also be used with respect to glazing that is not heat treated. The term "heat treatable glazing panel" as used in the present context means that the glazing panel supporting the cladding stack is adapted to be subjected to a bending and / or thermal tempering and / or tempering operation. heat curing and / or another heat treatment process without the fog of the glazing panel treated in this way exceeding a value of 0.5, and preferably without the fog exceeding the value of 0.3. Such heat treatment processes may involve heating or exposing the supporting glazing to the cladding stack or to a temperature greater than about 560 ° C located, for example, between 560 ° C and 700 ° C in the atmosphere. Other such 3 processes
ES 2 425 365 T3 heat treatment can be the sintering of a ceramic or enamel material, the hermetic sealing in a vacuum of a double glazing and / or the calcination of a low reflectivity coating or an anti-glare coating applied by a process. wet coating. The heat treatment process, especially when it is a bending and / or heat tempering and / or heat hardening operation, can be carried out at a temperature of at least 600 ° C for at least 10 minutes, 12 minutes or 15 minutes, at least 620 ° C for at least 10 minutes, 12 minutes, or 15 minutes, or at least 640 ° C for at least 10 minutes, 12 minutes, or 15 minutes.
The coating layers are preferably deposited by a vacuum deposition technique, particularly magnetron sputtering.
Glazing panels according to the invention may comprise one or more infrared ray reflective layers. These layers, which can be made of, for example, silver, act to reflect incident infrared radiation. The dielectric anti-reflective layers that sandwich the infrared reflective layers serve to reduce the reflection of the visible portion of the spectrum, which the silver layers would otherwise cause.
Each antireflective dielectric layer may be composed of a single layer or may comprise two or more sublayers that together form the antireflection dielectric layer. The anti-reflective dielectric layers, or at least a portion of the anti-reflective dielectric layers, may comprise an oxide, for example an oxide comprising zinc and tin and / or zinc and aluminum.
The coating stack may comprise one or more barrier layers located below and / or above the infrared reflective layer, as is known in the art. Barriers of, for example, one or more of the following materials can be used: Ti, Zn, Cr, "a stainless steel", Zr, Nb, Ni, NiCr, NiTi, ZnTi and ZnAl. Said barriers can be deposited as metallic layers, as sub-oxides (ie partially oxidized layers) or as fully oxidized oxides. Alternatively, nitrided barrier layers can also be used. Each barrier layer can be composed of a single layer or it can comprise two or more sublayers that together form the barrier layer. The barrier layer may comprise a first barrier layer in a substantially metallic form, eg comprising nickel and chromium, and a second barrier layer placed above it, with a different composition than the first barrier layer ( that eg comprises titanium), which is in a form selected from the set consisting of oxides, sub-stoichiometric oxides, nitrides, sub-stoichiometric nitrides, oxynitrides and sub-stoichiometric oxynitrides.
We have also found that the best tool to simulate what a coated glazing panel is subjected to when transported is the Automatic Web Rub Test (with the acronym AWRT). A piston covered with a cotton cloth (reference: CODE 40700004 supplied by ADSOL) is brought into contact with the coating and oscillates on the surface. The piston supports a weight in order to have a force of 33 N acting on a finger having a diameter of 17 mm. Cotton abrasion on the coated surface will damage (remove) the coating after a number of cycles. The test is used to define the threshold before the coating fades (by removing the top layer) and / or before scratches appear on the coating. This test is carried out for 10, 50, 100, 250, 500 and 1,000 cycles, at separate distances above the sample. The sample is observed under an artificial sky in order to determine if discoloration and / or scratches can be seen on the sample. The AWRT rating indicates the number of cycles that does not provide any degradation or that provides very slight degradation (not visible to the naked eye under a uniform artificial sky located at a distance of 80 cm from the sample). A “-” or a “+” is indicated after the AWRT rating depending respectively on whether slight scratches are appearing or no scratches at all. Preferably glazing panels according to the invention show AWRT values of at least 250, more preferably of at least 500.
The glazing panel coating stack of the present invention may be such that if applied on a 4mm transparent sheet of glass it could give a TL measured with illuminant C greater than about 25%, 30%, 35%, 40% , 45%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%. A heat treatment can cause an increase in the luminous transmittance (TL) of the glazing panel. Such an increase in TL can be advantageous to ensure that this TL is high enough for the glazing panel to be used in glazing with high light transmittance, for example in motor vehicle windshields or in architectural applications where it is desired that the glazing monolithic coated glazing panel has a TL greater than about 25%, 30%, 35%, 40%, 45%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, or in double glazed units where you want the double glazed unit to have a TL greater than about 55%, 60%, 65%, 70%, 75%, 80% or 85%. The TL may increase in absolute terms during a heat treatment by, for example, a value greater than about 2.5%, greater than about 3%, greater than about 4%, greater than about 6%, greater than about 8%, or greater than about 10%.
ES 2 425 365 T3
Glazing panels according to the invention may be suitable for assembly in a double glazing unit. They can be adapted, for example, for an assembly in a double glazing unit with the cladding stack in position 3 (inner surface of the inner glass sheet) or in position 2 (inner surface of the outer sheet of glass. ). At least one of the glazing panels that form the double glazing unit can be heat treated prior to assembly in the double glazing unit.
Embodiments of the invention will now be described, by way of example only, in conjunction with comparative examples.
The coating piles have been magnetron sputtered onto glass substrates in accordance with the tables below. The coating stacks are all described as exiting from the magnetron sputtering coater. The thickness of the glass for all Examples is 6 mm, except for Example 9, where it is 2.6 mm. Similar results are to be expected for glass with a different thickness, for example 4mm.
In Examples 1 to 6 and 11 and Comparative Examples 1 to 11, the coating stack is always the same, except for the top coating layer. The antireflection layers comprise mixed zinc and tin oxides in various proportions: Zn (50) Sn (50) Ox which means a mixed oxide with 50% Zn and 50% Sn, and Zn (90) Sn (10) Ox which means a mixed oxide with 90% Zn and 10% Sn. Actually, the exact composition of the target used to provide the Zn (50) Sn (50) Ox layer is Zn: 52% Sn: 48% by weight of these metals on the target. It corresponds to the composition that makes it possible to easily form a zinc stannate, known in the art for its blocking properties during heat treatments.
Comparative Examples 1 and 2 illustrate that a topcoat layer comprising a single TiN underlayer shows poor results in the AWRT test, with the coating deteriorating after less than 50 cycles, even when the thickness of the TiN underlayer is higher.
Comparative Examples 3 through 7 and Examples 1 through 3 illustrate the addition of a second SiO2 overcoat sublayer on top of a first TiN overcoat sublayer, these SiO2 sublayers showing different thicknesses. Comparative Example 3 shows that the addition of a 10 A SiO2 overcoat sublayer does not give better results in the AWRT test. Examples 1 to 3 and Comparative Examples 4 to 7 however show similar and good AWRT results, with SiO2 topcoat sublayers of from 15 to 300 A. However, these coating stacks differ from each other in their ability to be heat treated, eg tempered, showing no scratches after tempering. Comparative Examples 4 to 7, with SiO2 thicknesses between 36 and 100 A, show scratches both after tempering and after transport (simulated by an AWRT test) and after tempering. Whereas Examples 1, 2 and 3, with SiO2 thicknesses of 15, 25 and 300 A, offer the advantage of resisting well to the AWRT test and therefore transport, and of not showing scratches after tempering. Examples 1 and 2, which are a part of this invention, are therefore coatings offering good mechanical strength, eg good transport resistance, which have the advantage of being heat treatable. Referring to Example 3, which is not part of this invention, note that due to the increased thickness of SiO2, a color change may appear compared to the coated glazing panel without the SiO2 underlayer.
Comparative Examples 8, 9 and 11 illustrate the advantage of a first TiN topcoat sublayer to ensure good heat treatability and stability of the coated glazing panel.
Comparative Example 10 illustrates the advantage of having the second SiO2 overcoat sublayer on top of the first TiN overcoat sublayer in order.
Examples 4, 5 and 6 illustrate other embodiments of the invention: a first Ti topcoat sublayer, or a second SiC topcoat sublayer. Example 4 shows before heat treatment a light transmittance of 82%, an emissivity of 0.070 and an electrical resistance of 6 Ω / o, and after heat treatment a light transmittance of 89%, an emissivity of 0.045 and an electrical resistance 4.5 Ω / o. Example 6 shows a light transmittance of 78% before a heat treatment, and 89% after a heat treatment. Example 11 illustrates a first Zr overcoat sublayer.
Examples 7 to 9 illustrate the application of the invention to double silver coating stacks, with different first sub-layers of top coating, ie TiN, Ti and TiO2. Examples 7 and 8 are heat treatable coatings that offer high selectivity; they show a luminous transmittance of 74% before tempering and 81% after tempering, an emissivity of 0.018 and an electrical resistance per square section of 1.6 Ω / o. A glazing panel according to Example 9 can be used in the production of a heatable windshield for solar control for motor vehicles. Said windshield shows
ES 2 425 365 T3 has a luminous transmittance of 77% under illuminant A, an energy transmittance of 44% and an electrical resistance per square section of 2.2 Ω / Ο.
Example 10 is a transport test of glazing panels according to the invention (glass sheets supporting a coating stack according to Example 1, except that the thickness of SiO2 was 20 A) and about glazing panels not in accordance with the invention (glass sheets supporting a stack of cladding according to Comparative Example 2). All these glass sheets were subjected to the following stages:
Reunion of the glass sheets in the form of stacks of 2.5 T each, with 200 mg of a powder that can be intercalated between layers per m<sup>2</sup> of glass between the glass sheets.
Issued after storage for 3 months
Truck loading with cardboard spacers between the stacks
A pressure in the cushions of 4 bar
A journey of more than 1,000 km, passing through the Alps, which is a critical case because of the curves in the roads and the abrupt changes in temperature
Inspection of glass sheets under a spot light: good results (no scratches, no discoloration) for glass sheets with the SiO2 undercoat, as opposed to glass sheets without the SO2 undercoat
Return trip to starting point, re-inspection, and always good results for glass sheets with SiO2 undercoat
Shipment of the glass sheets with the SiO2 topcoat sublayer that have traveled as described above, to a tempering oven, 6 months after the glass sheets have been coated
Handling, cutting and treatment of glass sheets
Tempering
At the exit from the furnace, no mechanical defect is visible to the naked eye.
ES 2 425 365 T3
<td rowspan="2">Example comp. 6 |</td><td>6 mm</td><td>0 <0 < LD O r * o CM rd</td><td>107 A</td><td>10 AI</td><td>0 < LD CM</td><td>100 A 275 A</td><td>38 AI</td><td>0 <or LD</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>i-</td><td>OR (Z)</td><td></td><td></td><td></td><td></td><td> 500</td><td></td><td></td><td>Scratches</td><td>fine</td><td></td><td></td><td></td><td>Scratches</td>
<td rowspan="2">Example comp. 5 |</td><td>6mm</td><td>0 <0 < LD O r * o CM rd</td><td>107 A</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>36 A</td><td>40 A</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>i-</td><td>OR (Z)</td><td></td><td></td><td></td><td></td><td> 500-</td><td></td><td></td><td>Scratches</td><td>fine</td><td></td><td></td><td></td><td>Scratches</td>
<td rowspan="2">Example comp. 4 |</td><td>6 mm</td><td>0 <0 < LD O r * o CM rd</td><td>107 A</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>36 A</td><td>36 A</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>i-</td><td>OR (Z)</td><td></td><td></td><td></td><td></td><td> 500-</td><td></td><td></td><td>Many</td><td>scratches</td><td></td><td></td><td></td><td>Scratches</td>
<td rowspan="2">Example 2 |</td><td>6 mm</td><td>0 <0 < LD O r * o CM rd</td><td>107 A</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>36 A</td><td>25 A</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>i-</td><td>OR (Z)</td><td></td><td></td><td></td><td></td><td> 500-</td><td></td><td></td><td>c (Z)</td><td>scratches</td><td></td><td></td><td>c (Z)</td><td>scratches</td>
<td rowspan="2">Example 1 |</td><td>6 mm</td><td>0 <0 < LD O r * o CM rd</td><td>107 A</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>36 A</td><td>15 A</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>i-</td><td>OR (Z)</td><td></td><td></td><td></td><td></td><td> 500-</td><td></td><td></td><td>c (Z)</td><td>scratches</td><td></td><td></td><td>c (Z)</td><td>scratches</td>
<td rowspan="2">Example comp. 3 |</td><td>6 mm</td><td>0 <0 < LD O r * o CM rd</td><td>107 A</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>36 A</td><td>10 A</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>i-</td><td>OR (Z)</td><td></td><td></td><td></td><td></td><td>OR LD</td><td></td><td></td><td>c (Z)</td><td>scratches</td><td></td><td></td><td></td><td>Scratches</td>
<td rowspan="2">Example comp. 2 |</td><td>6 mm</td><td>0 <0 < LD O r * o CM rd</td><td>107 A</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>35 A</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>i-</td><td></td><td></td><td></td><td></td><td></td><td>OR LD</td><td></td><td></td><td>c (Z)</td><td>scratches</td><td></td><td></td><td></td><td>Scratches</td>
<td rowspan="2">Example comp. 1 |</td><td>6 mm</td><td>0 <0 < LD O r * o CM rd</td><td>107 A</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>25 A</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>i-</td><td></td><td></td><td></td><td></td><td></td><td>OR LD</td><td></td><td></td><td>c (Z)</td><td>scratches</td><td></td><td></td><td></td><td>Scratches</td>
<td></td><td>Glass substrate</td><td>Anti-reflective coating base</td><td>Infrared reflective layer</td><td colspan="2">Barrier layer</td><td>Superior anti-reflective layer</td><td>I Layer 1</td><td>coating</td><td>higher</td><td>I Results of 1</td><td>AWRT on glass</td><td>untreated coated</td><td>| thermally<sup>1</sup> |</td><td>I Observation 1</td><td>after having</td><td>tempered without transport before</td><td>tempering</td><td>I Observation 1</td><td>after rehearsal</td><td>ω 73> - 1- <ω 73</td><td>c ω E CD ω o. E ω (D</td>
<img file="ES2425365T3_D0001.tif" />
1: AWRT rating indicates the number of cycles that give no degradation or very slight degradation (not visible to the naked eye under a uniform artificial sky at a distance of 80 cm from the sample). We indicate a or a "+" depending on whether there are light scratches or not at all.
2: 660 ° C - 670 ° C for 6 min 20
3: 100 cycle AWRT test
4: 670 ° C for 10 min 30.
ES 2 425 365 T3
<td rowspan="2">Example comp. 10 |</td><td rowspan="2">6 mm glass |</td><td rowspan="2">Zn (50) Sn (50) Ox 275 A Zn (90) Sn (10) Ox 100 A</td><td rowspan="2">Ag 107 A</td><td colspan="2">10 A 25A</td><td rowspan="2">Zn (90) Sn (10) Ox 100 A Zn (50) Sn (50) Ox 275 A</td><td rowspan="2">SiO2 100 A TiN 30 A</td><td colspan="3" rowspan="2"> 250-</td><td colspan="2" rowspan="2">Scratches</td><td rowspan="2">scratches</td>
<td>NiCr</td><td>OR i-</td>
<td rowspan="2">Example comp. 9 |</td><td>EE IX)</td><td>0 <0 <LD O r * or CN rd</td><td>107 A</td><td>10 A</td><td>0 < LD CN</td><td>100 A 275 A</td><td>300 A</td><td></td><td></td><td></td><td></td><td>ω σ</td><td rowspan="2">some scratches</td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>taD <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>OR (Z)</td><td></td><td></td><td> 500+</td><td></td><td>Displacement Colour</td>
<td rowspan="2">Example comp. 8 |</td><td>AND AND X)</td><td>0 <0 <LD O r * or CN rd</td><td>107 A</td><td>10 A</td><td>0 < LD CN</td><td>100 A 275 A</td><td><100 A</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>OR (Z)</td><td></td><td></td><td></td><td></td><td>Many scratches</td><td>many scratches</td>
<td rowspan="3">Reference example * |</td><td>AND AND X)</td><td>0 <0 <LD O r * or CN rd</td><td>107 A</td><td>10 A</td><td>0 < LD CN</td><td>100 A 275 A</td><td>36 A 300 A</td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="3">if color shift check the stack</td><td rowspan="3">some scratches</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>TiN SiO2</td><td></td><td></td><td> 500</td><td>No scratch</td>
<td rowspan="2">Example comp. 7 |</td><td>AND AND X)</td><td>0 <0 <LD O r * or CN rd</td><td>107 A</td><td>10 A</td><td>0 < LD CN</td><td>100 A 275 A</td><td>36 A 100 A</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>TiN SiO2</td><td></td><td></td><td> 500-</td><td></td><td>Fine scratches</td><td>scratches</td>
<td></td><td>| Glass substrate |</td><td>Base anti-reflective coating</td><td>Infrared reflective layer</td><td colspan="2">Barrier layer</td><td>Superior anti-reflective layer</td><td>Top coating layer</td><td>I AWRT Results out of 1</td><td>untreated coated glass</td><td>| thermally<sup>1</sup> |</td><td>I Observation after having 1</td><td>tempered <sup>2</sup> without transport before tempering</td><td>Observation after AWRT test and warm-up</td>
ES 2 425 365 T3
<td></td><td>EE IX)</td><td>0 <0 <LD O r * or CM rd</td><td>0 <Γ or — 1</td><td>10 AI</td><td>0 < LD CM</td><td>100 A 275 A</td><td>35 A 17 A</td><td></td><td></td><td></td><td></td>
<td>Example 6</td><td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>TiN Sic</td><td></td><td> 500-</td><td>No scratches</td><td>No scratches</td>
<td rowspan="2">Example comp. 11 |</td><td>6 mm |</td><td>0 <0 <LD O r * or CM rd</td><td>0 <Γ O r — 1</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td><10 A</td><td></td><td></td><td rowspan="2">many scratches</td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>z</td><td></td><td> 500+</td><td>Scratches</td>
<td rowspan="2">Example 5 |</td><td>AND AND X)</td><td>0 <0 <LD O r * or CM rd</td><td>0 <Γ O r — 1</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>40 A 20 A</td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>You SiO2</td><td></td><td> 500-</td><td>No scratches</td><td>No scratches</td>
<td></td><td>AND AND X)</td><td>0 <0 <LD O r * or CM rd</td><td>0 <Γ O r — 1</td><td>10 A</td><td>0 < LD CM</td><td>100 A 275 A</td><td>50 A 25 A</td><td></td><td></td><td></td><td></td>
<td>Example 4</td><td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>You SiO2</td><td></td><td> 500-</td><td>Fog / no scratches</td><td>Fog / no scratches</td>
<td></td><td>| Glass substrate |</td><td>Base anti-reflective coating</td><td>| Infrared reflective layer |</td><td colspan="2">Barrier layer</td><td>Superior anti-reflective layer</td><td>Top coating layer</td><td>I AWRT results on glass 1</td><td>| coated not heat treated<sup>1</sup> |</td><td>Observation after tempering <sup>2 </sup>without transport before tempering</td><td>Observation after AWRT test<sup>3 </sup>and the tempering</td>
IT
ES 2 425 365 T3
<td rowspan="2">Example 11 |</td><td>AND AND ID</td><td>0 <0 <LD O Γ * or CM rd</td><td>107 A |</td><td>10 AI</td><td>0 < LD CM</td><td></td><td></td><td></td><td></td><td>100 A 275 A</td><td>40 A 20 A</td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>taD <</td><td>NiCr</td><td>OR i-</td><td></td><td></td><td></td><td></td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>O fxi! Z></td><td></td><td> 500-</td><td>No scratches</td><td></td><td>No scratches</td>
<td rowspan="2">Example 9 |</td><td>EE UD (N</td><td rowspan="2">Zn (50) Sn (50) Ox 180 A Zn (90) Sn (10) Ox 120 A</td><td>1 γοετ</td><td>20 A</td><td>0 < LD CM</td><td rowspan="2">Zn (50) Sn (50) Ox 680 A Zn (90) Sn (10) Ox 110 A</td><td>0 < LD LD r — 1</td><td>20 A</td><td>0 < LD CM</td><td rowspan="2">Zn (90) Sn (10) Ox 60 A Zn (50) Sn (50) Ox 120 A</td><td>55 A 17 A</td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>CAT <</td><td>i-</td><td>OR i-</td><td>CAT <</td><td>i-</td><td>TiO2</td><td>Ó or i— (Z)</td><td></td><td> 500-</td><td>No scratches</td><td></td><td>No scratches</td>
<td rowspan="2">Example 8 |</td><td>AND AND ID</td><td rowspan="2">Zn (50) Sn (50) Ox 200 A Zn (90) Sn (10) Ox 130 A</td><td>1 γοττ</td><td>10 A</td><td>0 < LD CM</td><td rowspan="2">Zn (50) Sn (50) Ox 680 A Zn (90) Sn (10) Ox 110 A</td><td>0 < LD LD r — 1</td><td>10 A</td><td>0 < LD CM</td><td rowspan="2">Zn (90) Sn (10) Ox 80 A Zn (50) Sn (50) Ox 190 A</td><td>46 A 18</td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>CAT <</td><td>NiCr</td><td>TiO2</td><td>You SiO2</td><td></td><td> 500-</td><td>No scratches</td><td></td><td>No scratches</td>
<td rowspan="2">Example 7 |</td><td>AND AND ID</td><td>200 A 130 A</td><td>1 γοττ</td><td>10 A</td><td>0 < LD CM</td><td>680 A 110 A</td><td>155 A</td><td>10 A</td><td>or < LD CM</td><td>80 A 200 A</td><td>40 A 21 A</td><td></td><td></td><td></td><td></td><td></td>
<td>Glass</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>OR i-</td><td>Zn (50) Sn (50) Ox Zn (90) Sn (10) Ox</td><td>CAT <</td><td>NiCr</td><td>TiO2</td><td>Zn (90) Sn (10) Ox Zn (50) Sn (50) Ox</td><td>TiN SiO2</td><td></td><td> 500-</td><td>No scratches</td><td></td><td>No scratches</td>
<td></td><td>| Glass substrate |</td><td>Base anti-reflective coating</td><td>| Infrared reflective layer |</td><td colspan="2">Barrier layer</td><td>Central anti-reflective layer</td><td>| Infrared reflective layer |</td><td colspan="2">Barrier layer</td><td>Superior anti-reflective layer</td><td>Top coating layer</td><td>I AWRT Results on Coated Glass 1</td><td>| not heat treated<sup>1</sup> |</td><td>I Observation after tempering <sup>2</sup> 1</td><td>without transport before tempering</td><td>Observation after AWRT test<sup>3</sup> and the tempering<sup>4</sup></td>
<img file="ES2425365T3_D0002.tif" />
IT
Contents10
2 sheets
Sheet 1 Sheet 2
15 members in 10 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 04105583 | European Patent Office (EPO) | A | |
| 04105583 | European Patent Office (EPO) | A | |
| 04105583 | European Patent Office (EPO) | – | |
| 2005055816 | European Patent Office (EPO) | W | |
| 2005055816 | European Patent Office (EPO) | W | |
| 04105583 | – | – | – |
| EP20040105583 | – | – | – |
| PCTEP2005055816 | – | – | – |
| WO2005EP55816 | – | – | – |
Members15
| Document | Office | Kind | |
|---|---|---|---|
| AU2005300506A1 | Australia | A1 | |
| WO2006048462A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2006048462A3 | World Intellectual Property Organization (WIPO) | A3 | |
| EP1817264A2 | European Patent Office (EPO) | A2 | |
| KR20070085962A | Republic of Korea | A | |
| CN101068755A | China | A | |
| RU2007121367A | Russian Federation | A | |
| US2009258222A1 | United States of America | A1 | |
| UA92901C2 | Ukraine | C2 | |
| RU2410340C2 | Russian Federation | C2 | |
| CN101068755B | China | B | |
| AU2005300506B2 | Australia | B2 | |
| EP1817264B1 | European Patent Office (EPO) | B1 | |
| ES2425365T3This record | Spain | T3 | |
| PL1817264T3 | Poland | T3 |
Numbers
- Publication
- 2425365
- Publication, DOCDB
- 2425365
- Publication, EPODOC
- ES2425365T
- Application
- 5803449
- Application, DOCDB
- 05803449
- Application, EPODOC
- ES20050803449T
Titles2
- Spanish
- Panel de acristalamiento
- English
- Glazing panel
Classification
- CPC, 12
- C03C17/36
- C03C17/34
- C03C17/3618
- C03C17/3626
- C03C17/3634
- C03C17/3639
- C03C17/3644
- C03C17/3652
- C03C17/366
- C03C17/3681
- C03C2217/78
- Y10T428/265
- IPC, 1
- C03C17 36