CZ297599A3 - Glass with coating for solar radiation control and process of its production - Google Patents

Abstract

In the present invention, there is disclosed a solar-control glass that has acceptable visible light transmission, absorbs near infrared wavelength light (NIR) and reflects midrange infrared light (low emissivity mid IR) along with a preselected color within the visible light spectrum for reflected light. The improved glass has a solar energy (NIR) absorbing layer comprising tin oxide having a dopant such as antimony and a low emissivity control layer (low emissivity) capable of reflecting midrange infrared light and comprising tin oxide having fluorine and/or phosphorus dopant. The NIR layer and the low emissivity layer can be separate portions of a single tin oxide film since both layers are composed of doped tin oxide. There is also disclosed a process for producing the improved, coated, solar-controlled glass.

Description

Technical field

*. The invention relates to coated glass used in residential building windows, architecture and vehicle windows where it is desirable to achieve both solar control and low emissivity, and a process for manufacturing such glass. Solar control coatings, which have low emissivity, contain tin oxide and various dopants. Glass articles can have any shape, but are usually flat or curved. The composition of the glass may vary widely, but soda-lime glass produced by float is usually used. The glass may be cooled, heat-strengthened or cured.

BACKGROUND OF THE INVENTION

Solar control is a term used to characterize the property of controlling the amount of solar thermal energy that is allowed to pass through a glass object into an enclosed space, such as a building or interior of a car. Low emissivity is a term that characterizes the surface property of an object in which absorption and emission of mid-wavelength infrared radiation are suppressed so that the surface becomes an infrared reflector and thus reduces heat flow through the object by dampening the radiation component heat transfer to and from the low emissivity surface (sometimes referred to as Low E). By suppressing the intake of solar heat, the interiors of buildings and cars remain cooler, resulting in a cooler interior, leaving the interior of buildings and cars cooler. ··· ·· ·· Reduces air conditioning needs and costs. Efficient, low-emission coatings improve comfort in both summer and winter by increasing the thermal insulation efficiency of the window.

Of course, for commercially acceptable coated glass articles having a solar control property and low emissivity, the economic aspects to be taken into account in the manufacture of these glass articles and the durability and retention of associated properties such as transmittance light, visibility, color, clarity and reflection.

As will be explained below, various technologies have been used to meet solar control and low emission capability requirements, but none of the systems has successfully met all the requirements to apply and implement these requirements in an economical manner.

Many coatings and coating systems also give rise to irritating colors on the coated article. This may be due to the chemical composition of the coating, the thickness of the individual layer or layers, or the interaction of the substrate and the coating under incident light. Such irritation can in some cases be reduced or eliminated by inserting an anti-iris layer between the glass substrate and the first coating. The use of an interference layer between the glass and the subsequent functional layer or layers to suppress irritation or reflection of colors was first accomplished by Roy.

G. Gordon, and this solution is protected by United States Patent No. 4,187,336 of February 5, 1980. Gordon's technology has become the state of the art for solar control coated glass, as shown in the recent U.S. Patent • · · · ··· · ··· ···· · · · ·

No. 5,780,149 (McCurdy et al., July 14, 1998), wherein two layers were applied to the top of the Gordon Interference Layer to obtain solar control. The interference layer often contains silica. Surprisingly, the present invention represents a dramatic breakthrough and eliminates the need for a Gordon-type backsheet for controlling reflected color.

U.S. Pat. No. 3,149,989 describes a coating composition suitable for producing radiation reflecting glass (solar control). According to this patent, at least two coatings are used, the first coating adhering to the glass substrate being composed of tin oxide doped with a relatively high proportion of antimony.

The second coating is also composed of tin oxide and is doped with a relatively small amount of antimony. The two layers may lie on top of each other, or may be applied to opposite sides of the glass substrate. In both cases, these coatings for controlling solar radiation do not give the glass article significantly low emission properties.

U.S. Patent No. 4,601,917 discloses a liquid coating composition for producing a high-quality, high-performance fluorine doped tin oxide coating by chemical vapor deposition. One use of such coatings is the production of energy efficient windows, also known in the trade as low-E, or low-E windows. Methods for producing coated glass are also described. However, this patent does not teach how to produce coated glass articles that exhibit solar control properties and low emissivity.

U.S. Patent No. 4,504,109, owned by Kabushiki Kaisha Toyota Chou, discloses glass coated with multiple infrared shielding layers and comprising a transparent substrate for visible light and a laminating component lying above it with at least one shielding layer infrared radiation and at least one interference reflective layer lying alternately on each other .... Sn doped indium oxide was used in the examples as an infrared shielding layer and TiO ₂ was used as the interference shielding layer. - To reduce irradiation, the thickness of the infrared shielding layer and the interference reflective layer having a quarter lambda (lambda / 4) value with a tolerance of from 75% to 130% lambda / 4. Although other compositions such as tin ( _II) SnO ₂ with or without dopants (see column 6, lines 12 to 27) are disclosed for the preparation of the infrared shielding and interference reflective layers, it is neither described nor described to suppress irritation or reflection of colors, no specific combination of doped tin oxide layers of SnO ₂ disclosed in the present invention is provided that provides solar control, low emissivity and irritation prevention without requiring a lambda / 4 thickness limitation.

In the United States patent no. No. 4,583,815, also owned by Kabushiki Kaisha Toyota Chou, describes a laminated heat shield consisting of two superposed layers of indium tin oxide containing different amounts of tin. Also disclosed in this patent are antireflection layers above or below these layers of indium and tin oxide. This patent discloses other compositions for infrared shielding layers and for interference reflective layers, such as SnO ₂ with a dopant that becomes a positive ion with a + 5 valence, such as O ··· · ♦ ······ Is, for example, Sb, P, As, Nb, Ta, V, or Mo, or with an element such as F, which easily becomes a negative ion with valence - 1 (see paragraph 22, lines 17 to 23). However, the specific combination of doped SnO ₂ layers of the present invention to achieve solar shading, low emissivity, and irritation prevention is nowhere generally described or exemplified in this patent. Nor is there any claim in the patent for a tin oxide layer, nor is there any mention in the specification of the composition of such layers, for example the ratio of dopant to tin oxide. It should also be noted that the description leads to the use of the same dopant in both layers (indium and tin oxide), whereas in the present patent application one layer must contain a different dopant than the other layer.

U.S. Patent No. 4,828,880, owned by Pilkington PLC, describes barrier layers which act to prevent the migration of alkali metal ions from the glass surface and / or act as a color suppression layer for layers located above the backing layer. , reflecting infrared or electrically conductive. Some of these color suppressing layers are used for controlling solar radiation or in the construction of low emissivity glass.

U.S. Patent No. 5,168,003, owned by the Ford Motor Company, describes a glazing product that is coated with a substantially transparent optically functional coating (which may have low emissivity or control solar radiation), and a thinner anti-iris layer which is a stepped layer with multiple gradients. Antimony doped tin oxide is mentioned as a possible alternative or optional component of the low emissivity layer mentioned in the example section.

U.S. Patent No. 5,780,149, owned by Libbey-Owens-Ford, describes glass with a solar control coating in which at least three coating layers are present, the first and second transparent coatings and the iris suppression layer lying therein. between glass with transparent top layers. The present invention provides transparent layers having different refractive indices in the near infrared region, the different refractive indices being greater than the difference in the refractive indices in the visible region. This difference causes solar heat to be reflected in the near infrared range and not absorbed. Doped metal oxides having low emissivity, such as fluorine doped tin oxide, are used as the first transparent layer. In the second layer, metal oxides such as undoped tin oxide are used. There is nowhere described in this patent a combination for absorbing near infrared (NIR) radiation.

In European patent EP 0-546-302-B1, assigned

July 16, 1997, owned by Asahi Glass Co., describes a solar control coating system for heat treated (tempered or bent) glass comprising a metal nitride protective layer. A protective layer or protective layers (to protect it from oxidation during heat treatment) are used to cover the solar control layer. With respect to the solar control layer, there are many examples of its composition including tin oxide doped with the sun radiation layer. • Antimony or fluorine. • • • • • • • • • • • • However, the specific combination of doped SnO ₂ layers described in the present invention to achieve solar control, low emissivity and anti-irradiation without being guided by Gordon's instructions is not mentioned or exemplified in this patent.

European patent EP 0-735-009-A1, the corresponding patent application was published in February 1996, owned by Central Glass Co., discloses a heat reflecting glass sheet having a multilayer coating consisting of a glass plate and two layers. The first layer is a high refractive index metal based on Cr, Mn, Fe, Co, Ni or Cu, the second layer is a lower refractive index film based on a metal oxide such as tin oxide. Doped layers and combinations with low emissivity or NIR absorbing properties are not discussed anywhere in this patent.

International patent application WO 98/11031 should also be included in the prior art. This patent application was published in March 1998 and is owned by Pilkington PLC. This international patent application discloses a high performance solar control glass comprising a glass substrate with coatings comprising a heat absorbing layer and a low emissivity metal oxide layer. The heat absorbing layer may be a metal oxide layer. This layer may be doped with tungsten, cobalt, chromium, iron, molybdenum, niobium or vanadium oxides, or mixtures thereof. The low emissivity layer may be doped tin oxide. In a preferred embodiment of the invention, the iris-suppression layer or layers is incorporated under a coating layer comprising a heat absorbing layer and a low

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9 · 4 emission abilities. In this international patent application, no specific combination of doped SnO ₂ layers according to the present invention is disclosed or mentioned that provides solar control, low emissivity and irritation prevention without requiring a Gordon-type backsheet to suppress irradiation or color reflection.

Canadian Patent No. 2,193,158 discloses an antimony doped tin oxide layer formed on glass, wherein the tin to antimony molar ratio is in the range of 1: 0.2 to 1: 0.5, and this layer reduces light transmission glass.

Dopant Effects in Sprayed Tin Oxide Films, E. Shanti, A. Banerjee, and K.L. Chopra, Thin Solid Films, vol. 88, 1981, pp. 93-100, discusses the effects of doping agents of antimony, fluorine, and antimony with fluorine on the electrical properties of tin oxide layers. No optical properties of antimony and fluorine films, nor any effect on transmitted or reflected color, are reported anywhere in this publication.

United Kingdom Patent No. 2,302,101 to Glaverbel discloses a glass article coated with an antimony / tin film of at least 400 nm thickness containing a Sb / Sn molar ratio in the range of 0.05 to 0.5 with visible light transmittance less than 35%. These films are applied with a CVD water spray and are intended for private use of glass.

This patent discloses haze limiting back coatings as well as thick layers with a low Sb / Sn ratio having low emission properties as well as high solar absorption. It also states that it is

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0 0 0 · · · 0 0 0 · • 0 ····>> 0 0 · «0 · 0 · 0 · 0 00« 00 «• 0 0 0 · 0 0 0000 0000 00 00 ·· 00 one additional layer of coating, or more such layers, to achieve the desired optical properties. However, none of these properties except haze are mentioned in this patent. There is also no mention of thinner layers, the use of more than one dopant or controlling the color of the film.

United Kingdom Patent No. 2,302,102 A, also owned by Glaverbel, describes a glass substrate coated with a Sn / Sb oxide layer containing tin and antimony in a molar ratio ranging from 0.01 to 0.5, which has been deposited by the CVD method, wherein the coated substrate has a solar factor (solar heat input coefficient) of less than 0.7. These coatings are intended for use on windows and have a light transmission of between 40 and 65% and a thickness in the range of 100 to 500 nm. Hazard-reducing backsheets are also protected according to this patent, while low emissivity can be imparted to the coating by careful selection of the Sb / Sn ratio. As in the foregoing solution, the teaching of adding one or more additional layers of coating to achieve certain desirable optical properties is mentioned. Also, low emissivity layers of fluorine doped tin oxide may be applied to the Sb / Sn layers or fluorine components may be added to the Sb / Sn reagents to provide low emissivity films containing F, Sb and Sn. The latter two methods are not preferred, given the additional time and cost of applying the third layer and the fact that the emission performance of Sb / F films has increased and not decreased. Also, no reference to color control or color neutrality has been found in this patent.

United Kingdom Patent No. GB 2 200 139, whose ··

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444 444 • 4 owned by Glaverbel, describes a process for depositing a coating by spraying solutions containing tin precursors, a fluorine compound and at least one other dopant selected from the group consisting of antimony, arsenic, vanadium, cobalt, zinc, cadmium, tungsten, tellurium or manganese .

Glass manufacturers have previously carried out control of the heat transfer through the window by using absorbent and / or reflective coatings, by coloring the glass and subsequently depositing films. Most of these coatings and films are designed to control only one portion of the solar thermal spectrum, either NIR, that is, near the infrared region of the electromagnetic spectrum with a wavelength in the range 750 to 2500 nm, or near the middle infrared regions of the electromagnetic spectrum with a wavelength in the range of 2.5 to 25 gm. A prior art product has been proposed to control the entire thermal spectrum, but metal and dielectric film assemblies deposited by plating, although effective, have a limited durability, and must be protected and enclosed in the middle of an insulated multi-pane glazing unit (IGU). According to the prior art, there is a need in the art to develop a solar control film or combination of films that can be easily applied by pyrolytic deposition during the glass manufacturing process to obtain an article having acceptable visible light transmittance, it reflects or absorbs NIR, reflects radiation from the middle infrared region and is neutral or near neutral in color.

The aforementioned prior art publications, either alone or in combination, do not disclose or suggest the possibility of forming a specific combination.

The doped layers of SnCl 2 which were invented according to the present invention and which can be used to control solar radiation, low emission capability and anti-irritating properties without the need for a Gordon-type backsheet.

SUMMARY OF THE INVENTION

The present invention provides improved solar control glass having acceptable visible light transmittance, absorbing near-infrared (NIR) wavelength light, and reflecting middle-infrared (Low Emission) wavelength radiation, together with a preselected color of the reflected light in the visible spectrum, which may be adjusted to a particular color, or may be substantially colorless (neutral as defined below). The present invention also provides a process for manufacturing such improved glass having a solar control coating. The improved glass has a solar energy absorbing (NIR) layer comprising tin oxide with dopants such as antimony and an emission capability control layer capable of reflecting a medium wavelength infrared radiation containing tin oxide doped with fluorine and / or phosphorus. A separate separate iridescent paint suppressing layer as described in the prior art is generally not needed to achieve the appearance of neutral (colorless) light reflected from the coated glass, but the iris suppression layer or other layers may be combined with a two layer stack according to the present invention. invention. If desired, multiple solar control layers and / or multiple low emissivity layers may be used. The NIR layer and the low emissivity layer can be separate portions of a single tin oxide film because both layers are composed of doped tin oxide. The present invention also includes a process for producing coated solar control glass. In addition, it is possible to control or change the color of the transmitted light by adding color additives to the NIR layer according to the present invention. Surprisingly, it has been found that doping fluorine, which provides an uncoloured tin oxide film, acts as a coloring additive when added to the NIR layer and modifies the color of the light transmitted by the NIR film.

Description of attached pictures

The accompanying drawings serve to further, in detail, explain the nature of the solution according to the present invention.

In Figures 1 to 4 and 8 to 13, different types of coated glass are shown in cross-section, having a different number of layers or films with different arrangements for depositing individual layers on a glass substrate.

Figures 5 and 6 show graphically the solar control achieved by antimony doped films with different dopant concentrations and different film thicknesses on window panes, i.e., on a single pane of glass, or on insulated glazing units (IGU), which are composed of at least two glass panes. blackboard.

Figure 7 shows the color spectrum in the x and y coordinates of the Commisional Internationale de L Eclairage (CIE) and the specific coloration that can be achieved by different film thicknesses and concentrations of doping agents. The English translation of C.I.E is International Commision on Illumination.

It is an object of the present invention to provide a transparent object with controlled reflected color (even with neutral color as defined herein) that absorbs near-infrared (NIR) wavelength radiation and reflects mid-wavelength infrared radiation (low emissivity) consisting of two thin film layers containing doped SnO ₂ . Another object is to apply layers by atmospheric pressure chemical vapor deposition (CVD) technology, or by using other methods such as spraying solutions, or vapor / sublimation of a liquid / solid. A preferred deposition method for the present invention is the CVD method carried out at atmospheric pressure and using vaporized liquid precursors. Another object of the invention is to provide multiple layers for controlling solar radiation and / or for achieving low emissivity together with other layers in combination with layers for controlling solar radiation and for achieving low emissivity. Another object is to provide a solar control film or a combination of films that can be readily deposited by pyrolytic deposition during the glass manufacturing process to obtain a product having acceptable visible light transmittance, NIR reflectance or absorbance, reflect infrared (low infrared) radiation -E) and is neutral or near neutral in coloring, and the present invention includes a process for the manufacture of these products. Another object of the invention is to control the color of transmitted light, independently of the color of the reflected light, by adding additives to the NIR layer.

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Low emissivity coated glass is produced by depositing at least two layers on a heated transparent substrate, namely a low emissivity layer consisting of a fluorine and / or phosphorus tin oxide film of SnO ₂ and a NIR absorbing layer of a SnO ₂ film ₂ containing antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel, or a mixture thereof as dopant. It has been found that this combination effectively controls a portion of the solar and radiation thermal portions of the electromagnetic spectrum, so that the film coating window has much better properties.

The solar control properties are usually expressed using the solar heat gain coefficient (SHGC) and the U value. The SHGC is a measure of the total solar heat gain through the window system relative to the incident solar radiation, while the U (U) is the total heat transfer coefficient for the window. . The SHGC of the coated glass is primarily dependent on the thickness and antimony content of the NIR absorbing film (see Figures 5 and 6), while the U value depends primarily on the film's emissivity and window construction. The SHGC value measured in the center of the glass may be in the range of about 0.40 to 0.80, while the U value measured in the center of the glass may vary in the range of about 0.7 to 1.2 for a single sheet coated with films formed according to the preferred embodiment. according to the invention. In an insulated glazing unit (IGU), the SHGC value drops to -0.30, while the U value drops to ~ 0.28.

It is possible to control both the reflected and transmitted color of the coated glass according to the present invention. In addition, it is possible to control the amount of visible light transmitted through the coated glass within the range of 25 to 80% by controlling the thickness of the NIR film and the low emissivity film, and the concentration of dopants in the NIR film. The transmitted color, i.e. the color of the light transmitted by the coated glass, can be controlled separately from the reflected color by the addition of a color effective amount of colorant in the NIR coating layer. The reflected color may vary from almost neutral to red, yellow, blue or green, and this color can be controlled by varying the film thickness and the dopant content in the layers. Surprisingly, an almost neutral coloration as defined herein can be achieved with the reflected coloration without the need to form an iris layer. Although the refractive indices of the NIR film and the low emissivity film are different, the reflected color does not depend on the classic interference phenomenon originally discovered by Gordon (see U.S. Patent No. 4,187,336). The observed reflected color is unexpectedly controlled by the combination of absorption and reflection achieved in the NIR (absorption) layer and the reflection achieved by the low emissivity layer or layers. The absorption of the NIR layer can be controlled by varying the thickness of its tin oxide layer, SnCl 2, and the concentration of dopant in the NIR layer, usually antimony. The reflectivity of the low emissivity layer can be controlled by varying the thickness of its SnCl 2 layer and the dopant concentration in the low emissivity layer, usually fluorine. The low emissivity layer composed of SnCl2 containing a fluorine or phosphorus dopant is sometimes abbreviated as TOF or TOP in the present disclosure, while the SnO2 NIR layer, if it contains antimony, is sometimes abbreviated herein as TOSb.

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Preferably, a combination of a fluorine doped tin oxide film (TOF) is used as a low emissivity layer and an antimony doped tin oxide film (TOSb) as an NIR layer. TOF films and glass coating processes are known in the art and are referred to herein as low emissivity films. The NIR absorbing film is also a SnCl2 based tin oxide film, but contains a dopant other than the low emissivity layer. The dopant in the NIR layer is preferably antimony, although the dopant may be an element selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel, or mixtures thereof. A mixture of one or more doping agents may be used in the NIR layer, but the low emissivity layer must include a low emissivity dopant that provides the layer with significant conductivity, such as fluorine or phosphorus, but may be combined with the dopant. other low-doping agents can be used for low emission capability. Because the low emissivity layer and the NIR layer both use tin (II) SnCl 2 as the dopant containing metal oxide matrix, the NIR layer and the low emissivity layer may form part of a single dopant gradient film. This single film using a dopant gradient is shown in Figure 3 as film 16. In this film 16, a dopant gradient is formed wherein the dopant NIR has a higher concentration than the second dopant on a single surface of the film, either on the surface 18. or 22, wherein the low emissivity dopant has a higher concentration than the other dopants on the second surface of the film. This leads to a change, or to a gradient, in the concentrations of doping agents for NIR and low emission. 9 9 9 9 9 99 99 9 9 9 9 9 9 9 9 9 9999 999 999

9 9 9 9 ·· · 99 99 ability between surface 18 and surface 22. At some intermediate point 20 between surface 18 and surface 22, the concentration of dopant for NIR changes from the highest concentration of dopant on one side of point 22 to the concentration on the other the side of this point 22, which is no longer the highest. Figure 8 shows the Low E 10 low emissivity film above the NIR 12 film. The NIR 12 film in Figure 8 has a NIR dopant concentration gradient in the lower tin oxide film closer to the low emissivity film 10. Coated glass in Figure 9 has a structure similar to that of FIG. 8 except that the concentration gradient of the dopant NIR, usually antimony, is higher near the low E10 film, and lower closer to the substrate. The film 12 is different from the film 16 shown in Figure 3 in that the film 12 is a NIR film, while the film 16 has both a NIR film and a low emissivity film and contains both a low emissivity dopant and a concentration gradient dopant. low-emission dopant dopant and NIR dopant dopant concentration gradient. Figures 10, 11, 12 and 13 show the NIR layer as two separate films 28 and 30. The film 28 is shown to be thicker than the film 30 and the total thickness of the NIR layer is the sum of the film thicknesses 28 and 30 and is within the thickness range given above. NIR layer and preferably from 80 to 300 nm. In Figures 10 and 11, films 28 and 30 are adjacent, while in Figures 12 and 13, films 28 and 30 are situated on opposite sides of the low emissivity film 10. The concentration of dopant in film 28 is preferably different from the concentration of dopant in the film. movie 30.

A preferred embodiment of the invention uses antimony doped film as NIR film. Such a film may be applied by a variety of technologies including pyrolysis spraying, PVD and CVD methods. Pyrolysis spraying is known in the art and is described in many patents, such as Canadian Patent 2,193,158. The CVD method for depositing SnO ₂ films with or without doping agent and chemical precursors for forming SnO films ₂ containing doping agents are well known in the art, such as are disclosed in U.S. Patent Nos. 4,601,917 and 4,285,974. It is preferred to deposit dopant-containing SnO ₂ layers by CVD by conventional methods directly on the float glass production line outside or inside the float glass chamber using conventional online technologies and with the aid of chemical precursors such as those disclosed in U.S. Patent No. 4,853,257 to Henery. However, SnO ₂ films containing doping agents can be applied as layers to glass by other techniques such as spraying solutions or burning / subliming liquids / solids at atmospheric pressure. A preferred deposition method for the present invention is the CVD method carried out at atmospheric pressure using liquid vapor precursors. This procedure is very adaptable to existing on-line application systems. Preferred are precursors that can be applied economically, allow long coating times, reduce system cleaning frequency, and are capable of use with or without modifying existing coating equipment on float glass lines.

The coating acts by a combination of reflection and absorption. Low emissivity film reflects mid-wavelength infrared thermal radiation in the range of 2.5 to 25 μιη

of the spectrum, while the absorbing NIR film absorbs heat primarily in the region of 750 to 2500 nm. While the following explanation is not bound by theory, it is believed that this effect can be explained by the fact that in the NIR region the plasma wavelength (PL - wavelength when the low emissivity film changes from transmitting light energy for reflecting light energy) of the low emissivity film falls within the NIR area. In the band around PL, the low emissivity film of NIR absorption is highest and when combined with the NIR absorbing film, increased absorption occurs. The NIR absorbing films according to the preferred embodiment of the invention are also doped semiconductors and thus have reflective properties at mid-wavelengths of infrared radiation. This reflectance together with the reflectivity of the low emissivity film provides an overall higher reflection of heat at the mid-wavelengths of infrared radiation.

In a preferred embodiment, SnCl2 is pyrolytically deposited on the glass by means of a tin precursor, in particular, organotin precursor compounds such as monobutyltin trichloride (MBTC), dimethyltin dichloride, dibutyltin diacetate, methyltin trichloride or any of the known Sn precursors may be used. CVD, such as disclosed in U.S. Patent No. 4,601,917, which is incorporated herein by reference. Such organotin compounds used as precursors for the pyrolytic deposition of SnCl 2 often contain stabilizers such as ethanol. The concentration of the stabilizer is preferably less than 1% to reduce the risk of fire when hot glass comes into contact with such a chemical agent in the presence of oxygen. NIR-doping dopant precursors (antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium)

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9

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(Cobalt and nickel) are preferably halides such as antimony trichloride, but alkoxides, esters, acetylacetonates and carbonyl groups can be used as well. Other suitable dopant precursors and SnCl 3 are well known to those skilled in the art. Suitable precursors and amounts of fluric dopant for low emissivity SnO 2 layers are disclosed and in U.S. Patent No. 4,601,917 and include trifluoroacetic acid, ethyltrifluoroacetate, ammonium fluoride, and hydrofluoric acid. Concentrations of dopant to achieve low emissivity are generally less than 30%, preferably from 1% to 15% by weight of the total weight of dopant precursor and tin precursor. This generally corresponds to the dopant concentration in the film to achieve a low emissivity of from 1 to 5% by weight of the tin oxide in the low emissivity film.

Preferably, the properties depend on the thickness of the low emissivity layer and the absorbent layer as well as the antimony content of the absorbent (NIR) film. The thickness of the low emissivity film may range from 200 to 450 nm, more preferably from 280 to 320 nm. The preferred NIR absorbent film can be deposited in a similar manner to the low emissivity films by the methods and means disclosed in U.S. Patent No. 4,601,917. The organotin precursors of SnO 2 can be vaporized in air or other suitable carrier gas. comprising an oxygen source in concentrations ranging from 0.25 to 4.0 mol% (preferably ranging from 0.5 to 3.0 mol%). Concentration of precursors

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SnO ₂ are expressed herein as a percentage of the molar content of the precursor and the molar content of the carrier gas. Preferred concentrations of doping agents for the NIR range from about 1% to about 20% (more preferably from 2.5% to 7.5%, more preferably from 3.0% to 6.0) %) and are calculated from the weight of the dopant precursor and the weight of the SnO ₂ precursor. Particularly preferred is an antimony dopant using antimony trichloride as a precursor in an amount in the range of about 2% to about 8% by weight, particularly preferably in the range of about 4.0% by weight. This content is consistent with a similar weight percent content in the NIR tin oxide film.

The coated glass of the present invention is shown in the accompanying drawings. Figure 1 shows the film in section. The thickness of these films may range from 200 to 450 nm for the low emissivity film (reference numeral 10) and from 80 to 300 nm for the NIR film (reference numeral 12). Preferred thicknesses in the low emissivity film are in the range of 250 to 350 nm and in the case of the NIR film in the range of 200 to 280 nm. More preferably, the low emissivity film is in the range of from 280 to 320 nm and the NIR film is in the range of from 220 to 260 nm. In a preferred embodiment of the present invention, the coated solar control glass may be produced in a neutral blue color, which is defined herein as reflected light coated glass, predominantly with C.I.E. x between 0.285 and 0.310 and y between 0.295 and 0.325. The definition of neutral blue is shown in Figure 7 by a flat window labeled neutral blue. As shown in Figure 7 and the values given in Examples 15, 20 and 22, it is possible to produce a controlled or preselected reflected color close to that of a neutral color but a neutral color.

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44 44 44 slightly to a red tint (x values up to 0.325 and y values up to 0.33), but such substantially neutral to slightly red shades of reflected color will not be seen by consumers. Figure 2 shows two films or layers in reverse order to Figure 1. In Figure 2, the low emissivity film is closer to the glass 14 than the NIR film 12. Figure 3 shows the NIR layer and the low emissivity layer integrated into a single film 16 tin (IV) oxide SnO 2, wherein a gradient of doping agents is formed in this layer 16. Film 16 has a predominant dopant (e.g., low emissivity, fluorine) dopant on the top surface 18 remote from the glass 14, and a predominant dopant (e.g., NIR dopant such as antimony) on the surface of the film 22 closer to the glass . The dopant concentration varies from surface 18 to surface 22 so that one dopant varies from more than 50% of dopant at surface 18 to about 0% at surface 22. At an intermediate point 20 below the top surface 18, the predominant dopant at at this point in the film, it changes from the predominant dopant at surface 18 to the predominant dopant at surface 22. The predominant dopant at surface 18 may be a NIR dopant or a low emissivity (fluorine) dopant, the second dopant being predominant at Figure 4 shows a coated glass having additional layers 24 and 26 to the low emissivity layer 10 and the NIR layer 12. The additional layers 24 and 26 may be additional low emissivity layers or NIR layers, or other conventional layers used for glass coating, such as a colored layer. For example, layer 12 may be a NIR layer (e.g., antimony doped tin), a low emissivity layer 10 (fluorine doped tin), and a layer 24 or other NIR layer. The layer 26 may be an additional 4 44 44 44 44 44 4 4 4 4 4 4 4 4

4 4444 4444 * · 44 4 4444 444 444

4444 4444 «4 · 4 44 44 low emissivity layer or some other conventional layer. The concentration of dopant, when more than one low emissivity layer is used, may be the same or different, and the thickness of each low emissivity layer may also be the same or different. Similarly, if more than one NIR layer is used, the concentration of dopant and choice of dopant (antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel) may be the same or different and the thickness of each layer The NIR may be the same or different. In general, the dopant for the NIR layer is mostly antimony, but it should be noted that the dopant for the NIR layer may be selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel, or mixtures thereof. Similarly, in the embodiment of the invention with the gradient layer shown in Figure 3, the predominant dopant at the NIR surface, either at surface 18 or at surface 22, may be selected from the group consisting of antimony, tungsten, vanadium, iron , chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof, but it is essential that the low emissivity dopant, e.g. fluorine, is the predominant dopant on the other side. One or more such or low emissivity layers such as layers 10 and 12 in Figures 1 and 3 and / or other conventional layers may be combined with a gradient layer.

Water is preferably used to accelerate the deposition of the SnO ₂ film on the glass as suggested in U.S. Patent No. 4,590,096 (Lindner) at a concentration of from about 0.75 to 12 mol% H ₂ O, based on the composition of the gas mixture.

• · · · ·

• ·

DETAILED DESCRIPTION OF THE INVENTION

The solution according to the invention will be explained in more detail in the following examples, which are given to illustrate preferred embodiments of the invention and are not to be construed as limiting the scope of the invention in any way. It will be apparent to those skilled in the art that other modifications beyond the embodiments disclosed herein may be made within the scope of the present invention.

The present most preferred embodiment for obtaining a low emissivity and neutral reflected color coated glass with only two films on glass is about 300 nm thick TO: F (fluorine doped tin oxide) film in combination with about 240 nm thick TO film: Sb (antimony doped tin oxide) on glass. The film thickness of the TO: F layer can range from 280 nm to 320 nm and still achieves a surprising result in terms of neutral reflected color. The fluorine concentration can range from about 1 to 5 atomic%. The thickness of the TO: Sb film may range from about 220 to 260 nm, with an antimony concentration of about 3 to 8% and still a surprising result of a neutral reflected color of the coated glass. Within the preferred thickness and concentration range of the dopant of the present invention, a coated solar control glass having a NIR layer and a low emissivity layer may be produced having a reflected blue color of neutral blue, i.e. coated glass having a reflected light color predominantly in CIE values the color coordinates x between 0.285 and 0.310 and y between 0.295 and 0.325, as shown in Figure 7 through the window

0 0

000 000

0 * 00 denoted neutral blue, or near neutral blue with x values of about 0.32, as shown in Examples 15, 20 and 22.

Examples 1 to 30

A 2.2 mm thick glass substrate (siliceous 9 soda-lime glass) with an area of 12.9 cm was heated on a heating block to a temperature of 605-625 ° C. The substrate was placed 25 mm below the central portion of a vertical concentric coating nozzle. The carrier gas, which was dry air flowing at a rate of 15 liters per minute (rpm), was heated to 160 ° C and then passed through a vertical hot-wall evaporator. The liquid coating solution, containing about 95% by weight monobutyltin trichloride and about 5% antimony trichloride, was fed to the vaporizer by a controlled flow rate syringe designed to achieve a concentration of 0.5 mol% organotin in the gas composition. Water was supplied to the vaporizer in a controlled amount in such a way as to achieve a concentration of 1.5 mol% water vapor in the gas composition. This gas mixture was allowed to impact the glass substrate at a front speed of 0.9 m / sec for about 6.1 seconds, resulting in an antimony doped tin oxide film of about 240 nm. Immediately thereafter, a second gas mixture consisting of a precursor composition containing 95% by weight of monobutyltin trichloride and 5% by weight of trifluoroacetic acid was used together with water at the same concentration and with the carrier gas used above to deposit the antimony doped tin oxide layer. This second gas composition was allowed to strike the coated substrate for about 6.7 seconds. In this way, a fluorine doped tin oxide film of about 280 nm was deposited. This two-layer film was very light blue in viewing and reflection.

0 · ·

000 000 ·

Φ · · ·

Optical properties were measured with a UV / VIS / NIR spectrophotometer and the layer strength was measured with a standard four-point probe. The solar heat gain coefficient, the U value, and the visible transmittance in the center of the glass were calculated using Vindow 4.1, developed by Lawrence Berkeley National Laboratory, Windows and Daylight Group, Building

Technologies Program, Energy and Environmental Division. The C.I.E color coordinates, i.e., x and y, were calculated according to ASTM E308-96 from visible light reflection data between 380-770 nm and tristimulus values for Illuminant C (light source C). The results of this film analysis are shown in Table 1, item 19. The procedure of this example was repeated twenty-nine times with varying concentrations of chemical precursors and deposition times to obtain coated glass samples with different NIR and low emissivity layer thicknesses and doping concentrations substances. The results are shown in Table 1.

Examples 31 to 38

In these examples, the procedure of Example 1 was repeated except that the vapor feed order was reversed. First, a fluorine doped tin oxide film was applied for about 8 seconds, and then an antimony doped tin oxide film was applied for about 6 seconds. The resulting film had a thickness of about 540 nm and was composed of a low emission capability (TOF) layer of about 300 nm and a NIR (TOSb) layer of about 240 nm and had a similar appearance and color of reflected light (neutral blue color) to the film Example 19. The analysis results are shown in Table 2, item 31. The procedure of this example was repeated seven more times with varying concentrations of chemical precursors and deposition times to obtain coated glass samples of different thicknesses.

Ftft NIR and low emissivity layers with varying concentrations of dopants. The results are shown in Table 2.

Example 39

The procedure of Example 1 was repeated except that three mixtures of feed precursors were used. The composition of the third mixture contained 90% monobutyltin trichloride, 5% trifluoroacetic acid and 5% antimony trichloride. The gradient film was deposited by first depositing only the antimony doped tin oxide precursor of Example 1 for 70% of the time required to deposit 240 nm. A mixed precursor doped with antimony and fluorine was then introduced. The feed of both precursor mixtures continued for 20% of the total deposition time and then the feed of the antimony precursor mixture was closed. The feed of mixed precursors with antimony and fluorine continued for the remaining 10% of the total deposition time for the 240 nm antimony film. At this point, the precursor feed for the fluorine doped tin oxide film was started. Both feeds continued for 20% of the time required to deposit a 300 nm fluorine doped tin oxide layer. The feed of the mixed antimony and fluorine precursors was closed and the feed of the fluorine doped tin oxide precursors continued for the rest of the time to deposit the fluorine doped film. The resulting gradient coating layer has a light blue color of transmitted and reflected light (x = 0.292, y = 0.316), SHGC = 0.50 and a U value of 0.6 and a visible light transmittance of about 45%. As can be seen from Figure 3, the surface 22 of the gradient film 16 has substantially 100% antimony dopant, while the surface 18 has substantially 100% fluorine dopant with a gradient of dopant concentration between surfaces 18 and 22. · ··· <

formed in the SnO ₂ film matrix.

Examples 40 to 43

Examples 40 to 43 also used the procedure of Example 1. The coating composition for the NIR layer in Examples 41 and 43 was composed of fluorine, antimony, and a tin precursor formed by the addition of SbClg and TFA to MBTC. This precursor contained 0-5% by weight of TFA, 5.2-5.5% by weight of SbClg and the remainder of the MBTC and fed with water to a second vaporizer. The carrier gas for the second vaporizer was dry air supplied at 15 liters / minute. The fluorine, antimony and tin precursors were added in an amount of 0.5 mol% of the total carrier gas flow, and the evaporator temperature was maintained at 160 ° C. The soda-lime silica glass substrate of 12.9 cm in size and 2.2 mm in thickness was preheated to a temperature of 605-625 ° C on the heating block. The heating block and the substrate were then moved to a position just below the vertical applicator nozzle, with the substrate positioned 25 millimeters below the applicator nozzle. Then, the F / Sb / Sn / H ₂ O pairs from the second vaporizer were directed to the glass substrate, and in Examples 41 and 43, an antimony and fluorine doped tin oxide backing layer was applied. The carrier gas velocity was 0.9 m / s and the thickness of the antimony and fluorine doped tin oxide film was about 240 nm. Reaction by-products and unreacted precursor vapors were aspirated from the substrate at 18 L / min. After deposition of the antimony and fluorine doped tin oxide backing, the applicator nozzle valve was switched from the second vaporizer to the first vaporizer. MBTC / TFA / H ₂ O vapor was then fed to the substrate and a fluorine doped tin oxide layer was deposited on the top surface of the antimony and fluorine doped tin oxide backing. Carrier gas velocity was 0.9 m / s • · • ·

• φφ · φ

and the fluorine doped tin oxide film thickness was about 300 nm. The two-layer films of Examples 41 and 43 (containing both an NIR substrate with both F and Sb) had a light gray color of transmitted light and a neutral color of reflected light. Examples 40 and 42 essentially reproduce Examples 40 and 43, respectively, but without the fluorine dopant in the NIR backing layer. The proportions were measured and the results are shown in Table 3. The results show how fluorine, as an additional dopant in the NIR layer, acts to change the color of reflected and transmitted light. Transmitted colors Tγ _: δ _with x and y films made with TFA and Sb doping agents in the NIR layer of Examples 41 and 43 have more neutral reflected colors and grayer transmittance colors than samples containing only Sb as dopant in the antimony doped NIR oxide layer of tin in Examples 40 and 42.

In addition, the NIR layer doped with antimony with an amount of fluorine dopant affecting color has a higher visible light transmittance (increase vz _γ χ ₅ from 54.5 to 58.5 in Example 41 versus Example 42 with the same amount of antimony dopant).

The following Examples 44 to 47 show the deposition of films with the following composition: TOF / TOSb (low Sb concentration) / TOSb (high Sb concentration) / glass, TOF / TOSb (high Sb / TOSb concentration (low Sb concentration) / glass, TOSb (low) concentration Sb) / TOF / TOSb (high Sb concentration) / glass and TOSb (high Sb concentration) / TOF / TOSb (low Sb concentration) / glass.

Example 44

In Example 1, the procedure of Example 1 was repeated except that the glass temperature was about 610 ° C and the reagent concentration was about 0 ° C. 63 mol% in air flowing at 20 liters per minute. First, about 40 nm of antimony doped tin oxide was deposited from a liquid coating solution composed of about 10% by weight antimony trichloride and about 90% by weight monobutyltin trichloride. Immediately thereafter, a layer of about 200 nm of antimony doped tin oxide consisting of 3.25% by weight of antimony trichloride and 96.75% by weight of monobutyltin trichloride was deposited from the liquid coating solution. A third layer of about 300 nm of fluorine doped tin oxide was deposited from a solution containing 5% by weight of trifluoroacetic acid and 95% by weight of monobutyltin trichloride. The resulting film showed a light blue-green color of reflected light and a light blue color of transmitted light. The film properties were measured in the same manner as in Example 1. The visible light transmittance was 64% with a calculated SHGC of 0.56. The x and y coordinates for the reflected light color were 0.304 and 0.299, respectively, which placed the film in the quadrant of the neutral blue color space C.I.E as defined above.

Example 45

The procedure of Example 44 was repeated, but this time the TOSb layers were applied in reverse order. The resulting film had a blue-red color of the reflected light with color coordinates (x) of 0.330 and optionally (y) of 0.293. The visible light transmittance was 59% and the SHGC was 0.54. it will be apparent to those skilled in the art that the TOSb layers may have different thicknesses and concentrations than those set forth herein, however, these solutions will be within the scope of the present invention.

4 4 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Example 46

The procedure of the example was repeated

44, but in this example the deposition sequence of the fluorine doped tin oxide layer and the solution layer containing 3.25 wt% antimony trichloride was reversed. The resulting film had a visible light transmittance of 62%, a SHGC value of 0.55, and this film exhibited a neutral blue color of the reflected light indicated by color coordinates (x) of 0.311 and (y) of 0.311.

Example 47

The procedure of the example was repeated

45, the sequence of deposition of the fluorine doped tin oxide layer and the solution layer containing 10.0 wt% antimony trichloride was reversed. The resulting film had a visible light transmittance of 57%, a SHGC value of 0.53, and the film showed a light green reflected color indicated by color coordinates (x) of 0.308 and (y) of 0.341. It will be appreciated by those skilled in the art that the TOSb layers may have different thicknesses and concentrations than those set forth herein, but such solutions will be within the scope of the present invention.

All SHGC and U values in the tables were determined using Vindow 4.1 NFRC single band aproach. Using a more accurate multi-band approach (necessary spectral data set) would improve the SHGC by about 14%. Tristimulus C.I.E. For reflected and transmitted colors of coated articles, they can be calculated according to ASTM E308 using Illuminant C (Standard Light C) as standard. From ASTM E308, the following may be used: • The ASTM E308 standard may: • Specify the color of the item on one of a number of different scales. The scale used for the coated articles of the present invention is the color coordinates x and y of C.I.E 1931. They can easily be converted to an opponent color scale of C.I.E.1976 L *, a *, b * using the following equations:

x = x / (x + y + z) y = y / (x + y + z)

L * = 116 (Y / Y _n) ^{Ly / 3-16} a * = 500 [(X / X _n) ^1/3 - (Y / Y _n) ^1/3 b 1 * = 200 [(Y / YJ ¹ / ³ - (Z / Z _n ) l / ³ ] in which:

X, Y, and Z are tristimulus C.I.E. a coated article, and

X _n , Y _n and Z _n are 98.074, respectively 100.00 and 118.232 for standard Illuminant C.

From the values L *, a *, b *, the color saturation index c * can be calculated using the equation:

c * = [(a *) ^2! ^ *) ^{2] 1/2.}

A color saturation index of 12 or less is considered neutral.

Definition of the neutral blue color of the reflected light, i.e. coated glass with reflected light, mainly within the C.I.E. x between 0.285 and 0.310 and y between 0.295 and 0.325, as shown in Figure 7 through the neutral blue window, correlates with C.I.E.1976 b * with values of 37.85, -1.25, -5.9 and 39.62,

-2,25,1,5.

··· • · 4 4 ·

The sample conversion is as follows:

Example 40 (Table 3)

5.5% SbCl ₃ 300/240 (F / Sb / Glass)

X = 9.797 Y = 9.404 Z = 12.438 x = 0.310 y = 0.297 L * = 36.751 _a * = 4.624 b * = -3.466 c * = 5.778

The sunlight properties of the glass windows were evaluated and evaluated using the United States of America, Environmetal Agency standard, using the Energy Star rating system. A US Energy Star rating requires a U factor of 0.40 or less and a SHGC of 0.55 or less. The NIR-coated and low emissivity coated glass according to the present invention has been awarded an Energy Star rating for the central and / or southern region upon insertion into conventional construction windows. For example, using a 91.44 cm wide and 121.92 cm tall vertical sliding window with a frame absorption value of 0.5 as rated by the National Fenestration Rating Council (NFRC) and assembled with the solar control glasses of the present invention with NIR film and film with a low emission capability in preferred ranges of neutral blue, a SHGC of less than 0.40 and a U of less than 0.64 were achieved for a monolithic glass structure with a U-frame value of 0.7 or less, and a SHGC of less than 0 , 38 and a U value of less than 0.48 for an insulated glazing unit (IGU) constructed of 2.5 mm clear glass with an air gap of 12.7 millimeters and a NIR coating and a low emissivity coating on the # 2 outer glass surface and a U-value of 1.0 or less.

The above examples confirm that with at least two doped layers of SnO ₂ it is possible to produce excellent coated solar control glass with a preselected reflected light color. In the tables 1, 2 and 3 below, the figures and graphically illustrated dependencies of FIGS. 5 and 6 show how the solar properties of the coated glass vary with the dopant concentration and the film thickness, in particular for the NIR film. Figure 7 shows the CIE color coordinates of a representative selection of coated glasses from Examples 1 to 39. As can be seen from Figure 7, specific film thickness combinations for both NIR and low emissivity films and specific dopant concentrations can be used to produce solar control glasses with any desired color of the glass reflected from the coated glass surface, such as red, green, yellow, blue and shades thereof, or a neutral blue color. In particular, it is surprising that a neutral blue color can be achieved with NIR layers and low emissivity, but without the anti-iris layer, as suggested by Gordon.

While it is possible to achieve the objective of the present invention with only two layers, a NIR layer and a low emissivity layer, multilayer embodiments are within the scope of the present invention. Multiple layers may be additional NIR or low emissivity layers or other functional or decorative layers.

· To to ► ► ► ► ► ► to to to <<<<<<<<<<<<<<<

• this ·· <

Multilayer designs include TOSb / TOF / TOSb / glass or TO / TOF / TOSb / glass or TO / TOSb / TOF / glass, where TO is a tin oxide film only. If multiple NIR or low emissivity layers are used, then these layers need not have the same dopant concentration or the same dopant selection in each NIR or low emissivity film. For example, when two NIR layers are used in combination with at least one low emissivity layer, one NIR layer may have a lower level of antimony dopant (e.g. 2.5%) to provide some reflection at the mid-wavelengths of infrared radiation, and one layer it may have a higher level (> 5%) to absorb less infrared radiation. The terms layer and film are used interchangeably herein and have the same meaning, except for the discussion of the gradient film shown in Figure 3, where part of the film is referred to as a layer with a dopant concentration different from that of the dopant in another film layer. In the manufacture of the coated glass of the present invention, as described in the examples, the glass is successively contacted with a carrier gas containing precursors. According to this process, the glass may have a coating on its surface at the second contact with the carrier gas containing the precursors. Therefore, the term contacting the glass means either direct contact or contact with a single coating or with multiple coatings previously applied to the glass.

In another embodiment, the color of the light transmitted through the coated glass can be changed. The term transmitted color refers to the color perceived by the observer on the opposite side of the coated glass to the light source, while the color of the reflected light is the color perceived by the observer on the same side as the source

9 9 9

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9999 9999 light that is observed. Transmitted light may be affected by the addition of additional dopants to the NIR film. As previously explained, the NIR layer comprises a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel. The color of the light transmitted by the NIR layer may be varied by the addition of an additional dopant other than the first dopant in the NIR layer selected from the group consisting of tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and fluorine, or a combination of more than one dopant in the NIR layer. As shown in Examples 40-43, by adding a fluorine precursor, such as trifluoroacetic acid (TFA), to a NIR precursor solution, such as SbCl 2 / MBTC, a fluorine containing film can be formed as an additional dopant in the NIR layer of antimony doped tin oxide. When fluorine is present as an additional dopant in the antimony doped tin oxide layer, the permeate color is gray, as opposed to the blue permeable color of the fluorine-free antimony doped tin oxide layer. The additional dopant has little or no effect on the reflected light and thus it is possible to produce coated glass with light reflected differently from the light transmitted.

NIR doping agents such as vanadium, nickel, chromium and non-traditional color additives such as trifluoroacetic acid (TFA) and HCl can be added to the TO: Sb precursor in an amount of 1 to 5% by weight (of the total weight of the precursor and additive) ), thereby achieving a change in the color of transmitted light in the final film structure without significantly affecting the overall neutrality of the reflected color.

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w ’> ω’> CD

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R Colors Blue-Gr Blue Blue Blue-Gr Yl-Green Blue Yl-Neu Red Yi-Green Neutral Blue-Gr Blue Yl-Green Neutral Yl-Green ··· ···

Table 2

Summary of TOSb / TOF dual-layer film properties

# 31 32 33 34 35 36 37 38 Composit. Sb / F / G Sb / F / G Sb / F / G Sb / F / G Sb / F / G Sb / F / G Sb / F / G Sb / F / G % Sb 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 Thick. nm 240/300 160/300 138/300 120/300 110/300 80/300 120/332 120/262 % Asol 47.9 36.1 29.2 27.2 25.6 23.5 28.5 26.8 % Tsol 45.9 55.5 61.1 63.3 64.3 65.8 62.5 63.4 % Rsol, 1 6.1 8.3 9.7 9.6 10.2 10.7 9.0 9.8 % Rsol, 2 8.2 9.3 10.1 9.5 9.2 9.2 9.2 9.6 % Tvis 53.2 63.2 67.2 69.0 69.5 71.8 69.0 68.1 % Rvis, 1 6.1 7.6 9.3 9.1 10.1 10.9 7.8 9.9 % Rvis, 2 7.6 8.9 10.7 10.4 10.5 10.9 8.9 11.6 % Tuv 38.5 43.4 47.0 48.7 49.2 49.1 47.7 49.6 S. R, 14.7 15.9 16.5 17.4 18.8 17.3 15 Dec 21.1 Emis-cal 0.14 0.15 0.15 0.16 0.17 0.16 0.14 0.19 SHGCc 0.54 0.61 0.66 0.68 0.69 0.7 0.67 0.68  IG 0.45 0.53 0.58 0.6 0.61 0.62 0.59 0.6 Uc 0.73 0.74 0.74 0.74 0.75 0.74 0.73 0.76  IG 0.28 0.28 0.29 0.29 0.29 0.29 0.28 0.3 Tvis-c 0.53 0.63 0.67 0.69 0.69 0.72 0.69 0.68  IG 0.48 0.57 0.61 0.63 0.63 0.65 0.63 0.62 X 0.289 0.309 0.310 0.311 0.313 0.302 0.306 0.292 y 0.300 0.283 0.274 0.275 0.306 0.364 0.281 0.349 % Rvis 6.2 7.7 9.3 9.1 10.1 10.9 7.8 9.9 R Colors I 3lue Blue-Neu Blue-Gr Blue-Gr Neutral Greeen Blue-Neu Green

• 4 44 44 44 44 • 4 4 4 · 4 «4 · 44 4

4 «444« 444

4 44 44444 444 444

4 4 4 4 4 • 444 4444 44 44 44 44

Explanatory notes

Composit.

% Sb.

Thick.nm% Asol%% Tsol% Rsol.1% Rsol, 2% Tvis

S.R to the legends of Tables 1 and 2

F / Sb / G = fluorine doped tin oxide / antimony doped tin oxide / glass

Sb / F / G = antimony doped tin oxide / fluorine doped tin oxide / glass% by weight SbCl ^ (antimony trichloride) in MBTC (monobutyltin trichloride)

Profile measurement of individual T0: F (fluorine doped tin oxide) and TO: Sb (antimony doped tin oxide)% solar absorbance ^ · from the glass side of the film (= 100 - (% Tsol +% Rsol, 1)) - 300-2500 nm % of the solar transmittance ^ from the glass side of the film

- 300-2500 nm% solar reflection from the film side

- 300-2500 nm% solar reflection from the back side of the glass 300-2500 nm% transmittance ^ in the visible range of the glass side of the film - 380-780 nm layer resistance, measured by a four point Alessi method

Emis.Cal.

SHGCc

Uc

IG

Tvis-c

IG ^x > y (i). .. - ·· ·· ··

Ϊ ·! · ·· · · ♦ ·.

• · ····. ··.

* · · · · ···. · «* * * * * * *

Emission ability, calculated from the measured resistance of the layer (= 1- (1 + 0,0053 * SR) ² )

Coefficient of solar heat gain in the center of glass / single pane

Coefficient of solar heat gain in the center of glass in IGU ³

O

Total heat transfer coefficient for glass center / single pane

Total heat transfer coefficient for glass center in IGU ³

Transmittance in the visible region of the spectrum in the center of the glass / single pane - 380-780 nm

Transmittance in the visible region of the center of the glass at IGU ³ - 380-780 nm color coordinates, calculated from% Rvis according to ASTM E308, Illuminant C, 1931 Observer, 10 nm interval (Table 5.5) - 380-780 nm

Weighted with solar spectral irradiation (ASTM) E891-87) using spectral data obtained with a P-E Lambda 9 spectrophotometer with a 150 mm integration sphere

Calculated using Windows 4.1 Windows and Daylighting Group, Lawrence Berkeley National Laboratory (2) · 4 · 4

4444 4444

44

4 4 4 • 4 44 4

4 4

44 • 4 44

4 4 4

4 4 4

444 444

4

44 (3) IGU = insulated glazing unit of 2.2 mm coated glass (on surface # 2) and of 2.5 mm clear sheet with 12.7 mm gap with argon gas

R Colors = the color of the reflected light

Blue-Gr = blue-green;

Neutral = neutral;

Green = green;

Green-Bl = green-blue;

Green-Yl = green-yellow;

Red = red;

Yl / Green = yellow-green;

Yl-Neu = Neutral Green ···················· 99 · · 99

9 9

99

99

9 9 9

9 9 9

999 ··· • t «·

Table 3

Summary of TOSb / TOF dual-layer film properties

Composit.

% SbCl3% TFA

Thick. nm% Asol% Tsol% Rsol, 1% Rsol, 2% Tvis% RviS, 1% Rvis, 2% Tuv

S. R,

Emis-cal

SHGCc

IG

Uc

IG

Tvis-c

IG.

R1 x R1 y% Rvis Tvis x Tvis y

F / Sb / G

5.5

300/240

45.5 45.0

9.5

8.0

50.9

9.4 8.0

40.1

11.9 0.12 0.53 0.45 0.72 0.27 0.51 0.46 0.310 0.297

9.4

0.295

0.308

F / Sb-F / G

5.2

300/240

35.7

54.2

10.1

8.9

58.5

10.1

9.0

41.1

13.7

0.13

0.60

0.52

0.73

0.28

0.59

0.53

0.297

0.313

10.1

0.308

0.315

F / Sb / G

5.2 0

300/240

41.8

48.2 10.0

8.4

54.5

10.4

8.5

41.6

11.8 0.11 0.55 0.47 0.72 0.27 0.55 0.50 0.302 0.299

10.4

0.297

0.310

F / Sb-F / G

5.36

2.5

300/240

39.1

50.6

10.3

8.7

55.6

10.3

9.0

39.8

12.5 0.12 0.57 0.49 0.72 0.27 0.56 0.51 0.303 0.307

10.3 0.304

0.314

Claims (47)

PATENT REQUIREMENTS • •• 0 ··· 0 · · · 0 0 0000 0000 0 0 0 0 000 0 000 000 0 0 0 0 0 0 0 0000 0000 00 00 00 00 A coated solar control glass having a preselected reflected light color and having a NIR solar absorbing layer and a low emissivity layer, characterized in that it comprises a glass having at least two layers, one layer comprising SnO 2 with a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel, and mixtures thereof, and the second low emissivity layer comprises SnO ₂ containing a dopant selected from the group consisting of fluorine and phosphorus. Glass according to claim 1, characterized in that the thickness of the solar absorbing layer is from 80 to 300 nanometers (nm) and the thickness of the low emissivity layer is from 200 to 450 nm. The glass of claim 1 wherein the thickness of the NIR solar absorbing layer is from 200 to 280 nanometers (nm) and the thickness of the low emissivity layer is from 250 to 350 nm. 4. A coated solar control glass having a preselected reflected light color, having a solar absorbing layer and a low emissivity layer, comprising a tin dioxide SnC > 2 film comprising at least two doping agents, and a different concentration of dopant from one surface of the film to the opposite surface of the film, wherein the first dopant is selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt, nickel φ. φ φ · · φ · · · · φ φ φ φ φ φ φ φ φ · · φ • • • φ φ φ φ φ φ φ φ φ φ a a a a a a a a jejich jejich constitutes at least 50% of the doping agent present on the first surface of said film SnO ₂ to create a solar absorbing layer within said film SnO ₂ adjacent to said first surface, and the second dopant forms a concentration of at least 50% of the dopant at a second surface of said film opposite to the said first surface to form a layer of low emissivity in said Sn0 ₂ film adjacent to said second surface. The coated solar control glass of claim 4, wherein the first dopant is present at a concentration of at least 75% of the dopant present in said SnO ₂ film, in the region of the film starting with said first surface and continuing into the SnO ₂ film to a depth of at least 80 nm above said first surface, and said second dopant is at least 75% of dopants present in said SnO ₂ film in the region of the film starting with said second surface and continuing into the SnO ₂ film with a concentration of at least 75% nm, wherein said area of said SnO ₂ film having at least 75% of the dopant functions as a low-emissivity layer and said area of said SnO ₂ film having at least 75% of said first dopant acts as the NIR layer. The coated solar control glass according to claim 1, wherein said solar absorbing layer has a thickness of 220 to 260 nm, a dopant concentration of 2.5% to 7% by weight on the weight of SnO ₂ in said absorbing layer solar radiation, and a layer of · e · · · · · · · · · · · · · · · · · · · · · · · · Low-emitting β with a thickness of 280 to 320 nm, with a doping fluorine concentration of 1% to 5% by weight on the weight of SnO ₂ in said low emissivity layer, and the coated glass has a neutral blue color of reflected light. Glass according to claim 1, characterized in that the solar absorbing layer is SnO ₂ with an antimony dopant in the range of 3% to 6% by weight on the weight of SnO ₂ in the solar control layer, the low emissivity layer. is an SnO ₂ layer containing a fluorine dopant in the range of 1% to 3% dopant on the weight of SnO ₂ in the low emissivity layer, and the improved glass has a neutral blue color of reflected light. 8. The glass of claim 1 wherein the solar absorbing layer is applied directly to the glass and the low emissivity layer is applied to the upper surface of the solar control layer. 9. The coated solar control glass of claim 1 wherein the preselected reflected light color is red. 10. The coated solar control glass of claim 1 wherein the preselected reflected light color is yellow. 11. The coated solar control glass of claim 1 wherein the preselected reflected light color is green. • 4 • 0 · 0 ·· · 000 ···· · · 0 · · · φ 0 ··· 000 000 0 · 0 • · 0 0 0 · 12. The coated solar control glass of claim 1 wherein the preselected reflected light color is blue. 13. The coated solar control glass of claim 1, wherein the preselected reflected light color is a neutral blue color. 14th coated glass for solar control according to claim 1 wherein said solar absorbing layer and a low emissivity are contained in a single film Sn0 ₂ containing at least two dopants wherein a first dopant is selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum niobium, cobalt, nickel and mixtures thereof, and the second dopant is fluorine or phosphorus, wherein the first dopant has a higher concentration than said second dopant on one film surface, and the first dopant has a lower concentration than said second dopant on the opposite surface of the film, and a portion of said film near the second opposite surface acts as a low emissivity layer in said film. 15. The coated solar control glass of claim 1 wherein the dopant for the solar absorbing layer is antimony. 16. The coated glass of claim 15 wherein the antimony dopant is obtained from a precursor comprising antimony trichloride, antimony trichloride, antimony triacetate, antimony triethoxide, antimony fluoride, antimony fluoride, or antimony acetylacetonate. · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · * · · · · · · · · · · · · 17. The coated glass of claim 1 wherein the dopant for the low emissivity layer is fluorine. 18. The coated glass of claim 17 wherein the doping fluorine reagent is obtained from precursors comprising trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, ammonium fluoride, ammonium hydrofluoride, or hydrofluoric acid. 19. The coated glass of claim 1 wherein each of the SnCl3 layers is obtained by pyrolytic decomposition of the tin precursor. 20. The coated glass of claim 19 wherein the tin precursor is selected from the group consisting of monobutyltin trichloride, methyltin trichloride, dimethytin dichloride, dibutyltin diacetate, and tin tetrachloride. 21. The coated glass of claim 1 wherein the solar absorbing layer is comprised of at least two solar absorbing films, wherein the total thickness of the solar absorbing films is from 80 to 320 nm. 22. The coated glass of claim 21 wherein the concentration of dopant in one of the sun-absorbing films is different than the concentration of dopant in the other of the sun-absorbing films. A coated glass according to claim 1, characterized in that 9 9 9 99 9 99 9 99 9 9 That the low emissivity layer is comprised of at least two low emissivity films and that the total thickness of the low emissivity films is from 200 to 450 nm. 24. The coated glass of claim 23 wherein the concentration of dopant in one of the low emissivity films is different than the concentration of dopant in another of the low emissivity films. 25. The coated glass of claim 1 wherein said solar absorbing layer comprises an additional dopant in an amount that changes the color of the transmitted light. 26. The coated glass of claim 25 wherein the color modifying dopant is fluorine or chlorine. 27. The coated glass of claim 1 wherein the solar absorbing layer comprises chlorine as a further dopant. A method for producing coated glass according to claim 1, characterized in that the glass is subsequently processed at a temperature above 400 ° C: a first carrier gas comprising an oxygen source, H ₂ O, a tin precursor and a dopant precursor selected from the group consisting of antimony trichloride, antimony trichloride, antimony triacetate, antimony triethoxide, antimony fluoride, antimony fluoride, or antimony acetylacetonate; and a second carrier gas containing an oxygen source, H ₂ O, 99 9 99 9 A tin precursor and a dopant precursor selected from the group of trifluoroacetic acid, ethyltrifluoroacetate, difluoroacetic acid, monofluoroacetic acid, ammonium fluoride, ammonium hydrofluoride and hydrofluoric acid; to form a pyrolysis-formed NIR layer consisting of SnO ₂ containing an antimony dopant and a low emissivity layer consisting of SnO ₂ containing a fluorine dopant. A method for producing coated glass according to claim 1, characterized in that the glass is successively processed at a temperature above 400 ° C: a first carrier gas containing an oxygen source, H ₂ O, an organotin precursor and a dopant precursor metal containing a metal selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt and nickel, and a second carrier gas containing an oxygen source, H ₂ 0 , an organotin precursor and a fluorine or phosphorus-containing dopant precursor; to form a pyrolysis-formed NIR layer of SnO ₂ containing antimony, tungsten, vanadium, iron, chromium, niobium, cobalt, or nickel or mixtures thereof, and a low emissivity layer of SnO ₂ containing fluorine or phosphorus as dopant . The method of claim 22, wherein said glass is contacted with the first carrier gas before it is contacted with the second carrier gas. The method of claim 22, wherein the first carrier gas also comprises a second carrier gas component to form a product, wherein the NIR layer comprises an NIR layer. Fluorine or phosphorus doping agent in addition to antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, or nickel as doping agents. The method of claim 22, wherein the first carrier gas also further comprises a fluorine, chlorine, or phosphorus-containing dopant precursor. 33. The process of claim 32, wherein said fluorine, chlorine or phosphorus-containing dopant precursor is either trifluoroacetic acid, HCl, or phosphorous trichloride. The method of claim 22, wherein the first carrier gas also further comprises a film modifying agent selected from the group consisting of a fluorine- or phosphorus-containing dopant precursor. A product made by the method of claim 21. 36. The coated glass of claim 1 further comprising a fluorine dopant in said NIR layer and wherein the color of reflected light from said glass is different from the color of transmitted light. 37. The coated glass of claim 26 wherein the reflected light color is neutral blue and the transmitted light color is blue. 38. The method of claim 22, wherein the first carrier gas further comprises a second fluorine or phosphorus-containing dopant precursor or a second dopant-containing dopant precursor selected from the group consisting of antimony, tungsten, vanadium, iron. , molybdenum, niobium, cobalt and nickel. 39. The method of claim 27 wherein the second dopant precursor is selected from the group consisting of trifluoroacetic acid, ethyltrifluoroacetate, difluoroacetic acid, monofluoroacetic acid, ammonium fluoride, ammonium hydrofluoride, and hydrofluoric acid. A product produced by the process of claim 28. 41. A NIR film comprising tin oxide containing a dopant for NIR selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt and nickel, and containing a fluorine dopant at an atomic concentration, than the concentration of dopant for NIR. 42. The film of claim 32, wherein the fluorine dopant is present in an amount sufficient to change the color of the film transmitted light. 43. A NIR film comprising tin oxide containing a NIR dopant selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt and nickel and containing a color modifying dopant present in an amount sufficient to a change in the color of the light transmitted by the film, and selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt and nickel and fluorine, provided that the choice of the color-changing dopant is different from that of the NIR dopant; 4 4 · If the selected dopant is fluorine, its atomic concentration is lower than the dopant concentration for NIR. 44. A coated solar control glass having a neutral reflected color blue and further having a solar absorbing NIR layer and a low emissivity layer of glass coated with at least two layers, wherein one layer is a solar absorbing layer comprising a dopant containing dopant selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt, nickel, and mixtures thereof, and the other layer is a low emissivity layer formed by a dopant containing dopant selected from the group fluorine or phosphorus. 45. A coated solar control glass having a color intensity index of 12 or less for reflected light and further having a NIR solar absorbing layer and a low emissivity layer, comprising a glass having a coating comprising at least two layers wherein one layer is a SnO2-absorbing solar layer comprising a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt, nickel, and mixtures thereof, and the other layer is a low emissivity layer of SnC comprising a dopant selected from the group consisting of fluorine and phosphorus. 46. A coated solar control glass having color coordinates of C.I.E 1931 x between about 0.285 and 0.310 and y between about 0.295 and 0.325 for reflected light and further having a solar-absorbing NIR layer and a layer> • 9,999,999 • 9,999,999 «99 9 9 9 9 9 9 • 999 9999 9 999 with low emissivity, characterized in that it consists of glass coated with at least two layers, one layer being a solar absorbing layer containing SnO ₂ containing a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt, nickel and mixtures thereof, and the other layer is a low emissivity layer consisting of SnO ₂ containing a dopant selected from the group consisting of fluorine and phosphorus. 47. A coated solar control glass having a CIE color coordinate of 1931 x between about 0.285 and 0.325 and y between about 0.295 and 0.33 for reflected light and further having a solar absorbing NIR layer and a low emissivity layer characterized by characterized in that it comprises glass which is coated with at least two layers, one layer being a solar absorbing layer containing SnO ₂ containing a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, molybdenum, niobium, cobalt, nickel and their the other layer is a low emissivity layer consisting of SnO ₂ containing a dopant selected from the group consisting of fluorine and phosphorus. Represented by: Dr. Miloš Všetečka w m- zm ··· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ··· · ··· ·····················