Glazing panel

These Invention relates to glazing panels and particularly, but not limited to, Sun protection glazing panes which, after application of a sunscreen filter a heat treatment to be subjected.

The <patcit><text>EP 233 003 A</text></patcit> describes a glazing panel which is applied by sputtering a optical filter having the structure glass substrate / SnO₂-Basisdielektrikum / First metallic barrier of Al, Ti, Zn, Zr or Ta / Ag / second metallic Barrier layer of Al, Ti, Zn, Zr or Ta / SnO outer₂-Dielectric wearing. The optical filter is designed so that it a significant Part of the incident radiation in the infrared range of the spectrum blocked while he passage of a significant portion of the incident radiation enables in the visible region of the spectrum. In this way acts the filter in that the heating effect of incident Sunlight is reduced while good visibility through the glazing is made possible, and the filter is particularly useful for Automotive windshields suitable.

at this type of structure affects the Ag layer in that incident Infrared radiation is reflected. To exert this effect must they are maintained as silver metal rather than silver oxide and must not be contaminated by adjacent layers. The dielectric layers surrounding the Ag layer is sandwiched, serve the reflection of the visible region of the spectrum to decrease, which would otherwise be caused by the Ag-layer. The second barrier serves to prevent oxidation of the Ag layer while the sputtering of the above lying dielectric SnO₂Layer in a oxidizing atmosphere. This barrier layer is during this process is at least partially oxidized. The main importance the first barrier layer is to provide an oxidation of the silver layer while heat treatment the coating (eg, during bending and / or tempering) of the glazing panel thereby prevent them itself is oxidized, rather than a passage to allow oxygen to the Ag layer. This oxidation of Barrier during heat treatment causes an increase in the TL (light transmittance) of the glazing panel.

The <patcit><text>EP 792 847 A</text></patcit> describes a heat treatable Sun protection glazing panel which is based on the same principle and the structure / Zn barrier / Ag / Zn barrier / ZnO dielectric / Zn barrier / Ag / Zn barrier / ZnO dielectric comprising glass substrate / ZnO dielectric. The Zn-barrier layers, the positio below each of the Ag layers ned are intended for heat treatment completely are oxidized and are used the Ag layers from oxidation to protect. It is known that a structure with two spaced Ag layers rather than a single Ag layer, the selectivity of the filter elevated.

The <patcit><text>EP 275 474 A</text></patcit> describes a heat treatable Sunscreen-disc having the structure glass substrate / zinc stannate dielectric / Ti barrier / Ag / Ti barrier / zinc stannate dielectric. Ti barrier layers be in this type of heat treatable Structure generally preferred because of their high affinity for oxygen and the relative ease with which it is oxidized to form titanium oxide can be.

According to a Aspect, the present invention provides a glazing panel ready Claim 1.

The Providing at least one of the anti-reflection layers that a mixture of Zn and one of the specified additional includes materials provides an advantageous combination of properties ready. The antireflection film has not only the main task of preventing excessive reflection run in the visible region of the spectrum, but they also must as compatible with the other layers in the coating stack, mechanical and chemically resistant and be suitable for the production in an industrial scale.

to Deposition of the coating layers can comprise any suitable Procedures or any suitable combination of methods be used. For example, evaporation (thermal or by means of electron), a Flüssigkeitspyrolyse, a chemical Vapor deposition, vacuum deposition and sputtering, particularly conducted a magnetron are, with the latter method is particularly preferred. Different layers of the coating stack may under Using various techniques are deposited.

The Anti-reflection layer according to the present Invention, the following advantageous Kombina&lt;?page 3?&gt;tion provide: <ul><li>• thermal stability when heating the glazing panel is, for example during tempering and / or bending. It should be noted that the Using the present invention the degradation of the infrared reflecting Layer compared to com- parable structures in which eg known ZnO or SnO₂-Antireflexionsschichten be used, may reduce</li><li>• simplicity and controllability of deposition: the antireflective layer according to the present Invention may be deposited more easily and controlled such as Al₂O₃ or SiO₂, While Al₂O₃ and SiO₂ show good thermal stability level, they are under using common Sputtering difficulties deposit</li><li>• Mechanical Resistance: The antireflection film according to the present Invention, without impairing the mechanical resistance the coating used. In particular, it shows in Pummeltests a good performance when the glazing panel laminated in a Structure is used</li><li>• compatibility with Ag: crystallisation of the Ag layer The influences their optical Characteristics. A pure ZnO layer adjacent the Ag can to to excessive crystallization of Ag and to problems of haze lead in the coating, especially during the heat treatment. However, if an anti-reflection layer is composed of ZnO, can insufficient recrystallization of the Ag layers are present, resulting in a level of infrared reflection and a level of electrical conductivity leads in the coating, those available under the Optimum lie. The present invention can be used to favor crystallisation to a sufficient degree to provide good infra-red reflective properties provide while excessive turbidity avoided is. In particular, the present invention can be compared an anti-reflection layer made of TiO₂ composite is providing an advantageous crystallization. One possible explanation for this could be that the presence of the material X in the crystal grain growth Zinkoxidstruktur may decrease in the mixed oxide layer, particularly perpendicularly to the substrate. This can more amorphous to a less crystalline, Structure lead, which reduces diffusion that might otherwise at crystal grain boundaries can take place</li><li>• Production cycle time: An oxide layer which is a mixture of Zn and at least to one of the specified additional These materials, in particular if the additional Material Ti, Ta, Zr, Nb, Bi or a mixture of these metals, generally higher Index of refraction than antireflective layers such as ZnO and SnO₂Which used used in similar structures be, and can be deposited more quickly than known yet Antireflective layers having relatively high refractive indices, such as eg TiO₂, Thus, this can improve enable the production cycle time</li><li>• Good Selectivity: The higher Refractive index can also addition, an increase in selectivity facilitate the coating stack, in particular then, when the additional Material Ti, Ta, Zr, Nb, Bi or a mixture of these metals.</li></ul>

The Use of the anti-reflection layer according to the present invention than the outer anti-reflective layer or as a part of the outer antireflection layer, in particular as a layer, which is exposed to the air, a provide good chemical and mechanical resistance. Further they can have good compatibility provide a lamination film, such as a PVB film when the glazing panel, for example, to form an automobile windshield are laminated or other laminated glazing panel should.

The advantageous properties of the antireflective layer according to the present Invention may optionally not be obtained when the atomic ratio X / Zn below the specified Minimum is, for example, if the material X only in the form an impurity is present or if the atomic ratio X / Zn is not sufficiently large. The atomic ratio X / Zn may be less than about 10th Further, it may be about 5 or less, or about 4 or less, or about 3 or less. This can be a sufficient amount of Zn sure in the anti-reflection layer to have advantageous properties provide.

The Infrared-reflective material is silver or a silver alloy can be, for example an alloy of silver containing one or more of Pd, Au, and Cu as an additional containing material. Such an additional Material may be in the silver alloy in an atomic ratio of 0.3 to 10%, preferably from 0.3 to 5%, and more preferably, especially then, when the additional Pd material is from 0.3 to 2%, based on the total amount of Silver and additional Metal present.

A or more of the antireflective layers may comprise an oxide, a nitride, comprise a carbide or a mixture thereof. For example, the antireflection layer include: &lt;?page 4?&gt;<ul><li>• An oxide of one or more of Zn, Ti, Sn, Si, Al, Ta or Zr, a Oxide of zinc containing Al, Ga, Si or Sn, or an oxide of indium, containing Sn</li><li>• on Nitride of one or more of Si, Al and B or a mixture (including a Doppelnitrid) nitride of Zr or Ti with one of the above said nitrides</li><li>• a Double compound such as SiO_xC_y, SiO_xN_y. SiAl_xN_y or SiAl_xO_yN_z,</li></ul>

The Anti-reflection layer may be a single layer or it may comprise two or more layers having different compositions. An oxide of zinc, preferably, a zinc oxide containing at least one contains from Sn, Cr, Si, B, Mg, In, Ga and preferably Al and / or Ti, is particularly preferred because the use of these materials, the stable Formation of an adjacent infra red reflecting layer with a high crystallinity can facilitate.

according to claim 2, the advantageous combination of properties associated with the Anti-reflection layer according to the present invention available is used in a coating stack having two, or comprises more than two spaced infra-red reflecting layers.

Several spaced infra-red reflecting layers may be used to provide the glazing panel with a selectivity that is greater than 1.5 or 1.7 is.

Especially advantageous properties can are obtained when the additional material X <ul><li>• in the Essentially of Ti</li><li>• out Ti with one or more additional Materials from the specified group of materials, such as Ti and Al</li><li>• in the Essentially of Al</li><li>• out Al with one or more additional Materials from the specified group of materials</li></ul>consists.

The Combination of properties obtained by the present invention can be provided, has relative heat treatable and heat-treated Glazing panes particular advantages. Nevertheless, the invention also respect Glazings are used which are not heat treated. The term "heat treatable glazing panel" which uses here is means that the glazing panel, the coating stack of the wearing, is adapted so that a bending and / or thermal tempering and / or thermal curing and / or a heat treatment method perform, without the haze the so treated glazing panel exceeding 0.5, and preferably, without the haze Exceeds 0.3. The term " Substantially haze free, heat treated Glazing panel " as used herein, represents a glazing panel carrying a coating stack, and bent after the deposition of the coating stack and / or thermally annealed and / or thermally hardened been subjected has been and / or to a further heat treatment is, and the turbidity which does not exceed 0.5 and preferably does not exceed 0.3. Such heat treatment processes can heating or exposing the glazing, the coating stack to wearing, on one or a temperature greater than about 560 ° C, for example, between 560 ° C and 700 ° C to the air include. Other such heat treatment processes may be a Sintering a ceramic or enamel material, a vacuum sealing a double glazing unit and calcination of a wet applied coating with low reflectivity or a wet be applied anti-glare coating. The heat treatment process can particular when this is a bending and / or thermal Annealing and / or a thermal curing process is in a temperature of at least 600 ° C for at least 10 min, 12 min or 15 min, at 620 ° C for at least 10 min, 12 min or 15 min, or at least 640 ° C for at least 10 min, are carried out 12 min or 15 min.

The Providing the thickness of the mixed oxide according to the present Invention so that it has a thickness of at least 50 Å, may provide a sufficient quantity so that a worthwhile or noticeable effect occurs. The geometrical thickness of the mixed oxide according to the present Invention, at least 80 Å, 100 Å, 120 Å, 140 Å or be 160 Å.

A Oxide layer, which is a mixture of Zn and at least to one of the specified additional These materials can be used to an anti-reflection layer, more than one anti-reflective layer or, preferably, all the anti-reflection layers to impart advantageous properties in the coating stack. The use of all anti-reflection layers of the coating stack , the process control and ordering and storage of simplify required targets. If more&lt;?page 5?&gt;as one of the anti-reflection layers comprises an oxide layer which is a mixture of Zn to and at least is one of the specified additional materials, can Such oxide layers have the same or substantially the same have composition.

A particularly advantageous combination of the properties discussed above can be obtained when the atomic ratio X / Zn in the range of about From 0.12 to 1, preferably preferably from about 0.15 to 0.6, and more is from about 0.2 to 0.5.

The Oxide layer according to the present Invention, for use with one or more of the anti-reflection layers with a layer comprising a nitride of aluminum or a nitride of silicon or a mixture thereof, be compatible and advantageously combined in one or more of these layers be. This can provide a particularly good stability Wärmesta, particularly when the combination in the base antireflective layer and / or the outer antireflection layer is used.

Of the Filter stack may comprise one or more barrier layer (s), the under and / or over the infrared-reflective layer is or are what is known is. It can Barrier layers, for example, from one or more of the following materials be used: Ti, Zn, Ta, Cr, "stainless steel", Zr, Ni, NiCr, ZnTi, NiTi and ZnAl. Such barrier layers may for example, as metallic layers or as sub-oxides (ie partially oxidized layers) are deposited. Alternatively, nitrided barrier layers may be used.

A or several such) barrier layer (s) may or may same materials as the mixed oxide layer, especially as the adjacent mixed oxide layer comprise. This can make the handling ease of targets and control of deposition conditions and in the latter case a good adhesion between the layers and thus good mechanical durability of the coating stack provide.

A heat treatment may cause an increase in the TL of the glazing panel. A Such an increase in TL may be advantageous in that it is ensured may be that the TL is sufficiently high so that the glazing panel in a vehicle windshield can be used. The TL can be based on the absolute value during the heat treatment for example, by more than about 2.5%, more than about 3%, more than about 5 %, More than about 8% or greater than about 10% increase.

According to a further aspect the present invention provides a method ready for manufacturing a glazing panel according to claim 15th such a The method can be prepared by eg heat treated architectural or building glazing panes used vehicle glazings and particularly windscreens will.

below Examples of the present invention with reference to the <figref idrefs="S18">1</figref> described in which it is a cross-sectional through a glazing panel prior to a bending and tempering operation is (for a simple illustration, the relative thicknesses of the glazing panel and the coating layers are not shown to scale).

example 1

The <figref idrefs="S18">1</figref> shows a heat treatable Coating layer with a double Ag layer formed on a glass substrate has been deposited by magnetron sputtering and substantially the following sequential structure: &lt;?page 6?&gt;<img img-content="tb" img-format="tif" he="72" wi="162" file="00080001.tif" />in which ZnTiO_x a mixed oxide, the Zn and Ti contains and in this example, by reactive sputtering of a target, Zn which is an alloy or a mixture of Ti and is, is deposited in the presence of oxygen. The ZnTiO_yBarrier layers are in accordance with Sputtering a target which is an alloy or a Mixture of Zn and Ti is, in an argon-rich, oxygen-containing the atmosphere deposited, to deposit a barrier layer that does not completely oxidized is.

alternative can be a mixed oxide layer by sputtering a target, wherein it is a mixture of zinc oxide and an oxide of a material X is, in particular, in argon gas or an argon-rich, oxygen-containing the atmosphere are formed.

Of the Oxidation state in each of the dielectric base, middle and outer ZnTiO_xlayers must not necessarily be equal. According to the oxidation state needs in each of the ZnTiO_yBarrier layers not be the same. equally has the Ti / Zn ratio not for all layers be the same. For example, a barrier layers Another Ti / Zn ratio have as the dielectric antireflection layers and the dielectric antireflection layers may different Ti / Zn ratios exhibit.

Each about that lying barrier protects the respective underlying silver layer from oxidation while sputter deposition of respective overlying ZnTiO_xOxide layer. While further oxidation of these barriers during the coating's deposition of its about that can take place lying oxide, a portion remains this Barrier layers, preferably in the form of an oxide that is not fully oxidised is, to a barrier layer for the subsequent heat treatment the glazing panel to provide.

These particular glazing panel is intended in a laminated vehicle windscreen are included and has the following properties:

<img img-content="tb" img-format="tif" he="36" wi="162" file="00090001.tif" />

note 1: Measured for a monolithic glazing panel with coating prior the heat treatment.

note 2: Measured following heat treatment at 650 ° C 10 min and then Bending and tempering, and lamination with a 2 mm clear glass and 0.76 mm clear PVB.

&lt;?page 7?&gt;

The heat treatment preferably causes substantially complete oxidation all barrier layers, so that the structure of the coating stack after heat treatment is as follows:

<img img-content="tb" img-format="tif" he="84" wi="163" file="00090002.tif" />

The about that lying TiO_x Layers may partially or completely to TiO₂ be oxidized, and depending on the conditions of heat treatment, of the glazing panel is subjected.

example 2

The Example 2 is similar to Example 1, However ZnAlO is_x in the anti-reflection layers used. The coating stack and properties of the Example are given below. <img img-content="tb" img-format="tif" he="72" wi="163" file="00100001.tif" />in which ZnAlO_x a mixed oxide, the Zn and Al contains and in this example, by reactive sputtering of a target, Zn which is an alloy or a mixture of Al and is, is deposited in the presence of oxygen. The Ti barriers be deposited by sputtering a titanium target in a substantially inert, oxygen-free atmosphere is deposited.

At least part of it lying barrier layers <figref>16</figref>. <figref>20</figref> While the Deposition of each about lying oxide oxidized. Nevertheless some remains of this Barrier layers preferably in metallic form, or at least in the form of an oxide that is not fully oxidised to provide a barrier layer for a subsequent heat treatment the glazing panel to provide.

These particular glazing panel is intended in a laminated vehicle windscreen included &lt;?page 8?&gt;be and has the following characteristics:

<img img-content="tb" img-format="tif" he="36" wi="162" file="00110001.tif" />

note 1: Measured for a monolithic glazing panel with coating prior the heat treatment.

note 2: Measured following heat treatment at 625 ° C for 14 min and then Bending and tempering, and lamination with a 2 mm clear glass and 0.76 mm clear PVB.

The heat treatment preferably causes substantially complete oxidation all barrier layers, so that the structure of the coating stack after heat treatment is as follows:

coating stack after heat treatment <img img-content="tb" img-format="tif" he="79" wi="162" file="00110002.tif" />

In an alternative embodiment, the dielectric base layer of Example 2, a first layer from ZnAlO_x with an atomic ratio of Al / Zn from 0.12 to 1 and an overlying layer of ZnAlO_x be with an atomic ratio of Al / Zn, the smaller than that of the first layer, such as 0.1.

Possibly can additional Layers, be disposed below or between the film stacking arrangement without departing from the invention.

In addition to the advantageous optical properties that can be obtained is, each of the examples a coating layer prepared, for example, in an electrically heated automobile windshield by The addition suitably arranged electrical connecting elements electrically can be heated to a demister and / or defrosting function provide.

The Color coordinates of the examples are in particular for motor vehicle windscreens suitable since they in reflection a neutral or slightly blue have appearance when the windshield at an angle in of the vehicle body is mounted. For other applications, such as Architectural applications, the reflection color can in known per se By adjusting the thicknesses of the dielectric layers and / or the silver layer (s) can be adjusted.

&lt;?page 9?&gt;

The TL of the glazing panel may be adjusted so that they for desired Application fits. For example, then,<ul><li>• if the Glazing panel to be used as a windscreen for the European market to which TL selected will be larger than 75% (according to European regulations)</li><li>• if the glazing panel to be used as a windscreen for the US market to which TL selected will be larger than 70% (according to the US regulations)</li><li>• if the glazing panel used as a vehicle front side window to which TL selected will be larger than 70% (according to the European regulations)</li><li>• if the glazing panel as the vehicle rear side window or rear window as for a Vehicle is to be used, which are selected TL so that they between about 30% and 70%</li></ul>

A Such adjustment of TL may be achieved for example by <ul><li>• To adjust the thicknesses of the layers of the coating stack, in particular the thicknesses of the dielectric layers and / or the infrared reflecting Layers)</li><li>• Combine the coating stack with a tinted glass substrate </li><li>• Combine the coating stack with a tinted PVB or other laminating</li></ul>

glossary

If it is clear from the context requires otherwise, have the following specified terms in this description have the following meanings:

&lt;?page 10?&gt;

<img img-content="tb" img-format="tif" he="182" wi="164" file="00130001.tif" />