MXPA99007735A - Glass coated for so control - Google Patents

Abstract

A glass for solar control is provided that has acceptable visible light transmission, absorbs near-infrared (NIR) wavelength light, and reflects mid-range infrared light (low intermediate IR emission) together with a preselected color within the spectrum of visible light for reflected light. A method for producing coated glass, for improved solar control, is also provided. The improved glass has a solar energy absorbing (NIR) layer comprising tin oxide having a softener such as antimony and a low emission (low emission) control layer capable of reflecting mid-range infrared light and comprising tin oxide which It has fluoride and / or phosphor softener. Generally, a separate irisdispersant color suppressor layer as described in the prior art is not needed to achieve a neutral (colorless) appearance for the coated glass, however a layer or other iris-suppressor layers can be combined with the two-layer assembly provided by the present invention. If desired, multiple layers of solar control and / or multiple low emission layers can be used. The NIR layer and the low emission layer can be separate portions of a single tin oxide film since both layers are composed of softened zinc oxide. A method for producing coated glass for sun control is also provided

Description

VI DR IO R EVESTI TION FOR SOLAR CO CONTROL This invention relates to coated glass used in residential, architectural and vehicle windows and miscellaneous applications where solar control and low emission properties are desired. The coatings for solar control and low emissivity contain tin oxide that has several softeners. The invention avoids the need for a lower anti-iridescent layer. Glass articles can be of any shape but are typically flat or curved. The composition of the glass can vary widely but is typically glass of sodium hydroxide and calcium oxide (soda lime) produced by a flotation process. It can be annealed, reinforced or heat tempered.

DESCR l ITION OF ANTERIOR ICA TECHNIQUE Solar control is a term that describes the property of regulating the amount of solar heat energy that is allowed to pass through a glass item into an enclosed space such as a building or an interior. of automobile. The low emissivity is a term that describes the property of a surface of an article where the absorption and emission of infrared radiation of intermediate range is suppressed, making the surface an infrared reflector of intermediate range and with this reducing the flow of heat to Through an article through the attenuation of transfer of the radiant component of heat to and from the low emission surface (sometimes referred to as Low E).

By suppressing the solar heat gain, the interiors of buildings and automobiles are kept colder; allowing a reduction in air conditioning requirements and costs. Efficient low emission coatings improve comfort during summer and winter by increasing the thermal insulation performance of a window. I mportants for commercially acceptable coated glass articles which possess both solar control and low emission properties are, of course, economic processes for producing the articles and durability and maintenance of associated properties such as light transmission, visibility, color, clarity and reflection. As explained below, several technologies have been employed to meet the requirements for solar control glass and low emissivity, however, no system has successfully met all the operating requirements in an economical manner. Many coatings and coatings systems cause the development of iridescent colors in the coated article. This may be caused by the chemical composition of the coating, the thickness of a single layer or layers, or an interaction of the substrate and coatings with the incident light. Such iridescence can, in some cases, be minimized or eliminated by placing an anti-iridescent layer between the glass substrate and the first coating. The use of an interference layer between the glass and a subsequent functional layer or layers to suppress iridescence or color reflection was first demonstrated by Roy G. Gordon, and was the subject of the U.S. Patent. , No. 4, 187,336, issued February 5, 1980. Gordon's technology has been the state of the art for glass coated solar control as evidenced by the recently granted U.S. Patent. , No. 5,780, 149 (McCurdy et al., July 14, 1998) which applies 2 layers to obtain solar control at the top of a Gordon-type interference layer. The interference layer frequently contains silicon dioxide. Surprisingly, the present invention represents dramatic progress and eliminates the need for a lower layer of Gordon type to control the reflected color. The Patent of E. U. , No. 3, 149,989 discloses coating compositions useful for producing radiation reflecting glass (solar control). At least two coatings are used with the first coating, adhered to the glass substrate, being made of tin oxide softened with a relatively high level of antimony. The second coating is also comprised of tin oxide and is softened with a relatively low level of antimony. The two films can be over-imposed, one over the other, or they can be applied on opposite sides of the film substrate. In any case, these solar control coatings do not contribute to the significantly low emission properties of the glass article. The Patent of E. U. , Do not . 4,601, 91 7 teaches liquid coating compositions to produce high-quality, high-yield tin oxide coatings, fluorinated softened by chemical vapor deposition. One of the uses of such coatings is in the production of energy efficient windows, also known in the trade as low-E or low-E windows. Methods for producing the coated glass are also described. This patent does not teach how to produce coated glass articles that possess both solar control and low emission properties. The Patent of E. U. , No. 4, 504, 109 assigned to Kabushiki Kaisha Toyota Chou, discloses glass coated with multiple infrared protective layers comprising a substrate transparent to visible light and a lamination of covering component consisting of "at least one protective layer of infrared and at least one layer of reflection interference that fall alternately on top of each other ... ". Indium oxide softened with tin is used in the examples as the infrared protective layer and TiO2 was used as the protective layer of interference. In order to reduce the iridescence, the thickness of the infrared protective layer and the reflection interference layer must have a value of a quarter of lambda (lambda / 4) with a permissible deviation from 75% to 130% of lambda / Four. Although other formulations are described for the infrared protective layer and the reflection interference layer such as SnO2 with or without softeners, (see column 6 lines 12 to 27), however, the specific combination of smoothed SnO2 layers of the present invention that performs solar control, low emission and anti-iridescence without requiring a thickness limitation of lambda / 4 is neither described nor exemplified to suppress iridescence or color reflection. The Patent of E. U. , No. 4,583,815, also assigned to Kabushiki Kaisha Toyota Chou describes a heat wave protective laminate consisting of two overlays of Indian tin oxide containing different amounts of tin. The anti-reflective layers, above or below the layers of Indian tin oxide are also described. Other formulations for the infrared protective layer and the reflection interference layer such as SnO2 are described with a softener which becomes a positive ion with a valence of + 5 such as Sb, P, As, Nb, Ta, W, or Mo or an element such as F which easily becomes a negative ion with a valence of -1, (see column 22 lines 17 to 23). However, the specific combination of smoothed SnO2 layers of the present invention that performs sun protection, low emission and anti-rinsing is neither described nor exemplified. There is no claim for tin oxide layers or any teaching in the specification to describe the composition of such layers, v. g. , the proportion of softener to tin oxide. It should also be noted that the teaching leads to the use of the same softener in both layers (indium tin oxide) while in the current patent application, one layer must contain a softener different from that of the other layer. U.S. Patent No. 4,828,880, assigned to Pilkington PLC, describes barrier layers that act to inhibit the migration of alkali metal ions from a glass surface and / or act as lower color suppressor layers to cover reflective layers of infrared or electrically conductive. Some of these color suppressor layers are used in construction of solar control or low emission glass. The U. U. Patent, No. 5, 168,003, assigned to Ford Motor Company, discloses a glass article having a substantially transparent coating comprising an optically functional layer (which may be low emission or solar control) and a thinner anti-iridescent layer than TS a multiple gradient step zone layer. Tin oxide softened with antimony is mentioned as a possible alternative or optional component of the exemplified low emission layer. U.S. Patent No. 5,780, 149, assigned to Libbey-Owens-Ford discloses coated glass for solar control where at least three coated layers are present, first and second transparent coatings and an iridescence suppressor layer falling between glass substrate and transparent top layers. The invention depends on the transparent layers that have a difference in refractive indexes in the near infrared region greater than the difference of indices in the visible region. This difference causes solar heat to be reflected in the nearby I R region as opposed to being absorbed. The softened metal oxides having low emission properties, such as fluoride-softened tin oxide, are used as the first clear coat. Metal oxides such as non-smoothed tin oxide are used as the second layer. No absorbent combinations are described R. R. EP 0-546-302-B1 granted on July 16, 1997 and assigned to Asahi Glass Co. This patent describes coating systems for solar control glass, heat treated (tempered or curved) ) comprising a protective layer based on a metallic nitride. The protective layer or layers are used to overcoat the solar control layer (to prevent oxidation during thermal treatment). As a solar control layer, many examples are provided including tin oxide softened with antimony or fluorine. However, the specific combination of smoothed SnO2 layers of the present invention that performs solar control, low emission and anti-iridescence without following Gordon's teachings is neither described nor exemplified. EP 0-735-009-A1 is a patent application that was published in February and 1996 and assigned to Central Glass Co. This patent application describes a heat reflective glass panel having a multilayer coating comprising a glass plate and two layers. The first layer is a high refractive index metal oxide based on Cr, Mn, Fe, Co, Nio Cu, the second layer is a film with a lower refractive index based on a metal oxide such as tin oxide. . The smoothed layers and combinations of low emission or absorbents of N I R are not described. WO 98/1 1031. This patent application was published in March 1998 and assigned to Pilkington PLC. Describes a high performance solar control glass comprising a glass substrate with coatings comprising a heat absorbing layer and a low emission layer of a metal oxide. The heat absorbing layer can be a metal oxide layer. This layer can be tungsten oxide, cobalt, chromium, molybdenum iron, niobium, or vanadium or mixtures thereof softened. The low emission layer can be smoothed tin oxide. In a preferred aspect of the invention, an iridescence suppressor layer or layers is incorporated under the coating comprising a heat absorbing layer and a low emission layer. This application does not disclose or suggest the specific combination of smoothed SnO2 layers of the present invention that performs solar control, low emission and anti-iridescence without requiring a lower "Gordon" type cover to suppress iridescence or heat reflection. Canadian Patent No. 2, 193, 158 discloses a layer of tin oxide softened with antimony in glass with a molar ratio of tin to antimony of 1: 0.2 to 1: 0.5 which reduces the light transmission of the glass. Dopant Effects in Sprayed Tin Oxide Films, by E. Shanthi, A. Banerjee and K. L. Chopra, Thim Solid Films, Vol. 88, 1981 pages 93 to 100 discusses the effects of antimony, fluoride, and antimony-fluoride softeners on the electrical properties of tin oxide films. The article describes some optical property of the antimony-fluorine films or the effect on transmitted or reflected color. The Patent Application of R. U. GB 2,302, 101 A assigned to Glaverbel describes a glass article coated with an antimony / tin oxide film of at least 400 nm containing a molar ratio of Sb / Sn from 0.05 to 0.5, with a visible transmittance of less than 35%. The films are applied by aqueous spray of CVD and are intended for applications of private glasses in sight. Lower veil reducing coatings are described as well as thick layers with low Sb / Sn ratios which have low emission properties as well as high solar absorbance. It also teaches that it is possible to provide one or more additional coating layers to achieve certain desirable optical properties. None of these properties besides the veil are mentioned. The application does not teach anything about thinner layers, the use of more than one softener, or film color control. The Patent Application of R. OR . GB 2, 302, 1 02 A also assigned to Glaverbel describes a glass substrate coated with a Sn / Sb oxide layer containing tin and antimony in a molar ratio from 0.01 to 0.5, said layer having been deposited by CVD, by what the coated substrate has a solar factor (solar heat gain coefficient) of less than 0.7. The coatings are intended for window applications and have light transmittances of between 40 and 65% and thicknesses ranging from 100 to 500 nm. Lower veil reducing coatings are claimed and low emission can be imparted to the coatings by judicious selection of the Sb / Sn ratio. As in the previous application, teaching is taught to provide one or more additional layers of coating to achieve certain desirable optical properties. Low fluoride-softened tin oxide layers can also be deposited on the Sb / Sn layers or fluorine components can be added to the Sb / Sn reagents to give low emission films containing F, Sb and Sn. The last two methods were not favored due to the added time and cost of adding a third layer and the fact that the emissivity of the Sb / F films was raised and not decreased. No mention of color control or color neutrality was found. GB 2,200, 139, assigned to Glaverbel teaches a method for depositing a coating by application of spray solutions containing tin precursors, fluorine-containing compounds and at least one different softener selected from the group of antimony, arsenic, vanadium, cobalt, zinc, cadmium, tungsten, tellurium or manganese. Previously, glass manufacturers have handled heat transport through windows through the use of absorbent and / or reflective coatings, glass dyes, and subsequently applied films. Most of these coatings and films are designed to control only a portion of the solar heat spectrum, either the NIR, that is, near-infrared component of the electromagnetic spectrum having a wavelength in the range of 750-2,500 nm or the intermediate IR component of the electromagnetic spectrum having a wavelength of 2.5-25 microns. A product has been designed to control the entire heat spectrum, however, the stacking of electrically deposited metal / dielectric films although effective has limited durability and must be protected and sealed within the central section of an insulated glass unit. Multiple panels (IGU). What is needed is a film or combination of total solar control films that can be easily applied by pyrolitic deposition during the glassmaking operation of an article having an acceptable visible transmission., reflect or absorb the N I R, reflect the intermediate I R, and be neutral or almost neutral in color. The above references either alone or in combination do not teach or suggest the specific combination of smoothing Sn02 layers of the present invention which performs solar control, low emission and anti-iridescence without requiring a lower layer of the "Gordon" type.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides an improved solar control glass that has acceptable visible light transmission, absorbs near-infrared (NIR) wavelength light and reflects intermediate-range infrared light (low emission or low E) together with a preselected color within the visible spectrum for reflected light which can be controlled for a specific color or made essentially colorless ("neutral" as defined hereinafter). A method for producing coated glass, for improved solar control, is also provided. The improved glass has a solar energy absorbing layer (NIR) comprising tin oxide having a softener such as antimony and a low emission control layer capable of reflecting intermediate range infrared light and comprising tin oxide having Fluorine and / or phosphor softener. A separate iridescent color suppressant layer as described in the prior art is not generally necessary to achieve a neutral (colorless) appearance for light reflected from the coated glass, however, an iridescence suppressor layer or other layers can be combined with the two-layer assembly provided by the present invention. The N I R layer and the low emission layer may be separate portions of a simple tin oxide film since both layers are composed of smoothed tin oxide. A method for producing coated glass for solar control is also provided. In addition, the present invention controls or changes the color of light transmitted through the addition of color additives to the NI R layer. Surprisingly, the softening fluorine that produces a colorless tin oxide film functions as a color additive. when it is added as an additional softener to the NIR layer and modifies the color of the light transmitted through the N IR film.

BRIEF DESCRIPTION OF THE INVENTION Figures 1 to 4 and 8 to 13 represent a cross section of coated glass having different numbers of layers or films in different stacking sequences for the layers in glass substrates. Figures 5 and 6 graphically represent the solar control achieved with antimony-softened films in various concentrations of softener and various film thicknesses in windowpanes, ie, a single glass side, or insulated glass units (IGU) that they are a composite of at least two-glass crystals. Figure 7 represents the color spectrum in terms of x and y coordinates of the Commission Internationale de L'Exclairage (C.I.E.) and the specific color achievable with various film thicknesses and smoothing concentrations. The English translation for C. I. E. is International Commission on Illumination.

OBJECTIVES OF THE I NVENC TION A purpose of the invention is to prepare a transparent article with controlled reflected color (uniform neutral color as defined herein), which will absorb solar radiation of near infrared (NIR) wavelength and reflect medium range infrared heat (low emission) comprising two layers of thin film containing smoothed SnO2. Another objective is the application of the layers by vapor deposition techniques (CVD) at atmospheric pressure, or by other processes such as solution spray or vaporized / sublimated liquids / solids can be used. The preferred method of application for this invention is CVD at atmospheric pressure using vaporized liquid precursors. Another objective is to provide multiple layers for solar control and / or low emission together with other layers in combination with the layer for solar control or low emission. Another objective is to provide a film or combination of films for solar control which can be easily applied by pyrolytic deposition during the manufacturing operation of the glass which gives an article which has an acceptable visible transmission, reflects or absorbs the NIR, reflects the IR medium (low-E), and is neutral or almost neutral in color, the production of which is an objective of the present invention. Another objective of the invention is to control the color of transmitted light regardless of the color of the reflected light by the addition of color additives in the layer N I R.

I -I DETAILED DESCRIPTION OF THE NORTHERN NORTH N. YMODA LI ADES P REFERI DAS The glass for solar control and low emission is produced by depositing on a transparent substrate heated at least two layers, a layer of low emission comprising a film SnO2 particle containing a fluoride and / or phosphor softener and an NIR absorbent layer comprising an SnO2 film containing antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel or mixtures thereof as a softener . It has been found that this combination effectively controls the solar heat and radiation portions of the electromagnetic spectrum such that a window coated with these films will have greatly improved properties. The solar control properties are typically expressed in terms of solar heat gain coefficient (SHGC) and U value. The SHGC is a measure of the total solar heat gain through a window system in relation to incident solar radiation, while the U (U) value is the total heat transfer coefficient for the window. The SHGC of the coated glass depends mainly on the thickness and the antimony content of the absorbent film of N I R (see Figures 5 and 6) while the U value depends mainly on the emissivity of the film and the construction of the window. The SHGC measured at the center of the glass can range from about 0.40 to 0.80 while the U-values measured at the center of the glass can vary from about 0.7-1.2 for a single glass coated with the preferred embodiment films. In an isolated glass unit (IG U) the SHGC decrement down to ~ 0.30 with U values as low as ~ 0.28. Both, the reflected and transmitted color of the coated glass of the present invention can be controlled. In addition, the amount of visible light transmitted through the coated glass can be controlled between about 25-80% by controlling the thickness of the NIR films and low emission and softener concentration in the NI R film. The color transmitted, ie , the color of light transmitted through the coated glass can be controlled separately from the reflected color by the addition of an effective amount of color of a color additive to the N IR layer of the coating. The reflected color can vary from almost neutral to red, yellow, blue or green and can be controlled by varying the film thickness and softener content of the layers. Surprisingly, the color close to neutrality as defined herein can be achieved for the reflected color without the need for an anti-iridescent layer. Although the refractive indices of NI R films and low emission are different, the reflected color does not depend on the classical interference phenomenon originally discovered by Gordon (U.S. Patent No. 4,187,336). The observed reflected color is controlled unexpectedly by the combination of absorption and reflection achieved by the N I R (absorption) layer and the reflection achieved by the low emission layer or layers. The absorption of the N I R layer can be controlled by varying the thickness of its SnO2 layer and the concentration of the softener in the N I R layer, usually antimony. The reflectance of the low emission layer can be controlled by varying the thickness of its SnO2 layer and the concentration of the softener in the low emission layer, usually fluorine. The low emission layer composed of SnO2 containing a fluorine or phosphor softener is sometimes abbreviated here as TOF or TOP while the NIR layer of SnO2 when containing an antimony softener is sometimes abbreviated herein as TOSb . The preferred embodiment of this invention uses a combination of a fluoride-softened tin oxide (TOF) film as the low emission layer with a film. of antimony-tinned tin oxide (TOSb) as the N I R layer. TOF films and their deposition process on glass are known in the art and are referred to as low emission films. The absorbent film of N I R is also a SnO2 film but contains a softener different from that of the low emission layer. The softener in the N I R layer is preferably antimony although the softener may be an element selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and their mixtures. A mixture of one or more softeners can be used in the NIR layer, however, the low emission layer must contain a low emission softener that imparts significant conductivity to the layer such as fluorine or phosphorus, although other softeners may be used in combination with the low emission softener. Since the low emission and NIR layers of the present invention both use SnO2 as the metal oxide matrix containing a softener, the NIR and low emission layers can be part of a simple film having a gradient. of smoothing. A simple film using a smoothing gradient is depicted in Figure 3 as the film 16. In film 16 there is a smoothing gradient with the NIR smoother having a higher concentration than the other (s) softener (s) on one surface of the film, either surface 18 or 22, and the low emission softener having a higher concentration than the other softeners on the other surface of the film. This results in a change or gradient in the concentrations of the NIR softeners and low emission between the surface 18 and the surface 22. At some intermediate point 20 of the surface 18 and the surface 22 the concentration of the softener of NI R changes from being the highest concentration softener on one side of point 22 to no longer the highest concentration smoother on the other side of point 22. Figure 8 shows the low E film, 10, above the NI 12 film The NIR film 12 in Figure 8 has a concentration g for the NIR softener in the tin oxide film with a lower concentration of the softener near the low E film 10. The coated glass of Figure 9 it is similar to the structure shown in Figure 8 with the exception that the concentration gradient of the NIR softener, usually antimony, is higher near the film 1 0 of low E and lower near its substrate. The film 12 is then different to the film 16 shown in Figure 3 because the film 12 is a NIR film while the film 16 has both NIR and low E properties and contains both a low E softener and a NIR smoother with a concentration gradient for the low E smoother and a concentration gradient for the NI R smoother. Figures 10, 11, 12 and 13 show the NIR layer as two separate films, 28 and 30. The film 28 is shown as being thicker than the film 30 and the total thickness of the NIR layer is the sum of the thicknesses of the films 28 and 30 and must be within the range of thicknesses established above for the NI R layer and preferably from 80 to 300 nm. In Figures 10 and 11, the films 28 and 30 are adjacent to one another, while in Figures 12 and 13, the films 28 and 30 are on opposite sides of the low-E film 10. The concentration of softener in the film 28 it is different from preference that the softener concentration in the film 30. The preferred embodiment of this invention uses an antimony-softened film as the NI R film. Such a film can be deposited by a number of techniques including methods Spray pyrolysis, PVD and CVD. Spray pyrolysis is known and described in patents such as Canadian Patent 2, 193, 158. CVD methods for depositing SnO2 films with or without softeners and the chemical precursors for forming SnO2 films containing softeners are well known. and described in U.S. Patent Nos. 4,601, 917 and 4,285, 974. CVD deposition of SnO2 layers containing softeners is preferred according to known methods directly in a float glass manufacturing line outside or inside. of the float glass chamber using conventional in-line deposition techniques and chemical precursors as taught in the U.S. Patent., Do not . 4,853,257 (Henery). However, SnO2 films containing softeners can be applied as layers on glass using other processes such as solution spray or liquids / solids vaporized / sublimated at atmospheric pressure. The preferred method of application for this invention is CVD at atmospheric pressure using vaporized liquid precursors. The process is highly advisable for existing commercial online deposition systems. The precursors of the preferred embodiments are economical to apply, will allow long coating times, will reduce the cleaning frequency of the system, and should be able to be used with little or no modification to the existing float glass inline coating equipment. The coatings work through a combination of reflection and absorption. The low emission film reflects heat of I R medium in the 2.5-25 micron region of the spectrum while the absorbing film of N I R absorbs heat mainly in the region of 750-2, 500 nm. Although not limited by this, the theory with which we have for this effect is that in the NIR region, the wavelength of the plasma (PL- the wavelength where the low emission film changes from a transmitter to a light energy reflector) for the low emission film falls in the NI R region. In the area around the PL, the NIR absorption is the highest for the low emission film and when combined with a film NIR absorber, an increased absorbance takes place. The N I R absorbing films of our preferred embodiments are also semi-conductive 70 smoothed and therefore have reflecting properties in the intermediate I R. This reflection coupled with the reflection of the low emission film gives a higher overall heat reflectance in the intermediate I R. Preferably the SnO2 is pyrolytically deposited in the glass using a tin precursor, especially an organotin precursor compound such as monobutyltin trichloride (M BTC), dimethyltin dichloride, dibutyltin diacetate, methyltin trichloride or any of the known precursors for deposition of SnO2 CVD such as that described in US 4,601,917 incorporated herein by reference. Frequently such organotin compounds used as precursors for pyrolitic SnO2 deposition contain stabilizers such as ethanol. Preferably the concentration of the stabilizers is less than 1% in order to reduce the risks of fire when there is contact with the hot glass with such chemicals in the presence of oxygen. Precursors for the softener in the NIR layer (antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel) are preferably halides such as antimony trichloride, however, alkoxides, esters, acetylacetonates can also be used and carbonyls. Other suitable precursors for the softener and Sn02 are well known to those skilled in the art. Suitable precursors and amounts for the fluoride softener in the low emission SnO2 layer are described in U.S. Patent No. 4,601,917 and include trifluoroacetic acid, ethyl trifluoroacetate, ammonium fluoride, and hydrofluoric acid. The concentration of the low emission softener is usually less than 30% with preferred concentrations of the low emission softener from 1% to 15% by weight of softener precursor based on the combined weight of softener precursor and tin precursor. This generally correlates with a softener concentration in the film of low e from 1% to 5% based on the weight of tin oxide in the film of low e. In our preferred embodiments, the properties depend on the thickness of the low emission and absorbent layers as well as the antimony content of the absorbent film (N I R). The thickness of the low emission film can fluctuate from 200-450 nm with 280 to 320 nm being most preferred. The preferred NIR absorber films can be deposited in a manner similar to that of low emission films using such methods as described in the U.S. Patent. , No. 4,601, 917. The organostanose precursors for SnO2 may be vaporized in air or other suitable carrier gases containing an O2 source and in precursor concentrations from 0.25-4.0 mol% (more preferred from 0.5 to 3.0 mol%). The concentrations of SnO2 precursor are expressed herein as a percentage based on the moles of precursor and the moles of carrier gas. Preferred concentrations of N-N-softener precursor are from about 1% to about 20% (more preferred from 2.5% to 7.5%, and most preferably from 3.0% to 6.0%) and are calculated using the weight of the softener precursor and the weight of the SnO2 precursor. Particularly preferred is an antimony softener which uses antimony trichloride as the precursor from about 2% to about 8% by weight with particularly preferred being about 4.0% by weight. This correlates with a mass percent of antimony similar in the tin oxide N I R film. The coated glass of the present invention is shown in the figures. Figure 1 shows the films in cross section. The film thicknesses can fluctuate from 200 to 450 nm for the low emission film (item 10) and for the NIR film (item 12) from 80 to 300 nm. The preferred thickness is 250 to 350 nm for the low emission film and 200 to 280 nm for the N I R film. Most preferred is 280 to 320 nm for the low e film and 220 to 260 nm for the N IR film. Using films of the preferred modalities, coated glasses for solar control can be produced with a Neutral Blue Color which is defined herein as coated glass having predominantly reflected light within coordinated chromaticity values of x between 0.285 and 0.310 e and between 0.295 and 0.325. The definition of Neutral Blue is shown in Figure 7 by the area inside the box marked Neutral Blue Color. As shown in Figure 7 the information for examples 15, 20 and 22, color reflected controlled or preselected close to neutral color but slightly to red tone from neutral can be produced (values of x up to 0.325 and values of y up to 0-33), but such a neutral essentially to slightly red tones of reflected color are not attractive to the customers. Figure 2 shows the two films or layers in the opposite sequence to that shown in Figure 1. In Figure 2, the low emission film is closer to the glass 14 than the film 12 of N I R. Figure 3 shows the NIR and the low emission layers integrated in a single SnO2 film 16 having a smoothing gradient inside the film 16. The film 16 has a preponderance of a softener (eg, the low-emission softener, fluorine ) on the upper surface, 18, away from the glass 14 and a preponderance of the other softener (eg, the NIR softener such as antimony) on the surface 22 of the film closer to the glass. The softener concentration changes from the surface 18 to the surface 22, such that a softener changes from greater than 50% of the softeners on the surface 18 to about 0% on the surface 22. At an intermediate point 20, below the upper surface 18, the predominant softener at that point in the film changes from the predominant softener on the surface 18 to the predominant softener on the surface 22. Either the NIR softener or the low-emission softener (fluorine) may be the predominant softener in the surface 18 with the other softener the predominant softener on the surface 22. Figure 4 depicts a coated glass having additional layers 24 and 26 in addition to a low emission layer 10 and a layer 12 of NI R. The additional layers 24 and 26 may be additional low emission and / or NI R layers or other conventional layers used to coat glass such as a dyeing layer. For example 12 can be a layer of NIR (eg, antimony smoothed tin), 10 a low emission layer (tin smoothed with fluorine) and another layer of NI R. 26 can be another low emission layer or some other layer conventional. The concentration of softener when more than one low emission layer is used may be the same or different and the thickness of each of the low emission layers may also be the same or different. Similarly, when more than one layer of NIR is used, the softener concentration and the softener selection (antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel) may be the same or different and the The thickness of each NIR layer can be the same or different. Generally the softener for the NIR layer has been discussed herein primarily in terms of antimony, it should be understood that the softener in the NIR layer can be selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and their mixtures. Similarly in the gradient layer embodiment of the invention as depicted in Figure 3, the predominant softener on the surface of NIR either surface 18 or 22 can be selected from the group consisting of antimony, tungsten, vanadium, iron , chromium, molybdenum, niobium, cobalt, nickel and their mixtures, being essential only that the softener of low e, v. g. , fluorine, is the predominant softener on the opposite surface. Combined with a gradient layer may be one or more layers of N I R or low emission such as layers 10 and 12 in Figures 1 to 3 and / or other conventional layers. Water is preferably used to accelerate the deposition of SnO2 film on the glass as taught in the U.S. Patent., No. 4,590,096 (Lindner) and used in concentrations from -0.75 to 12.0% in mol of H20 based on the composition of the gas. The preferred embodiments of our invention will be exemplified by the following examples. A person skilled in the art will realize that minor variations outside the modalities set forth herein do not depart from the spirit and scope of this invention. The most preferred embodiment at this time to obtain a coated glass with low e and NIR properties with neutral reflected color with only two films on the glass is approximately a TO film of a thickness of 3,000 A: F (tin oxide smoothed with fluorine) in combination with approximately 2,400 A: F TO film (antimony antimony smoked tin) on glass. The film thickness for the TO: F layer can fluctuate from ~ 2,800-3,200? and still achieve the surprising result of a neutral reflected color. The concentration of fluorine can fluctuate from -1 -5% atomic. The film thickness of TO: Sb can fluctuate from - 2,200-2,600? with a concentration of antimony from - 3-8% and still achieve the surprising result of a neutral reflected color for the coated glass. Within the preferred thickness and concentration ranges of softener of the present invention, a coated glass for solar control having a NIR layer and a low ey layer having a Neutral Blue color for reflected light can be produced, i.e. , coated glass having predominantly reflected light within coordinated chromaticity values C. I. E. of x between 0.285 and 0.310 e and between 0.295 and 0.325 as shown in Figure 7 by a box labeled Neutral Blue Color or near Neutral Blue Color with values 2 (>; of x as high as about 0.32 as shown in Examples 15, 20 and 22.

EJ EM PLOS 1 to 30 A glass substrate with a thickness of 2.2 mm (silica lime caustic soda), of 12.9 square centimeters, was heated on a hot block at 605-625 ° C. The substrate was placed 25 mm under the central section of a vertical concentric tube coating nozzle. A carrier gas of dry air flowing at a rate of 15 liters per minute (l / m in) was heated to 160 ° C and passed through a vertical hot-wall vaporizer. A liquid coating solution containing - 95% by weight of monobutyltin trichloride and -5% by weight of antimony trichloride was fed to the vaporizer via a syringe pump at a volume flow designed to give an organotin concentration of 0.5% in mol in the gas composition. A quantity of water was also fed to the vaporizer at a flow designed to give 1.5 mole% water vapor in the gas mixture. The gas mixture was allowed to collide on the glass substrate at a front speed of 0.9 m / sec for - 6.1 seconds resulting in the deposition of a tin oxide film softened with antimony of - 240 nm thickness. Immediately afterwards, a second gas mixture consisting of a precursor composition of 95% by weight tributyl trichioride and 5% by weight of trifluoroacetic acid was used, together with water in the same concentrations and carrier gas as used before to deposit the SnO2 layer softened with antimony. This second gas mixture was allowed to collide on the coated substrate for -6.7 seconds. A film - 280 nm of tin oxide softened with fluorine was deposited. The bi-layer film was very light blue in transmission and reflection. The optical properties were measured in a UV / VIS / N I R spectrophotometer and the sheet strength was measured in a standard four-point probe. The coefficient of solar heat gain, U value and visible transmission for the center of the glass were calculated using the Window 4.1 program developed by Lawrence Berkeley National Laboratory, Windows and Daylight Group, Building Technologies Program, Energy and Environmental Division. The color coordinates x and y of chromaticity C. I. E. were calculated using ASTM E 308-96 from the visible reflectance data between 380-770 nm and the tristimulus values for Illuminant C. The results of the analysis for this film are shown in Table 1, number 19. The procedure of this example was repeated 29 additional times with varying chemical precursor concentrations and deposition times in order to produce coated glass samples having different thicknesses for the NIR and low emission layers and different concentrations of softener. The results are presented in Table 1.

EXAMPLES 31 to 38 The procedure of Example 1 was repeated, except that the order of steam feed was reversed. The fluoride-softened tin oxide film was first deposited for -8 seconds followed by the tin oxide film softened with antimony for -6 seconds. The resulting film was -540 nm thick and composed of a low emission layer (TOF) of approximately 300 nm and an NI R (TOSb) layer approximately 240 nm and tube a similar appearance and color of reflected light (Color Neutral Blue) as the film of Example 19. The results of the analysis appear in Table 2, number 31. The procedure of this example was repeated seven times more with varying chemical precursor concentrations and deposition times in order to produce coated glass samples having different thicknesses for N I R layers and low emission and different concentrations of softener. The results are presented in Table 2.

EXAMPLE 39 The procedure of Example 1 was repeated, but using three precursor feed mixtures. The composition of the third mixture was 90% by weight of monobutyltin trichloride, 5% by weight of trifluoroacetic acid, and 5% by weight of antimony trichloride. A gradient film was deposited by first depositing only the tin oxide precursor smoothed with antimony of Example 1 for 70% of the time necessary to deposit 240 nm. Then the antimony / precursor mixture softened with fluorine was started. Both precursor mixtures would continue for 20% of the total deposition time at which point the antimony precursor mixture was stopped. The mixed antimony / fluorine precursor was continued for the remaining 10% of the total deposition time for the antimony film of 240 nm. At this point, the power went on d? precursor d? movie d? oxide d? tin softened with fluoride. Both feeds were continued for 20% of the total time needed to deposit 300 nm of fluoride-softened tin oxide. The antimony / fluorine mixed precursor feed was turned off and the fluorine-softened tin precursor was continued for the remaining deposition time for the fluoride-softened film. The resulting gradient coating layer is pale blue in transmitted and reflected color (x = 0.292, y = 0.316) a SHGC = 0.50, a U = 0.6 value, and a visible transmission of approximately 45%. As shown in Figure 3, the surface 22 of the gradient film 16 would have essentially 100% antimony softener while the surface 18 would have essentially 100% fluoride softener with a gradient in concentration of softener between the surfaces 18. and 22 and all within an SnO2 film matrix.

EXAMPLES 40 to 43 The procedure of Example 1 was used in Examples 40 to 43. The coating composition for the NIR layer in Examples 41 and 43 was composed of a precursor of fluorine, antimony, and tin made by the addition of SbCI3. and TFA to MBTC. This precursor contained 0-5% by weight of TFA, 5.2-5.5% by weight of SbCI3, and the remainder of M BTC, and was co-fed with water to the second vaporizer. The carrier gas used for the second vaporizer was dry air at a rate of 15 l / min. The fluorine / antimony / tin precursor was added at a rate of 0.5 mol percent of total carrier gas flow, water was added at a rate of 1.5 mol percent of the total carrier gas flow, and the The temperature of the vaporizer was maintained at 160 ° C. A caustic-lime-silica glass substrate of 12.90 square centimeters and 2.2 mm thick was preheated in a heating block at 605-625 ° C. The heating block and the substrate were moved then to a position directly below the vertical coater, with the substrate being 25 mm under the coater nozzle. The F / Sb / Sn / H2O vapors of the second vaporizer were then directed onto the glass substrate, depositing a layer below the tin oxide coating smoothed with antimony and fluorine in Examples 41 and 43. The carrier gas velocity was 0.9 m / s and the thickness of the tin oxide film softened with fluorine and antimony was ~ 240 nm. Reaction byproducts and unreacted precursor vapors were expelled from the substrate at a rate of 1.8 L / min. After the lower coating of tin oxide softened with antimony and fluorine was deposited, the valve of the coating nozzle was changed from the second feed of the vaporizer to the first feed of the vaporizer. The M BTC / TFA / H2O vapors from the first vaporizer feed were then directed onto the substrate, depositing a fluoride-softened tin oxide layer directly over the top of the antimony / fluorine-softened tin oxide lower coating. The carrier gas velocity was 0.9 m / s and the thickness of the fluoride-softened tin oxide film was -300 nm. The dicap films in Examples 41 and 43 (both containing F and Sb in the lower coating of N I R) were pale gray in transmitted color and neutral in reflected color. Examples 40 and 42 essentially reproduce Examples 40 and 43 respectively, but without fluorine softener in the lower coating layer of NI R. The properties were measured and the results appear in Table 3. The results show how fluorine, as an additional softener in the NIR layer, acts as a color modifier for both, reflected and transmitted color. The transmitted colors, Tvis, x and y, of the films made with TFA and Sb softeners in the NIR layer, Examples 41 and 43, are more neutral in reflected color and more gray in transmitted color than those that only contained Sb as a softener in the NIR layer of tin oxide softened with antimony in Examples 40 and 42. In addition, the NIR layer softened with antimony with a color effecting the amount of fluoride softener has greater visible light transmission (increase in Tvis from 54.5 to 58.5 in Example 41 versus Example 42 with some level of antimony softener). Examples 44 to 47 demonstrate the deposition of films with the following composition: TOF / TOSb (low conc of Sb) / TOSb (high conc of Sb) / Glass, TOF / TOSb (high conc of Sb) / TOSb ( low Sb) / Glass, TOSb (low Sb) / TOF / TOSb (high Sb) / Glass, and TOSb (high Sb) / TOF / TOSb (low conc Sb) / Glass.

EXAMPLE 44 The procedure of Example 1 was repeated except that the glass temperature was about 610 ° C and the reagent concentration was about 0.63 mol% in air flowing at a rate of 20 liters per minute. A tin oxide softened with antimony of about 400 was deposited. first from a liquid coating solution composed of about 10% by weight of antimony trichloride and -90% of monobutyltin trichloride. Following immediately, a second layer of about 2,000,000 tin oxide antimony-softened was deposited from a liquid coating solution composed of 3.25% antimony trichloride and 96.75% monobutyltin trichloride. A third layer composed of about 3,000 A of fluoride-softened tin oxide was deposited from a solution containing 5% by weight of trifluoroacetic acid and 95% by weight of monobutyltin trichloride. The resulting film appeared to have a pale blue-green color for reflected light and a pale blue color for transmitted light. The film properties were measured as described in Example 1. The visible light transmission was 64% and the SHGC was calculated to be 0.56. The coordinates of x and y for the color of reflected light were 0.304 and 0.299, respectively, placing the film in the neutral blue quadrant of the color space of C. I .E. as defined before.

EXAMPLE 45 The procedure of Example 44 was repeated, but this time the TOSb layers were deposited in reverse order. The resulting film was blue-red in color with color coordinates of (x) 0.330 e (y) 1 I 0. 293, respectively. A visible transmission of 59% and a SHGC of 0.54 were obtained. One skilled in the art will appreciate that the TOSb layers may be of thicknesses and concentrations differing from those described herein and still be within the scope of this invention.

EXAMPLE 46 The procedure of Example 44 was repeated, but in this example the deposition sequence of the fluoride-softened tin oxide layer and the 3.25% solution of antimony trichloride were reversed. The resulting film had a visible transmission of approximately 62%, a SHGC of 0.55 and a neutral blue-red reflected color characzed by color coordinates (x) 0.31 1 e (y) 0.31 1.

EXAMPLE 47 The procedure of Example 45 was repeated, but in this example the deposition sequence of the fluoride-softened tin oxide layer and the 0.01% solution layer of antimony trichloride were reversed. The resulting film had a visible transmission of approximately 57%, a SHGC of 0.53, and a pale green reflected color characzed by color coordinates (x) 0.308 e (y) 0.341. One skilled in the art will appreciate that the TOSb layers may be of different thicknesses and concentrations than those described herein and still be within the scope of this invention. All values of SHGC and U in the tables have been deined using the single-band approach of the NFRC Window 4.1 program. The use of the more accurate multi-band approach (spectra information records are required) will improve the SHGC's by approximately 14%. The tristimulus values of C.I.E. for the reflected and transmitted colors of the coated articles can be calculated in accordance with ASTM Standard E 308, with llluminant C used as the standard illuminant. From this ASTM Standard E 308, the color of an object can be specified with one of several different scales. The scale used for the articles coated in this invention is the x and y coordinates of chromaticity C.I.E. 1931. One can easily transfer to the opposing color scale C.I.E. 1976 L *, a *, b * using the following equations: x = X / (X + Y + Z) y = Y / (X + Y + Z) L * = 116 (Y / Yp) 1 3-16 a * = 500 [(X / Xn) 3- (Y / Yn) 1 3] b * = 200 [(Y / Yn) 1 3- (Z / Zn) 1 / 3J where X, Y, and Z are the values CIE tristimulus of the coated article, and Xn, Yn, and Z ", are 98,074, 100,000, and 118,232, respectively, for Standard llluminant C. From the values L *, a *, b *, the color saturation index, c *, can be calculated by the equation: c * = [(a *) 2+ (b *)] 1 2. A color saturation index of 12 or less is considered neutral. The definition of Neutral Blue Color for reflected light, i.e. coated glass having reflected light predominantly within the x-values of chromaticity coordinates of C.I.E. between 0.285 and!? 0. 310 e and between 0.295 and 0.325 as shown in Figure 7 by a box marked Neutral Blue Color correlates with C. I. E. 1976 L *, a *, b * of 37.85, - 1 .25, - 5.9 and 39.62, - 2.25, 1 .5. Follow a sample conversion: Example 40 (Table 3) 5.5% SbCI3 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 solar control properties of glass windows have been evaluated and classified by the Environmental Protection Agency of the United States of America, using an Energy Star classification system. An Energy Star classification for the central region of the United States requires a U-factor classification of 0.40 or less and a SHGC rating of 0.55 or below. An Energy Star classification for the southern region of the United States requires a U-factor classification of 0.75 or less and a SHGC rating of 0.40 or below. The coated glass having the N I R and Low e coatings of the present invention and when ST incorporates conventionally designed windows achieves the Energy Star ratings for the central and / or southern region. For example, a vertical sliding design window of 0.91 meters wide by 1.22 meters high and having a frame absorption value of 0.5 as classified by the National Fenestration Rating Council (N FRC) and assembled with coated glasses for control of the present invention having a N IR film and a low e film inside d? the preferred ranges for a Neutral Blue Color reach a SHGC of less than 0.40 and a U value of less than 0.64 for a monolithic glass construction with a frame U value of 0.7 or less and reach a SHGC of less than 0.38 and a value U of less than 0.48 for an Insulated Glass Unit (IG U) construction made with a 2.5 mm free light, an air space of 1 .27 centimeters and coatings of NI R and Low e on surface # 2 of the exterior light and a frame value of 1.0 or less. The examples justify that with a minimum of two layers of smoothed Sn02, coated glass for excellent solar control having a preselected reflected color can be produced. Tables 1, 2 and 3 present the information while Figures 5 and 6 show graphically how the solar properties of the coated glass vary with the softener and film thickness concentrations principally of the NI R film. Figure 7 graphs the coordinates of chromaticity of C. I. E. x and y of a representative selection of coated glass of Examples 1 to 39. As seen in Figure 7, specific combinations of film thicknesses can be used for both, NIR and low emission films and softener concentrations ( s) specific for producing a coated glass, for solar control with any desired color for light reflected from the coated surface of the glass, such as red, green, yellow, blue and shades thereof or Neutral Blue Color. It is particularly surprising that a Neutral Blue Color can be achieved with layers of N I R and low emission, but without an anti-iridescent layer as taught by Gordon. Although the inventive aspects of the present invention can be achieved with only two layers, multiple layer modalities, a N I R layer and a low emission layer, they are within the scope and content of the invention. The multiple layers may be additional to the N I R and / or low emission layers or other functional or decorative layers. Multiple layer modalities include TOSb / TOF / TOSb / Glass, or TOF / TOSb / Glass, or TO / TOSb / TOF / Vid rio with TO being only a tin oxide film. When multiple layers of N I R or low emission are used, the softener or softener selection concentrations in each N I R or low emission film need not be the same. For example, when using two layers N I R in combination with at least one layer d? low emission, a layer of NIR may have a low level of antimony softener (eg, 2.5%) to give some reflectance in the middle range of IR and a layer may have a higher level (> 5%) to give absorbance of NI R. The terms layer and film are generally used herein interchangeably except in the discussion of the gradient film shown in Figure 3 in which a portion of the film is referred to as a layer having a concentration of softener different from the concentration of softener in another layer of the film. In the method for making the ed glass of the present invention as demonstrated in the examples, the glass is contacted sequentially with carrier gas containing precursors. Consequently, the glass can have a ing on it when it is contacted a second time with a carrier gas containing precursors. Therefore, the term "contacting glass" refers to either direct contact or contact with one or more ings previously deposited on the glass. Another embodiment of the invention provides the ability to change the transmitted color of the ed glass. The color transmitted refers to the color perceived by an observer on the opposite side of the ed glass then the light source being viewed while the reflected color is the color perceived by an observer on the same side as the light source is being viewed. The transmitted light can be effected by adding additional softeners to the N IR film. As previously explained, the N I R layer contains a softener selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel. The color of light transmitted through the NIR layer can be changed by adding a different additional softener to the first softener in the NIR layer and selected from the group consisting of tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel , and fluorine or a combination of more than one additional softener to the NI R layer. As shown in Examples 40-43, the .IV addition of a fluorine precursor, such as trifluoroacetic acid (TFA) or a NIR precursor solution such as SbCI3 / MBTC, produces a fluorine-containing film as an additional softener in the tin oxide NIR layer smoothed with anti-fluoride. monio When fluorine is present as an additional softener in a tin oxide layer smoothed with antimony, the transferred color is gray versus a blue transmitted color for a tin oxide layer smoothed with antimony without fluoride softener. The additional softener has little or no effect on the reflected light and consequently, a ed glass can be produced having a reflected light that is different from its transmitted light. The softeners in the NIR layer such as vanadium, nickel, chromium and non-traditional color additives such as trifluoroacetic acid (TFA) and HCl can be added to the TO: Sb precursors in 1-5% by weight (based on the total weight of precursor and additive) to effect changes in color transmitted in the final construction of the film while not significantly affecting the overall neutrality of reflected color.

TABLE 1 Summary of Properties; of Bi-caoa Movies TOF / TOSb # 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Composition i F / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / G 1 r / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / G % Sb 2.5 2.5 2.5 2.5 2.5 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 Thickness nm 300/240 300/160 300/80 400/240 400/80 300/240 300/240 300/160 300/80 300/240 300/252 300/232 300/225 300/240 400/240 % Asol 16.1 12.7 9.7 17.0 11.0 40.8 39.2 31.1 20.7 39.2 41.5 39.0 37.1 40.1 40.3 % Tsol 72.0 74.6 76.4 72.0 76.9 50.0 51.1 58.2 67.5 51.6 49.2 52.2 53.9 51.0 50.6 % Rsol, 1 11.8 12.7 13.9 11.0 12.1 9.2 9.6 10.7 11.8 9.2 9.3 8.9 9.1 8.9 9.1 % Rsol, 2 10.9 11.7 12.8 10.3 11.5 8.2 9.2 9.4 10.8 8.5 8.5 8.4 8.6 8.4 8.2 % Tvis 78.0 80.5 80.0 77.7 82.0 57.4 58.5 65.5 72.7 57.6 54.8 58.0 59.8 56.8 56.5 % Rvis, 1 12.0 12.1 14.6 11.2 11.9 9.2 9.8 10.1 14.0 8.9 9.0 8.4 8.4 8.6 8.6 % Rvis, 2 10.9 11.3 13.4 10.5 11.6 8.3 9.3 8.6 11.3 8.6 8.5 8.3 8.2 8.2 8.3 % Tuv 52.3 52.9 55.2 51.1 53.6 41.2 41.5 45.3 50.6 43.1 42.6 44.3 44.9 42.4 42.1 S. R. 12.4 13.2 16.0 10.4 13.3 11.2 11.8 13.3 15.6 12.2 12.5 13.4 13.8 13.1 9.7 Emis-cal 0.12 0.13 0.15 0.10 0.13 0.11 0.11 0.13 0.15 0.12 0.12 0.13 0.13 0.13 0.10 SHGCc 0.74 0.77 0.78 0.75 0.79 0.57 0.58 0.63 0.71 0.58 0.56 0.59 0.6 0.58 0.57"IG 0.67 0.70 0.71 0.67 0.71 0.49 0.5 0.56 0.63 0.51 0.48 0.51 0.52 0.5 0.49 Uc 0.72 0.72 0.74 0.71 0.73 0.71 0.72 0.72 0.74 0.72 0.72 0.73 0.73 0.73 0.71 "IG 0.27 0.28 0.28 0.27 0.28 0.27 0.27 0.28 0.28 0.27 0.27 0.28 0.28 0.28 0.27 Tv¡s-c 0.78 0.81 0.80 0.78 0.82 0.57 0.58 0.66 0.73 0.58 0.55 0.58 0.6 0.57 0.56"IG 0.71 0.73 0.73 0.71 0.74 0.52 0.53 0.59 0.66 0.52 0.5 0.53 0.54 0.52 0.51 X 0.291 0.329 0.295 0.326 0.323 0.293 0.292 0.331 0.318 0.288 0.291 0.294 0.302 0.294 0.322 and 0.336 0.289 0.377 0.317 0.282 0.303 0.309 0.280 0.364 0.300 0.3O0 0.309 0.315 0.306 0.318 % Rvis 12.0 12.1 14.7 11.2 11.9 9.2 9.8 10.1 13.9 9.0 9.0 8.4 8.4 8.6 8.6 Colors R Blue-V of Neutral Green Vde-Azui Neutral Blue Blue Neutral Vde-Am Blue Blue Blue Blue Blue Red TABLE 1 Continuation Summary of Properties of Bi-layer Films TOF / TOSb # 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Composition F / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / GF / Sb / G % Sb 56 56 56 56 56 65 100 100 100 100 100 100 146 146 146 Thickness nm 370/240338/240300/240280/240262/40300/24 300/240300/160 300/80300/300400/240 400/80300/240300/160300/80 % Asol 450 402 403 432 394 296 545 418 259 625 554 248 599 478 299% Tsol 454 507 506 466 512 464 370 478 624 297 359 636 319 429 575% Rsol, 1 96 91 91 102 94 99 85 104 117 78 87 116 82 93 126 % Rsol, 2 80 84 85 84 85 84 78 91 112 75 75 107 77 86 112 % Tvis 510 565 565 516 572 512 364 486 640 285 348 683 283 413 581 % Rvis, 1 88 88 89 100 90 99 85 100 133 77 76 101 89 78 147% Rvis, 2 83 87 83 79 80 85 72 78 96 69 76 100 71 72 99% Tuv 398 430 428 416 448 407 351 410 488 304 332 489 275 349 444 S R 115 113 136 137 15 129 154 177 188 15 128 154 151 157 186 Emis-cal 011 011 013 013 014 012 015 016 017 014 012 014 014 015 017 SHGCc 053 057 057 054 058 054 047 055 067 041 045 068 042 051 063"IG 045 049 049 046 05 046 038 047 059 032 039 060 034 043 055 Uc 072 071 073 073 073 072 074 074 075 073 072 073 073 074 075 "IG 027 027 028 028 028 028 029 029 029 028 027 028 028 028 029 Tvis-c 051 056 056 052 057 051 036 049 064 028 035 068 028 041 058"IG 046 051 051 047 052 046 033 044 058 026 032 062 026 037 053 X 0306 0296 0298 0303 0318 0297 0320 0353 0324 0343 0299 0299 0331 0344 0335 and 0320 0308 0312 0321 0324 0305 0327 0294 0378 0306 0322 0312 0329 0305 0393 % Rvis 90 88 89 100 90 99 85 99 132 11 76 101 88 7 8 146 Colors R Blue-Vde Blue Blue Blue-vde Am-Vde Blue Am-Neu Red Am-Vde Neutral Blue-Vde Blue Am-Vde Neutral Am-Vde AJ TABLE 2 Summary of Bi-layer Film Properties TOSb / TOF # 31 32 33 34 35 36 37 38 Composition 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 56 56 56 56 56 56 56 56 Thickness nm 240/300 160/300 138/300 120/300 110/300 80/300 120/332 120/262% Asol 479 36 1 292 272 256 235 285 26 8% Tsol 459 555 61 1 633 643 658 625 634% Rsol, 1 6 1 83 97 96 102 107 9 0 98% Rsol, 2 82 93 10 1 9 5 92 92 92 96% Tvis 532 632 672 690 695 71 8 690 68 1% Rvis, 1 61 76 93 91 101 109 78 99% Rvis, 2 76 89 107 104 105 10 9 89 11 6 % Tuv 385 434 470 487 492 49 1 477 496 SR 147 159 165 174 18 8 173 15 21 1 Emis-cal 0 14 0 15 0 15 0 16 0 17 0 16 0 14 0 19 SHGCc 054 061 066 068 069 07 067 068"IG 045 053 058 06 061 062 059 06 Uc 073 074 074 074 075 074 073 076" IG 023 028 029 029 029 029 028 03 Tvis-c 053 063 067 069 069 072 069 068"IG 048 057 061 063 063 065 063 062 X 0289 0309 0310 0311 0313 0 302 0 306 0292 and 0300 0283 0274 0275 0306 0364 0281 0349 % Rvis 62 1.1 93 9 1 10 1 109 78 99 Colors R Blue Blue-Neu Blue-Gr Blue-Gr Neutral Green Blue-Neu Green Explanation key for Tables 1 and 2: Composition: F / Sb / G = tin oxide tinned with fluorine / tin oxide smoothed with antimony / glass Sb / F / G = tin oxide smoothed with antimony / tin oxide softened with fluorine / glass% Sb% SbCÍ3 (antimony trichloride) by weight in MBTC ( monobutyltin trichloride) Measured nm thickness of profilometer of individual films TO: F (tin oxide softened with fluorine) and TO: Sb (tin oxide softened with antimony i% Asol% of solar absorbance1 on the side of the glass film (= 100- (% Tsol +% Rsol, 1)) - 300 - 2,500 pm% Tsol% of solar transmission1 from the side of the glass film - 300 - 2,500 nm% Rsol, 1% of solar reflection1 from the side of the film of the glass - 300 - 2,500 nm% Rsol, 2% of solar reflection1 of the rear side of the glass - 300 - 2,500 nm 10% Tvis% of transmission 'in the visible region of the glass film side spectrum - 380 - 780 nm SR Sheet resistance as measured on a 4-point Alessi probe Emis.cal Emissivity calculated from the measured sheet resistance (= 1 - (1 + 0.0053 * SR) 2) SHGCc Coefficient2 of solar heat gain for the center of the glass / single panel "IG Coefficient2 of solar heat gain for the center of the glass in one IGU3 15 Uc Coefficient2 of solar heat gain for the center of the glass / single panel "IG Coefficient2 of solar heat transfer to the center of the glass in a IGU3 Tvis-c Transmission1 in the visible region of the center of the glass spectrum / single panel - 380 - 780 nm" IG Transmission1 in the visible region of the center of the glass spectrum at an IGU3 - 380 - 780 nm x, and color coordinates calculated from% Rvis according to ASTM E 308 - 96, Illuminant C, 1931 Observer, Interval of 10 nm (Tabra 5.5 ) twenty - . 20 - 380 - 770 nm% Rvis% reflection1 in the visible region of the glass film side spectrum - 380 - 770 nm (1) Weighing with a solar spectrum irradiation function (ASTM E 891 - 87) using data of spectrum obtained in a Lambda £ PE spectrophotometer with 150 mm integrating sphere (2) Calculated using the Window 4.1 program of Windows and Daylightlng Group, Lawrence Berkeley National Laboratory 25 (3) IGU = unit of glass insulated using a coated glass light of 2.2 mm (on the surface # 2) and a free light of 2.5 mm with an argon gas space of 1.27 cm TABLE 3 e Films Bi-layer TOSb / TOF 40 41 42 43 Composition F / Sb / G F / Sb-F / G F / Sb / G F / Sb-F / G% SbCI3 5.5 5.2 5.2 5.36 % TFA (below) 0 5 0 2.5 Thickness nm 300/240 300/240 300/240 300/240 % Asol 45.5 35.7 41.8 39.1 % Tsol 45.0 54.2 48.2 50.6% Rsol, 1 9.5 10.1 10.0 10.3 % Rsol, 2 8.0 8.9 8.4 8.7 % Tvis 50.9 58.5 54.5 55.6 % Rvis, 1 9.4 10.1 10.4 10.3 % Rvis, 2 8.0 9.0 8.5 9.0% Tuv 40.1 41.1 41.6 39.8 S. R. 11.9 13.7 11.8 125 Emis-cal 0.12 0.13 0.11 0.12 SHGCc 0.53 0.60 0.55 0.57"IG 0.45 0.52 0.47 0.49 Uc 0.72 0.73 0.72 0.72"IG 0.27 0.28 0.27 0.27 Tvis-c 0.51 0.59 0.55 0.56"IG 0.46 0.53 0.50 0.51 R1 x 0.310 0.297 0.302 0.303 R1 and 0.297 0.313 0.299 0.307 % Rvis 9.4 10.1 10.4 10.3 Tvis x 0.295 0.308 0.297 0.304 Tvis and 0.308 0.315 0.310 0.314

Claims (47)

1. R? I N D ICAC ION FS 1. A coated glass, for solar control having a preselected reflected color and having a solar absorbing layer of NIR and a low emission layer, comprising glass having a coating containing at least two layers with a layer being an absorbent layer A sun comprising Sn02 containing a softener selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and their mixtures and another layer which is a low emission layer comprising SnO2 which contains a softener selected from the group of fluorine or phosphorus. The glass of claim 1 wherein the thickness of the solar absorbent layer is from 80 to 300 nanometers (nm) and the thickness of the low emission layer is from 200 to 450 nm. The glass of claim 1 wherein the thickness of the solar absorbing layer of N I R is from 200 to 280 nanometers (nm) and the thickness of the low emission layer is from 250 to 350 nm. 4. A coated glass, for solar control having a preselected reflected color and having a solar absorbing layer and a low emission layer, comprising an SnO2 film containing at least two softeners and a difference in concentration of the softeners of a surface of the film with the opposite surface of the film, said first softener being selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt nickel and their mixtures, and said second softener which is fluorine or phosphorus, said first softener comprising at least 50% of the softeners present in a first surface of said SnO2 film to form a solar absorbent layer within said SnO2 film adjacent to said first surface, and said second softener which is present in a concentration of at least 50% of the softener on a second surface of said opposite film ad. The first surface to form a low emission layer within said SnO2 film adjacent to said second surface. 5. The coated glass for solar control of claim 4 wherein said first softener is present in a concentration of at least 75% of the softeners present in said SnO2 film in an area of the film beginning with said first surface and continuing in the SnO2 film at a depth of at least 80 nm above said first surface, and said second softener comprises at least 75% of the softeners present in said SnO2 film in an area of the film starting with said second surface and continuing in the SnO2 film at a concentration of at least 75% of the softeners at a depth of at least 80 nm, wherein said area of said SnO2 film having a at least 75% of said second softener functions as a low emission layer and said area of said SnO2 film having at least 75% of said first softener functions as a layer of NI R. 6 The coated glass for solar control of claim 1 wherein said solar absorbent layer has a thickness from 220 to 260 nm, a concentration d? softener desdo? 5% up to 7% on said solar absorber layer based on the weight of SnO 2 in said solar absorber layer, and the low emission layer has a thickness from 280 to 320 nm, a concentration of fluoride softener from 1% up to 5% by weight in said low emission layer based on the weight of SnO2 in said low emission layer, and the coated glass has a Neutral Blue Color for the reflected light. The glass of claim 1 wherein the solar absorbent layer is SnO2 having an antimony softener within the range of 3% to 6% by weight based on the weight of the SnO2 tin oxide in the solar control layer, the low emission control layer is SnO2 having a fluoride softener within the range of 1% to 3% by weight softener based on the weight of Sn02 in the low emission layer, and the improved glass has a Neutral Blue Color for reflected light. The glass of claim 1 wherein the solar absorbent layer is coated directly on the glass and the low emission layer is coated on top of the solar control layer. 9. The coated glass for solar control of claim 1 wherein the preselected reflected color is red. 10. The coated glass for solar control of claim 1 wherein the preselected reflected color is yellow. eleven . The coated glass for solar control of claim 1 wherein the preselected reflected color is green. 12. The coated glass for solar control of claim 1 wherein the pre-selected reflected color is blue. 13. The coated glass for solar control of claim 1 wherein the preselected reflected color is Neutral Blue Color. 14. The coated glass for solar control of claim 1 wherein the solar absorbent layer and the low emission layer are contained within a single SnO2 film containing at least two softeners with the first softener selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt nickel and their mixtures, and the second softener which is fluorine or phosphorus, said first softener being at a higher concentration than said second softener on a film surface. and said first softener which is at a lower concentration than said second softener on the opposite surface of the film and wherein the portion of said film in proximity with said first surface functions as a solar absorbent layer within said film and wherein the portion of said film in proximity to said opposite surface functions as a low emission layer within said film. 15. The coated glass of claim 1 wherein the softener for the solar absorbent layer is antimony. 16. The coated glass of claim 1 wherein the antimony softener is obtained from a precursor containing antimony trichloride, antimony pentachloride, antimony triacetate, antimony triethoxide, antimony trifluoride, antimony pentafluoride, or antimony acetylacetonate. TO') 17. The coated glass of claim 1 wherein the softener for the low emission layer is fluorine. 18. The coated glass of claim 1 wherein the fluorine softener is obtained from a precursor containing trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, ethyl trifluoroacetate, ammonium fluoride, ammonium bifluoride, or hydrofluoric acid. . 19. The coated glass of claim 1 wherein each of the SnO2 layers is obtained by pyrolytic decomposition of a tin precursor. 20. The coated glass of claim 19 wherein the tin precursor is selected from the group consisting of monobutyltin trichloride, methyltin trichloride, dimethyltin dichloride, dibutyltin diacetate, and tin tetrachloride. twenty-one . The coated glass of claim 1 wherein the solar absorbent layer is composed of at least two solar absorbing films and the total thickness of the solar absorber films is from 80 to 320 nm. 22. The coated glass of claim 21 wherein the concentration of softener in one of the two solar absorbing films is different from the concentration of softener in another of the solar absorbent films. 23. The coated glass of claim 1 wherein the low emission layer is composed of at least two low emission films and the total thickness of the low emission films is from 200 to 450 nm. 24. The coated glass of claim 23 wherein the concentration of softener in one of said low emission films is different from the softener concentration in another of the low emission films. 25. The coated glass of claim 1 further comprising an amount of a color modifying softener conveyed in said solar absorbent layer. 26. The coated glass of claim 25 wherein said color modifying softener is fluorine or chlorine. 27. The coated glass of claim 1 further comprising chlorine as a softener in said solar absorbent layer. 28. A method for producing the coated glass of claim 1 which comprises treating glass sequentially at a glass temperature above 400 ° C with: a first carrier gas containing an oxygen source, H20, a tin precursor and a softener precursor selected from the group consisting of antimony trichloride, antimony pentachloride, antimony triacetate, antimony triethoxide, antimony trifluoride, antimony pentafluoride, or antimony acetylacetonate; and a second carrier gas containing an oxygen source, H 2 O, a tin precursor and a softener precursor selected from the group consisting of trifluoroacetic acid, difluoroacetic acid, M acid monofluoroacetic, ethyl trifluoroacetate, ammonium fluoride, ammonium bifluoride, and hydrofluoric acid; for forming by pyrolysis a N I R layer comprising SnO2 containing an antimony softener and a low emission layer comprising SnO2 containing a fluoride softener. 29. A method for producing the coated glass of claim 1 which comprises treating glass sequentially at a glass temperature above 400 ° C with: a first carrier gas containing an oxygen source, H2O, a precursor of organotin and a softener precursor selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel, and, a second carrier gas containing an oxygen source, H2O, a tin precursor and a softener precursor that contains fluorine or phosphorus; to form by pyrolysis a layer of NIR comprising SnO2 containing an antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt or nickel softener or mixture of softeners and a low emission layer comprising SnO2 containing a softener of fluorine or phosphorus. 30. The method of claim 22 wherein said glass is contacted with the first carrier gas before being brought into contact with the second carrier gas. 31 The method of claim 22 wherein said first carrier gas also contains the components of said second carrier gas to produce a product in which the NIR layer contains a fluoride or phosphorus softener other than the antimony, tungsten, vanadium, iron softener , chromium, molybdenum, niobium, cobalt or nickel. 32. The method of claim 22 wherein further said first carrier gas also contains a softener precursor that contains fluorine, chlorine or phosphorus. 33. The method of claim 32 wherein said softener precursor containing fluorine, chlorine or phosphorus is any of trifluoroacetic acid, HCl, or phosphorus trichloride. 34. The method of claim 22 wherein further said first carrier gas also contains a film modifier selected from the group consisting of fluoride or phosphorus-containing softening precursor. 35. The product produced by the process of claim 21. 36. The coated glass of claim 1 further comprising a fluoride softener in said layer of N I R and wherein the reflected color of said glass is different from the transmitted color. 37. The coated glass of claim 26 wherein the reflected color is Blue N eutro color and the transmitted color is blue. 38. The method of claim 22 wherein said first carrier gas also contains a second softening precursor containing fluorine or phosphorus or a second softening precursor containing a metal selected from the group consisting of antimony, iron, chromium, molybdenum, niobium, cobalt and nickel. 39. The method of claim 27 wherein said second softener precursor is selected from the group consisting of trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, ethyl trifluoroacetate, ammonium fluoride, ammonium bifluoride, and hydrofluoric acid. 40. The product produced by the process of claim 28. 41. A NIR film comprising tin oxide containing a NIR softener selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel and containing a fluorine softener at an atomic concentration less than the concentration of the NI R. 42 softener. The film of claim 32 wherein the fluorine softener is present in an amount sufficient to modify the color of light transmitted through the film. 43. A N I R film comprising tin oxide containing an N I R softener selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel and containing a color modifier softener present in an amount sufficient to modify the color of light transmitted through the film and selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and fluorine, provided that the selection of color modifier softener is different from the selection of the NIR softener and when fluorine is the selected softener its atomic concentration is lower than the concentration of the NI R. 44 softener. A coated glass, for solar control having a Neutral Blue color for reflected light and having a NIR solar absorber layer and a low emission layer, comprising glass having a coating that contains at least two layers with a layer being a solar absorbent layer comprising SnO2 containing a softener selected from the group consisting of anti monium, gastone, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and their mixtures and another layer which is a low emission layer comprising Sn02 containing a softener selected from the group of fluorine or phosphorus. 45. A coated glass, for solar control having a color intensity index of 12 or less for reflected light and having a solar absorbent layer and a low emission layer, comprising a glass having a coating that contains less two layers with one layer being a solar absorbent layer comprising SnO2 containing a softener selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and their mixtures and another layer which is a low emission layer comprising SnO2 containing a softener selected from the group of fluorine or phosphorus. 46. A coated glass, for solar control that has x-coordinates of color C. I. E. 1931 between about 0.285 and 0.310 e and between about 0.295 and 0.325 for reflected light and having a solar absorbing layer of N I R and a low emitting layer, comprising ?? glass having two layers coated thereon with a layer which is a solar absorbent layer comprising SnO 2 containing a softener selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and its mixtures and a second layer which is a low emission layer comprising SnO2 containing a softener selected from the group of fluorine or phosphorus. 47. A coated glass, for solar control that has x-coordinates of color C. I. E. 1 931 between about 0.285 and 0.325 ey between about 0.295 and 0.33 for reflected light and having a solar absorbing layer of NIR and a low emission layer, comprising glass having at least two layers coated thereon, with a layer which is a solar absorbent layer comprising Sn02 containing a softener selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof and a second layer which is a layer of low emission comprising SnO2 containing a softener selected from the group of fluorine or phosphorus.