Solar control coatings with discontinuous metal layer

[0001] The invention relates generally to sunscreens, and in one particular embodiment of the invention, a sunscreen with increased absorbance and asymmetric reflectance. Technical considerations [0002] Sunscreens are known in the field of transparent architectural and automotive materials. Such sunscreens block or filter selected ranges of electromagnetic radiation, for example in the infrared or ultraviolet range of solar radiation, to reduce the amount of solar energy entering the vehicle or building. This reduction in solar permeability helps to reduce the load on the cooling units of the vehicle or buildings. For automotive applications, transparent materials (such as a windshield) typically should have a relatively high visible light transmission, for example greater than 70 percent so that passengers can see the exterior of the vehicle. In architectural applications, the transmission of visible light may be lower. In some architectural applications, it may be desirable to have a reflective outer surface to reduce the visibility of the interior of the building in order to preserve as much privacy as possible, allowing visible light to enter the building and allowing outside workers to look outside. Such transparent materials are also typically tempered or heat treated to increase safety. so that passengers can see the outside of the vehicle. In architectural applications, the transmission of visible light may be lower. In some architectural applications, it may be desirable to have a reflective outer surface to reduce the visibility of the interior of the building in order to preserve as much privacy as possible, allowing visible light to enter the building and allowing outside workers to look outside. Such transparent materials are also typically tempered or heat treated to increase safety. so that passengers can see the outside of the vehicle. In architectural applications, the transmission of visible light may be lower. In some architectural applications, it may be desirable to have a reflective outer surface to reduce the visibility of the interior of the building in order to preserve as much privacy as possible, allowing visible light to enter the building and allowing outside workers to look outside. Such transparent materials are also typically tempered or heat treated to increase safety. In some architectural applications, it may be desirable to have a reflective outer surface to reduce the visibility of the interior of the building in order to preserve as much privacy as possible, allowing visible light to enter the building and allowing outside workers to look outside. Such transparent materials are also typically tempered or heat treated to increase safety. In some architectural applications, it may be desirable to have a reflective outer surface to reduce the visibility of the interior of the building in order to preserve as much privacy as possible, allowing visible light to enter the building and allowing outside workers to look outside. Such transparent materials are also typically tempered or heat treated to increase safety.

The performance is improved by applying on one or more substrates a transparent coating (16) with a high refractive index under the metal film. The material with a high refractive index is preferably a synthetic bismuth oxide with a high oxygen content that facilitates the cost-effective production of the sun film.

US 2004/0146645 A1 describes a product having a sealed laminar edge, e.g. a car laminate and a multiple glazed unit comprising a pair of glass sheets in a fixed position relative to each other. The sputter coating is deposited on the main surface of one of the plates and includes at least one combination of a metal layer, e.g. a silver layer, and a dielectric film. The discontinuities of the metal film at the marginal edges of the coated plate provide gaps in the metal film that inhibit or resist corrosion of the metal film. The discontinuities include (1) crack lines or segments in the coating, (2) changes in coating thickness due to abrasion of the coating, and (3) discontinuous areas of the coating spaced apart at the marginal edges of the coated plate. The discontinuities can be produced in the metal layer using laser technology, with an abrasive surface, with a coating mask and / or with coating removal. Japanese Patent Application No. 2000180759 describes transparent laminates suitable as an electromagnetic radiation filter comprising a transparent substrate, thin metal films, each with a thickness of 1-30 nm and transparent thin films, each with a thickness of 10-150 nm, which are laminated

EP 2 552 846 alternately, and these thin films are connected to the surface of the transparent substrate to form a transparent layered block. At least one thin metal film in a transparent layered block is not a continuous film.

[0004] In one known architectural transparent material, the thermally reinforced glass substrate is coated with a sunscreen comprising an absorbing substance, such as a nickel-chrome alloy (e.g., Inconel).^®), for absorbing visible light to darken the window. Such a transparent material also includes a relatively thick, continuous, infrared reflection metal layer for reflecting solar energy, such as solar infrared energy. However, the problem associated with this known transparent material is that the glass substrate must be cut to the desired shape and hardened before applying the coating. If the coating is applied before the glass substrate is toughened, the resulting coating becomes fogged during the high-temperature processing necessary in the hardening process. This haze is aesthetically undesirable.

[0005] It would be desirable to be able to apply a sunscreen to unheated glass plates and send glass sheets to the manufacturer, which would then cut the plates to the desired size for a specific task and then subject the cut pieces to hardening or heat treatment without adversely affecting aesthetic or solar properties the resulting transparent material.

SUMMARY OF THE INVENTION [0006] In one broad aspect of the invention, the coating of the invention is as defined in claim 1, comprising two or more continuous reflective infrared metal layers in combination with a subcritical (i.e., discontinuous) metal layer. The discontinuous metal layer increases the visible absorption absorption of the coating, and in combination with dielectric layers of appropriate thickness, it can also impart to the coated article an asymmetrical reflectance.

[0007] The coating according to the invention comprises a plurality of metal layers alternating with a plurality of dielectric layers, at least one of the metallic layers being a sub-critical metal layer having a discontinuous metal area.

[0008] The coated article of the present invention comprises a substrate and a stack of coatings according to the present invention on at least a portion of the substrate as defined in claim 1. The stack of coatings comprises a plurality of metallic layers and a plurality of dielectric layers, wherein at least one of the metallic layers comprises a subcritical metallic layer. having discontinuous metallic areas.

DESCRIPTION OF THE DRAWINGS [0009] The invention will be described with reference to the following drawings in which like numerals identify like parts throughout the description.

Fig. 1 is a side view (not scale) of an IGU unit having a coating according to the invention;

Fig. 2 is a side view (not scale) of a coating exhibiting features according to the invention;

Fig. 3 is a cross-sectional view (not in scale) of a subcritical metal layer with a priming layer;

Fig. 4 is a side view (not scale) of another coating exhibiting features according to the invention;

Fig. 5 is a side view (not scale) of another shell exhibiting features according to the invention.

DESCRIPTION OF EMBODIMENTS [0010] As used herein, spatial or directional terms such as "left", "right", "internal", "external", "above", "below", and the like, refer to the invention shown in

EP 2 552 846 drawing. However, it should be understood that the invention may take various alternative orientations and accordingly such terms are not considered limiting. Accordingly, unless indicated to the contrary, the numerical values ​​set forth in the following description and claims may vary depending on the desired properties sought in the present invention. At least, and not to limit the application of the equivalence doctrine to the scope of the claims, each numerical value should at least be interpreted in the light of the number of significant figures given and by the use of usual rounding techniques. In addition, as used herein, the terms "formed into", "embedded in" or "delivered to" means formed, embedded or provided with, but not necessarily in contact with, the surface. For example, the coating layer "formed on" the substrate does not exclude the presence of one or more other coating layers or films of the same or a different composition placed between the formed coating layer and the substrate. As used herein, the terms "polymer" or "polymeric" include oligomers, homopolymers, copolymers and terpolymers, e.g. polymers formed from two or more types of monomers or polymers. The terms "visible" or "visible light" refer to electromagnetic radiation with a wavelength in the range from 380 nm to 800 nm. The terms "infrared area" or "infrared radiation" refer to electromagnetic radiation with a wavelength in the range of over 800 nm to 100,000 nm. The terms "ultraviolet area" or "ultraviolet radiation" mean electromagnetic energy with a wavelength in the range from 300 nm to less than 380 nm. As used herein, the term "film" refers to a coating area with a desired or selected coating composition. A "layer" may include one or more "films" and a "coating" or "stack of coatings" may include one or more "layers". The term "asymmetrical reflectance" means that the visible reflection coefficient of the coating on one side is different from the coefficient of the coating on the opposite side. The term "critical thickness" means the thickness above which the coating material forms a continuous, uninterrupted layer and below which the coating material forms discontinuous areas or islands of the coating material, rather than a continuous layer. The term "subcritical thickness" means a thickness below the critical thickness, such that the coating material forms separated, unbonded areas of the coating material. The term "islet" means that the coating material is not a continuous layer, but that the material is embedded to form separated areas or islands.

[0011] For purposes of the following discussion, the invention will be discussed with reference to a use in an architectural transparent material such as, but not limited to, IGU (insulating glass unit). As used herein, the term "architectural transparent material" refers to any transparent material placed on a building, such as, but not limited to, a window and a skylight. However, it is to be understood that the invention is not limited to use with such architectural transparent materials, but can be implemented with transparent materials in any desired field, such as, but not limited to, laminated or non-laminated residential and / or commercial windows, insulated glass and / or transparent materials for land, air and space vehicles, underwater and submersible. Thus, it should be understood that the specifically disclosed exemplary embodiments are only provided to explain the general ideas of the invention and that the invention is not limited to these specific example embodiments. In addition, while a typical "transparent material" may have sufficient visible light transmission, so that objects can be viewed through a transparent material, in the practice of the invention "transparent material" need not be transparent to visible light, but may be translucent or opaque.

[0012] A non-limiting transparent material 10 exhibiting the features of the invention is set forth in Fig. 1. The transparent material 10 may exhibit any desired transmission and / or reflection of visible light, infrared radiation or ultraviolet radiation. For example, the transparent material 10 may have visible transmission of any desired size, e.g., greater than 0% to 100%.

[0013] An exemplary transparent material 10 of Fig. 1 is in the form of a conventional double glazing unit and comprises a first layer 12 with a first major surface 14 (surface No. 1) and an opposite second major surface 16 (surface No. 2). In the illustrated, non-limiting embodiment, the first major surface 14 is directed outside the building, i.e., is the outer major surface and the second main surface 16 is directed towards the inside of the building. The transparent material 10 also includes a second layer 18 having an outer (first) major surface (surface 3) and an inner (second) major surface 22 (surface 4) and spaced from the first layer 12. This numbering of the surface layers coincides with conventional practice in the field windows of buildings. First and second layer 12, 18 may be connected to each other in any suitable manner, such as by gluing to a conventional spacer frame 24. A gap or chamber 26 is formed between the two layers 12, 18. The chamber 26 may be filled with a selected atmosphere, such as air, or with an unreactive gas such as like argon or krypton. The sunscreen 30 (or any of the other coatings described below) is formed on at least part of one of the layers 12, 18, such as, but not limited to, at least a portion of the surface No. 2 16 or at least a part of the surface No. 3. 20. If this is desirable, the coating could also be surface # 1 or surface # 4. Examples of composite glazing units can be found, for example, in U.S. Patent Nos. 4,193,366; 4,464,874; 5,088, 258; and 5,106,663. such as by adhesive bonding to a conventional spacer frame 24. Between the two layers 12, 18 a gap or chamber 26 arises. The chamber 26 can be filled with a selected atmosphere, such as air, or a non-reactive gas such as argon or krypton. The sunscreen 30 (or any of the other coatings described below) is formed on at least part of one of the layers 12, 18, such as, but not limited to, at least a portion of the surface No. 2 16 or at least a part of the surface No. 3. 20. If this is desirable, the coating could also be surface # 1 or surface # 4. Examples of composite glazing units can be found, for example, in U.S. Patent Nos. 4,193,366; 4,464,874; 5,088, 258; and 5,106,663. such as by adhesive bonding to a conventional spacer frame 24. Between the two layers 12, 18 a gap or chamber 26 arises. The chamber 26 can be filled with a selected atmosphere, such as air, or a non-reactive gas such as argon or krypton. The sunscreen 30 (or any of the other coatings described below) is formed on at least part of one of the layers 12, 18, such as, but not limited to, at least a portion of the surface No. 2 16 or at least a part of the surface No. 3. 20. If this is desirable, the coating could also be surface # 1 or surface # 4. Examples of composite glazing units can be found, for example, in U.S. Patent Nos. 4,193,366; 4,464,874; 5,088, 258; and 5,106,663. The chamber 26 can be filled with a selected atmosphere, such as air, or a non-reactive gas such as argon or krypton. The sunscreen 30 (or any of the other coatings described below) is formed on at least part of one of the layers 12, 18, such as, but not limited to, at least a portion of the surface No. 2 16 or at least a part of the surface No. 3. 20. If this is desirable, the coating could also be surface # 1 or surface # 4. Examples of composite glazing units can be found, for example, in U.S. Patent Nos. 4,193,366; 4,464,874; 5,088, 258; and 5,106,663. The chamber 26 can be filled with a selected atmosphere, such as air, or a non-reactive gas such as argon or krypton. The sunscreen 30 (or any of the other coatings described below) is formed on at least part of one of the layers 12, 18, such as, but not limited to, at least a portion of the surface No. 2 16 or at least a part of the surface No. 3. 20. If this is desirable, the coating could also be surface # 1 or surface # 4. Examples of composite glazing units can be found, for example, in U.S. Patent Nos. 4,193,366; 4,464,874; 5,088, 258; and 5,106,663. on at least a portion of the surface No. 2 16 or at least a portion of the surface No. 3. 20. If desired, the coating could also be surface # 1 or surface # 4. Examples of glazing units can be found, for example, in U.S. Patent Nos. 4,193,366; 4,464,874; 5,088, 258; and 5,106,663. on at least a portion of the surface No. 2 16 or at least a portion of the surface No. 3. 20. If desired, the coating could also be surface # 1 or surface # 4. Examples of glazing units can be found, for example, in U.S. Patent Nos. 4,193,366; 4,464,874; 5,088, 258; and 5,106,663.

[0014] In the broad practice of the invention, the layers 12, 18 of the transparent material 10 can be of the same or different materials. Layers 12, 18 can include any desired material having any desired characteristics. For example, one or more layers 12, 18 may be transparent or translucent to visible light. By "transparent" is meant a visible transmission of more than 0% to 100%. Alternatively, one or more layers 12, 18 may be translucent. By "translucent" is meant allowing the passage of electromagnetic energy (e.g., visible light), but the dissipation of this energy so that the objects on the side opposite to the viewer are not clearly visible. Examples of suitable materials include, but are not limited to, plastic substrates (such as acrylic polymers such as polyacrylates, polyalkyl methacrylates, such as polymethyl methacrylates, polyethyl methacrylates, polypropyl methacrylates, and the like; polyurethanes, polycarbonates, polyether phthalates, such as polyethylene terephthalate (PET), polypropylene terephthalates, polybutylene terephthalates, and the like; containing polysiloxane, or copolymers of any monomers for their preparation, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the foregoing. For example, one or more layers 12, 18 may include conventional soda-lime-silica glass, borosilicate glass, or lead glass. The glass can be transparent glass. By "transparent glass" is meant non-colored or uncoloured glass. Alternatively, the glass may be glass colored in a mass or colored differently. The glass may be annealed or heat treated glass. As used herein, the term "heat treated" means tempered or at least partially tempered. The glass may be of any type, such as conventional float glass, and may be any composition having any optical properties, e.g. any value of visible transmission, ultraviolet transmission, infrared transmission and / or total solar energy permeability. By "floEP 2 552 846 at glass" is meant a glass produced in a conventional float process in which molten glass is applied to a molten metal bath and cooled in a controlled manner to form a float ribbon.

[0015] The first and second layers 12, 18 may be, for example, clear float glass or they may be colored or colored glass, or one layer 12, 18 may be transparent glass and the other layer 12, 18 be colored glass. Although not limiting the invention, examples of glass suitable for the first layer 12 and / or the second layer 18 are described in US Patent Nos. 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5 240 886; 5,388, 872; and 5,393,593. The first and second layers 12, 18 can have any desired dimensions, e.g., length, width, shape or thickness. In one exemplary transparent vehicle material, each first and second layer may have a thickness of 1 mm to 10 mm, such as 1 mm to 8 mm, such as 2 mm to 8 mm, such as 3 mm to 7 mm, such as 5 mm up to 7 mm, just like 6 mm. Non-limiting examples of glass, which may be used in the practice of the invention include transparent glass, Starphire®, Solargreen®, Solextra®, GL-20®, GL-35 ™, Solarbronze®, Solargray® glass, Pacifica® glass, SolarBlue® glass and Optiblue® glass, all commercially available from PPG Industries Inc. from Pittsburgh, Pennsylvania.

[0016] The sun coating 30 according to the invention is deposited on at least a part of at least one main surface of one of the glass layers 12, 18. In the example shown in Fig. 1, the coating 30 is formed on at least a part of the inner surface 16 of the outer glass layer 12 As used herein, the term "sunscreen" refers to a coating comprising one or more layers or films affecting the sun's properties of a coated article, such as, but not limited to, an amount of solar radiation, e.g. visible, infrared or ultraviolet radiation, reflected, absorbed, or passing through the coated article; shading coefficient; emission factor, etc. Sunscreen 30 can block,

[0017] The sunscreen 30 may be deposited by any conventional method, such as, but not limited to, conventional methods of chemical vapor deposition (CVD) and / or physical vapor deposition (PVD). Examples of CVD processes include spray pyrolysis. Examples of PVD processes include evaporation using an electron gun and vacuum evaporation (such as magnetron sputtering vapor deposition (MSVD)). Other coating methods may also be used, such as, but not limited to, sol-gel deposition. In one non-limiting embodiment of the invention, the coating 30 may be deposited by the MSVD method. Examples of devices and methods for coating MSVD will be well known to one of ordinary skill in the art and are described, for example, in US Patent Nos. 4,379,040; 4,861, 669; 4 898 789; 4,898,790; 4,900,633; 4,920,006; 4,938,857; 5,328, 768; and 5,492,750.

Islet Metal Layer An example of a non-limiting sunscreen 30 according to the invention is shown in Fig. 2. This exemplary coating 30 includes a substrate layer or a first dielectric layer 40 deposited on at least a portion of the main surface of the substrate (e.g., surface No. 2 of the first 16) layers 12). The first dielectric layer 40 may be a single layer or may comprise more than one layer of metal oxides, metal oxide oxides, nitrides, oxynitrides or mixtures thereof. The first dielectric layer 40 may be transparent to visible light. Suitable metal oxides for the first dielectric layer 40 include oxides of hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin

EP 2 552 846 and mixtures thereof. These metal oxides may contain small amounts of other substances, such as manganese in bismuth oxide, tin in indium oxide, etc. In addition, oxides of metal alloys or mixtures of metals, such as oxides containing zinc and tin (e.g., zinc cyanate, as defined herein) may be used. below), oxides of indium tin alloys, silicon nitrides, silicon aluminum nitrides, or aluminum nitrides. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 40 may be substantially a single phase film, such as a metal oxide alloy film, e.g. zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers.

For example, the first dielectric layer 40 (single film or multilamellar layer) may have a thickness ranging from 10 nm (100 A) to 60 nm (600 A), such as 20 nm (200 A) to 50 nm (500 A) ), such as 25 nm (250 A) to 35 nm (350 A), such as 25 nm (250 A) to 31 nm (310 A), such as 28 nm (280 A) to 31 nm (310 A), such as 30 nm (300 A) to 33 nm (330 A), such as 31 nm (310 A) to 33 nm (330 A). The first dielectric layer 40 may include a multi-layered structure having a first film 42, e.g., a metal oxide alloy film deposited on at least a portion of the substrate (such as the inner main surface 16 of the first layer 12) and a second film 44, e.g., a film an oxide or mixture of metal oxides deposited on the first metal oxide layer. In one not limiting form of the invention, the first film 42 may be zinc / tin alloy oxide. By "zinc / tin alloy oxide" is meant real alloys as well as mixtures of oxides. The zinc / tin alloy oxide may be the oxide obtained from the vapor deposition by magnetron sputtering from a cathode of zinc and tin. One non-limiting cathode may include zinc and tin in a 5 wt% proportion. up to 95% by weight zinc and 95% by weight up to 5% by weight tin, such as 10 wt.%. up to 90% by weight zinc and 90% by weight up to 10% by weight tin. However, other ratios of zinc to tin may also be used. One suitable metal oxide oxide that may be present in the first film 42 is zinc cyanate. By "zinc cyanate" is meant the composition ZnXSn1-XO2-X (Formula 1) where "x" ranges from greater than 0 to less than 1. For example, "X" may be greater than 0 and may be any fractional or decimal from greater than 0 to less than 1. For example, when x = 2/3, formula 1 is Zn2 / 3Sn1 / 3O4 / 3, more commonly described as "Zn2SnO4 ". The film comprising zinc stannate has one or more forms of the formula (I) in a predominant amount in the film.

[0021] The second film 44 may be a metal oxide film such as zinc oxide. The zinc oxide film may be deposited from a zinc cathode that contains other materials to improve the cathode sputtering characteristics. For example, the zinc cathode may comprise a small amount (e.g., up to 10 wt%, such as up to 5 wt%) of tin to improve the atomisation. In this case, the resulting zinc oxide film will contain a small admixture of tin oxide percentage, e.g., up to 10 wt.%. tin oxide, e.g., up to 5 wt.% tin oxide. A coating layer deposited from a zinc cathode of up to 10% by weight. tin (added to improve the cathode conductance) is referred to herein as a "zinc oxide film" even if there may be a small amount of tin. It is contemplated that a small amount of tin in the cathode (e.g., less than or equal to 10 wt%, such as less than or equal to 5 wt%.

[0022] For example, the first film 42 may be zinc cyanate and the second film 44 may be zinc oxide (e.g., 90% by weight zinc oxide and 10% by weight tin oxide). For example, the first film 42 may include zinc stannate having a thickness in the range of 5 nm (50 A) to 60 nm (600 A), such as 5 nm (50 A) to 50 nm (500 A), such as 7.5 nm (75 A) to 35 nm (350 A), such as 10 nm (100 A) to 25 nm (250 A), such as 15 nm (150 A) to 25 nm (250 A), such as 19.5 nm (195 A) to 25 nm (250 A), such as 20 nm

EP 2 552 846 (200 A) to 25 nm (250 A), such as 20 nm (200 A) to 22 nm (220 A).

[0023] The second film 44 may include zinc oxide having a thickness in the range of 5 nm (50 A) to 20 nm (200 A), such as 7.5 nm (75 A) to 20 nm (200 A), such as nm (100 A) to 15 nm (150 A), such as 10 nm (100 A) to 11 nm (110 A).

[0024] The first reflective heat and / or radiation metal layer 46 is deposited on the first dielectric layer 40. The first reflective layer 46 may include a reflective metal, such as, but not limited to, metallic gold, copper, palladium, aluminum, silver, or mixtures, alloys or combinations thereof. In one embodiment of the invention, the first reflective layer 46 comprises a metallic silver layer having a thickness in the range of 5 nm (50 A) to 30 nm (300 A), e.g., 5 nm (50 A) to 25 nm (250 A), e.g. . 5 nm (50 A) to 20 nm (200 A), such as 7 nm (70 A) to 20 nm (200 A), such as 10 nm (100 A) to 20 nm (200 A), such as

12.5 nm (125 A) to 20 nm (200A), such as 15 nm (150 A) to 18.5 nm (185 A). The first metal layer 46 is a continuous layer. By "continuous layer" is meant that the coating forms a continuous film of material rather than separated coated areas.

[0025] The first priming layer 48 is placed on the first retroreflective layer 46. The first priming layer 48 may be a single film or a multilayer layer. The first priming layer 48 may include an oxygen intercepting material that can be sacrificed during the deposition process to prevent degradation or oxidation of the first retroreflective layer 46 during the sputtering process or subsequent heating processes. The first priming layer 48 may also absorb at least a portion of the electromagnetic radiation, such as visible light, passing through the envelope 30. Examples of materials suitable for the first primer layer 48 include titanium, silicon, silicon dioxide, silicon nitride, silicon oxynitride, nickel-chromium alloys ( such as Inconel), zirconium, aluminum, silicon and aluminum alloys, alloys containing cobalt and chromium (e.g., Stellite®), and mixtures thereof. For example, the first primer layer 48 may be titanium and may have a thickness ranging from 0.5 nm (5 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 4 nm (40 A), e.g., 2 nm (20 A) to 4 nm (40 A), e.g., 2 nm (20 A) to 3.5 nm (35 A). [0026] The second dielectric layer 50 is placed on the first priming layer 48). The second dielectric layer 50 may comprise one or more layers comprising a metal oxide or a metal alloy oxide, such as those described above with reference to the first dielectric layer 40. For example, the second dielectric layer 50 may comprise a first metal oxide film 52, e.g. a film zinc oxide, deposited on the first prime layer 48 and second layer 54 of a metal oxide, e.g.

[0027] The second dielectric layer 50 may have a combined thickness (e.g., combined layer thicknesses) in the range of 5 nm (50 A) to 100 nm (1000 A), e.g., 5 nm (50 A) to 50 nm (500 A), e.g., 10 nm (100 A) to 37 nm (370 A), e.g., 10 nm (100 A) to 30 nm (300 A), e.g., 10 nm (100 A) to 20 nm ( 200 Å), e.g., 15 nm (150 A) to 20 nm (200 A), e.g., 18 nm (180 A) to 19 nm (190 A).

For example, for a multi-layer layer, a zinc oxide film 52 (and an optional second zinc oxide layer 56, if present) may have a thickness in the range of 1 nm (10 A) to 20 nm (200 A), e.g., 5 nm (50 A) to 20 nm (200 A), e.g., 6 nm (60 A) to 15 nm (150 A), e.g., 7 nm (70 A) to 8.5 nm (85 A). The metal oxide alloy layer (zinc cyanate) may have a thickness ranging from 5 nm (50 A) to 80 nm (800 A), e.g., 5 nm (50 A) to 50 nm (500 A), e.g. nm (100 A) to 30 nm (300 A), e.g., 11 nm (110 A) to

23.5 nm (235 A), e.g., 11 nm (110 A) to 12 nm (120 A).

[0029] The second metal layer 58 with a subcritical thickness (discontinuous) is placed on the second dielectric layer 50 (e.g., on the second zinc oxide layer 56, if present, or on the zinc zinc layer 54, if not). A metallic material such as, but not limited to, metallic gold, copper, palladium, aluminum, silver, or mixtures, alloys or combinations thereof, is applied at a subcritical thickness, such that separate areas or islands of material are formed rather than a continuous layer of material . For silver, the critical thickness is less than 5 nm (50 A), such as less than 4 nm (40 A), such as less than 3 nm (30 A), such as less than 2.5 nm (25 A). ). For silver, the transition between the continuous layer and the subcritical layer takes place in the range from 2.5 nm (25 A) to 5 nm (50 A). It is estimated that copper, gold and palladium will exhibit similar subcritical behavior in this regard. The second metal layer 58 may include any one or more of the materials described above with respect to the first reflective layer 46, but these materials do not appear as a continuous film. In one non-limiting embodiment of the invention, the second layer 58 includes islet-type silver with islands having an effective thickness in the range of from 0.1 nm (1 A) to 7 nm (70 A), e.g., 1 nm (10 A) to 4 nm (40 A), e.g., 1 nm (10A) to 3.5 nm (35 A), e.g., 1 nm (10 A) to 3 nm (30 A), e.g., 1.5 nm (15 A). ) up to 3 nm (30 A), e.g., 2 nm (20 A) to 3 nm (30 A), e.g., 2.5 nm (25 A) to 3 nm (30 A). The subcritical metallic layer 58 absorbs electromagnetic radiation in accordance with the plasmon resonance theory. This absorption depends at least partly on the boundary conditions at the interface between the metallic islets. The subcritical metallic layer 58 is not an infrared reflective layer, like the first metal layer 46. The subcritical silver layer 58 is not a continuous layer. It is estimated that for silver, metallic islets or spheres of metallic silver deposited below the subcritical thickness may have a height of about 2 nm to 7 nm, such as 5 nm to 7 nm. It is estimated that if the subcritical silver layer could be evenly spaced, it would have a thickness of about 1.1 nm. It is estimated that the discontinuous metal layer behaves optically as a layer with an effective thickness of 2.6 nm. Deposition of the discontinuous metal layer on the zinc cyan instead of the zinc oxide appears to increase the light absorbance of the visible coating, e.g., the discontinuous metal layer.

[0030] The second priming layer 60 may be deposited on the second metal layer 58. The second primer layer 60 may be as described above with respect to the first primer 48. In one example, the second primer layer may be a nickel-chromium alloy (such as as Inconel) with a thickness ranging from 0.5 nm (5 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 2.5 nm (25 A), e.g., 1.5 nm (15 A) to 2.5 nm (25 A), e.g., 1.5 nm (15 A) to 2.2 nm (22 A). Since the absorbance of the subcritical material depends at least partly on the boundary conditions, different primers (e.g., having different refractive indices) may provide a coating with different absorbance spectra, and therefore different colors.

[0031] The third dielectric layer 62 is deposited on the second metal layer 58 (e.g., on a second priming film 60). The third dielectric layer 62 may also include one or more layers comprising a metal oxide or a metal alloy oxide as discussed above with respect to the first and second dielectric layers 40, 50. In one example, the third dielectric layer 62 is a multi-layer layer similar to the second one. dielectric layer 50. For example, the third dielectric layer 62 may include a first metal oxide layer 64, e.g., a zinc oxide layer, a second layer 66 comprising a metal oxide alloy, e.g., a zinc zinc layer deposited on the zinc oxide layer 64, and an optional third layer 68, e.g. a different layer of zinc oxide, deposited on the zinc zinc layer 66. In one example, there are both layers 64, 68 of zinc oxide and each has a thickness in the range of 5 nm (50 A) to 20 nm (200 A), such as 7.5 nm (75 A) to 15 nm (150 A) such as 8 nm (80 A) to 15 nm (150 A), such as 9.5 nm (95 A) to 12 nm (120 A). The metal oxide layer 66 may have

EP 2 552 846 a thickness ranging from 10 nm (100 A) to 80 nm (800 A), e.g., 20 nm (200 A) to 70 nm (700 A), e.g., 30 nm (300 A) to 60 nm (600 A), e.g., 38 nm (380 A) to 50 nm (500 A), e.g., 38 nm (380 A) to 45 nm (450 A).

[0032] In one example, the combined thickness of the third dielectric layer 62 (e.g., combined thicknesses of the zinc oxide and zinc stannate layers) is in the range of 20 nm (200 A) to 100 nm (1000 A), e.g., 40 nm. (400 A) to 90 nm (900 A), e.g., 50 nm (500 A) to 90 nm (900 A), e.g., 65 nm (650 A) to 80 nm (800 A), e.g., 69 nm (690 A) to 72 nm (720 A).

[0033] The third reflective heat and / or radiation metal layer 70 is deposited on the third dielectric layer 62. The third reflective layer 70 can be of any of the materials discussed above with respect to the first reflective layer. In one non-limiting example, the third reflective layer 70 includes silver and has a thickness ranging from 2.5 nm (25 A) to 30 nm (300 A), e.g., 5 nm (50 A) to 30 nm (300 A ), e.g., 5 nm (50 A) to 20 nm (200 A), such as 7 nm (70 A) to 15.1 nm (151 A), such as 10 nm (100 A) to 15 nm (150 A), such as 13.7 nm (137 A) to 15 nm (150 A). The third metal layer is a continuous layer.

[0034] A third priming layer 72 is placed on the third retroreflective layer 70. The third priming layer 72 may be as described above with respect to the first or second priming layer. In one non-limiting example, the third primer is titanium and has a thickness ranging from 0.5 nm (5 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 3.3 nm ( 33 A), e.g., 2 nm (20 A) to 3 nm (30 A).

[0035] A fourth dielectric layer 74 is placed on the third priming layer 72. The fourth dielectric layer 74 may comprise one or more layers comprising a metal oxide or a metal alloy oxide such as those discussed above with respect to the first, second or third dielectric layer. , 50, 62. In one non-limiting example, the fourth dielectric layer 74 is a multi-layer layer having a first metal oxide layer 76, e.g., a zinc oxide layer deposited on a third priming film 72, and a second metal oxide alloy layer 78, e.g. , a layer of zinc cyanate, deposited on the zinc oxide layer 76. In one non-limiting embodiment of the invention, the zinc oxide layer 76 may have a thickness in the range of 2.5 nm (25 A) to 20 nm (200 A), such as 5 nm (50 A) to 15 nm (150 A), such as 6 nm (60 A) to 10 nm (100 A), such as 8 nm (80 A) to 9 nm (90 A). The zinc zinc layer 78 may have a thickness in the range of 2.5 nm (25 A) to 50 nm (500 A), e.g., 5 nm (50 A) to 50 nm (500 A), e.g., 10 nm (100 A) up to 40 nm (400 A), e.g., 15 nm (150 A) to 30 nm (300 A), e.g., 15 nm (150 A) to 20 nm (200 A), e.g., 17 nm ( 170 Å) to 19 nm (190 A).

In one non-limiting example, the combined thickness of the fourth dielectric layer 74 (e.g., combined thicknesses of the zinc oxide and zinc stannate layers) is in the range of 10 nm (100 A) to 80 nm (800 A), e.g. , 20 nm (200 A) to 60 nm (600 A), e.g., 25 nm (250 A) to 40 nm (400 A), e.g., 25 nm (250 A) to 27 nm (270 A).

[0037] The top layer 80 may be provided on the fourth dielectric layer 74. The top layer 80 may help to protect the underlying coating layers from mechanical and chemical attack. The top layer 80 may, for example, be a metal oxide or metal nitride layer. For example, the surface layer 80 may be titanium oxide with a thickness in the range of 1 nm (10 A) to 10 nm (100 A), such as 2 nm (20 A) to 8 nm (80 A), such as 3 nm (30 A) up to 5 nm (50 A), such as 3 nm (30 A) to 4.5 nm (45 A). Other materials useful for the top layer include other oxides, such as silica, alumina, or a mixture of silica and alumina.

[0038] In one non-limiting embodiment of the invention, the transparent material 10 of claim 2 552 846 has the reflectivity (% R) of visible light from surface 1 in the range of 5% to 50%, such as 20% to 40% , like 25% to 30%. The transparent material 10 has a visible transmission of more than 20%, such as greater than 30%, such as greater than 40%. The transparent material has a heat gain / solar gain (SHGC) less than 0.3, such as less than 0.27, such as less than 0.25.

[0039] In contrast to previous articles, the coating layer 30 may be tempered or heat treated without adversely affecting the performance of the article or generation of haze. Also, the article of the invention has a neutral or moderate reflective color, such as blue or cyan, both in reflection and in transmission.

[0040] The absence of haze upon heating is believed to be due to the islet structure of the discontinuous intermediate metal layer. A side view of a subcritical metallic layer 90 having discontinuous coated areas 91 formed on the dielectric layer 92 and coated with a primer layer 94 is shown in Fig. 3. The thickness of the subcritical metal causes the metal material to form discrete areas or islets of metal or metal oxide on the dielectric layer 92. the primer is applied to the subcritical metal layer, the material of the primer layer covers the islands and may also extend into gaps between neighboring islets of subcritical metal and contact with the underlying layer 92.

[0041] The coating 30 according to the invention has various advantages over the known coatings. For example, a subcritical metallic layer increases the absorbance of visible light through the coating, which makes the coated article darker. The combination of a subcritical metallic layer with selected thicknesses of dielectric layers can give the coated article an asymmetric reflectance. The product color can be adjusted by passing through changing the primer (s) used in the coating. Also, the coating of the invention can be heat treated without fogging.

[0042] Although the above example includes two continuous metal layers and one discontinuous metal layer, it should be understood that this is only one non-limiting example. In the broad practice of the invention, the coating of the invention may comprise a plurality of continuous metallic layers and a plurality of discontinuous metallic layers. For example, the coated article may comprise a single subcritical metallic layer sandwiched between two dielectric layers. The coating may also comprise 3 or more metallic layers, such as 4 or more metallic layers, such as 5 or more metal layers, such as 6 or more metal layers, at least one of the metallic layers being a subcritical metallic layer. .

Titanium primer [0043] Another example coating 130 according to the invention is shown in Fig. 4. This exemplary coating 130 includes a substrate layer or a first dielectric layer 140 deposited on at least a portion of the main substrate surface (e.g., surface No. 16 of first layer 12) . The first dielectric layer 140 may be similar to the first dielectric layer 40 described above. The first dielectric layer 140 may be a single layer or may comprise more than one layer of metal oxides, metal alloy oxides, nitrides, oxynitrides, or mixtures thereof. The first dielectric layer 140 may be transparent to visible light. Suitable metal oxides for the first dielectric layer 140 include oxides of hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides may contain small amounts of other materials, such as manganese in bismuth oxide, tin in oxygen, indium, etc. Additionally, oxides of metal alloys or mixtures of metals, such as oxides containing zinc and tin (e.g. zinc cyanate, defined below), oxides of indium tin, silicon nitrides, silicon aluminum nitrides, or aluminum nitrides. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 140 may be substantially a monophasic film, such as a metal oxide alloy film, e.g., zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers. tin in oxygen 2 552 846 towards indium, etc. Additionally, oxides of metal alloys or metal mixtures, such as oxides containing zinc and tin (e.g., zinc cyanate, defined below), oxides of indium tin, silicon nitrides, nitrides can be used. silicon aluminum, or aluminum nitrides. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 140 may be substantially a monophasic film, such as a metal oxide alloy film, e.g., zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers. tin in oxygen 2 552 846 towards indium, etc. Additionally, oxides of metal alloys or metal mixtures, such as oxides containing zinc and tin (e.g., zinc cyanate, defined below), oxides of indium tin, silicon nitrides, nitrides can be used. silicon aluminum, or aluminum nitrides. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 140 may be substantially a monophasic film, such as a metal oxide alloy film, e.g., zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers. oxides of indium tin alloys, silicon nitrides, silicon-aluminum nitrides, or aluminum nitrides. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 140 may be substantially a monophasic film, such as a metal oxide alloy film, e.g., zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers. oxides of indium tin alloys, silicon nitrides, silicon-aluminum nitrides, or aluminum nitrides. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 140 may be substantially a monophasic film, such as a metal oxide alloy film, e.g., zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers.

[0044] For example, the first dielectric layer 140 (single layer or multilevel layer) may have a thickness ranging from 10 nm (100 A) to 60 nm (600 A), such as 10 nm (100 A) to 50 nm (500 A) ), such as 10 nm (100 A) to 35 nm (350 A), such as 15 nm (150 A) to 30 nm (300 A), such as 20 nm (200 A) to 25 nm (250 A), such as 21 nm (210 A) to 22 nm (220 A).

The first dielectric layer 140 may include a multi-layer structure having a first film 142, e.g., a metal oxide alloy film deposited on at least a portion of the substrate (such as the inner main surface 16 of the first layer 12) and a second film 144, e.g., a film an oxide or a mixture of metal oxides deposited on the first oxide layer 142 of a metal alloy. In one non-limiting embodiment of the invention, the first film 142 may be zinc cyanate.

[0046] For example, the first film 142 may be zinc cyanate and the second film 144 may be zinc oxide (e.g., 90 wt% zinc oxide and 10 wt% tin oxide). For example, the first film 142 may include zinc stannate having a thickness in the range of 5 nm (50 A) to 60 nm (600 A), such as 5 nm (50 A) to 50 nm (500 A), such as 7.5 nm (75 A) to 35 nm (350 A), such as 10 nm (100 A) to 25 nm (250 A), such as 10 nm (100 A) to 20 nm (200 A), such as 10 nm (100 A) up to 15 nm (150 A), such as 14 nm (140 A) to 15 nm (150 A).

[0047] The second film 144 may include zinc oxide having a thickness in the range of 5 nm (50 A) to 20 nm (200 A), such as 5 nm (50 A) to 15 nm (150 A), such as 7 nm ( 70 A) to 10 nm (100 A).

[0048] The first reflective heat and / or radiation metal layer 146 is deposited on the first dielectric layer 140. The first reflective layer 146 may include a reflective metal, such as, but not limited to, metallic gold, copper, palladium, silver, or mixtures thereof. , rates or combinations. In one embodiment of the invention, the first reflective layer 46 comprises a metallic silver layer having a thickness in the range of 2.5 nm (25 A) to 30 nm (300 A), e.g., 5 nm (50 A) to 30 nm (300 A) , e.g., 5 nm (50 A) to 25 nm (250 A), e.g., 5 nm (50 A) to 20 nm (200 A), such as 7 nm (70 A) to 20 nm (200 A) such as 10 nm (100 A) to 20 nm (200 A), such as 12 nm (120 A) to 18 nm (180 A).

[0049] The first priming layer 148 is placed on the first retroreflective layer 146. The first priming layer 148 may be a single film or a multilayer layer. The first priming layer 148 may include an oxygen scavenging material that may be sacrificed during the deposition process to prevent degradation or oxidation of the first reflective layer 146 during the sputtering process or subsequent heating processes. The first priming layer 148 may also absorb at least a portion of electromagnetic radiation, such as visible light, passing through the envelope 130. Examples of materials suitable for the first priming layer 148 include titanium, Inconel, Stellite®, and mixtures thereof. For example, the first priming layer 148 may have a thickness ranging from 0.5 nm (5 A) to 5 nm (50 A), e.g. 1 nm (10 A) to 4 nm (40 A), e.g., 2 nm (20 A) to 4 nm (40 A), e.g., 2 nm (20 A) to 3 nm (30 A). In one example, the first primer 148 is titanium.

[0050] The second dielectric layer 150 is placed on the first priming layer 48. The second dielectric layer 150 may comprise one or more layers comprising a metal oxide or a metal alloy oxide such as those described above with respect to the first dielectric layer 140 For example, the second dielectric layer 150 may include a first metal oxide film 152, e.g., a zinc oxide film deposited on the first primer film 148, and a second metal oxide alloy film 154, e.g., a zinc cyanate film (Zn2SnO4) embedded in a first film. 152 zinc oxide. The optional third metal oxide film 156, e.g., another zinc oxide layer, may be deposited on the zinc stannate layer.

The second dielectric layer 150 may have a combined thickness (e.g., the combined thickness of the layers, if there is more than one layer) is in the range of 5 nm (50 A) to 100 nm (1000 A), e.g., 5 nm (50 A) to 50 nm (500 A), e.g., 10 nm (100 A) to 40 nm (400 A), e.g., 20 nm (200 A) to 40 nm (400 A), e.g., 30 nm (300 A) to 40 nm (400 A), e.g., 35 nm (350 A) to 40 nm (400 A), e.g., 35 nm (350 A) to 37 nm (370 A). For example, for a multi-layer layer, the zinc oxide film 152 (and the optional second zinc oxide layer 156, if present) may have a thickness in the range of 10 nm (10 A) to 20 nm (200 A), e.g., 5 nm (50 A) to 20 nm (200 A), e.g., 5 nm (50 A) to 15 nm (150 A), e.g., 5 nm (50 A) to 8.5 nm (85 A). The metal oxide alloy layer (zinc cyanate) may have a thickness in the range of 5 nm (50 A) to 80 nm (800 A), e.g.

The subcritical (discontinuous) metal layer 158 is placed on the second dielectric layer 150 (e.g., on the second zinc oxide layer 156, if present, or on the zinc stannate layer 154, if not). The second metal layer 158 may include any one or more of the metallic materials described above with respect to the first retroreflective layer 146. In one non-limiting embodiment, the second metal layer 158 includes islet-type silver with islands having an effective thickness in the range of 0.1 nm (1 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 4 nm (40 A), e.g., 1 nm (10 A) to 3.5 nm (35 A), e.g. , 1 nm (10 A) to 3 nm (30 A), e.g., 1.5 nm (15 A) to 3 nm (30 A), e.g., 2 nm (20 A) to 3 nm (30 A) ), e.g., 2.5 nm (25 A) to 3 nm (30 A).

The second priming layer 160 may be deposited on the second metal layer 158. The second primer layer 160 may be as described above with respect to the first priming layer 148. For example, the second priming layer may be titanium having a thickness in the range of 0, 5 nm (5 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 3.5 nm (35 A), e.g., 1.5 nm (15 A) to 3.5 nm ( 35 A), e.g., 2 nm (20 A) to 3 nm (30 A).

[0055] The third dielectric layer 162 is embedded in the second retroreflective layer 158 (e.g., on the second priming layer 160). The third dielectric layer 162 may also include one or more layers comprising a metal oxide or a metal alloy oxide as discussed above with respect to the first and second dielectric layers 140, 150. In one example, the third dielectric layer 162 is a multi-layer layer similar to the second one For example, the third dielectric layer 162 may include a first metal oxide layer 164, e.g., a zinc oxide layer, a second layer 166 comprising a metal alloy oxide, e.g., a zinc zinc layer deposited on the zinc oxide layer 164, and an optional third layer Of a metal oxide, e.g., a different layer of zinc oxide, deposited on the zinc zinc layer 166. In one example, both zinc oxide layers are present, and each has a thickness ranging from 5 nm (50 A) to 20 nm (200 A), such as 7.5 nm (75 A) to 15 nm (150 A), such as 8 nm (80 A) to 15 nm (150 A), such as 9.5 nm (95 A) to 10 nm (100 A). Layer 166 of oxide

The metal alloy may have a thickness in the range of 10 nm (100 A) to 80 nm (800 A), e.g., 20 nm (200 A) to 70 nm (700 A), e.g., 30 nm (300 A) up to 60 nm (600 A), e.g., 50 nm (500 A) to 60 nm (600 A), e.g., 56 nm (560 A) to 60 nm (600 A).

[0056] In one example, the combined thickness of the third dielectric layer 162 (e.g., combined thicknesses of the zinc oxide and zinc stannate layers) is in the range of 20 nm (200 A) to 100 nm (1000 A), e.g., 40 nm. (400 A) to 90 nm (900 A), e.g., 50 nm (500 A) to 90 nm (900 A), e.g., 65 nm (650 A) to 80 nm (800 A), e.g., 69 nm (690 A) to 76 nm (760 A).

[0057] The third reflective heat and / or radiation metal layer 170 is deposited on the third dielectric layer 162. The third reflective layer 170 may be any of the materials discussed above with respect to the first and second reflective layers. In one non-limiting example, the third reflective layer 170 includes silver and has a thickness ranging from 2.5 nm (25 A) to 30 nm (300 A), e.g., 5 nm (50 A) to 30 nm (300 A ), e.g., 5 nm (50 A) to 20 nm (200 A), such as 7 nm (70 A) to 20 nm (200 A), such as 10 nm (100 A) to 20 nm (200 A) , such as 17 nm (170 A) to 20 nm (200 A).

The third primer layer 172 is placed on the third retroreflective layer 170. The third primer layer 172 may be as described above with respect to the first or second priming layer. In one non-limiting example, the third primer is titanium and has a thickness ranging from 0.5 nm (5 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 3 nm (30 A ), e.g., 2 nm (20 A) to 3 nm (30 A).

[0059] A fourth dielectric layer 174 is placed on the third priming film 172). The fourth dielectric layer 174 may comprise one or more layers comprising a metal oxide or a metal alloy oxide, such as those discussed above with respect to the first, second or third dielectric layer 140, 150, 162. In one non-limiting example, the fourth dielectric layer 174 is a multi-layered layer having a first metal oxide layer, e.g., a zinc oxide layer deposited on a third primer coating 172, and a second metal oxide alloy layer 178, e.g., a zinc stannate layer deposited on the zinc oxide layer. In one non-limiting embodiment of the invention, the zinc oxide layer may have a thickness in the range of 2.5 nm (25 A) to 20 nm (200 A), such as 5 nm (50 A) to 15 nm (150 A), such as 6 nm (60 A) to 10 nm (100 A), such as 7 nm (70 A) to 9 nm (90 A). The zinc zinc layer 178 may have a thickness in the range of 2.5 nm (25 A) to 50 nm (500 A), e.g., 5 nm (50 A) to 50 nm (500 A), e.g., 10 nm (100 A) up to 40 nm (400 A), e.g., 15 nm (150 A) to 30 nm (300 A), e.g., 15 nm (150 A) to 20 nm (200 A), e.g., 17 nm ( 170 Å) to 20 nm (200 A).

[0060] In one non-limiting example, the combined thickness of the fourth dielectric layer 174 (e.g., combined thicknesses of the zinc oxide and zinc stannate layers) ranges from 10 nm (100 A) to 80 nm (800 A), e.g. , 20 nm (200 A) to 60 nm (600 A), e.g., 25 nm (250 A) to 40 nm (400 A), e.g., 25 nm (250 A) to 27 nm (270 A).

[0061] The top layer 180 may be disposed on the fourth dielectric layer 174. The top layer 180 may help protect the underlying coating layers from mechanical and chemical attack. The top layer 180 may, for example, be a metal oxide or metal nitride layer. For example, the surface layer 180 may be a titanium oxide having a thickness in the range of 1 nm (10 A) to 10 nm (100 A), such as 2 nm (20 A) to 8 nm (80 A), such as 3 nm (30 A) up to 5 nm (50 A), such as 3 nm (30 A) to 4 nm (40 A).

Capsule

[0062] Another exemplary non-limiting coating 230 of the invention is shown in Fig. 5. This exemplary coating 230 includes a substrate layer or a first dielectric layer 240 deposited on at least a portion of a major substrate surface (e.g., surface No. 2 16 first layer 12). The first dielectric layer 240 may be a single layer or may comprise more than one layer of metal oxides, metal alloy oxides, nitrides, oxynitrides, or a mixture thereof. The first dielectric layer 240 may be transparent to visible light. Suitable metal oxides for the first dielectric layer 240 include oxides of hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin and mixtures thereof. These metal oxides may contain small amounts of other materials, such as manganese in bismuth oxide, tin, indium oxide, etc. In addition, oxides of metal alloys or metal blends can be used, such as oxides containing zinc and tin (e.g., zinc cyanate, defined below), indium oxide alloys, silicon nitrides, silicon aluminum nitrides, or nitrides. aluminum. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 240 may be substantially a monophasic film, such as a metal oxide alloy film, e.g., zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers. Silicon-aluminum nitrides, or aluminum nitrides. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 240 may be substantially a monophasic film, such as a metal oxide alloy film, e.g., zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers. Silicon-aluminum nitrides, or aluminum nitrides. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or doped with nickel or boron silicon oxides. The first dielectric layer 240 may be substantially a monophasic film, such as a metal oxide alloy film, e.g., zinc cyanate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of multiple layers.

[0063] For example, the first dielectric layer 240 (single film or multilevel layer) may have a thickness in the range of 10 nm (100 A) to 60 nm (600 A), such as 20 nm (200 A) to 50 nm (500 A) ), such as 25 nm (250 A) to 35 nm (350 A), such as 25 nm (250 A) to 31 nm (310 A), such as 28 nm (280 A) to 31 nm (310 A), such as 29 nm (290 A) to 30 nm (300 A).

The first dielectric layer 240 may include a multi-layered structure having a first film 242, e.g., a metal oxide alloy film deposited on at least a portion of the substrate (such as the inner main surface 16 of the first layer 12) and the second film 244, e.g., a film an oxide or mixture of metal oxides deposited on the first metal oxide layer 242. In one non-limiting embodiment of the invention, the first film 242 may be zinc cyanate.

[0065] For example, the first film 242 may be zinc cyanate and the second film 244 may be zinc oxide (e.g., 90% by weight zinc oxide and 10% by weight tin oxide). For example, the first film 242 may comprise zinc stannate with a thickness in the range of 5 nm (50 A) to 60 nm (600 A), such as 5 nm (50 A) to 50 nm (500 A), such as 7.5 nm (75 A) to 35 nm (350 A), such as 10 nm (100 A) to 25 nm (250 A), such as 15 nm (150 A) to 25 nm (250 A), such as 20 nm (200 A) up to 25 nm (250 A), such as 20 nm (200 A) to 24 nm (240 A).

[0066] The second film 244 may include a zinc oxide having a thickness in the range of 5 nm (50 A) to 20 nm (200 A), such as 5 nm (50 A) to 17.5 nm (175 A), such as 5 nm (50 A) to 15 nm (150 A), such as 5 nm (50 A) to 10 nm (100 A).

[0067] The first reflective heat and / or radiation metal layer 246 is deposited on the first dielectric layer 240. The first reflective layer 246 may include a reflective metal, such as, but not limited to, metallic gold, copper, palladium, silver or mixtures thereof, feet or combinations. In one embodiment of the invention, the first reflective layer 246 comprises a metallic silver layer having a thickness in the range of 5 nm (50 A) to 30 nm (300 A), e.g., 5 nm (50 A) to 25 nm (250 A), e.g. . 5 nm (50 A) to 20 nm (200 A), such as 7 nm (70 A) to 20 nm (200 A), such as 10 nm (100 A) to 20 nm (200 A), such as 14 nm (140 A) to 18 nm (180 A).

[0068] The first primer layer 248 is placed on the first reflective layer 246. The first primer layer 248 may be a single film or multi-layer layer. First

The priming layer 248 may comprise an oxygen scavenging material that may be sacrificed during the deposition process to prevent degradation or oxidation of the first reflective layer 246 during the sputtering process or subsequent heating processes. The first priming layer 248 may also absorb at least a portion of the electromagnetic radiation, such as visible light, passing through the coating 230. Examples of materials suitable for the first priming layer 248 include titanium, Inconel, Stellite®, and mixtures thereof. For example, the first primer layer 248 may have a thickness ranging from 0.5 nm (5 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 4 nm (40 A), e.g., 1, 5 nm (15 A) to 3 nm (30 A), e.g., 1.6 nm (16 A) to 3 nm (30 A).

The second dielectric layer 250 is placed on the first primer layer 248. The second dielectric layer 250 includes one or more layers comprising a metal oxide or a metal alloy oxide as described above with respect to the first dielectric layer 240. For example, the second dielectric layer 250 may comprising a first metal oxide layer 252, e.g., a zinc oxide film deposited on the first priming film 248 and a second metal oxide alloy film 254, e.g., a zinc cyanate film (Zn2SnO4, deposited on the first zinc oxide film 252, possibly a third oxide film 256; of metal, e.g. a different layer of zinc oxide, may be deposited on a layer of zinc cyanide.

[0070] The second dielectric layer 250 may have a combined thickness (e.g., combined layer thicknesses) in the range of 5 nm (50 A) to 100 nm (1000 A), e.g., 5 nm (50 A) to 50 nm (500 A), e.g., 10 nm (100 A) to 37 nm (370 A), e.g., 10 nm (100 A) to 30 nm (300 A), e.g., 10 nm (100 A) to 25 nm ( 250 Å), e.g., 20 nm (200 A) to 23 nm (230 A).

For example, for a multi-layer layer, the zinc oxide film 252 (and optionally the third zinc oxide layer 256, if present) may have a thickness in the range of 1 nm (10 A) to 20 nm (200 A), e.g., 5 nm (50 A) to 20 nm (200 A), e.g., 6 nm (60 A) to 15 nm (150 A), e.g., 7.5 nm (75 A) to 8.5 nm (85 A). The metal oxide alloy layer (zinc cyanate) may have a thickness ranging from 5 nm (50 A) to 80 nm (800 A), e.g., 5 nm (50 A) to 50 nm (500 A), e.g. nm (100 A) to 20 nm (200 A), e.g., 15.5 nm (155 A) to 20 nm (200 A).

[0072] The absorber layer 257 is placed on the second dielectric layer 250 (e.g., on a third zinc oxide layer 256, if present, or on a zinc zinc layer 254, if not). The absorbing layer 257 is a multilayer structure having a first absorbing layer 259, a metal layer 261, and a second absorbing layer 263. The first and second absorbing layer 259, 263 may be the same or different materials. Suitable material for absorbing layers includes metal or silicon oxide or azhammers. For example, the first and second absorbing layer 259, 265 may be silicon nitride. The first absorbing layer 259 may have a thickness in the range of 1 nm (10 A) to 20 nm (200 A), e.g., 5 nm (50 A) to 20 nm (200 A), e.g., 6 nm (60 A) up to 15 nm (150 A), e.g., 8 nm (80 A) to 9 nm (90 A). The second absorbing layer 263 may also be silicon nitride and may have a thickness ranging from 1 nm (10 A) to 20 nm (200 A), e.g., 5 nm (50 A) to 20 nm (200 A), e.g. 6 nm (60 A) to 15 nm (150 A), e.g., 7.5 nm (75 A) to 10 nm (100 A).

[0073] The metal layer 261 is a layer of subcritical thickness as described above. In one example, the metal layer 261 is a cobalt-chromium alloy (such as Stellite®) and has a thickness in the range from 0.1 nm (1 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 4 nm (40 A), e.g., 1 nm (10 A) to 3.5 nm (35 A), e.g., 1 nm (10 A) to 3 nm (30 A), e.g., 1.5 nm (15 A) to 3 nm (30 A), e.g., 2 nm (20 A) to 3 nm (30 A), e.g., 2.5 nm (25 A) to 3 nm (30 A).

In one example, the first zinc oxide layer 264 (if present) and the third zinc oxide layer 268 may have thicknesses in the range of 5 nm (50 A) to 20 nm (200 A), such as 7.5 nm (75 A) to 15 nm (150 A), such as 8 nm (80 A) to 15 nm (150 A), such as 9.5 nm (95 A) to 10.5 nm (105 A). The metal oxide alloy layer 266 (second) may have a thickness ranging from 10 nm (100 A) to 80 nm (800 A), e.g., 20 nm (200 A) to 70 nm (700 A), e.g., 30 nm. (300 A) to 60 nm (600 A), e.g., 38 nm (380 A) to 50 nm (500 A), e.g., 42 nm (420 A) to 45 nm (450 A).

[0075] In one example, the combined thickness of the third dielectric layer 262 (e.g., combined thicknesses of the zinc oxide and zinc stannate layers) is in the range of 20 nm (200 A) to 100 nm (1000 A), e.g., 40 nm (400 A) to 90 nm (900 A), e.g., 50 nm (500 A) to 90 nm (900 A), e.g., 50 nm (500 A) to 60 nm (600 A), e.g., 52 5 nm (525 A) to 55 nm (550 A).

[0076] The third reflective heat and / or radiation metal layer 270 is deposited on the third dielectric layer 262. The third reflective layer 270 may be of any of the materials discussed above with respect to the first and second reflective layers. In one non-limiting example, the third reflective layer 270 includes silver and has a thickness in the range of 5 nm (50 A) to 30 nm (300 A), e.g., 5 nm (50 A) to 20 nm (200 A), such as 7 nm (70 A) to 15 nm (150 A), such as 10 nm (100 A) to 15 nm (150 A), such as 12.8 nm (128 A) to 15 nm (150 A).

The third priming layer 272 is placed on the third retroreflective layer 270. The third priming layer 272 may be as described above with respect to the first or second priming layer. In one non-limiting example, the third primer is titanium and has a thickness ranging from 0.5 nm (5 A) to 5 nm (50 A), e.g., 1 nm (10 A) to 3 nm (30 A ), e.g., 1.7 nm (17 A) to 3 nm (30 A).

[0078] A fourth dielectric layer 274 is placed on the third priming layer 272). The fourth dielectric layer 274 includes one or more layers comprising a metal oxide or a metal oxide alloy as discussed above with respect to the first, second or third dielectric layers 240, 250, 262. In one non-limiting example, the fourth dielectric layer 274 is a multi-layer layer having a first metal oxide layer 276, e.g., a zinc oxide layer, deposited on a third priming film 272, and a second metal oxide alloy layer 278, e.g., a zinc stannate layer deposited on the zinc oxide layer 276. In one non-limiting embodiment of the invention, the zinc oxide layer 276 may have a thickness in the range of 2.5 nm (25 A) to 20 nm (200 A), such as 5 nm (50 A) to 15 nm (150 A), such as 6 nm (60 A) to 10 nm (100 A), such as 6 nm (60 A) to 7 nm (70 A). The zinc zinc layer 78 may have a thickness in the range of 2.5 nm (25 A) to 50 nm (500 A), e.g., 5 nm (50 A) to 50 nm (500 A), e.g., 10 nm (100 A) up to 40 nm (400 A), e.g., 15 nm (150 A) to 30 nm (300 A), e.g., 15 nm (150 A) to 20 nm (200 A), e.g., 18 nm ( 180 Å) to 19 nm (190 A).

[0079] In one non-limiting example, the combined thickness of the fourth dielectric layer 274 (e.g., combined thicknesses of the zinc oxide and zinc stannate layers) is in the range of 10 nm (100 A) to 80 nm (800 A) ), e.g., 20 nm (200 A) to 60 nm (600 A), e.g., 25 nm (250 A) to 40 nm (400 A), e.g., 25 nm (250 A) to 27 nm (270 AND).

[0080] The top layer 280 may be disposed on the fourth dielectric layer 274. The top layer 280 may help protect the underlying coating layers from mechanical and chemical attack. The top layer 280 may, for example, be a metal oxide or metal nitride layer. For example, the surface layer 280 may be a titanium oxide with a thickness in the range of 1 nm (10 A) to 10 nm (100 A), such as 2 nm (20 A) to 8 nm (80 A), such as 3 nm (30 A) up to 5 nm (50 A), such as 3 nm (30 A) to 4 nm (40 A).

Low-band gap semiconducting materials as an absorbing layer [0081] In certain applications, it may be desirable to modify a particular transferred color without affecting the sun's performance of the coating. One way to accomplish this would be to integrate a semiconductor material with a sun coating that has the edge of the band gap in the visible region of the electromagnetic spectrum. As will be appreciated by those skilled in the art, at the edge of the band gap of the semiconductor, the radiation of a lower wavelength is absorbed by the semiconductor material, while energy with a larger wavelength is transmitted through the material. This means that the material is transparent to radiation above the edge of the band gap. By selecting the material having the edge of the band gap in the visible region, the wavelength of the electromagnetic radiation that is absorbed or passed through the semiconductor material can be selected. Using semiconductor materials with small bandgas, such as, but not limited to, germanium or germanium-based alloys, the absorption edge may be placed close to the side of the larger wavelength of the visible spectrum. In this way, the optical transmittance can be reduced without absorbing near or far infrared radiation, minimizing unnecessary heating of the glass upon absorption. Such a semiconductor material may be placed in a conventional solar coating, e.g. between two silver layers, above the silver layer, below the silver layer, or anywhere else in the stack.

[0082] The following Examples illustrate various embodiments of the invention. However, it should be understood that the invention is not limited to these particular embodiments of the invention.

EXAMPLES [0083] In the following Examples, "Rf" refers to the reflectance on the film side, "Rg" refers to the glass side reflectance ratio, "T" refers to the product transmissivity, "Rg60" refers to the reflectance From the glass side at an angle of 60 degrees, "Rx" refers to the reflectance outside the standard IGU from surface # 1, "Rint" refers to the reflectance of IGU from the inner surface (No. 4), "VLT" refers to the light transmission visible and "SHGC" refers to the heat gain coefficient from insolation. "Standard IGU" has an outer layer of glass 6 mm thick, an inner layer of glass 6 mm, a 0.5 inch (1.27 cm) gap filled with air, a coating on surface No. 2. "SC" means "subcritical" thickness (i.e. the layer was not a continuous layer,

[0084] In the following Examples, "heat treated" means that the coated substrate was heated in a furnace to 1185 ° F to simulate quenching, and then cooled in air to room temperature before measuring the optical characteristics.

[0085] Color coordinates a *, b *, and L * are coordinates from conventional CIE systems (1931) and

EP 2 552 846

CIELAB, which will be understandable to the average specialist in the field.

[0086] In order to model the subcritical structure's reaction to electromagnetic radiation so that the optical properties of the entire stack can be optimized and controlled, the subcritical layer can be modeled as two idealized layers. Such idealized layers have homogeneous optical properties (i.e., refractive index (n) and specific absorption coefficient (k)) over their entire thickness, as for the other layers in the stack. Thus, the thicknesses given in the examples are the thicknesses of these idealized layers and have meaning in the context of calculating the optical response of a given stack of coatings containing these layers.

[0087] Also, the thickness values ​​associated with the "subcritical" layers in the following Examples mean "effective thickness" calculated based on a coating reference rate that is less than the actual coating speed of an industrial coater. For example, the silver layer is applied to the substrate at the same coating speed as in an industrial coating pan, but at a reduced line speed (reference coating rate) compared to a commercial coater. The thickness of the coating deposited at the reference coating rate is measured and then the "effective thickness" extrapolated to the coating deposited at the same coating speed, but the higher linear speed of the industrial coating machine. For example, if the specific coating rate provides a 25 nm silver coating (250 A) at a reference coating rate of one tenth the linear speed of the industrial coating machine, & quot; effective thickness & quot; of the silver layer at the same coating rate but at the linear speed of the industrial coating machine (i.e., ten times as large) than for the reference coating) is extrapolated to 2.5 nm (25 A) (i.e., one-tenth of the thickness). However, as can be seen, the silver layer at this effective thickness (below the subcritical thickness) will not be a continuous layer, but will be a discontinuous layer having discontinuous silver areas. ten times higher than for the reference coating) is extrapolated to 2.5 nm (25 A) (i.e., one-tenth of the thickness). However, as can be seen, the silver layer at this effective thickness (below the subcritical thickness) will not be a continuous layer, but will be a discontinuous layer having discontinuous silver areas. ten times higher than for the reference coating) is extrapolated to 2.5 nm (25 A) (i.e., one-tenth of the thickness). However, as can be seen, the silver layer at this effective thickness (below the subcritical thickness) will not be a continuous layer, but will be a discontinuous layer having discontinuous silver areas.

EXAMPLE 1 [0088] A coating was deposited using a conventional MSVD coating machine (commercially available from Applied

Materials) on a 6-mm piece of clear glass. The coated glass had the following structure:

titanium oxide zinc cyano nm (40 A) zinc oxide (90/10) nm (190 A) 8 nm (80 A) titanium silver nm (30 A) zinc oxide zinc cyanide zinc oxide Inconel silver SC zinc cyanide zinc oxide titanium nm ( 150 A) 12 nm (120 A) 45 nm (450 A) 12 nm (120 A) 2.2 nm (22 A) 2.5 nm (25 A) 11 nm (110 A) 7 nm (70 A) nm (30 A) silver zinc oxide zinc cynic nm (180 A) 11 nm (110 A) 20 nm (200 A)

EP 2 552 846 6 mm clear glass [0089] This coated glass was heat treated as described above and had the optical characteristics shown in Table 1 below. The product was included in the standard IGU as the outer layer (the inner layer was uncoated 6-mm clear glass) and had the optical characteristics shown in Table 2 below.

EXAMPLE 2 [0090] A coating was deposited using a conventional Airco MSVD coating machine on a 6-mm piece of Starphire® glass. The coated glass had the following structure:

<td>titanium oxide</td><td>4 nm (40 A)</td>

<td>zinc zinc</td><td>17 nm (170 A)</td>

<td>zinc oxide (90/10)</td><td>8 nm (80 A)</td>

<td>titanium</td><td>2 nm (20 A)</td>

<td>silver</td><td>15 nm (150 A)</td>

<td>zinc oxide</td><td>12 nm (120 A)</td>

<td>zinc zinc</td><td>48 nm (480 A)</td>

<td>zinc oxide</td><td>12 nm (120 A)</td>

<td>Inconel</td><td>2.2 nm (22 A)</td>

<td>silver SC</td><td>2.5 nm (25 A)</td>

<td>zinc zinc</td><td>11 nm (110 A)</td>

<td>zinc oxide</td><td>7 nm (70 A)</td>

<td>titanium</td><td>2 nm (20 A)</td>

<td>silver</td><td>18 nm (180 A)</td>

<td>zinc oxide</td><td>11 nm (110 A)</td>

<td>zinc zinc</td><td>22 nm (220 A)</td>

<td>Starphire® glass</td><td>6 mm</td>

[0091] This coated glass was heat treated as described above and had the optical characteristics shown in Table 1 below. The product was included in the standard IGU as the outer layer (the inner layer was uncoated 6-mm Starphire® glass) and had the optical characteristics shown in Table 2 below.

EXAMPLE 3 [0092] A coating was deposited using a conventional Airco MSVD coating machine on a 6-mm piece of glass

Optiblue®. The coated glass had the following structure:

<td>titanium oxide</td><td>4 nm (40 A)</td>

<td>zinc zinc</td><td>17 nm (170 A)</td>

<td>zinc oxide (90/10)</td><td>8 nm (80 A)</td>

<td>titanium</td><td>2 nm (20 A)</td>

<td>silver</td><td>15 nm (150 A)</td>

<td>zinc oxide</td><td>12 nm (120 A)</td>

<td>zinc zinc</td><td>48 nm (480 A)</td>

EP 2 552 846

<td>zinc oxide</td><td>12 nm (120 A)</td>

<td>Inconel</td><td>2.2 nm (22 A)</td>

<td>silver SC</td><td>2.5 nm (25 A)</td>

<td>zinc zinc</td><td>11 nm (110 A)</td>

<td>zinc oxide</td><td>7 nm (70 A)</td>

<td>titanium</td><td>2 nm (20 A)</td>

<td>silver</td><td>18 nm (180 A)</td>

<td>zinc oxide</td><td>11 nm (110 A)</td>

<td>zinc zinc</td><td>22 nm (220 A)</td>

<td>Optiblue® glass</td><td>6 mm</td>

[0093] This coated glass was heat treated as described above and had the optical characteristics shown in Table 1 below. The product was included in the standard IGU as the outer layer (the inner layer was uncoated 6-mm Starphire® glass) and had the optical characteristics shown in Table 2 below.

EXAMPLE 4 [0094] A coating was deposited using a conventional MSVD Airco coating machine on a 6-mm piece of clear glass. The coated glass had the following structure:

<td>titanium oxide zinc zinc</td><td>4 nm (40 A) 20 nm (200 A)</td>

<td>zinc oxide (90/10)</td><td>7 nm (70 A)</td>

<td>titanium</td><td>3 nm (30 A)</td>

<td>silver</td><td>17 nm (170 A)</td>

<td>zinc oxide</td><td>10 nm (100 A)</td>

<td>zinc zinc</td><td>56 nm (560 A)</td>

<td>zinc oxide</td><td>10 nm (100 A)</td>

<td>titanium</td><td>3 nm (30 A)</td>

<td>silver SC</td><td>2.5 nm (25 A)</td>

<td>zinc oxide</td><td>5 nm (50 A)</td>

<td>zinc zinc</td><td>27 nm (270 A)</td>

<td>zinc oxide</td><td>5 nm (50 A)</td>

<td>titanium</td><td>3 nm (30 A)</td>

<td>silver</td><td>12 nm (120 A)</td>

<td>zinc oxide</td><td>7 nm (70 A)</td>

<td>zinc zinc</td><td>14 nm (140 A)</td>

<td>transparent glass</td><td>6 mm</td>

[0095] This coated glass was heat treated as described above and had the optical characteristics shown in Table 1 below. The product was included in the standard IGU as the outer layer (the inner layer was uncoated 6-mm clear glass) and had the optical characteristics shown in Table 2 below.

EXAMPLE 5

EP 2 552 846 [0096] A coating was deposited using a conventional Airco MSVD coating machine on a 6-mm piece of clear glass. The coated glass had the following structure:

<td>titanium oxide</td><td>4 nm (40 A)</td>

<td>zinc zinc</td><td>17 nm (170 A)</td>

<td>zinc oxide (90/10)</td><td>8 nm (80 A)</td>

<td>titanium</td><td>3 nm (30 A)</td>

<td>silver</td><td>13.7 nm (137 A)</td>

<td>zinc oxide</td><td>9.5 nm (95 A)</td>

<td>zinc zinc</td><td>38 nm (380 A)</td>

<td>zinc oxide</td><td>9.5 nm (95 A)</td>

<td>Inconel</td><td>1.5 nm (15 A)</td>

<td>silver SC</td><td>3 nm (30 A)</td>

<td>zinc zinc</td><td>23.5 nm (235 A)</td>

<td>zinc oxide</td><td>8.5 nm (85 A)</td>

<td>titanium</td><td>3 nm (30 A)</td>

<td>silver</td><td>12.5 nm (125 A)</td>

<td>zinc oxide</td><td>10 nm (100 A)</td>

<td>zinc zinc</td><td>20 nm (200 A)</td>

<td>transparent glass</td><td>6 mm</td>

[0097] This coated glass was heat treated as described above and had the optical characteristics shown in Table 1 below. The product was included in the standard IGU as the outer layer (the inner layer was uncoated 6-mm clear glass) and had the optical characteristics shown in Table 2 below.

EXAMPLE 6 (not according to the present invention) [0098] A coating was deposited using a conventional Airco MSVD coating machine on a 6-mm piece of clear glass. The coated glass had the following structure:

<td>titanium oxide</td><td>4 nm (40 A)</td>

<td>zinc zinc</td><td>32 nm (320 A)</td>

<td>zinc oxide (90/10)</td><td>15 nm (150 A)</td>

<td>titanium</td><td>1.5 nm (15 A)</td>

<td>Inconel</td><td>1.5 nm (15 A)</td>

<td>silver</td><td>17 nm (170 A)</td>

<td>zinc oxide</td><td>7.5 nm (75 A)</td>

<td>zinc zinc</td><td>50 nm (500 A)</td>

<td>zinc oxide</td><td>7.5 nm (75 A)</td>

<td>titanium</td><td>1.5 nm (15 A)</td>

<td>Inconel</td><td>0.5 nm (5 A)</td>

<td>silver</td><td>7.3 nm (73 A)</td>

<td>zinc oxide</td><td>8.5 nm (85 A)</td>

<td>zinc zinc</td><td>35.5 nm (355 A)</td>

EP 2 552 846 6 mm clear glass [0099] This coated glass was heat-treated and had the optical characteristics shown in Table 1 below. The product was included in the standard IGU as the outer layer (the inner layer was uncoated 6-mm clear glass) and had the optical characteristics shown in Table 2 below.

EXAMPLE 7 (not according to the invention) [0100] A coating was deposited using a conventional Airco MSVD coating machine on a 6-mm piece of clear glass. The coated glass had the following structure:

<td>titanium oxide</td><td>4 nm (40 A)</td>

<td>zinc zinc</td><td>19 nm (190 A)</td>

<td>zinc oxide (90/10)</td><td>6 nm (60 A)</td>

<td>titanium</td><td>1.7 nm (17 A)</td>

<td>silver</td><td>12.8 nm (128 A)</td>

<td>zinc oxide</td><td>10.5 nm (105 A)</td>

<td>zinc zinc</td><td>42 nm (420 A)</td>

<td>zinc oxide</td><td>12 nm (120 A)</td>

<td>silicon nitride</td><td>10 nm (100 A)</td>

<td>Stellite®</td><td>3 nm (30 A)</td>

<td>silicon nitride</td><td>8 nm (80 A)</td>

<td>zinc zinc</td><td>15.5 nm (155 A)</td>

<td>zinc oxide</td><td>7.5 nm (75 A)</td>

<td>titanium</td><td>1.6 nm (16 A)</td>

<td>silver</td><td>14 nm (140 A)</td>

<td>zinc oxide</td><td>5 nm (50 A)</td>

<td>zinc zinc</td><td>24 nm (240 A)</td>

<td>transparent glass</td><td>6 mm</td>

6 mm clear glass [0101] This coated glass was heat-treated and had the optical characteristics shown in Table 1 below. The product was included in the standard IGU as the outer layer (the inner layer was uncoated 6-mm clear glass) and had the optical characteristics shown in Table 2 below.

EXAMPLE 8 (not according to the invention) [0102] A coating was deposited using a conventional Airco MSVD coating machine on a 6-mm piece of clear glass. The coated glass had the following structure:

titanium oxide 4 nm (40 A) zinc zinc 18 nm (180 A) zinc oxide (90/10) 7 nm (70 A) titanium 3 nm (30 A) silver 12.8 nm (128 A) zinc oxide 10.5 nm (105 A)

EP 2 552 846

<td>zinc zinc</td><td>42 nm (420 A)</td>

<td>zinc oxide</td><td>12 nm (120 A)</td>

<td>silicon nitride</td><td>10 nm (100 A)</td>

<td>Stellite®</td><td>3 nm (30 A)</td>

<td>silicon nitride</td><td>8 nm (80 A)</td>

<td>zinc zinc</td><td>15.5 nm (155 A)</td>

<td>zinc oxide</td><td>7.5 nm (75 A)</td>

<td>titanium</td><td>3 nm (30 A)</td>

<td>silver</td><td>14 nm (140 A)</td>

<td>zinc oxide</td><td>5 nm (50 A)</td>

<td>zinc zinc</td><td>24 nm (240 A)</td>

<td>transparent glass</td><td>6 mm</td>

[0103] This coated glass was heat treated as described above and had the optical characteristics shown in Table 1 below. The product was included in the standard IGU as the outer layer (the inner layer was uncoated 6-mm clear glass) and had the optical characteristics shown in Table 2 below.

EXAMPLE 9 [0104] A coating was deposited using a conventional Airco MSVD coating machine on a 6-mm piece of clear glass. The coated glass had the following structure:

<td>titanium oxide</td><td>4.3 nm (43 A)</td>

<td>zinc zinc</td><td>19.6 nm (196 A)</td>

<td>zinc oxide (90/10)</td><td>8.1 nm (81 A)</td>

<td>titanium</td><td>3.3 nm (33 A)</td>

<td>silver</td><td>15.1 nm (151 A)</td>

<td>zinc oxide</td><td>12 nm (120 A)</td>

<td>zinc zinc</td><td>44.8 nm (448 A)</td>

<td>zinc oxide</td><td>12 nm (120 A)</td>

<td>Inconel</td><td>2.2 nm (22 A)</td>

<td>silver SC</td><td>2.6 nm (26 A)</td>

<td>zinc zinc</td><td>11.6 nm (116 A)</td>

<td>zinc oxide</td><td>7 nm (70 A)</td>

<td>titanium</td><td>3.5 nm (35 A)</td>

<td>silver</td><td>18.2 nm (182 A)</td>

<td>zinc oxide</td><td>11 nm (110 A)</td>

<td>zinc zinc</td><td>19.8 nm (198 A)</td>

<td>transparent glass</td><td>6 mm</td>

TABLE 1

<td>Example No.</td><td>RFL *</td><td>rfa *</td><td>rfb *</td><td>RGL *</td><td>rg *</td><td>RGB *</td><td>TL *</td><td>this *</td><td>tb *</td><td>Rg60L *</td><td>RG60 *</td><td>Rg60b *</td>

<td>1</td><td>31.4</td><td>-3.15</td><td>-22.31</td><td>61.58</td><td>-0.86</td><td>-0.54</td><td>73.97</td><td>-4.61</td><td>-3.32</td><td>63.10</td><td>-7,10</td><td>-1.30</td>

EP 2 552 846

<td>2</td><td>34.6</td><td>6.2</td><td>19.3</td><td>62.6</td><td>1.0</td><td>-0.9</td><td>75.2</td><td>4.0</td><td>2.2</td><td>lack</td><td>lack</td><td>lack</td>

<td>3</td><td>31.6</td><td>-5.1</td><td>-20.7</td><td>49.6</td><td>0.2</td><td>-6.9</td><td>65.4</td><td>-3.8</td><td>-7.3</td><td>lack</td><td>lack</td><td>lack</td>

<td>4</td><td>44.5</td><td>-0.5</td><td>-9.7</td><td>58.6</td><td>-3.2</td><td>0.4</td><td>76.3</td><td>-6.3</td><td>-6.0</td><td>lack</td><td>lack</td><td>lack</td>

<td>5</td><td>30.4</td><td>-6.7</td><td>-9.5</td><td>44</td><td>-1.7</td><td>-3.5</td><td>84.9</td><td>-3.0</td><td>0.9</td><td>lack</td><td>lack</td><td>lack</td>

<td>6</td><td>57.53</td><td>1.65</td><td>-3.83</td><td>58,19</td><td>-1.69</td><td>2.07</td><td>72.23</td><td>-3.46</td><td>3.57</td><td>lack</td><td>lack</td><td>lack</td>

<td>7</td><td>31.0</td><td>-1.8</td><td>-12.1</td><td>58.1</td><td>-1.3</td><td>1.7</td><td>73.0</td><td>-5.7</td><td>-0.7</td><td>lack</td><td>lack</td><td>lack</td>

<td>8</td><td>33.2</td><td>-1.3</td><td>-12.1</td><td>61.5</td><td>-2,2</td><td>2.2</td><td>72.2</td><td>-4.5</td><td>-1.4</td><td>lack</td><td>lack</td><td>lack</td>

TABLE 2

<td>Example No.</td><td>RxL *</td><td>rxa *</td><td>rxb *</td><td>RintL *</td><td>Rinta *</td><td>Rintb *</td><td>TL *</td><td>this *</td><td>tb *</td><td>Rx</td><td>rint</td><td>VLT</td><td>SHGC</td>

<td>1</td><td>63.07</td><td>-1,16</td><td>-0.87</td><td>44.02</td><td>-2.57</td><td>-13</td><td>70.75</td><td>-5.81</td><td>3.53</td><td>32</td><td>14</td><td>42</td><td>0.232</td>

<td>2</td><td>64.2</td><td>0.4</td><td>-1.0</td><td>45.8</td><td>-3.9</td><td>-12.2</td><td>72.6</td><td>-4.1</td><td>-2.3</td><td>33</td><td>15</td><td>44</td><td>0.234</td>

<td>3</td><td>50.8</td><td>0.8</td><td>-8.2</td><td>43.6</td><td>-2.6</td><td>-13.2</td><td>62.4</td><td>-5.3</td><td>-7.1</td><td>19</td><td>13</td><td>31</td><td>0.2</td>

<td>4</td><td>60.7</td><td>-3.6</td><td>-0.5</td><td>51.8</td><td>-1.9</td><td>-6.9</td><td>73.4</td><td>-7.5</td><td>-5.6</td><td>29</td><td>20</td><td>45</td><td>0.27</td>

<td>5</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td><td>lack</td>

<td>6</td><td>60.0</td><td>-2,2</td><td>1.4</td><td>61.1</td><td>-3.6</td><td>-2.7</td><td>69.8</td><td>-4.5</td><td>-3.5</td><td>28</td><td>29</td><td>40</td><td>0,240</td>

<td>7</td><td>59.4</td><td>-1.2</td><td>1.0</td><td>43.6</td><td>-1.5</td><td>-7.6</td><td>69.7</td><td>-6.8</td><td>-0.7</td><td>28</td><td>14</td><td>40</td><td>0.23</td>

<td>8</td><td>62.5</td><td>-1.8</td><td>1.4</td><td>44.6</td><td>-1.1</td><td>-8.2</td><td>69.1</td><td>-5.7</td><td>-0.9</td><td>31</td><td>14</td><td>39</td><td>0.23</td>