Solar control coated glass

Coated glass to control sunlight

Full description

Background of the invention

This invention relates to coated glass used in residential, architectural and vehicle windows and in various applications where both solar control and low emissivity properties are desired. Coatings used to control low-emissivity sunlight contain tin oxide with various dopants. The invention eliminates the need to use an anti-iridescence underlayer. Glass materials may have any shape but are usually flat

Or curved. The composition of the glass can vary greatly, but it is usually plain glass, soda lime glass, produced by the float process. The glass may be annealed, heat-strengthened, or tempered.

The term solar-control describes the property of regulating the amount of solar thermal energy that has to pass through a glass material into an enclosed space such as a building or an area inside a car. The term low emissivity describes a property of the surface of a material that can absorb and emit mid-range infrared radiation, making the surface reflective of mid-range infrared radiation and thus reducing heat flow through the material by reducing the radiant component of heat transfer to and from A surface with low emissivity (sometimes referred to as low E). By preventing solar heat gain, the interior of buildings and cars is kept cooler; This allows for reduced air conditioning requirements and costs. Effective low-E coatings increase comfort during the summer and winter seasons by increasing the thermal insulation performance of a window.

Of course, the use of economically viable material production processes and the persistence and maintenance of associated properties such as light transmittance, visibility, color, clarity and reflectivity are essential to produce commercially acceptable coated glass materials that possess both solar control and emissivity properties.

As described below, various technologies have been used to meet the need for low-emissivity solar control glass, but no system has met all of the performance requirements in an economically viable manner.

Many paints and coating systems cause iridescent colors to appear in the coated material. This may be due to the chemical composition of the coating, the thickness of the layer or individual layers, or the mutual effect of the substrate and coatings on incident light. In some cases, such iridescence can be minimized or eliminated by applying an anti-iridescence layer between the glass base layer and the first coating. The use of an interference layer between the glass and the subsequent functional layer or layers to prevent iridescence or color reflection was initially demonstrated by Roy. Roy G. Gordon, which was the subject of US Patent No. 4,187,336, issued on February 5, 1980. The Gordon technology is the current technology for coated glass that controls sunlight as proven in US Patent No. 5,780,149 (on behalf of McCurdy and his associates, issued on July 14,

1998), which used two layers to control sunlight on the top of a Gordon type interference layer. The interfering layer often contains silicon dioxide. The current invention represents an amazing advance and eliminates the need for a Gordon type underlayer to control reflected color.

US Patent No. 3,149,989 describes coating compositions useful for producing radiation-reflecting (sunlight-controlling) glass. At least two coatings are used, with the first coating, bonded to the glass base layer, consisting of tin oxide mixed with a relatively high percentage of antimony. The second coating also consists of recombinant tin oxide

With a relatively low percentage of antimony. The two membranes may be superimposed on each other

Some, or they can be placed on opposite sides of the glass base layer. In neither case do these solar control coatings contribute to the perceived low emissivity properties of the glass material.

US Patent No. 4,287,009 describes a heat-absorbing glass designed to convert incident sunlight into thermal energy that is transferred to a working fluid for heat transfer. Accordingly, coated glass absorbs at least 85% of the rays in the wavelength range of sunlight and has a relatively low emissivity of less than 0.2. The coatings are placed on the outside of the glass (or on the side facing the sun) and the heat transfer fluid is in contact with the inside of the glass. The coatings include a first coating of metal oxides deposited on the smooth glass layer, where the oxides are selected from tin, antimony.

antimony, indium, iron, and a second coating of metal oxides deposited on the first coating, chosen from the same group of metals. Membranes designed in this way transmit visible light very little, and no teachings are mentioned regarding controlling reflected color.

US Patent No. 4,601,917 describes liquid coating compositions for producing coatings of high quality and performance containing tin oxide adducted with fluorine.

via chemical vapor deposition (CVD). One use of such coatings is to produce energy-efficient windows, also known in the trade as low-E or low-E windows. Methods for producing coated glass are also described, but the patent does not describe This is how to produce coated glass materials that have both sunlight control and low emissivity properties.

U.S. Patent No. 4,504,109, assigned to Kabushiki Kaisha Toyota Chou, describes a glass coated with multiple infrared-blocking layers comprising a visible light-permeable base layer and an overlying composite thin sheet consisting of at least one infrared-blocking layer and one cross-reflection layer. at least

They are placed one on top of the other in an alternating manner. Indium oxide doped with Sn (tin) is used in the examples as a layer that blocks infrared rays, and TiO2 is used as an interference-blocking layer. To reduce iridescence, the thickness of the layer that blocks infrared rays and the interference-reflection layer should be a quarter of a range. (Lambda/4) with a permissible deviation ranging from 75% to 130% of Lambda/4. Although other compositions of the infrared blocking layer and the cross-reflection layer such as SnO2 containing or without doping agents are described (see column 6, lines 12 to 27), the particular combination of doped SnO2 layers in accordance with the invention is not described or illustrated in examples. Walls that achieve sunlight control, low emissivity and resistance to iridescence without the need to limit the thickness to a lambda/4 value, to prevent iridescence or color reflection.

U.S. Patent No. 4,583,815, also assigned to Kabushiki Kaisha Toyota Chou, describes a thin heat wave blocking plate consisting of two superimposed layers of indium tin oxide containing different amounts of tin. Anti-reflective layers above or below the two indium tin oxide layers. Other compositions are described for the layer that blocks infrared rays and the interference reflection layer, such as SnO2 containing a doping agent that turns into a positive ion with a valence of +5, such as Sb (antimony (p), (antimony (phosphorus As), phosphorus (arsenic arsenic), Nb (niobium Ta, Niobium (tantalum, tungsten), Mo (molybde.num) or an element such as F (fluorine) converts to a negative ion easily with a valence of -1 (see column 22, lines 17 to 23). However, the special combination of recombinant SnO2 layers of the present invention that achieves solar blocking, emissivity and resistance has not been described or illustrated in examples. There is no protection element related to tin oxide layers and there are no instructions in the standard to describe the composition of such layers, such as the ratio of doping agent to tin oxide. It should also be noted that the teachings indicate that the same doping agent is used in both layers (indium and tin oxide

indium tin oxide) while in the current patent application one layer should contain a different doping agent than the doping agent in the other layer.

U.S. Patent No. 4,828,880, assigned to Pilkington PLC, describes barrier layers that inhibit the migration of alkali metal ions from

The surface of the glass and/or act as discoloration-preventing underlayments for overlying infrared reflective or electrically conductive layers. Some of these discolouration coatings are used in solar-controlled or low-emissivity glass compositions.

U.S. Patent No. 4900634 assigned to Glaverbel describes a pyrolytic coating of tin oxide containing a mixture of fluorine and antimony doping agents coated on glass and conferring emissivity.

Low and a specified haze reduction factor of 1.5 at most.

U.S. Patent No. 5,168,003, assigned to Ford Motor Company, describes a glazing article having a substantially transparent fold comprising a layer with an optical function (which may be of low emissivity or solar control) and a thinner anti-iridescence layer which is Layer with multi-gradient region

Multiple gradient step zone layer. Tin oxide doped with antimony is mentioned as a possible alternative or optional component of the low-emissivity layer shown in the examples.

U.S. Patent No. 5,780,149, assigned to Libbey-Owens-Ford, describes a coated glass that controls sunlight in which there are at least three coating layers, namely a first and second transparent coating and an anti-iridance layer placed between the glass base layer and the upper transparent layers. The invention is based on transparent layers in which the difference in refractive indexes in the region with wavelengths close to the infrared wavelengths is greater than the difference in their refractive indexes in the visible region. This difference causes the heat of the sun's rays to be reflected in the region whose wavelengths are close to the wavelengths of infrared rays, instead of being absorbed. Oxides are used

Recombinant metal oxides with low emissivity properties, such as tin oxide recombinant with fluorine, as the first transparent layer. Metal oxides such as undoped tin oxide are used as the second layer. None were described

Absorption combinations for rays with wavelengths close to infrared wavelengths

Near infla red (NIR) absorbing combinations.

European Patent No. 0-546-302-B1 issued on July 16 describes,

1997 AD and assigned to Asahi Glass Co. Asahi Glass Co., coating systems for solar-controlled, heat-treated (tempered or curved) glass incorporating a metal nitride-based protective layer

metal nitride. The protective layer or layers are used to cover the layer that controls sunlight (to protect it from oxidation during heat treatment). Several examples are given of a layer that controls sunlight, including tin oxide impregnated with antimony or fluorine. However, the particular combination of recombinant SnO2 layers of the present invention that achieves solar control, low emissivity and resistance to iridescence without following Gordon's teachings is not described or illustrated in examples.

European Patent No. A1- 009- 3500-0 is a patent application published in February 1996 and assigned to Central Glass Co. Central Glass Co. This patent application describes a heat-reflective glass panel that has a multi-layer coating that includes a sheet of glass and two layers. The first layer is a metal oxide

High refractive index based on Cr (Mn), chromium (Fe), manganese (iron), Co (Ni), cobalt (nickel) or Cu (copper) and the second layer is

It is a film with a lower refractive index based on a metal oxide, such as tin oxide. Low-emissivity or NIR-absorbing recombinant layers and combinations have been described. International Patent Application No. 98/11031, issued in March 1998 and assigned to Pilkington PLC, aims for a high-performance glass that controls sunlight, including a base layer with coatings that include a heat-absorbing layer and a heat-absorbing layer.

Low emissivity of metal oxide. The heat-absorbing layer may be a metal oxide layer. This layer may be mixed with tungsten oxide, cobalt, chromium, iron, molybdenum, niobium, vanadium, or mixtures of these compounds. The low emissivity layer may be recombinant tin oxide. In a preferred aspect of the invention, an anti-iridance layer or layers are incorporated beneath the coating comprising an endothermic layer and a low-emissivity layer. This application does not describe or suggest the particular combination of recombinant SnO2 layers according to the present invention that achieves solar control, low emissivity and resistance.

For iridescence without the need for a Gordon type underlayer to prevent iridescence or color reflection.

Canadian Patent No. 2,193,158 describes a layer of tin oxide doped with antimony placed on glass with a molar ratio of tin to antimony ranging from 1:0.2 to 1:0.5 that reduces light transmission through the glass.

The reference Dopant Effects in Sprayed Tin Oxide Films, by E. Shanthi, A 100 Banerjee and KL Chopra, Thin Solid Films, Vol 88, 1981 pages 93 to explains the effects of factors.

Doping of antimony, fluorine, antimony, fluorine, fluorine-antimony on the electrical properties of tin oxide films. The article does not describe any optical properties of antimony-fluorine films, nor even the effect on transmitted or reflected color.

British Patent Application No. A 2302101 assigned to Glaverbel describes a glass material coated with a thick film of antimony/tin oxide.

400 Nanometer (nm) has at least a molar ratio of Sn/sb ranging from 0.05 to 0.5 with a visible transmittance factor of less than 35%. The films are applied by chemical vapor deposition (CVD) by water spraying and are used in glass applications that ensure confidentiality. Low haze-reducing undercoatings as well as thick layers with low Sn/sb ratios are described

Low emissivity properties in addition to great absorption of sunlight. It further describes that it is possible to provide one or more additional coating layers to obtain certain desired optical properties. None of these properties were mentioned other than blur. The application did not describe anything about thin layers, the use of more than one doping agent, or controlling the color of the film.

British Patent Application No. A 2302102, also assigned to Glaverbel, describes a glass substrate coated with a layer of Sb/Sn oxide containing tin and antimony in a molar ratio of 0.01 to 0.5, where the said layer is deposited by CVD, thus The painted base layer shall have a solar factor (coefficient of solar heat gain) of less than 0.7. The coatings are used for window applications and have optical transmittance coefficients between 40 and 65% and thickness values ​​ranging from 100 to 500 nanometers. Undercoatings are required to reduce haze and the coatings can be given low emissivity by judicious selection of the Sn/sb ratio. Similarly to the previous application, instructions for providing an additional coating layer and one or more indications for obtaining certain desired optical properties are mentioned. Low emissivity layers consisting of tin oxide doped with fluorine can also be deposited over the Sn/sb layers, or fluorine components can be added to the reactants.

of Sn/sb to produce low-emissivity films containing Sn and Sb, F. The latter two methods were preferred because of the additional time and cost of adding a third layer and the fact that the emissivity of the F/Sb films increased rather than decreased. He did not mention color control or color neutrality.

British Patent No. 2200139 assigned to Glaverbel describes a method of depositing a coating by spraying solutions containing tin sources, compounds containing fluorine and at least one other doping agent chosen from the group consisting of antimony, arsenic arsenic, vanadium, and cobalt. Zinc, cadmium, tungsten, tellurium or manganese.

In the past, glass manufacturers have controlled heat transfer through windows using absorbent and/or reflective coatings, glass tints, and later applied films. Most of these coatings and films are designed to control only one part of the solar heat spectrum, either the NIR, that is, the component with a wavelength close to the infrared wavelength of the electromagnetic spectrum, whose wavelength ranges from 750 to 2500 nanometers, or the mid-infrared component. The range of the electromagnetic spectrum, whose wavelength ranges from 2.5 to 25 microns. A product has been designed to control the overall thermal spectrum, and although sprayed metal/insulating film stacks are effective, they have limited load capacity and must be protected and sealed in the center section of a multi-panel insulated glass unit (IGU). A membrane or combination of Films that completely control sunlight and can be easily applied by thermal deposition

pyrolytic deposition during glass making that produces a material with acceptable visible transmittance, reflects or absorbs NIR, reflects mid-range infrared rays, and has a neutral or near-neutral color.

The above references, individually or together, do not describe or suggest the particular combination of recombinant SnO2 layers according to the present invention that achieves solar control, low emissivity and resistance to iridescence without the need for a Gordon-type substrate.

General description of the invention

The present invention provides improved sunlight-controlled glass that transmits visible light tolerably, absorbs light with a wavelength close to the near-infrared (NIR) wavelength, and reflects mid-range infrared light (low emissivity or low E) with a preselected color within the spectrum. Visible reflected light can be tuned to a specific color or can be made essentially colorless (neutral, as it will be known below). The invention also provides a method for producing improved coated glass that controls sunlight. The enhanced glass coating is a tin oxide coating, containing various doping agents and modifying materials.

Blur has special layers of coating. One layer is a solar absorber with a wavelength close to the wavelength of infrared radiation (NIR) that includes tin oxide with a doping agent such as antimony. Another layer of the tin oxide coating is a low-emissivity control layer capable of reflecting mid-range infrared light and comprising tin oxide with an agent.

An alloy of fluorine and/or phosphorus. There is generally no need for a layer

Separate to prevent peeling as described in the prior art such as Gordon's layer to obtain a neutral (colourless) appearance of light reflected from the coated glass, however the iridescence prevention layer or other layers may be combined with the multi-layer tin oxide coating provided by the invention Current. If desired, multiple layers that control sunlight and/or multiple layers with low emissivity can be used. The NIR-absorbing layer and the low-emissivity layer are separate parts of a single tin oxide film, with both layers consisting of doped tin oxide. The invention also provides a method for producing coated glass that controls sunlight. In addition, the present invention controls or changes the color of the transmitted light by adding color additives to the NIR absorbing layer. Surprisingly, fluorine, a doping agent that produces a colorless tin oxide film, acts as a color additive when added as an additional doping agent to the NIR-absorbing film and modifies the color of the light that passes through the NIR-absorbing film. The invention also provides fog-reducing doping agents in specific tin oxide coating layers.

Brief explanation of fees

Shapes from

1 to 4 and 8 to 15: Shows a cross-section of glass coated with a different number of

Layers or films in different stacking arrangements of tin oxide layer on a glass substrate.

Figures 5 and 6: graphically illustrate the sunlight control he obtained

Using antimony recombinant films at different dopant concentrations and different film thicknesses on window panes, i.e. a single pane of glass, or on insulated glass units (IGU) consisting of at least two panes.

Figure 7: shows a color spectrum in terms of the x and y coordinates according to a system

Commission Internationale Libre Commission

(Internationale de L'Exclairage (CIE). The specific color that

It can be obtained using different values ​​of film thickness and different doping agent concentrations.

The English translation of .CIE is International Commission on Illumination

International Commission on Illumination (CIE).

Figure 15: shows the haze reduction values ​​for tin oxide coatings

oxide according to the present invention contains blur-reducing additives in the NIR absorbing layer and others that do not contain them,

٢٨.

Figures 16, 17, 18 and 19: graphically illustrate the data that appeared in the examples.

The invention aims to prepare a transparent material with a controlled reflective color (even neutral color as defined herein) that absorbs solar radiation with a wavelength close to the wavelength of near-infrared (NIR) radiation and reflects the heat of mid-range infrared radiation (low emissivity) comprising a glass It has a tin oxide coating consisting of two thin film layers, each containing doped SnO2 with reducing additives.

of blurring or doping agents in at least one of the layers. Another object of the invention is to layer layers using chemical vapor deposition (CVD) techniques at atmospheric pressure, or using other processes such as spraying a solution or vaporizing liquids and sublimated solids can be used. The preferred method of application according to this invention is the CVD method at atmospheric pressure using evaporating liquid sources. Another goal is to provide solar control multilayers and/or low emissivity multilayers as well as other layers in combination with a solar control or low emissivity layer. Another goal is to provide a solar control film or combination of films that can be easily applied by thermal deposition during the glass making process that produces a material with acceptable visible transmittance, reflects or absorbs NIR, reflects mid-range infrared (low E) and is A neutral or close-to-neutral color, the production process of which is the object of the present invention. Another object of the invention is to control the color of the transmitted light independently of the color of the reflected light by adding color additives to the absorbing layer.

NIR.

Detailed description

A low-emissivity, solar-controlling coated glass is produced by depositing at least two layers on a heated transparent substrate, a low-emissivity layer comprising a film of SnO2 containing a fluorine and/or phosphorus dopant, and an NIR-absorbing layer comprising a film of SnO2 containing antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel or mixtures thereof as doping agents. It has been found that this combination controls the solar thermal and radiative portions of the electromagnetic spectrum so effectively that a window coated with these films has greatly enhanced properties.

Solar control properties are usually expressed in terms of the solar heat gain coefficient (SHGC) and the U-value. SHGC is a measure of temperature

The total solar radiation absorbed by a window system relative to the incident solar radiation, while the U-value (U) is the total heat transfer coefficient of the window. The SHGC of coated glass depends mainly on the thickness of the NIR-absorbing film and its antimony content (see Figures 5 and 6), while the U value depends mainly on the emissivity of the film and the composition of the window. The SHGC value 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 0.0 to 1.2 for a single film-coated glass pane according to a preferred embodiment. In an insulated glass unit (IGU), the SHGC values ​​decrease and are approximately 0.3, with the U-values ​​being low, for example, around 0.28.

Both the color reflected and transmitted from the coated glass can be controlled in accordance with the present invention. In addition, the amount of visible light that passes through coated glass can be controlled to between about 0.25 and 80% by controlling the thickness of the low-emissivity NIR-absorbing films and the concentration of the doping agent in the NIR-absorbing film. The transmitted color, i.e. the color of light that passes through the coated glass, can be controlled separately from the reflected color by adding a color-effective amount of a color additive to the NIR-absorbing layer of the coating. The reflected color can vary from almost neutral to red, yellow, blue or green and can be controlled by changing the thickness of the film and the content of the doping agent in the layers. Surprisingly, color neutrality as defined in this statement of reflected color can be achieved without the need for an anti-iridance coating. Although the refractive indices of NIR-absorbing films with low emissivity differ, the reflected color does not depend on the classical interference phenomenon originally discovered by Gordon (according to US Patent No. 41,887,336). The unexpectedly observed reflected color is controlled by the combination of absorption achieved by the NIR-absorbing layer (absorption) and reflection achieved by the low-emissivity layer or layers. The absorption achieved by the NIR absorbing layer can be controlled by varying the thickness of the SnO2 layer and the concentration of the doping agent in the NIR absorbing layer, usually antimony. It can be controlled

The reflection is achieved by the low-emissivity layer by changing the thickness of the SnO2 layer and the concentration of the doping agent in the low-emissivity layer, usually fluorine. A low-emissivity layer consisting of SnO2 containing a fluorine or phosphorus dopant is sometimes referred to in this statement by the abbreviation TOF or TOP while a NIR absorbing layer consisting of SnO2 when containing an antimony dopant is sometimes referred to in this statement by the abbreviation TOF or TOP. TOSb.

A preferred embodiment of this invention uses a tin oxide coating containing a layer of tin oxide doped with fluorine (TOF) as the low-emissivity layer and a layer of tin oxide doped with antimony (TOSb) as the NIR absorbing layer. With a fog-reducing additive in at least one layer, preferably in a layer deposited directly on the glass. TOF films and their deposition on glass are known in the technology and are referred to as low-emissivity films. The NIR absorbing film is also a SnO2 film but contains a different doping agent than the low-emissivity layer. It is preferable that the doping agent in the NIR absorbing layer be antimony, although the doping agent could be an element chosen from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, and cobalt. Cobalt, nickel and mixtures thereof. A mixture of one or more doping agents may be used in the NIR-absorbing layer, but the low-emissivity layer should contain a low-emissivity doping agent that imparts apparent conductivity to the layer, such as fluorine or phosphorus, although other doping agents may be used In combination with a low-emissivity doping agent. Whereas, in both the low-emissivity and NIR-absorbing layers according to the present invention, SnO2 is used as a base layer of metal oxide on a doping agent, and it is preferable for the NIR-absorbing layer and the low-emissivity layer to be part of a single membrane in which the concentration of the doping agent is graduated. or

Layers containing different doping agents. A single membrane with a gradient of dopant concentration is described in Figure 3 for membrane 16. In membrane 16, there is a gradient in the concentration of the doping agent, provided that the concentration of the doping agent in the NIR absorbing layer is higher than the concentration of the other doping agent (concentrations of doping agents) on one of the surfaces of the membrane, surface 18 or 22, and that the concentration of the doping agent is of low emissivity. Higher than the concentration of other doping agents at the other surface of the membrane. This leads to a change or gradient in the concentrations of the doping agents in the NIR-absorbing layer and the doping agents in the low-emissivity layer between surface 18 and surface 22. At a certain intermediate point 20 between surface 18 and surface 22, the concentration of the doping agent in the NIR-absorbing layer changes from being the doping agent. The one with the highest concentration on one side of point 22 indicates that it is the doping agent that no longer has the highest concentration on the other side of point 22. Figure 8 shows the membrane with a low E, 10, above the NIR-absorbing membrane 12. The NIR-absorbing membrane 12 shown in Figure 8 has a graduated concentration of the doping agent in the NIR-absorbing layer in the tin oxide membrane, with the lower concentration of the doping agent being closer. To the membrane with low E 10. The coated glass shown in Figure 9 is similar to the composition shown in Figure 8 except that the gradient in the concentration of the NIR-absorbing layer doping agent, antimony, is highest near the low-E 10 film and lowest in a region closer to the base layer. The membrane 12 differs from the membrane 16 shown in Figure 3 in that the membrane 12 is a NIR-absorbing membrane, while the membrane 16 has NIR absorption properties and low emissivity. It contains both a high doping agent with a low E and a doping agent. A NIR absorbing layer with a factor concentration gradient. The low-E doping and doping agent concentration gradient of the NIR absorbing layer. Figures 10, 11, 12 and 13 show the NIR absorbing layer as two separate films, 28 and 30. The membrane 28 appears to have a thickness greater than the thickness of the membrane 30, and the total thickness of the NIR absorbing layer is the sum of the thicknesses of the two membranes 28 and 30 and should be within the range of thickness values ​​mentioned above for the NIR absorbing layer, preferably ranging from 80 to 300 nanometers. In Figures 10 and 11.

The membranes 28 and 30 are adjacent, while in Figures 12 and 13, the membranes 28 and 30 are on opposite sides of the low-emissivity membrane 10. The dopant concentration in the membrane 28 is preferably different from the dopant concentration in the membrane 30.

Figure 14 shows a two-layer film of tin oxide deposited directly on the glass substrate 14 such that the bottom layer 32 has one section 34 containing a haze-reducing additive and another section 36 does not contain a haze-reducing additive, while the upper layer 10 is a layer Low emissivity such as tin oxide doped with fluorine.

Figure 15 shows the haze reduction values ​​for tin oxide coatings according to the present invention that contain haze-reducing additives in the NIR 32 absorbing layer and others that do not contain them. It shows four glass substrates, each with an NIR-absorbing layer of tin oxide doped with antimony, 32, about 2,400 Angstroms (Å) thick, below a layer of low-emissivity doped with fluorine 10, each about 3,000 Angstroms thick. In the coated glass on the left, the blur rate reached 1.13% compared to 0.72% when adding TFA to the NIR-absorbing layer shown in the second coated glass on the left. Continuing right in Figure 15, the haze ratio of the 32 and 10 bipolar coatings is 0.84 when water is blocked during deposition of the first 550 angstroms (approximately) of the NIR absorbing layer, compared to the haze ratio of 0.70 shown in the maximum bilayer coated glass. The right is where there is TFA and no water between the sources used to deposit the first 550 angstroms of the NIR 32 absorbing layer.

In a preferred embodiment of this invention an antimony-doped membrane is used as the NIR absorbing membrane. Such a film can be deposited using a number of techniques including spray pyrplysis, PVD and PVD methods. Spray pyrolysis is also known as spray pyrolysis and is described in patents such as Canadian Patent No. 2,193,158. CVD methods are used to deposit films of SnO2 with or without

The doping agents and chemical sources used to form films of SnO2 containing doping agents are well known and described in US Patent Nos. 4601917 and 4265974. It is preferable to use the CVD method to deposit SnO2 layers containing doping agents according to known methods directly on a float glass manufacturing line outside or inside a float glass chamber using conventional continuous deposition techniques and chemical sources as described in US Patent No. 4,853,257 (as Henery ). However, films of SnO2 containing dopant agents can be applied as layers on glass using other processes such as solution spraying or processes in which evaporating liquids and sublimated solids are used at atmospheric pressure. When the films are applied using the solution spray method, the SnO2 sources and doping agents themselves are dissolved in a suitable non-reactive solvent and applied using known spraying techniques to the heated glass tape at atmospheric pressure. Suitable solvents for solution spray application as described in Canadian Patent Application No. 2,193,158 include alcohols such as ethanol and isopropanol, ketones such as acetone and 2-butanone, and esters such as ethyl acetate and butyl acetate. The preferred method of application according to this invention is CVD at atmospheric pressure using vaporized liquid sources. The process can be widely applied in commercially available continuous sedimentation systems. Use of sources according to preferred embodiments is economical, will allow coatings to remain for long periods of time, reduce system cleaning frequency, and should be usable with little or no modification to the available float glass line coating equipment.

Coatings perform their function using a combination of reflection and absorption. The low-emissivity film reflects mid-range infrared heat in the 2.5 to 25 micron spectrum region while the NIR absorbing film absorbs heat mainly in the 750 to 2500 nm spectrum region. The theory relied upon to explain this effect, without being limited to that, is:

In the NIR-absorbing region, the plasma wavelength (pl represents the wavelength at which the low-emissivity membrane changes from being permeable to reflecting light energy) of the low-emissivity membrane is located in the NIR-absorbing region. In the region surrounding the PL, the NIR absorption is highest for the low-emissivity membrane and the absorbance increases when combined with the NIR-absorbing membrane. NIR-absorbing films according to preferred embodiments are also considered recombinant semiconductors and thus have reflective properties in the mid-range infrared region. This reflection combined with the lower emissivity film reflectance results in a higher total thermal reflectivity in the mid-range infrared region.

It is preferable to thermally deposit a SnO2 layer on glass using a tin source, in particular an organotin precursor compound such as trichloride.

monobutyltin trichloride (MBTC), dimethyltin dichloride, dibutyltin diacetate, methyl tin tichloride or any of the known sources of SnO2 layer deposition according to a CVD method such as that described in US Pat. No. 4601917 and incorporated into this statement for reference and are often organic tin compounds

Organotin compounds of this nature are used as sources for thermal deposition of SnO2 layers on

Stabilizers such as ethanol. It is preferable that the concentration of stabilizers be less than 1% to reduce the risk of ignition occurring when hot glass comes into contact with such chemicals in the presence of oxygen. It is preferable that the sources of the doping agent in the NIR absorbing layer (antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel) are halides such as antimony trichloride, but it can Also used are alkoxides, esters, acetylacetonates, and carbonyls. Other suitable sources of doping agent and SnO2 are well known

For those who are tech savvy. Sources of suitable quantities of fluorine doping agent in the low-emissivity SnO2 layer are disclosed in US Patent No. 4601917 and include trifluoroacetic acid, ethyltrifluoroacetate, ammonium fluoride, and hydrofluoric acid. The concentration of the low-emissivity doping agent is usually less than 30%, so the preferred concentrations of the low-emissivity doping agent range from 1% to 15% of the weight of the dopant source based on the sum of the weight of the dopant source and the tin source. This is usually related to a dopant concentration in the low-emissivity film ranging from 1% to 5% based on the weight of tin oxide in the low-emissivity film.

In preferred embodiments of the invention, the properties depend on the thickness of the low-emissivity and absorbing layers as well as the antimony content of the NIR-absorbing film. The thickness of the low-emissivity film can range from 200 to 450 nm with a thickness of 320 nm being the most preferred. Preferred NIR absorbing films can be deposited in a manner similar to the deposition of low-emissivity films using methods such as those in US Patent No. 4601917. Organic sources of tin for the SnO2 layer can be evaporated into air or other suitable carrier gases containing an O2 source with source concentrations ranging from 0.25 to 4.0 mol% (preferably 0.5 to 3 mol%). Source concentrations of SnO2 are expressed in this statement as a percentage based on moles of source and moles of carrier gas. Preferred dopant source concentrations for the NIR absorbing layer range from about 1% to about 20% (preferably from 205% to 7.5% and most preferably from 3% to 6.0%) and are calculated using the weight of the dopant source and the weight of the SnO2 source. Specifically, an antimony doping agent using antimony trichloride as the source is preferred in a concentration ranging from about 2% to

About 8 wt% with a concentration of about 4 wt% being particularly preferable.

This is related to a similar mass percentage of antimony in the NIR-absorbing film of tin oxide.

Glass coated according to the present invention is shown in Figs. Figure 1 shows a cross section of the membranes. Film thicknesses can range from 200 to 450 nm for the low-emissivity membrane (Section 10) and for the NIR-absorbing membrane (Section 12) from 80 to 300 nm. The preferred thickness ranges from 250 to 350 nm for a low-emissivity membrane and from 200 to 280 nm for a NIR absorbing membrane. The most preferable range is from 280 to 320 nm for a low-emissivity membrane and from 220 to 260 nm for a NIR absorbing membrane. Using films in accordance with preferred embodiments, a neutral blue solar control coated glass can be produced, defined herein as coated glass that reflects light within predominantly CIE color coordinate values ​​with X between 0.285 and 0.310 and between 0.295 and 0.325. The definition of the term neutral blue is shown in Figure 7 by the framed area labeled neutral blue. As shown in Figure 7, and by following the procedures described in Examples 15, 20, and 22, a set or preselected reflected color that is close to the neutral color but slightly closer to the yellow side of neutral can be produced (X values ​​no more than 0.325 and y values ​​no more About 0.33), but this gradation of the reflected color from mainly neutral to slightly yellow is not to the liking of consumers. Figure 2 shows the two membranes or layers in the opposite arrangement to that shown in Figure 1. In Figure 2, the low-emissivity film is closer to glass 14 than to the NIR-absorbing film 12. Figure 3 shows the fusion of the NIR absorbing layer and the low-emissivity layer into a single film of SnO2 16 with a graded amount of doping agent. The film 16 contains one doping agent dominantly (e.g., a low-emissivity doping agent, fluorine) at the upper surface, 18, away from the glass 14, and contains another doping agent dominantly (e.g., an NIR-absorbing layer doping agent, such as antimony). At the surface of the film 22 closest to the glass. The concentrations of doping agents change from surface 18 to surface 22, so that...

The concentration of one of the doping agents at the surface 18 ranges from more than 50% to almost zero percent at the surface 22. Counting an intermediate point 20, below the upper surface 18, the predominant dopant at that point in the film changes from the predominant dopant at surface 8 1 to the predominant dopant at surface 22. The dopant of the NIR absorbing layer or the dopant of the low-emissivity layer (fluorine) may be the predominant dopant at surface 8 1 with the other dopant being the predominant dopant at surface 22. Figure 4 shows a coated glass with additional layers 24 and 26 in addition to the low-emissivity layer 10 and the NIR-absorbing layer 12. Additional layers 24 and 26 may be low-emissivity and/or additional NIR absorbing layers or other conventional layers used to coat glass such as a lightly tinted film. For example, layer 12 may be an NIR absorbing layer (e.g., tin with antimony), layer 10 may be a low-emissivity layer (tin with fluorine), and layer 4 may be another NIR absorbing layer. Layer 26 may be another low-emissivity layer or any other conventional layer. The concentration of the doping agent may be similar or different when using more than one low-emissivity layer, and the thickness may also be similar or different for each low-emissivity layer. Likewise, when using more than one NIR absorbing layer, the concentration and choice of doping agent (antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel) may be similar or different. The thickness varies for each NIR absorbing layer. In general, the description of the doping agent for an NIR absorbing layer in this statement is mostly in terms of antimony, and it should be realized that the doping agent for the NIR absorbing layer can be chosen from the group consisting of antimony, tungsten, vanadium, iron, and chromium. Molybdenum, niobium, cobalt, nickel and mixtures thereof. Likewise, in the gradient layer embodiment of the invention as shown in Figure 3, the predominant doping agent at the surface of the NIR absorbing layer may be chosen as either surface 18 or 22 of the group consisting of antimony.

antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium; Cobalt, nickel and mixtures thereof. It is only necessary that the doping agent of the low-emissivity layer, for example fluorine, be the dominant doping agent at the opposing surface. One or more NIR absorbing layers or one or more low-emissivity layers such as layers 10 and 12 in Figures 1 to 3 and/or other conventional layers may be combined with a gradient layer.

It is preferable to use water to accelerate the deposition of the SnO2 film on glass, as described in US Patent No. 4,590,096 (in the name of Lindner), and is used in concentrations ranging from approximately 0.75 to 12.0 mol%, based on the gas composition.

Another embodiment according to this invention is a reduced blurring of the membrane. Blur results from the scattering of incident light when it strikes a surface. Surface roughness due to large crystalline particle size can result in a wide range of crystalline particle size and/or embedded particles in the film surface. It can also result from voids (gaps) in the membrane resulting from the evaporation of an intermediate byproduct such as NaCl. The films deposited by this invention have a blurring that results mainly from surface roughness. The haze is reduced by including or appropriately displacing certain additives in the coating process either at the glass-film interface or at the film interface between the two layers. By controlling the wrinkling within the film layers in this way, wrinkling and thus the blurring of the top layer in the two-layer tin oxide coating are reduced. This is an improvement over the previous technique, which achieves a reduction in blur by adding an additional layer on top of the functional layer. The sole purpose of the additional layer according to the previous technique is to smooth out the rough surface of the functional layer by filling in the areas between the peaks and valleys of the crystalline grains.

Among these wrinkle-reducing additives is fluorine, either in an inorganic form, such as HF, or in an organic form, such as trifluoroacetic acid (TFA) or ethyl trifluoroacetate, for example. Another source of fluorine suitable for reducing blurring is difluoroacetic acid. acid,

monofluoroacetic acid, antimony trifluoride, antimony pentafluoride, and ethyl trifluoroacetoacetate. When fluorine is present in all or part of the TOSb substrate, the crystalline grain size is significantly reduced and the overall film opacity is reduced. The microscopic images of the scanning electron microscope show that the size of the crystalline grains of the upper coating is affected by the reduced size of the crystalline grains of the lower coating. Other additives that have been found to be effective in reducing haze are acids such as acetic acid, formic acid, propionic acid, and methanesulfonic acid.

Butyric and its brothers, nitric and nitrous. Haze can also be reduced by removing certain additives such as water. When water is not present during deposition of the first few hundred angstroms of the bottom coating, the overall crystalline grain size is reduced. Blur can also be reduced by merging one or more of the previous faces. If TFA is included in the deposition process when the water is removed, the overall film opacity is reduced. For example, when water is removed from the deposit of the first 50 to 60 nm of the TOSb layer, the overall film shape is reduced and blur values ​​of approximately 0.8% are obtained. If TFA is added and water is removed from the deposition of the first 50 to 60 nanometers of the TOSb layer, similar morphological effects and blur values ​​result.

When fluorine is added as a doping agent in the tin oxide film,

It lowers the emissivity and increases the membrane conductivity. However, it does not act as a conventional doping agent in this invention when added to the antimony doped layer in the tin oxide coating. In the antimony-doped layer, it acts as a modifier for the size of the crystalline grains of tin oxide doped with antimony, as shown by the reduction of the overall membrane opacity (as measured using a hazemeter and proven by microscopic images using a scanning electron microscope). The rise in plate resistance with the rise in emissivity, shown in the results in Table 3, confirms the function of the fluorine added to the tin oxide layer doped with antimony (TOSb). And when

As fluorine is present in the TOSb layer, the resulting emissivity of the combined layer is increased, but not decreased as would be expected if it acts as a dopant. The explanation for this is that he believes that fluorine might bind preferentially to the antimony sites and in that way be effectively removed as doping agents in the membrane and thus the overall emissivity of the membrane might increase, but he does not wish to adhere to this interpretation.

Another embodiment according to the invention provides the ability to change the color transmitted in coated glass. The transmitted color refers to the color observed by the viewer on the opposite side of the coated glass with respect to the visible light source, while the reflected color refers to the color observed by the viewer on the same side of the visible light source. Transmitting light can be affected by adding additional doping agents to the NIR-absorbing film. As previously described, the NIR absorbing layer contains a doping agent selected from a class consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel. The color of the light that passes through the NIR-absorbing layer can be changed by adding an additional doping agent that differs from the first doping agent in the NIR-absorbing layer and is chosen from the category that consists of tungsten, vanadium, iron, chromium, molybdenum, niobium, and cobalt. cobalt, nickel or a combination of more than one additional doping agent to the NIR absorbing layer. The additive that affects blur, fluorine, can also affect the color rendering. As shown in Examples 40 through 43, adding a fluorine source, such as trifluoroacetic acid (TFA) to the source solution in the NIR-absorbing layer, such as MBTC/SbCl3, produces a film that is gray in color as opposed to the blue color of the tin oxide layer. tin oxide, which is added to antimony without the presence of a fluorine doping agent. The additive has little or no effect on reflected light, and accordingly, coated glass can be produced with a different reflected light than its transmitted light.

Doping agents such as vanadium, nickel, chromium, and unconventional color additives such as trifluoroacetic acid (TFA) can be added to TO:Sb sources in a ratio ranging from 1 in 5% by weight (on

based on the total weight of the source and additive) to change the color of the light transmitted into the final film composition without significantly affecting the color of the overall neutral reflected light.

Preferred embodiments of this invention will be represented by the following examples. One skilled in the art will recognize that minor variations outside of the embodiments shown herein are not outside the principle and scope of this invention.

The most preferred embodiments are described herein for its coated glass

NIR properties and low emissivity give a neutral reflected color from the tin oxide coating, which consists of only two layers, apart from the blurring in examples 1 to 30. One layer consists of a 3000 fluorine-doped TO:F film. In combination with a TO:Sb (tin oxide antimony) film thickness of 2400 angstroms on glass, the TO:F film thickness can range from approximately 2800 to 3200 angstroms and still achieves the amazing result of neutral reflected color. The concentration of fluorine can range from approximately 1 to 5% of the atomic weight. The thickness of the TO:Sb film can range from approximately 2200 to 2600 angstroms with an antimony concentration of approximately 3 to 8% and still achieve the amazing result of neutral reflected color of the coated glass. Within the preferred range of thickness and doping agent concentration according to the present invention, it is possible to produce a coated glass that controls sunlight containing a NIR absorbing layer and a low emissivity layer and giving a neutral blue color to the reflected light, i.e. a coated glass with reflected light that falls predominantly within the color coordinate values ​​according to . CIE where located

x shows 0.285 and 0.310 and y lies between 0.295 and 0.325 as shown in Figure 7 by the framed area written in neutral blue.

All SHGC and U-values ​​in the tables were determined using the single band approach from NFRC Windows version 4.1. A more accurate multiband approach (spectral data file required) will improve SHGC values ​​by approximately 14%.

Tristimulus values ​​can be calculated according to CIE. For colors reflected and transmitted from coated materials according to ASTM (American Society for Testing Materials) standards, E308, such that light source C is the standard illuminant. From these ASTM standards, E308, the color of a material can be specified within one of several different ranges. The range used for coated materials in this invention is the x and y color coordinate system according to CIE 1931. One can translate into a color range corresponding to *a*, L and *b according to CIE, 976 1 easily using the following equations:

(x= /3- (Y/Yn [1/3 b* = 200[(Y/Yn)1/3- (Z/Zn)

Where Y, From the values ​​of *b*, a*, and L, the color saturation factor, *c, can be calculated using the equation A1/2[2(*b + 2(*c*=[(a). The value of 12 or less is considered the color saturation factor. Neutral value.

It explains the definition of a neutral blue color for reflected light, i.e. coated glass has dominant reflected light within the color coordinate values ​​according to CIE, which are for

The neutral blue frame is connected to values ​​of L, *b* and a* of 37.85, -1.25, -5.9 and 39.62, -2.25, 1.5 according to CIE 1976. Here are the sample transformation values:

Example 40 (Table 3)

5.5% of SbCl3

300/240 (F/Sb/Glass) 9,797=XY=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 control properties of glass windows were evaluated and assessed by the states

United States of America, Environmental Protection Agency using the Energy Star rating system. The Energy Star rating for the central region requires...

The United States has a U-factor estimate of 0.40 or less and a SHGC estimate of 0.55 or less. The Energy Star estimate for the southern region of the United States requires a U-factor estimate of 0.75 or less and a SHGC estimate of 0.40 or less. Coated glass with NIR-absorbing coatings and low-emissivity coatings of the present invention when incorporated into conventionally designed windows achieves Energy Star ratings for the central and/or southern region. For example, a window with a vertical sliding design achieves a width and height of 0.91 meters (3 feet).

It is 1.2 meters (4 feet) and has a frame absorption value of 0.5 as shown.

Estimated by the National Fenestration Rating Council (NFRC) and comprising solar control coated glass according to the present invention having a NIR-absorbing film and a low-emissivity film within the preferred range for a neutral blue color, an SHGC value of less than 0.40. A U-value of less than 0.64 is achieved for a single-pane glazing installation where the U-value of the frame is 0.7 or less and a SHGC value of less than 0.38 and a U-value of less than 0.48 are achieved for an insulated glazing unit (IGU) structure made of laminate. pure lite with a thickness of 2.5 mm, It has an air gap diameter of 1.3 cm (0.5 inch), an NIR absorbing coating and a low emissivity coating on the second surface of the outer lite, and has a frame U-value of 1.0 or less.

Examples demonstrate that using a minimum of two layers of recombinant SnO2, it is possible to produce coated glass with excellent sunlight control and a pre-selected reflective color. Tables 1, 2 and 3 provide the data while Figures 5 and 6 graphically show how the sun control properties of coated glass vary with doping agent concentrations and NIR-absorbing film thickness. Figure 7 shows a graph of the CIE's Especially to produce coated glass that controls sunlight with any desired color of radiation reflected from the coated glass surface, such as red, green, yellow, blue and shades thereof, or a neutral blue color. In particular, it was surprisingly found that a neutral blue color could be obtained for NIR-absorbing and low-emissivity layers but without the use of an iridescence-preventing layer such as the one described by Gordon.

While the inventive features of the present invention may be obtained by using only two layers, an NIR absorbing layer and a low emissivity NIR layer, embodiments of using multiple layers are within the scope and content of the invention. Your plate can be multi-layered NIR absorbent and/or additional low-emissivity NAT layers or other functional or decorative layers.

Embodiments of the use of the multilayer include TOSb/TOF/TOSb glass, TOSb/TOF/TO glass/TOSb glass, or TOSb/TOSb/TO glass/TOSb being only a tin oxide film. When using multiple NIR or low-emissivity absorbing layers, there is no need for the dopant concentrations or dopant selection to be equal in each NIR or low-emissivity film. For example, when two NIR absorbing layers are used in combination with at least one low-emissivity layer, one NIR absorbing layer may contain a low level of antimony doping agent (e.g. 2.5%) to give low range reflectivity Mid-IR One layer may contain a higher level of antimony doping agent (≥ 5%) to give NIR absorbance. The terms layer and film are usually used interchangeably in this statement except in the discussion of the gradient film shown in Figure 3, where a portion of the film is referred to as a layer with a dopant concentration different from the dopant concentration in another layer of the film. In the method of making coated glass according to the present invention as shown in the examples, the glass is sequentially in contact with sources containing a carrier gas. Accordingly, the glass may have a coating on it when it comes into further contact with sources containing a carrier gas. Therefore, the term 'contacting glass' refers to either direct contact or contact with one or more coatings previously deposited on the glass. The best methods for applying blur reductions according to this invention are described in Examples 40 to 43 and 48 to 61. The results are summarized in Tables 3, 4 and 5.

Examples 1 to 30

A base layer of glass with a thickness of 2.2 mm (consisting of soda lime silica), with an area of ​​12.9 cm2 (2 inches2), was heated on a hot mold to a temperature ranging from 605 to 625°C. The base coat was placed 25 mm below the central part of the nozzle of a vertically centered coating tube. A carrier gas of dry air flowing at a rate of 15 liters per minute (L/min) is heated to 1.60°C and passed through a vertical hot-wall evaporator. A liquid coating solution containing approximately 95% by weight of monobutyltin trichloride and approximately 5% by weight of antimony trichloride was fed to the evaporator by means of an injection pump at a volume flow designed to give an organotin concentration in the gas composition of 0.5%. mall. A quantity of water was also enriched into the evaporator at a flow designed to give 1.5% mole of water vapor in the gas mixture. The gas mixture was left to collide with the underlying glass layer at an apparent face velocity of 0.9 m/s for approximately 6.1 seconds, which led to the deposition of an antimony-doped tin oxide film whose thickness reached approximately 2.40 nanometers. Immediately thereafter, a second gas mixture was used consisting of a source composition of 95% by weight monobutyltin trichloride and 5% by weight trifluoroacetic acid, in addition to water at the same concentrations and the carrier gas as previously used to deposit the antimony-doped SnO2 layer. antimony. This second gas mixture was left to impact the painted base layer for approximately 6.7 seconds. A film approximately 280 nanometers thick was deposited from tin oxide doped with fluorine. The color of the bilayer film was light blue in both transmission and reflection. Optical properties were measured with a spectrophotometer using UV (=ultraviolet radiation)/VIS (=visible radiation)/NIR and the sheet resistance was measured with a standard four-point probe. The solar heat gain coefficient, U-value and visible transmittance of the center of the glass were calculated using Windows and Daylight Group version 4.1 software developed by Lawrence Berkeley National Laboratory.

Windows and Daylight Group, Building Technologies Program, Energy and Environmental Division. The CIE color coordinates for x and y were calculated using ASTM E308-96 from visible reflectivity data between 380 to 770 nm and three-sample values ​​for light source C. Analysis results for this film are shown in Table 1, Issue 19. This example was repeated an additional 29 times using different chemical source concentrations and deposition times to produce coated glass samples with different NIR-absorbing and low-emissivity layer thicknesses and different doping agent concentrations. The results are represented in Table 1.

Examples 31 to 38

Repeat the procedure described in Example 1, except that the steam feed order is reversed. The tin oxide film recombined with fluorine was deposited first for about 8 seconds and then the tin oxide film recombined with antimony for about 6 seconds. The thickness of the resulting film was approximately 540 nm and consisted of a low-emissivity (TOF) layer about 300 nm thick and a TOSb (NIR) absorbing layer about 240 nm thick. It had an appearance and color of reflected light (neutral blue) similar to the membrane in example 19. The results of the analysis are shown in Table 2, Issue 31. The procedure described in this example was repeated 7 additional times by varying the concentrations of chemical sources and deposition times to produce coated glass samples with different NIR-absorbing and low-emissivity layer thicknesses and different doping agent concentrations. The results are shown in Table 2.

Example 39

The procedure described in Example 1 was repeated but using three sources of feed mixtures.

The composition of the third mixture included 90% by weight of monobutyltin trichloride, 5% by weight of trifluoroacetic acid, and 5% by weight of antimony trichloride. A gradient film was first deposited by depositing only the tin oxide source recombinant with antimony used in...

Example 1: For a period of 70% of the time required to deposit a layer with a thickness of 204 nm. Then he began to precipitate the recombinant source with a mixture of antimony and fluorine. The two sources of the mixture continued to precipitate for a period amounting to 20% of the total deposition time, and at this stage the deposition of the source of the antimony mixture stopped. The source mixed with antimony and fluorine continued to deposition for the remaining deposition period, which amounted to 0.10% of the total deposition time for deposition of the antimony recombinant film, which had a thickness of 240 nanometers. At this point, a fluorine-conjugated tin oxide food source was started. The feeding continued for a period amounting to 20% of the total time required to deposit a layer of tin oxide doped with fluorine whose thickness reached 300 nanometers. The feeding of a source mixed with antimony and fluorine was stopped, and the deposition of the fluorine-recombinant tin oxide source continued for the remaining deposition period of the fluorine-recombinant film. The transmitted and reflected color in the resulting gradient coating was light blue (x value = 0.292 y = 0.316) SHGC = 0.5 U = 0.6 and the visible transmittance was about 45%. As shown in Figure 3, surface 22 of the graded film has 16 essentially 100% antimony alum, while surface 18 has 100% essential fluorine doping agent, with a gradient of doping agent concentration between surfaces 18 and 22. Both are present in the membrane template SnO2. Examples 40 to 43

Use the procedure described in Example 1 in Examples 40 through 43. The coating composition for the NIR absorbing layer in Examples 41 and 43 is from a source of fluorine, antimony, and tin produced by adding TFA and SbCl3 to MBTC. This source contained a percentage ranging from 0 to 5% by weight of TFA, 5.2 to 5.5% by weight.

Of SbCl3, the remaining material was MBTC, and was co-fed with water to the second evaporator. The carrier gas used for the second evaporator was dry air flowing at a rate of 15 L/min. The fluorine source fluorine/antimony tin was added at a rate of 0.5% mole of

Total carrier gas flow rate. Water was added at a rate of 1.5% mole of the total carrier gas flow rate, and the evaporator temperature was maintained at 160°C. The base glass layer, consisting of soda-lime-silica, with an area of ​​12.9 cm2 (2 inches2) and a thickness of 2.2 mm, was preheated on a heated mold to a temperature ranging from 605 to 625°C. Then move the heating mold and the base layer to a position directly below the nozzle of the vertical paint tube, so that the base layer is 25 mm below the nozzle of the paint tube. H2O/Sn/Sb/F vapors from the second evaporator were then directed onto the underlying glass layer, resulting in the deposition of the bottom coating layer of tin oxide alloyed with antimony and fluorine in Examples 41 and 43. The carrier gas velocity was 0.9 m/s and the thickness of the recombinant tin oxide film was approximately 240 nanometers. Reaction byproducts and unreacted source vapors were removed from the substrate at a rate of 18 L/min. After deposition of the bottom coating layer of tin oxide combined with antimony and fluorine, the nozzle valve of the coating tube from the feeder is turned around.

The second evaporator to the first evaporator. The h2o/tfa/MBTC vapors from the first evaporator feed were then directed onto the substrate, resulting in the deposition of the fluorine-doped tin oxide layer directly on top of the antimony- and fluorine-doped tin oxide bottom coating layer. The velocity of the carrier gas was 0.9 m/s, and the thickness of the tin oxide film recombinant with fluorine was approximately 300 nanometers. The color transmitted from the bilayer films in Examples 41 and 43 (which contain Sb and F in the NIR-absorbing bottom coating) was light gray and the color reflected from them was neutral. The steps of Examples 40 and 42 were essentially repeated in Examples 41 and 43, respectively, but without the presence of fluorine in the NIR-absorbing bottom coating layer. The properties were measured and the results are presented in Table 3. The results show how fluorine, as an additive in the NIR absorbing layer, acts as a color modifier as well as a haze reducer for reflected and transmitted color. The transmittance colors, visible light transmittance and Tvis, yx

Films prepared using dopant agents of Sb and TFA in the NIR-absorbing layer, according to Examples 41 and 43, are darker gray and the colors reflected from these films are more neutral than those from films containing only Sb as the dopant in the NIR-absorbing layer. NIR, which consists of tin oxide doped with antimony in Examples 40 and 42. Furthermore, the antimony recombinant NIR absorbing layer with the amount of fluorine dopant affecting the color has a greater visible light transmittance (with the Tvis value increasing from 54.5 to 58.5 in Example 41 versus Example 42 using the same Antimony doping agent ratio.

Table 3

Summary of properties of TOF/TOSb bilayer films

<img file="SA1857B1_D0001.tif" />

<img file="SA1857B1_D0002.tif" />

Where the symbols indicate: G: glass

Solar heat gain coefficient for the center of the glass/single glass unit.

IG&amp;: Solar heat gain coefficient of the glass center of the IGU. Uc: Total heat transfer coefficient of the center of the glass/single glass pane. IG&amp;: Total heat transfer coefficient of the glass center in the IGU.

Visible light transmittance-c: Transmittance in the visible region of the spectrum at the center of the glass/single glass pane 380 to 780 nm.

IG&amp;: Transmittance in the visible region of the spectrum at the center of the glass in IGU-380 to 780

nm.

Examples 44 through 47 show the deposition of films using the following compositions: TOSb/TOF (low TOSb/(Sb)/high Sb)/glass, TOSb/TOF (high TOSb/(Sb) low Sb)/ Glass, TOSb (low TOSb/TOF/(Sb) (high Sb)/glass, TOSb (high TOSb/TOF/(Sb) low Sb/glass.

Example 44

The procedure described in Example 1 was repeated except that the glass temperature was about 610°C and the reactant concentration was about 0.63 mol% in air flowing at a rate of 20 L/min. A layer of tin oxide doped with antimony about 400 angstroms thick was deposited from a liquid coating solution consisting of about 10% by weight antimony trichloride and about 90% monobutyltin trichloride. Immediately thereafter, a second layer about 2,000 angstroms thick of antimony tin oxide was deposited from a liquid coating solution consisting of 3.25% antimony trichloride and 96.75% monobutyltin trichloride. A third layer consisting of a fluorine-doped tin oxide layer about 3000 angstroms thick was deposited from a solution containing 5% by weight of trifluoroacetic acid and 95% by weight of monobutyltin trichloride. It turns out that the resulting membrane has a light blue-green color for reflected light and a light blue color for transmitted light. The membrane properties were measured as described in Example 1. The visible light transmittance rate was 64%, and the SHGC value was calculated as 0.56. The x and y coordinate values ​​for the color of the reflected light were 0.304 and 0.299, respectively, which places the film in the neutral blue square sector of the CIE color space, as previously defined.

Example 45

The procedure described in Example 44 was repeated, but this time the TOSb layers were deposited in a reversed order (sometimes referred to in this statement as reverse construction). The color of the resulting film was bluish-red with respect to the reflected light, with color coordinates for (x) of 0.330 and (y) of 0.293, respectively. It obtained a percentage of visible light transmittance of 59% and a SHGC value of 54. Those familiar with the technology will realize that TOSb layers can vary in thickness and concentrations compared to what is described in this statement while remaining within the scope of this invention.

Example 46

The procedure described in Example 44 was repeated, but in this example the order of deposition of a fluorine-doped tin oxide layer and a layer of a 73.25% antimony trichloride solution was reversed. The resulting film had a transmittance to visible light of about 62%, a SHGC value of 0.55, and the color of the reflected light was a neutral bluish red characterized by color coordinates D (x) of 0.311 and L (y) of 0.311.

Example 47

The procedure described in Example 45 was repeated, but in this example the order of deposition of a fluorine-doped tin oxide layer and a 10.0% antimony trichloride solution was reversed. The resulting film had a transmittance to visible light of approximately 57%, a SHGC value of 0.53, and the color of the reflected light was light green with color coordinates of x of 0.308 and y of 0.341. Those skilled in the art will recognize that TOSb layers can vary in thickness and concentrations compared to what is described herein while remaining within the scope of this invention.

Example 48

The procedure described in Example 41 was repeated with the following changes. Where the composition of the coating source for the NIR absorbing layer is 75% by weight of TFA, 74.35% by weight of SbCl3,

The remaining substance was MBTC. The carrier gas used for evaporation was dry air flowing at a rate of 20 liters/minute. The fluorine source fiuorine/antimony/tin was added at a rate of 1.5% mole of the total carrier gas flow rate, and water was added at a rate of 7.5% mole of the total carrier gas flow rate, and the evaporator temperature was maintained at 1.60°C. The base glass layer, consisting of soda-lime-silica, with an area of ​​12.9 cm3 (2 in2) and a thickness of 2.2 mm, was preheated on a preheated mold to 640°C. The vapors from the sources were directed onto the underlying glass layer at a speed of approximately 1.2 meters/second, and a tin oxide film containing fluorine and antimony with a thickness of approximately 2.4 nanometers was deposited at a rate of 1200 angstroms/second. Immediately after this deposition, a fluorine-doped tin oxide layer approximately 300 nm thick was deposited at the same rate of vapor composition containing 1.5 mole% of mbtc/tfa (5 wt% TFA and 95 wt% MBTC). 7.5% mole of water vapor and the remaining amount was air. The color of light reflected from the bilayer film was bluish-green and had a haze value of 1.20% as measured using a Gardner haze meter.

Gardner Hazemeter

Example 49

The procedure described in Example 48 was repeated but water was removed from the steam stream to precipitate the first approximately 300 to 600 angstroms of the first tin oxide layer containing antimony and fluorine. The resulting film had a measured blur of 0.97%, a 20% reduction in blur compared to the previous example.

Comparison example 50

Repeat the procedure described in Example 40 with the following changes. The composition of the coating source for the NIR absorbing layer was 6.75% by weight of SbCl3 and the remaining material was MBTC. The carrier gas used for evaporation was dry air flowing at a rate of 20 L/min. The anion source tin/antimony was added at a rate of 1.5 mol%

of the total carrier gas flow rate, and water was added at a rate of 7.5% mole of the total carrier gas flow rate, and the evaporator temperature was maintained at 1.60°C. The base glass layer, consisting of soda-lime-silica, with an area of ​​12.9 cm2 (2 inches2) and a thickness of 2.2 mm, was preheated on a preheated mold to 648°C. The vapors from the sources were directed onto the underlying glass layer at a speed of approximately 1.2 m/s, and a film of tin oxide doped with antimony was deposited, which reached a thickness of

240 Approximately nanometers at a rate of approximately 1200 angstroms per second. Immediately after this deposition, a layer of tin oxide doped with fluorine was deposited, which reached a thickness of

300 Approximately nanometers at the same rate of composition of a vapor containing 1.5 mol% of MBTC/TFA (5 wt% TFA and 95 wt% MBTC), 7.5 mol% water vapor and the remaining amount was air. The color of the reflected light from the bilayer film was bluish-green and had a haze value of 1.34% as measured using a Gardner Hazemeter.

Example 51

The procedure described in Example 50 was repeated but water was removed from the vapor stream for a first precipitation

300 to approximately 600 angstroms of the first tin oxide layer doped with antimony. The resulting film had a measured blur of 0.90%, a 33% reduction in blur compared to the previous example.

Example 52

The procedure described in Example 51 was repeated but 5 wt% TFA was added to the source solution to precipitate the first approximately 300 to 600 angstroms of the first antimony-doped tin oxide layer. The resulting film had a measured blur of 0.83%, a 38% reduction in blur compared to Example 50.

Example 53

The procedure described in Example 50 was repeated but 5 wt% TFA was added to the source solution to precipitate the first tin oxide layer doped with antimony. The resulting bilayer film had a measured haze of 1.17%.

Example 54

Repeat the procedure described in Example 40 with the following changes. The composition of the coating source for the NIR absorbing layer was 6.75% by weight of SbCl3 and the remaining material was MBTC. The carrier gas used for evaporation was dry air flowing at a rate of 20 L/min. The antimony/tin source was added at a rate of 1.5% mole of the total carrier gas flow rate, and water was added at a rate of 1.5% mole of the total carrier gas flow rate, and the evaporator temperature was maintained at 160°C. The base glass layer, which is made of soda-lime-silica, was preheated to an area of ​​12.9 cm2.

(2 inches2) and 2.2 mm thick on a mold heated to 663°C. The vapors from the sources were directed onto the glass substrate at a speed of approximately 1.2 m/s, and an antimony tin oxide film with a thickness of approximately 240 nanometers was deposited at a rate of approximately 1050 angstroms/s. Immediately after this deposition, a fluorine-doped tin oxide layer approximately 300 nm thick was deposited at the same rate of vapor composition containing 1.5 mole% of MBTC/TFA (5 wt% TFA and 95 wt% MBTC). 1.5% mole of water vapor and the remaining amount was air. The color of the reflected light from the bilayer film was bluish-green and had a haze value of 1.13% as measured using a Gardner Hazemeter.

Example 55

The procedure described in Example 54 was repeated but water was removed from the vapor stream during the deposition of the first approximately 300 to 600 angstroms of the first recombinant tin oxide layer.

With antimony. The resulting film had a measured blur of 0.90%, a 20% reduction in blur compared to the previous example.

Example 56

The procedure described in Example 55 was repeated but 5 wt% TFA was added to the source solution during the deposition of the first approximately 300 to 600 angstroms of the first antimony-doped tin oxide layer. The resulting film had a measured blur of 0.70%, a 23% reduction in blur compared to the previous example.

Example 75

The procedure described in Example 54 was repeated but 5 wt% TFA was added to the source solution used to deposit the first antimony-doped tin oxide layer. The resulting bilayer film had a measured blur of 0.72%, a 63% reduction in blur compared to Example 54.

The following examples illustrate the blurring obtained when the bilayer film was deposited in reverse order.

Example 58

Repeat the procedure described in Example 31 with the following changes. The composition of the coating source for the bottom layer is 5.0 wt% TFA and 95 wt% MBTC. The carrier gas used for evaporation was dry air flowing at a rate of 20 L/min. The source solution was added at a rate of 1.5% mole of the total carrier gas flow rate, water was added at a rate of 1.5% mole of the total carrier gas flow rate, and the evaporator temperature was maintained at 160°C. The base glass layer, which was made of soda-lime-silica, with an area of ​​12.9 cm2 (2 inches2) and a thickness of 2.2 mm, was preheated on a heated mold to a temperature of 663°C. The vapors from the sources were directed onto the glass substrate at a speed of approximately 1.2 m/s and a fluorine-doped tin oxide film approximately 300 nanometers thick was deposited at a rate of approximately 1050 angstroms/s. And after

Through this deposition, a layer of tin oxide doped with antimony was directly deposited, which reached a thickness of approximately 240 nm at the modified temperature from a vapor composition containing 1.5 mol% of MBTC/SbCl3 (6.75% by weight of SbCl3 and 93.25% of MBTC) 1.5% mole of water vapor and the remaining amount was air. The color of the reflected light of the resulting bilayer film was neutral blue and had a haze value of 0.68%.

Measured using the Gardner Hazemeter.

Example 59

The procedure described in Example 58 was repeated, but 5 wt% TFA was added to the source solution used to deposit the first antimony-doped tin oxide layer. The color of the reflected light of the resulting bilayer film was neutral blue and had a haze value of 0.67%.

Example 60

The procedure described in Example 54 was repeated, but 2.9 wt% acetic acid was added to the 5.75 wt% MBTC/SbCl3 source solution used to deposit the first tin oxide layer doped with antimony. The color of the reflected light of the resulting bilayer film was neutral blue and had a haze value of 0.95%.

Comparison example 61

Repeat the procedure described in Example 60, but with no acetic acid present in the source solution. The color of the reflected light of the resulting bilayer film was neutral blue and had a haze value of 1.37%.

The results of examples 48 to 61 are given in Tables 4 and 5.

Composition*: 1=300nm TOF/240nm G/TOSb 2=300nm TOF/240nm G/TOSbF 3=240nm TOSb/300nm G/TOF 4=240nm TOSbF/300nm G/TOF

Table 4 Effects of trifluoroacetic acid and/or water on the blurring of bilayer films.

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Table 5

Effects of acetic acid on blurring of bilayer membranes

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Composition * : 1=300 nm TOF/240 nm G/TOSb 2=300 nm TOF/240 nm G/TOSb F 3=240 nm TOSb/300 nm G/TOF 4=240 nm TOSb F/300 nm G/TOF

Silica can also act as a haze-reducing additive in the NIR-absorbing tin oxide layer adjacent to the glass, particularly when added to the top of the NIR-absorbing layer before depositing the low-emissivity layer on top of the NIR-absorbing layer. The preferred source of silica is tetramethylsilucane

Cyclic tetramethylcyclotetrasiloxane (TMCTS). It obtained a decrease in blurring rate of

33% when TMCTS was used in the last approximately 600 angstroms of the bottom coating. Examples 62 and 63 and their results in Table 6 illustrate the effects of silica as a haze-reducing additive in the tin oxide layer doped with antimony. Example 62

Repeat the procedure described in Example 1 with the following changes. The composition of the coating source for the NIR absorbing layer consisted of two solutions, a solution of 5.75% by weight of SbCl3, and the remaining material was MBTC fed to both evaporators and a pure solution of tetramethyl.

Tetramethylcyclotetrasiloxane (TMCTS) was fed to the second evaporator only. The carrier gas used for evaporation was dry air flowing at a rate of 15 L/min. The tin/antimony source was added at a rate of 0.5% mole of the total carrier gas flow rate, and water was added in The top mixer was divided from the coating device at a rate of 1.5 mol% of the total carrier gas flow rate, and the evaporator temperature was maintained at 160°C. When TMCTS was used, it was fed at a rate of 0.05 mol%. The base glass layer, consisting of soda-lime-silica, with an area of ​​12.9 cm2 (2 inches2) and a thickness of 2.2 mm, was preheated on a preheated mold to 663°C. The vapors of the sources used to form the NIR absorbing layer were directed onto the underlying glass layer at a speed of approximately 0.88 m/s, and an antimony tin oxide film with a thickness of approximately 185 nm was deposited at a rate of approximately 55 nm/s. Immediately after this deposition, an antimony-doped tin oxide film containing silica from the second evaporator precipitated at the same rate to a thickness of approximately 61 nanometers. Then a layer was deposited

Tin oxide doped with fluorine, approximately 298 nanometers thick, which was deposited

From the first evaporator at the same rate of composition of steam containing 0.5% mole of

MBTC/TFA (5 wt% TFA and 95 wt% MBTC), 1.5 mol% water vapor

The remaining amount was air. The color of the light reflected from the deposited film was neutral blue and had a haze value of 0.81% as measured using a Gardner haze meter.

Gardner Hazemeter

Comparison example 63

The procedure described in Example 62 was repeated except that the thickness of the tin oxide layer doped with antimony was 223 nm, no layer containing silica was deposited, and the thickness of the TOF layer was 291 nm. The haze value of the resulting film was 1.20% as measured using a Gardner Hazemeter.

Table 6

The effect of TMCTS on the blurring of sunlight-controlled films

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Table 1

Summary of properties of TOF/TOSb bilayer films

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Table 1

Summary of properties of TOF/TOSb bilayer films

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Table 1

Summary of properties of TOF/TOSb bilayer films

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Table 1

Summary of properties of TOF/TOSb bilayer films

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