UA65556C2 - A coated glass (variants), a method for making the same and coating absorbing radiation of the spectral region adjacent to that infrared - Google Patents

Abstract

The invention relates to the improved glass regulating solar radiation, which glass has an acceptable visible light transmission, absorbs IR (infrared) radiation of the long-wavelength infrared (LIR) and reflects IR - radiation of medium range (low emission ability or low E) along with preselected color within the visible light spectrum. Besides there is proposed a method for producing an improved coated glass regulating sun radiation, and having a layer absorbing solar energy involving stannum oxide with such alloying additives as stibium, and also a layer giving a low emission and able to reflect the IR-light of medium range and comprises stannum oxide with such alloying additives as fluor and/or phosphorus. The layer suppressing iridescence or other layers may be combined with combination of two layers proposed according to the invention. It is possible to use coat of many regulating sun radiation and/or having low emission ability. The LIR-layer and the layer with a low emission may be separate parts of unique film from stannum oxide, because both layers are made on the basis of alloyed stannum oxide.

Description

According to the invention, coated glass is proposed for use in windows of residential premises, architectural structures and vehicles, as well as various applications for which regulation of solar radiation parameters and low emissivity are desirable. Coatings for adjusting the parameters of solar radiation and with low emissivity include stanium oxide with various doping impurities. The invention eliminates the need for an anti-iris sublayer. Glass products can be of any shape, but are usually flat or bent. The glass can be of any composition, but usually it is sodium-calcium glass obtained in the float process. It can be annealed, heat-strengthened or hardened.

Regulation of solar radiation parameters means the ability to change the amount of heat inflow of solar radiation energy that can pass through the glass product into such a closed space as a building structure or the interior of a car. Low emissivity refers to the ability of a product's surface to suppress absorption and emission of mid-infrared radiation, making the surface specular for mid-infrared radiation, and thus reducing heat flow through the product, weakening the component of radiative heat transfer to or from a low-emissivity surface ( which is sometimes designated as low E). As a result of suppression of the heat radiation of the sun, the interior of buildings and cars become cooler, which allows to reduce the need for air conditioning and its losses. Coatings with significantly low emissivity improve comfort in summer and winter by increasing thermal insulation due to the operational properties of windows. Essential to commercially viable coated glass products that are capable of regulating solar radiation parameters and have low emissivity are certainly economical methods of production and durability and maintenance of associated properties such as light transmission, visibility, color, transparency and reflectivity.

As shown below, various technologies have been applied to meet the requirements of solar regulation and low emissivity, but none of the systems have achieved the required performance sufficiently in view of the economic requirements.

Many coatings and coating systems cause the appearance of iridescent colors on the coated product. They can be due to the chemical composition of the coating, the thickness of a separate layer or layers, or the interaction of the substrate and the coating with incident light. Such iridescence can in many cases be minimized or reduced by placing an anti-iridescent layer between the glass substrate and the first coating. The use of an interference layer between the glass and the next functional layer or layers to suppress iridescence or light reflection was first demonstrated by Knowe p. Sogaop in US patent 4187336 dated 02.05.1980. Gordon's method can be applied to glass that adjusts the parameters of solar radiation, as was shown recently in US patent 5780149 (MeSygau et al., 14.07.1998), according to which two layers were applied to adjust the parameters of solar radiation on the surface of an interference layer of the type Gordon. The interference layer often includes silicon dioxide. According to the invention, an unexpected spectacular discovery is presented, which eliminates the need to use a Gordon-type coating layer to adjust the parameters of the reflected color radiation.

U.S. Patent 3,149,989 discloses coating compositions useful in the production of reflective (solar radiation) glass. At least two coatings are used, the first of which is connected to the glass substrate and includes stanium oxide with the addition of a relatively large amount of stibium. The second coating also includes stanium oxide with the addition of a relatively small amount of stibium. Two films can be combined with each other, or applied on different sides of the glass substrate. In both cases, these regulatory parameters of solar radiation of the coating do not give the glass products significantly reduced emissive properties.

US Patent 4,601,917 describes coating compositions for the high-throughput production of high-quality fluorine-doped coatings from gas phase deposition. One of the applications of such coatings is in the production of energy-saving windows sold under the name "Im E" or "low E windows". Methods of production of coated glass are also described. The patent does not specify exactly how to produce coated glass products that regulate the parameters of solar radiation and have a low emissivity.

US Patent 4,504,109 to Karizpika Kaispa Touoya Spo discloses a glass coated with multiple infrared radiation shielding layers that includes a light-transparent substrate and a covering laminating component that includes "at least one infrared radiation shielding layer , and at least one interference reflective layer, which are alternatively located on top of each other...” Stannium-doped indium oxide is used in the examples as an infrared shielding layer, and titanium dioxide is used as an interference shielding layer. To reduce iridescence, the thickness of the infrared shielding layer and the interference reflective layer should be a quarter lambda (lambda/4) with a possible deviation of 75-13095 from lambda/4. Although other compositions of the infrared protective layer and the interference reflective layer have been disclosed, such as carbon dioxide with or without doping additives (see column b, lines 12-27), however, the specific combination of carbon dioxide doped layers according to the present invention, which provides solar control, low emissivity, and anti-iridescence without the need for a thickness limit lambda/4 has not been disclosed or described as suppressing iridescence or iridescence.

U.S. Patent 4,583,815, also owned by Karivpika Kaizpa Tousoia Spoi, describes a heat wave protective laminate that includes two covering layers of indium and stanium oxides that contain varying amounts of stanium. Also described are anti-reflective layers above or below the indium and stannium oxide layers.

Other compositions are disclosed for such layers as the one that protects against infrared radiation, as well as an interference protective layer, such as steel dioxide with alloying additives that become positive ions with a valency of 5, such as 50, P, Av, MBO, Ta , M/ or Mo, or an element such as fluorine, which easily becomes a negative ion with a valency of -1 (see column 22, lines 17-23). However, the specific combination of doped layers of stanium dioxide according to the present invention, which provides control of solar radiation parameters, low emissivity and anti-iridescence, has not been disclosed or described. There is no point in the claims relating to a layer of stanium oxide, and the description does not contain any evidence describing the composition of such layers, for example, the ratio of alloying additive and stanium oxide. It should also be noted that it is proposed to use such an alloying additive in both layers (indium and stanium oxides), while according to the presented patent application both layers should include different alloying additives.

U.S. Patent 4,828,880 to Rikipdiup RI C describes barrier layers that prevent the migration of alkali metal ions from the glass surface and/or act as color-suppressing layers that cover infrared-reflective or electrically conductive layers. Some of these color-suppressing layers are used in glass structures that provide regulation of solar radiation parameters and low emissivity.

US Patent 5,168,003 to Roga Moig Sotrap describes a glazed article bearing a substantially transparent coating that includes an optically functional layer (which can have low emissivity and adjust solar radiation parameters) and a thinner anti-irid layer that is multi-gradient stepped. Stibium doped oxide will be mentioned as a possible alternative or optical component of the described layer with low emissivity.

U.S. Patent 5,780,149 to I Yerbeu-Omjepv-Roga describes a coated glass that regulates solar radiation parameters and has at least three covering layers - a first and second clear coating, and an iridescence suppressing layer located between the glass substrate and transparent top coatings. According to the invention, transparent layers have a difference in refractive indices in the near-infrared region greater than in the visible region. This difference results in the reflection of the sun's thermal radiation in the near-infrared region as a countermeasure to absorption. Doped metal oxides with low emissivity, such as fluorine-doped stanium oxide, are used as the first transparent layer. Such metal oxides as unalloyed stanium oxide are used as a second transparent layer. No combination has been described that absorbs radiation in the near infrared (NIR) region.

EPO patent 0546302, issued on 16.07.1997, belongs to Azap Siav55 So. This patent describes coating systems for regulating solar radiation parameters of heat-treated (tempered or bent) glass, which includes a protective layer based on metal nitride. A protective layer or layers are used for the coating, which regulates the parameters of solar radiation (to prevent oxidation during heat treatment). As a layer that regulates the radiation of the sun, many examples with doped stibium or fluorine oxide of stanium have been proposed. However, the specific combination of the doped layer of carbon dioxide according to the present invention that achieves control of solar radiation parameters, low emissivity, and anti-iridescence properties is not Gordon's disclosed or described.

EPO application 0735009 published in February 1996 belongs to Sepiga! Siaz5 So. This application describes heat-reflective multi-coated window glass that includes a glass plate and two layers.

The first layer is a metal oxide with a high refractive index based on chromium, manganese, ferrum, cobalt, nickel or copper, the second layer is a film with a lower refractive index based on stannous oxide. Doped layers with low emissivity or capable of absorbing BIR have not been disclosed.

Application PCT 98/11031, published in March 1998, belongs to Riikipdiop RI C and describes a high-performance glass comprising a glass substrate with a coating that includes a heat-reflective layer with low emissivity of a metal oxide. The heat-reflecting layer can be metal oxide and doped with oxides of tungsten, cobalt, chromium, ferrum, molybdenum, niobium or vanadium or their mixtures. A layer with low emissivity can be doped with stanium oxide. According to a preferred aspect of the invention, the iridescence suppressing layer or layers are located under the coating, which includes a heat-reflective layer and a layer with low emissivity. This application does not disclose or suggest a specific combination of a doped layer of stannium dioxide according to the present invention, which achieves control of solar radiation parameters, low emissivity and anti-raining properties without the need for an underlying layer of

Gordon to suppress iridescence or light reflection.

Canadian patent 2193158 discloses a stbium-doped stanium oxide layer on glass with a stanium/stibium molar ratio of 1:0.2-1:0.5, which reduces the transparency of the glass to light.

In Yuorape Enesiv ip 5rgauei Tip Ohide Rite5 (Alloying effect of deposited tin oxide films) E

Zpapiyi, AVapegiei KII Zorga, Tip boiiy Rytv, M88 (1981) p 93-100 discussed the effect of doping with stybium, fluorine and their combination on the electrical properties of stanium oxide films. The article does not disclose any optical properties of stybium-fluoride films, nor the effect on transparency or the reflection of colored light.

UK application 2302101, owned by Siamageya, describes a glass substrate coated with a film of at least 400nm thick stibium/stannium oxides with a molar ratio of 5bp/560 0.05-0.5 and a light transparency of less than 3595. The film is deposited by a chemical deposition from the gas phase. Haze-reducing substrates as well as thick layers with low 5B/5n ratio that have low emissivity and high solar absorptivity are suggested. Possibility of applying one or more additional coating layers to achieve some desired optical properties is also indicated. None of these properties except fogging is not mentioned. The application does not say anything about thinner layers, using more than one dopant or adjusting the color parameters of the film.

UK application 2302102, also owned by Siamega!, describes a glass substrate coated with a stanium/stibium oxide layer with a bp/50 molar ratio of 0.01-0.5, which is deposited by chemical vapor deposition, and the rough substrate has a factor of solar radiation (coefficient of increase in heat absorption) is less than 0.7. Coatings are intended for windows and have a light transmission of 40-6595 and a thickness of 100-500 nm. A reduction in substrate haze is claimed, and the low emissivity of the coating is achieved by choosing a reasonable stibium/stannium ratio. As in the previous application, one or more additional coating layers are mentioned to achieve the desired optical properties. To obtain a film with low emissivity containing E, 56 and Zn, layers of stanium oxide doped with fluorine can be deposited on the stbium/stannium oxide layer, or a fluorine component can be added to the stanium/stannium reagents.

The latter two methods are disadvantageous due to the increase in time and cost when adding the third layer and scaling up, as well as the fact that the emissivity of the 5B/E films has not decreased, but increased. There is no mention of adjusting the color parameters or its neutrality.

UK application 2200139, owned by Siamegrea, describes a method of coating by sputtering solutions containing precursors, compounds containing fluorine and at least one alloying additive selected from the group consisting of stibium, arsenic, vanadium, cobalt, zinc, cadmium, tungsten , tellurium or manganese.

Existing types of industrial glass control heat flow through windows using absorptive and/or reflective coatings, glass dyes, and post-applied films. Most of these coatings and films are designed to regulate the parameters of only one part of the spectrum of thermal radiation from the sun, or

BIR - the near-infrared component of the electromagnetic spectrum with a wavelength of 750-2500nm, or the mid-infrared component of the electromagnetic spectrum with a wavelength of 2.5-25μm. Products have been developed to control parameters across the thermal spectrum, however, spray-applied metal/dielectric film kits, while effective, have limited durability and require protection and placement within the center section of the multi-unit insulating glass unit (IGU). Therefore, there is a need to develop a coating that regulates all solar radiation, in the form of a film or combination of films that can be easily pyrolytically deposited in the glass manufacturing process, as well as glass that has acceptable transparency for visible light, absorbs or reflects BIR, reflects the mid-range 14 and has a neutral or close to neutral color.

None of the above sources of information or a combination of them suggests or suggests a specific combination of doped layers with ZpSb that would provide control of solar radiation parameters, low emissivity and anti-raining properties without the use of an underlayer type

Gordon.

The object of the invention is to create a transparent product with adjustable color of reflected light (even neutral), which absorbs solar radiation in the near infrared range (NIR) and reflects radiation in the mid-infrared range (low emissivity), which has two layers of thin films consisting of doped 5pO ". Another object of the invention is to apply layers at atmospheric pressure by chemical vapor deposition or other methods such as solution spraying or evaporation/sublimation of liquid/solid products. The best method according to the invention is a method of chemical deposition from the gas phase using evaporation of a liquid precursor. Another object of the invention is to develop layers that regulate the parameters of solar radiation and/or layers that have a low emissivity, together with other layers in combination with a layer that regulates the parameters of solar radiation or has a low emissivity. ANOTHER object of the invention is a film or combination of films that regulate solar radiation parameters that can be readily pyrolytically applied in the manufacture of glass to produce a product with acceptable visible light transparency, IR absorption or reflection, mid-IR reflectance, and a neutral or near-neutral color. Another task of the invention is to adjust the color parameters of the transmitted light regardless of the color of the reflected light by adding coloring additives to the BIR layer.

The invention provides an improved solar radiation regulating glass that has acceptable transparency to visible light, absorbs near-infrared (NIR) and reflects mid-infrared (low emissivity or low E) along with a preselected color within the visible spectrum to reflect the light. In addition, a method is proposed for the production of improved regulatory solar radiation coated glass, which has a solar absorbing layer (SIR) that includes stanium oxide with doping additives such as stibium, as well as a low-emissivity layer that is capable of reflecting IR- mid-range light and includes stanium oxide with doping additives such as fluorine and/or phosphorus. There is no general need for a separate iridescence-suppressing layer as described earlier to achieve neutral (colorless) light reflection from the coated glass, however, an iridescence-suppressing layer or other layers can be combined with the two-layer combination proposed in accordance with the invention. Optionally, multi-layer coatings that regulate solar radiation and/or have low emissivity can be used. The BIR layer and the low-emission layer can be separate parts of the stanium oxide monolayer, since both layers are based on doped stanium oxide. A method of production of coated solar radiation regulating glass is also proposed. In addition, according to the invention, it is possible to adjust or change the color of transmitted light by adding dyes to the BiCh layer. It was unexpectedly found that the dopant fluorine, which discolors the stannous oxide film, functions as a coloring additive when added as an additional dopant to the BiIC layer and changes the color of the light transmitted through the BiIC film.

Fig. 1-4 and 8-13 show a cross-section of coated glass with a different number of layers or films in a different sequence of layering on glass substrates. Figures 5 and 6 graphically depict the achieved regulation of solar radiation parameters with a stibia-doped film on window glass, including single glass or multi-section insulated glass (IGP), which is composed of at least two sheets of glass, with different concentrations of alloying additive and different thickness of films. Fig. 7 shows the color spectrum according to S.I.E. -

Ipiegpaiopaie Sottivvziop de I'EEhsiaiade (International Commission on Illumination) x and y coordinates and the specific color that can be achieved with different concentrations of dopant and different film thicknesses.

Glass that regulates the parameters of solar radiation and has a low emissivity is produced by applying at least two layers to a heated transparent substrate. The low emissivity layer includes a Zp film doped with fluorine and/or phosphorus, and the BiIR absorbing layer includes a 5pO film doped with stybium, tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium or vanadium or their mixtures. Such a combination was invented to effectively regulate the parameters of solar radiation and parts of thermal radiation of the electromagnetic spectrum, so that windows covered with these films have greatly improved properties.

The ability to regulate the parameters of solar radiation is usually expressed in terms of the coefficient of heat flow of solar radiation (KTSV) and O-value. KTOV is measured by the ratio of the total heat inflow of solar radiation through the window system to the falling solar radiation, while the O value - (I) - the total heat transfer coefficient for the window. KTSV of coated glass primarily depends on the thickness and content of stibium in the BiIR-absorbing film (see Fig. 5-6), while the O value primarily depends on the ability of the film to emit and the design of the windows. The CTOV measured at the center of the glass may be 0.40-0.80, and the O-value measured at the center of the glass may be 0.7-1.2 for a single sheet of glass coated with the best of the proposed films. On the insulated glass unit (ISP), the KTOV decreases to approximately 0.3, a

The O value is up to about 0.28.

The color of both reflected and transmitted light of the coated glass according to the invention can be adjusted. In addition, it is possible to adjust the amount of visible light transmitted through the coated glass, within 25-8095, by adjusting the thickness of the BCH or low-emissivity films and the content of the alloying additive in the BCH film. The color of the light transmitted through the coated glass can be adjusted separately from the color of the reflected light by adding a sufficient amount of coloring additive to the BIR layer of the coating. The color of the reflected light can be changed from almost neutral to red, yellow, blue or green and adjusted by changing the thickness of the film and the content of additives in the layers. Unexpectedly, it was discovered that near-neutral reflected light could be achieved without the need for an anti-iridescent layer. Although the refractive indices of BIR or low emissivity films are different, the color of the reflected light is independent of the classic interference phenomenon discovered by Gordon (US patent 4187336). The observed color of the reflected light is an unexpectedly tunable combination of absorption and reflection due to the BIR layer (absorption) and reflection from the low-emissivity layer or layers. Absorption by the BiCh layer can be adjusted by changing the thickness of the ZpSb layer and the content of the additive in this layer, usually stibium. The degree of reflection of the layer with low emissivity can be adjusted by changing the thickness of the layer 5pO» and the content of the additive in this layer, usually fluorine.

A low-emissivity layer consisting of 5nOg with a fluorine or phosphorus dopant will hereafter sometimes be designated as 5nO:E or 5nO:P, and a BIR layer consisting of 5nO" when it contains a stibium dopant will hereafter sometimes be marked as 5pO:56.

According to the best embodiment of the invention, a fluorine-doped stannous oxide film (5pO:E) is used as a layer with low emissivity, and together with it, a stibium-doped stannous oxide film (5pO.560) is used as a BIR layer. 5pO:E-films and methods of applying them to glass are known to specialists, they are defined as films with low emissivity. BiIR-absorbing films are also bpsr films, but contain other doping additives compared to the low-emissivity layer. The alloying additive is preferably stybium, although it can be an element selected from the group consisting of stybium, tungsten, vanadium, ferrum, chromium, molybdenum, niobium, cobalt, nickel and their mixtures. A mixture of one or more dopants may be used in the BIR layer, but the low-emissivity layer must include a low-emissivity dopant that provides significant conductivity to the layer, such as fluorine or phosphorus, although in combination with the low-emissivity dopant other alloying additives can be used. Since the BIR and low emissivity layers of the invention both use a 5pO doped metal oxide matrix, the BIR and low emissivity layers can be part of the same dopant gradient film. A single film with a dopant gradient is represented in Fig. 3 as film 16, in which the dopant gradient corresponds to a higher concentration

of the BIR dopant compared to the other dopant(s) on one surface of the film - surface 18 or 22, and the low emissivity dopant has a higher concentration than the other dopant on the second surface films The result is a change or gradient in the concentration of BIR and low emissivity dopants between surfaces 18 and 22. At an intermediate point 20 between surfaces 18 and 22, the BIR dopant concentration changes from a higher concentration on one side of point 20 to a no longer higher concentration on the other on the side of point 20, Fig. 8 shows a film 10 with a low E above the BiH film 12. The BiH film 12 in Fig. shown in Fig. 9 is similar to the structure shown in Fig. 8 except that the content of the BIR dopant, typically stibium, is higher near the low E film 10 and lower near the substrate Film 12 differs from film 16 in Fig. .3 in that film 12 is a BiH film, while film 16 has BiH and low E properties and contains a low E dopant and a BiH dopant with a concentration gradient of low E dopant and conc 10, 11, 12 and 13 show the BIC layer as two separate films 28 and 30. Film 28 is shown as thicker than film 30, and the total thickness of the BIC layer is the sum of the thicknesses of films 28 and to be within the limits of the thickness specified above for the BIC layer, preferably 80-300 nm. In fig. 10 and 11 films 28 and 30 are adjacent to each other, and in fig. 12 and 13 films 28 and 30 are located on both sides of film 10 with low E. It is better when the concentration of dopant in film 28 is different from the concentration of dopant in film 30.

According to the best embodiment of the invention, a film doped with stybium is used as a BIR film. Such a film can be applied in several ways, including pyrolytic deposition, methods of chemical vapor deposition (CVD) and physical vapor deposition (PWD). Pyrolytic deposition is known and disclosed in patents such as Canadian patent 2193158. The XOH method of depositing a 5pO film with or without doping additives and chemical precursors for the formation of a 5pO2 film with doping additives are well known and disclosed in patents

US 4,601,917 and 4,285,974. Preferably, according to known methods, 5pOo layers with doping additives are deposited directly on the float glass production line outside or inside the float glass chamber, using conventional on-line deposition techniques and chemical precursors described in US Pat. No. 4,853,257 (Nepegu). . However, doped 5pO2 films can be deposited on glass as layers by other methods such as solution sputtering or vaporization/sublimation of liquid/solid products at atmospheric pressure. The best method of application according to the invention is COX at atmospheric pressure using evaporation of a liquid precursor. The method is well suited for implementation on existing commercial coating lines. Precursors according to the preferred embodiment are economical, will provide longevity of the coating, reduce the frequency of cleaning the system, and can be used with little or no modifications on existing float glass line equipment.

Coatings function as reflective and absorbing at the same time. The film with low emissivity reflects thermal radiation of the middle range of the IR spectrum 2.5-25μm, and the BiIR-absorbing film primarily absorbs thermal radiation of the short range of 750-2500nm. According to our theory, this effect is that in the BiH range, the RI plasma wavelength (the length at which the low-emissivity film changes from transmissive to reflective) for the low-emissivity film lies in the BiH range. In the range near RI, the BIR absorption is higher for films with low emissivity, and in combination with a BIR-absorbing film, the absorption increases. BiIR-absorbing films according to the best embodiment of the invention are also doped with semiconductors, and therefore have reflective properties in the mid-IR range. This reflection combined with the reflection of the film with low emissivity gives an overall higher thermal reflection in the mid-IR range. It is preferable to pyrolytically deposit 5pSp onto glass using a precursor, especially an organic compound such as monobutylstannum trichloride (MTCB), dimethylstannum dichloride, dibutylstannum diacetate, monomethylstannum trichloride, or any of the known precursors for COX deposition, such as those disclosed in patent

US 4,601,917 Often, the organic compounds used as precursors for splicing include stabilizers such as ethanol. It is better when the stabilizer concentration is less than 195, in order to reduce the risk of contact of hot glass with such reagents in the presence of oxygen. Precursors of alloying additives for the BIC layer (stibium, tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium or vanadium) are mainly such halides as stibium trichloride, however, alkoxides, esters, acetylacetonates and carbonyls can also be used. Other suitable alloying additives and 5pO2 precursors are well known to those skilled in the art. Suitable fluoride dopant precursors for low emissivity 5pO" layers and their amounts are disclosed in U.S. Patent 4,601,917 and include trifluoroacetic acid, ethyl trifluoroacetate, ammonium fluoride, and hydrofluoric acid. Dopant concentration for layers

ZpO" with low emissivity is usually less than 3095, preferably 1-1595 of the dopant precursor relative to the combined mass of the dopant precursor and the precursor state. This usually correlates with the concentration of the dopant in the layer with low E 1-595 relative to the mass of the steel oxide in this layer.

According to the best embodiment of the invention, the properties of the coating depend on the thickness of the absorbing and low-emissivity layers, as well as on the content of stibium in the absorbing (BIC) film. The thickness of the film with low emissivity can be within 200-450nm, and preferably - 280-320nm. Better BIR-absorbing films can be applied similarly to low-emissivity films using methods such as those disclosed in US Patent 4,601,917. Organic stanium precursors for 5pO2 can be evaporated into air or other suitable gaseous media containing an O2 source to a precursor concentration of 0, 25-4.0 mole (better 0.5-

Z, Omolov). The concentration of the precursor 5pO" is expressed as a percentage of the number of moles of the precursor and the number of moles of the gaseous carrier. The best concentration of the precursor of the BiIC-doping additive is 1-2095 (even better 2.5-7.595, best 3.0-6.095), which is calculated relative to the mass of the precursor of the doping additive and the mass of the precursor

From to". In particular, a stibiium-doping additive that uses stibium trichloride as a precursor in an amount of 2-89% by weight is best, preferably 495% by weight. This correlates with the same percentage by mass of stibium in the stannium oxide BIP film.

Glass with a coating according to the invention is shown in the drawings. Fig. 1 shows a cross section of the films.

The film thickness can be in the range of 200-450 nm for a film with low emissivity (position 10), and for

BIC films - 80-300nm (position 12). The best thickness is in the range of 250-350nm for a film with low emissivity, and for BiH film - 200-280nm. The best thickness is between 280-320nm for low emissivity film, and 220-260nm for BiH film. Using the films according to the best embodiment of the invention, it is possible to produce glass with a coating that regulates the parameters of solar radiation, of a neutral blue color, which is designated here as a coated glass that reflects light mainly within the limits of the values of the chromatic coordinates according to S.I.E. for x - 0.285-310, and for y - 0.295-325. The definition of neutral blue is presented in fig. 7 zone within the "neutral blue color" mark (Metsiga! Vishe Soiog). As can be seen from Fig. 7 for the data of examples 15, 20 and 22, it is possible to obtain an adjustable or preselected color of reflected light close to neutral, but with a weak suppression of red compared to neutral (the value of x reaches 0.325, and the value of y - 0.33 ), but such a practically neutral color with weak red suppression is not attractive to consumers. Fig. 2 shows two films or layers arranged in reverse sequence to that shown in Fig. 1. In Fig. 2, the low emissivity film is closer to the glass 14 than the BiIR film 12. Fig. 3 shows the BiIR layer and the low emissivity layer integrated into a single 5pO" film 16 having a dopant gradient within the film 16. The film 16 has the advantage of one dopant (eg, a low emissivity dopant, fluorine) on the top surface 18 away from the glass 14 and the advantage of a second dopant (eg, a BiIR dopant, such as stibium) on the surface 22 closer to the glass .The dopant concentration from surface 18 to surface 22 varies so that the content of one dopant varies from more than 5095 of the dopant content on surface 18 to 0 on surface 22. At an intermediate point 20 below the upper surface 18, the dopant is dominant at that point in the film changes from a surface-dominant dopant 18 to a surface-dominant dopant 22. Either of the BiHC dopant and the low emissivity dopant can be dopant surface 18, while the other is on surface 22. Figure 4 shows a coated glass that, in addition to the low emissivity layer 10 and BIR layer 12, includes layers 24 and 26. These additional layers may be additional BIR layers or layers with low emissivity, or such other conventional layers that are used to cover glass, such as a paint layer. For example, layer 12 may be a BIR layer (e.g., Stybium doped), layer 10 may be a low emissivity layer (e.g., fluorine doped), 24 may be another BIR layer, and 26 may be another low emissivity layer or some other normal layer. The concentration of the dopant in the presence of more than one layer with low emissivity can be the same or different, and the thickness of each of the layers with low emissivity can also be the same or different. Similarly, the concentration of the dopant and its choice (from the group consisting of stibium, tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium or vanadium) in the presence of more than one BIR layer can be the same or different, and the thickness of each of The beam layers can also be the same or different. In general, the dopant for the BIR layer according to the description of the invention is mainly stibium, but it should be understood that the dopant for

The BIC layer can be selected from the group consisting of stybium, tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium or vanadium or mixtures thereof. Similarly, in the case of the gradient layer according to the invention, which is presented in Fig. 3, the dominant dopant for the BiIC surface 18 or 22 can be selected from the group consisting of stybium, tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium or vanadium or their mixtures, it is essential only that the dopant for low E, for example, fluorine, is dominant on the opposite surface. It is possible to combine with the gradient layer such one or more BIR-layer or a layer with a low emissivity, as layers 10 or 12 in Fig. 1-3, or other conventional layers.

To speed up the application of the film 5pO" on the glass, water is used, which can be seen from the US patent 4590096 (I ipapeg), in a concentration of approximately 0.75-12.0 molob" relative to the gas composition.

The best embodiments according to the invention will be shown in the following examples. It is clear to those skilled in the art that small deviations from the presented embodiments are beyond the scope of the present invention.

The best embodiment of obtaining a coated glass with BIR properties and low E with a neutral color of reflected light at this time is a double-film glass with a thickness of a thick 5pO:P film (fluorine-doped stannous oxide) of about 3000 angstroms in combination with a ZpO:5p film (doped with fluorine oxide) with a thickness of approximately 2400 angstroms. The film thickness for the 5pO:E layer can be in the range of about 2800-3200 angstroms and, surprisingly, is still sufficient to achieve a neutral color of reflected light.

The concentration of fluorine can be in the range of approximately 1-5 parts. The film thickness for a 5pO:50 layer can be in the range of about 2200-2600 angstroms, and the concentration of stybium can be in the range of about 3-8 atoo, and surprisingly, still sufficient to achieve a neutral color of reflected light. Within the framework of the best thickness and concentration of the dopant according to the invention, coated glass with a neutral-blue color of reflected light can be produced with a BIR layer and a layer with a low emissivity, i.e. the coated glass will have within the limits of the values of the chromatic coordinates according to the invention

S.I.E. values for x - 0.285-310, and for y - 0.295-325, which is shown in Fig. 7 by the zone marked "neutral blue color" or close to it with a value of x higher than 0.32, which is shown in examples 15 , 20 and 22.

Examples 1-30

A square glass substrate 5x5cm2 with a thickness of 22mm (soda-vagayu-silicon dioxide) was heated in a heating device to 605-6257"С and placed 25mm below the central section of a vertical concentric tubular nozzle. A gaseous carrier heated to 160"С - dry air was passed at a speed of 15l /min. through a vertical evaporator with hot walls. A liquid coating solution containing about 9595 by weight of monobutyltin trichloride and about 595 by weight of stibium trichloride was introduced into the evaporator via a syringe pump at a volumetric rate providing a 0.5 mollobo concentration of the stanium-organic compound in the gas composition. Water was also added to the evaporator at a rate that ensures a 1.5-molob concentration of water in the gas mixture. The gas mixture was directed onto the glass substrate at a speed of 0.9 m/s for about 6.1 s, which led to the deposition of a stibium-doped oxide film with a thickness of about 240 nm. Immediately after that, a second gas mixture was used, containing a composition of precursors of 9595 by mass of monobutyltin trichloride and 59% of trifluoroacetic acid together with water in the same concentrations, and a gaseous carrier that was used earlier to apply the stibium-doped layer of stannous oxide. This second gas mixture was directed onto a glass substrate for approximately 6.7s, resulting in the deposition of a fluorine-doped state oxide film approximately 280 nm thick. The bilayer film had a very blue color in transmitted and reflected light. the surface resistance was measured by a standard four-point probe. The coefficient of heat flow of solar radiation, the O value and the transmission of visible light through the center of the glass were calculated using the M/ipdom/ 4.1 program developed by I azhtepse VeiKkeIeu Maiyopa! And arogaigu, UMipdomv 8

Oauiidni Stor, Viiidipud Tesppoiodiee Rgodgat, Epegdu apa Epmigoptepia! Oimiviop The values of chromatic coordinates according to S.I.E x and y were calculated using A5TM EZ308-96 based on light reflection data in the range of 380-77O0nm, and color coordinates - for Shitipapi C. The results of the analysis for this film are presented in table 1 under number 19 The procedure from this example was repeated another 29 times with variable concentrations of chemical precursors and application time to obtain coated glass samples with different thicknesses of BIR layers and with low emissivity and different concentrations of dopant. The results are presented in Table 1.

Examples 31-38

The procedure from example 1 was repeated, except that the order of gas supply was changed

First, a fluorine-doped stannous oxide film was deposited for about 8 s, and then a stybium-doped stannous oxide film was deposited for about bs. A film with a thickness of about 54 Ohm was formed, which included a low emissivity layer (5pO:E) with a thickness of about 300nm and a BIR layer (5pO: 56) with a thickness of approximately 24 Ohms and had the appearance and color of the reflected light (neutral blue color) the same as the film of example 19. The results of the analysis for this film are presented in Table 2 under number 31. The procedure of this example was repeated 7 more times with variable concentrations of chemical precursors and application time to obtain samples of coated glass with different thicknesses of BIR layers and with low emissivity and different concentration of dopant. The results are presented in Table 2.

Example 39

The procedure from example 1 was repeated, but three nutrient mixtures of precursors were used. The third mixture contained about 9095 by weight of monobutyltin trichloride, about 595 by weight of trifluoroacetic acid, and about 595 by weight of stibium trichloride. The gradient film was applied by first depositing only the stibium-doped oxide precursor from example 1 during the 7095 time required to apply a coating with a thickness of 240 nm. Then they began to give a precursor doped with stybium/fluorine. Both precursor mixtures continued to be fed for 2095 of the total coating time, after which the feed of the precursor mixture with stibium was stopped. Giving the stybium/rluor doped precursor was continued for the remaining 1095 of the total time required to deposit the 240 nm thick stybium film. At this moment, the feeding of the fluorine-doped precursor of the stanium oxide film was started. Both nutrient mixtures of precursors were given within 2095 of the total time required for the application of fluorine-doped oxide to a thickness of 30 nm. The feeding of the mixture of stybium/fluorine-doped precursors was stopped and the fluorine-doped precursor was continued for the remainder of the time required for deposition of the stybium film. The formed gradient covering layer had a light blue color of transmitted and reflected light (х-0.292, х0.316), KTOV-0.50, O-value: -0.6, and the transmittance of visible light was approximately 4595. As can be seen from Fig. 3, surface 22 of gradient film 16 should have substantially 10095 stybium dopant, while surface 18 should have substantially 100905 fluorine dopant with a dopant concentration gradient between surfaces 18 and 22 in the matrix film of

Examples 40-43

Examples 40-43 repeated the procedure from example 1. The coating composition for the BiCh layer in these examples was composed of fluorine, stibium and a precursor of the steel by adding stibium trichloride and trifluoroacetic acid (TFOC) to monobutyltin trichloride. This precursor contained 0-595 by weight of trifluoroacetic acid, 5.2-5.595 by weight of stibium trichloride, and monobutylstannum trichloride, which, together with water, fed the second evaporator. The gas used in the second evaporator was dry air, the speed of which was 15 l/min. Stibium/fluorine/stannium precursor was added at a rate of 0.5 moloo from the total gas flow, water - at a rate of 1.5 moloo from the total gas flow, and the evaporation temperature was maintained at 1602С. A square glass substrate 5x5cm2 with a thickness of 22mm (soda-lime-silicon dioxide) was preheated in a heating device to 605-6257"C and then placed directly under the vertical nozzle for coating at a distance of 25mm from it. Steam P/50/5p/H2gO from the second the evaporator was directed further onto the glass substrate, depositing the inner layer of stbium-fluorine-doped stanium oxide in Examples 41 and 43. The velocity of the gaseous carrier was 0.9 m/s, and the thickness of the stibium-fluorine-doped stanium oxide film was approximately 240 nm. A couple of byproducts and unreacted reactants was diverted away from the substrate at a rate of 18 L/min. After the inner layer of stb-doped and fluorine-doped stanium oxide was applied, the coating nozzle valve was switched from the second evaporator to the feed from the first evaporator. The trifluoroacetic acid/monobutyltin trichloride/water vapor from the first feed evaporator was then directed directly to the substrate , applying a solid layer on top of a layer of oxide doped with stibia and fluorine fluorine-doped oxide of steel. The velocity of the gaseous medium was 0.9 m/s, and the thickness of the fluorine-doped oxide film was approximately 30 Ohm. Double-layer films from examples 41 and 43 (with content in the lower BIC layer

E and 55) had a light gray color of transmitted light and a neutral color of reflected light. Examples 40 and 42 basically repeated examples 41 and 43, but with the base fluoride dopant in the lower BiIC layer.

The results of the parameter measurement are presented in Table C. These results show how fluorine as an alloying additive in the lower BIR layer modifies the colors of transmitted and reflected light. Color of transmitted light,

Tmv, x and y, of the film doped with TFOC and 56 in the BIR layer of Examples 41 and 43 was more neutral for reflected light and grayer for transmitted light compared to the doped BIR layer with only 50 in examples 40 and 42. In addition, the BIR layer obtained with a stibium dopant and a color-affecting amount of fluoride dopant showed better visible light transmission (an increase in Tu" from 54.5 to 58.5 in example 41 versus example 42 with the same content of the stibial alloying additive.

Examples 44-47 demonstrate the application of films of the following composition: 5pO:P/5pO:55 (low Sev)/5pO:56 (high

Ser)/glass, ZpO:P/5pO:5b (high Sev)/ZpO:5b (low Svv)/glass, 5pO:50 (low Sev)/5pO:P/5pO:56 (high

Sev)/glass and 5p0:55 (high Sev)/ZPpO:E/5p0:56 (low Szev)/glass.

Example 44

The procedure of Example 1 was repeated except that the temperature of the glass was 610°C and the concentration of the reactants was approximately 0.6395 in an air stream at a speed of 20 l/min. Initially from a liquid coating solution containing approximately 1095 by weight of stibium trichloride and approximately 9095 of monobutyltin trichloride, approximately 400 angstroms of stibium doped stanium oxide were deposited. Immediately thereafter, approximately 2000 angstroms of stibium doped stanium oxide were deposited from a liquid coating solution containing 3.2595 wt. stibium trichloride and 96.7595 wt. with fluorine-doped stannous oxide was deposited from a liquid coating solution containing 595 by weight of trifluoroacetic acid and 9595 of monobutyltin trichloride. The resulting film had a light green-blue reflected light color and a light blue transmitted light color. The film properties were measured as in Example 1 The transmission of visible light was 6495, and the calculated KTOV was 0.56 . The x and y coordinates for the color of the reflected light were 0.304 and 0.299, respectively, corresponding to the neutral blue quadrant of the a.e. as defined earlier.

Example 45

The procedure from example 44 was repeated, except that the layers 5pО0:56 were arranged in the reverse order. The resulting film had a red-blue reflected light color with x and y color coordinates of 0.330 and 0.293, respectively. The transmission of visible light was 5995, and the calculated KTOV was 0.54. Those skilled in the art will understand that the 5pO:56 layers may differ in thickness and concentration from those given here, but still remain within the scope of the invention.

Example 46

The procedure from example 44 was repeated, except that the sequence of application of the fluorine-doped layer of the steel oxide and the layer corresponding to 3.2595% of the solution by mass of stibium trichloride were arranged in the reverse order. The resulting film had a visible light transmittance of 6295, and the calculated

КТОоВ-0.55, and the neutral blue color of reflected light with x and y color coordinates of 0.311 and 0.311, respectively.

Example 47

The procedure from example 45 was repeated, but in this example, the sequence of application of the fluorine-doped layer of stannous oxide and the layer corresponding to 1090 of the solution by mass of stibium trichloride were arranged in reverse order. The resulting film had a visible light transmittance of 5795, and the calculated

KTOoV: -0.53, and the light green color of the reflected light with x and y color coordinates of 0.308 and 0.341, respectively.

It is clear to those skilled in the art that the 5n0:56 layers may differ in thickness and concentration from those given here, but still remain within the scope of the invention.

All values of KTSV and Ш in the tables were determined by one-group approximation using the MENS program

M/ipdom 4.1. The use of a more accurate multi-group approximation (required for a number of spectral data) increases the KTOV by approximately 1495. Color parameters S.I.E. for transmitted and reflected light of coated products can be calculated according to the standard A5TM EZ308-96 with Shitipapi C as the brightness standard. According to the ATM EZ308-96 standard, the color of the object can be specified on one of several different scales. The scale used for coated products according to the invention represents chromatic coordinates x and y S.I.E. 1931. it can easily be translated into the S.I.E. color scale. 1976 I", a", p", using the equation: хЕХХ у) ух Ам 2)

C -116 (U/mp)"5-16 a" e500|(X/Xa)!3-( n) Z) p-200|( Zh/M n)175-(2/2n)113) where X , U and 7 - parameters of S.I.E. of the color of the coated product, and Xp, Mp and 7p - 98.074, 100.00 and 118.232, respectively, for the Shitipapi S standard. From the values of I", a", p" the color saturation index c" can be calculated according to the equation sa") -( 6732172, A color saturation index of 12 or less means neutral.

Definition of neutral blue color for reflected light, i.e. for coated glass that reflects light mainly within the framework of S.I.E. chromatic coordinates. for x 0.285-0.310 and for y 0.295-0.325, as shown in Fig. 7 by the zone marked "neutral blue color", correlated with S.I.E. 1976 17", a", B" as 37.85, -1.25, - 5.9 and 39.62, -2.25, 1.5. neutral blue color neutral blue color

Sample conversion gives:

Example 40 (table 3) 5,595 GRADE 300/240 (R/5r/glass) x-9,797

У-9.404 2-12.438 х-0.310 у-0.297

I" -36.751 a -4.624 p'--3.466 si -5.778

The properties of window glass to regulate the parameters of solar radiation were evaluated according to O5A,

Epmigoptepi Rgoiesiop Adepsu, using the Epegdu ag gayipd system. Epegdu 5iag gypd for the central region of the USA requires an O-factor value of 0.40 or lower, and a KTOV - 0.55 or lower. Epegdu 5iag gypd for the southern region of the USA requires an O-factor value of 0.75 or lower, and a KTSV - 0.40 or lower. Glass with BIR and low E coatings according to the invention, which is inserted into a window of conventional construction, achieves Epegd

Zag gajpdud for the central and/or southern region of SILA. For example, a casement window 3 feet wide and 4 feet high with a frame absorption value of 0.5 installed at Maiyop! Repevigaiop Naipd Soipsii (MEVS) in combination with the solar control coated glass according to the invention, which has a BiIR film and a low E film with predominant parameters corresponding to a neutral blue color, exhibits a CTOV of less than 0.40, and the O-value is less than 0.64 for a monolithic glass structure with a U-value of the frame of 0.7 or less, and KTOV is less than 0.38 for the construction of an insulated glass unit (ISP) made of transparent sheet glass 2.5 mm thick with air with a gap of 1.27 cm and coatings

BIR and with a low E surface Me2 of the outer glass sheet and with an O value of the frame of 1.0 or less.

The examples show that with a minimum of two doped layers of stannium oxide, it is possible to produce an excellent coated glass that adjusts the parameters of solar radiation and has a preselected color of reflected light. The data are presented in Tables 1, 2 and 3, and Figs. 5 and 6 graphically show how these properties of the coated glass change depending on the concentration of alloying additives and the thickness of the first BiH film. Fig. 7 represents the chromatic coordinates x and y of S.I.E. from a representative sample of coated glasses from examples 1-39.

As can be seen from Fig. 7, specific combinations of film thicknesses for both -BIR and low-emissivity layers and specific concentrations of doping additives can be used to obtain a coated glass that regulates the parameters of solar radiation, with any such desired color reflected from the surface of the coated glass of light, such as red, green, yellow, blue and their shades or neutral blue. In particular, it was surprising that a neutral blue color could be achieved with BiCh and low emissivity layers, but without such an anti-iridescence layer as proposed by Gordon.

Although the characteristic features according to the invention can be achieved with only two layers -BIR and with low emissivity, but multilayer embodiments are also within the scope of the invention and its content.

Multilayer coatings can include additional layers - BiIR and/or with low emissivity, including bpO:P/5pO:5p/5pO:5p/glass, bpO 0 B/5pO:5B6/5pO:5Bb/glass, 5pO:5B/5pO :R/5pO:5r/glass and

ZpO:5B/ZpO:P/5pO:5B/glass, where 5pO represents a stannous oxide film. When using many layers of BIR and/or with low emissivity, the choice of alloying additives and their concentrations in each of the films of BIR and/or with low emissivity should not necessarily be the same. For example, when two BiH layers are used in combination with at least one low-emissivity layer, one BiH layer may have a low doping content of stibium (eg, 2.595) to produce some reflection on average

IR range, and the second BiH layer can have a higher content (eg 2595) to obtain IR absorption.

As used herein, the terms "layer" and "film" are generally used interchangeably except when discussing the gradient film shown in Fig. 3, where a portion of the film is designated as a layer having a dopant concentration that is different from the dopant concentration in the rest of the film layer. According to the method according to the invention for manufacturing coated glass, described in the examples, the glass is successively contacted with a gaseous carrier containing precursors. Accordingly, the glass can have a coating that can be contacted a second time with the gaseous carrier containing the precursors. Therefore, the term "contact glass" means direct contact or contact with one or more coatings previously applied to the glass.

Another embodiment of the invention provides the ability to change the color of the light transmitted through the coated glass.

The color of the transmitted light refers to the color perceived by the observer from the side of the glass opposite to the light source, and the color of the reflected light - the color perceived by the observer from the same side of the glass as the light source. Transmitted light can be influenced by adding additional alloying additives to the BiH film. As mentioned earlier, the BIC layer contains an alloying additive selected from the group consisting of stybium, tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium, or vanadium. The color of the light transmitted through the BIR layer can be changed by adding to the BIR layer an additional dopant, which is different from the first dopant in the BIR layer and which is selected from the group formed by tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium, vanadium and fluorine or a combination of more than one additional dopant. As shown in Examples 40-43, the addition of a fluoride precursor such as trifluoroacetic acid (TFOA) to a solution of a BIR precursor such as stibium trichloride/monobutyltin trichloride produces a film containing as an additional dopant fluorine in the stibium-doped BIR layer oxide will become. When fluorine is present as an additional dopant in the stibium-doped stanium oxide layer, the color of the transmitted light is gray versus blue for the stibium-doped stanium oxide layer without the fluorine dopant. The additional alloying additive has little or no effect on reflected light, so it is possible to produce coated glass with a color of reflected light that is different from the color of transmitted light.

Alloying additives for the BiIC layer, such as vanadium, nickel, chromium, and such unconventional color additives as

TFOC and NSI can be added to the 5pO:50 precursor in an amount of 1-595 by weight (based on the combined weight of the precursor and additive) to affect the color change of the transmitted light in the final film construction with little effect on the overall neutral color of the reflected light.

Table 1

Properties of two-layer films 5PO 5B/5pO E i | 1 | 2 | with | 4 | 5 | 6 | 7 | 8 | 9 | lo | 11 | 12 | 13 | and | 75 be Nvo!.1| 11.8 | 12.7 113.9 11.0 |t121| 92 | 96 | 107 |118)| 92 | 93 | 89 | 91 | 89 | 9 eNvoi.2| 10.9 | 11.7 | i2a | 10.3 | 11.5) 82 | 92 | 94 |1081 85 | 85 | 84 | 86 | 84 | 822 lands.1| 12.0 | 12.1 /146| 11.2 111.9 92 | 9.8 | 7101/1401 89 | 90 | 84 | 84 | 86 | 8.6 lands.2| 10.9 | 11.3 / 13.4 | 1051116 63 | 93 | 86 |11.3Y| 86 | 85 | 53 | 82 | 82 | 83 "a 0.67 | 0.70 10.71 | 0.67 | 0.71 | 0.49 0.5 0.56 | 0.53 1 0.51 048 | 051 GP 7 0.49 "a 027 | 028 (0231 027 10231 027 | 027 | 028 10281 027 027 | 028 | 0.28 | 0.28 | 0.27 "A 0.71 0.73 10.73) 0.71 10.74 0.52 | 0.53 | )| 0.317 10.2821| 0.303 | 0.309 | 0.280 10.364| 0.300 | 0.300 | 0.309 | 0.315 | 0.306 | 0.318

ZoAmiz | 12.0 | 12.1 14.7 | 11.2 |11.9.| 8.2 9.8 10.1 /|13.9| 9.0 9.0 8.4 8.4 8.6 8.6 t wheels| room

Continuation of table 1 p: R/BB/ R/BB/ R/BB/ 9о5б | 5.6 | 6.6 | 5.6 | 56 | 56 | 65100 | 10017100) 100 | 100 | 10.01 14.6 | 14.6 / 146 nm! HER YY HER YY 1 1 1 her her 1 1 1 her 1 stitches | South yaz vv yu|nit te | vl pe| va for | oh! senvoi2| 8.0 | 8.4 | 85 | 84 | 85 | 84 78 | 91 |112| 75 | 75 1107 77 | 86 | 112 orms.1| 8.8 | 8.8 | 8.9 | 10.01 9.0 19.9 8.5 | 10.0 |13.3| 77 | 76 /t101| 89 | 78 | 147 oNmiz.2| 8.3 | 87 | 83 | 70 | 80 185) 72 | 78 | 96) 69 | 76 |100| 71 | 72 | 98 "Cha 0.45 | 0.49 | 0.49 | 0.46 0.5 0.46 0.38 | 0.47 0591 0.32 | 0.39 10.60 0.34 | 0.43 | 0.55 "And 0.27 | 0.2.7 | 028 | 0.28 028 10281 0291 029 10291 028 | 027 0281 0.28 | 0.28 | 0.29 "CHA 0.46 | 0.51 0.51 0.47 0.52 10461 033 | 0.44 10581 026 | 032 10.62) 025 | 0.37 | 0.53 x 0.306) 0.296 | . Med train, Neyte river - erv. eitr. eitr. zel. zel. zel. neutr. zel.

Table 2

Properties of two-layer films 5pO:5B/5pO:E and | with | 32 | zz | 34 | with 5 | with 6 | 37 | z o zevBoM! | 81 | 83 | 97 | 96 | 102 | 107 | 90 | 98 about your2 | 82 | 93 | 101 | 95 | 92 | 02 | 92 | 96 lands 53.2 | 632 | 672 | 68.0 | 69.55 | 718 | 690 | 68 lands! | 61 | 2 sh.76 | 93 | 91 | 01 |109| 78 | 99. about zenmv2 | 76 | 89 | 107 | 104 | 105 | 109, 89 | 116 "а 0.45 0.53 0.58 0.6 0.61 0.62 0.59 0.6 "а 0.28 0.28 29 0.29 0.29 0.29 0.23 0.3 "а 0.48 0.57 0.61 0.63 0.63 0.65 0.63 0.62 х 0.289 0.309 0.283 0.310 0.311 0.313 | 0.302 0.306 0292 у 0.300 І 7 7 0.274 0.275 0.306 0.364 0.281 0.349

Fo Vmiv 6.2 Y 9.3 9.1 10.1 10.9 7.8 9.9 (| AColor | Black | Black-neutral | Black-green | Black-green | Neutral | Green | Black-neutral | Green

Explanation to tables 1 and 2

Composition B/5B0/y4 - doped E bpOg/doped 50 ZpOg/glass 5B/E/3 - doped 50 bpOg/doped E zZpOg/glass 65 95 by mass of stibium trichloride in monobutyltin trichloride

Thickness, nm Dimensions of the profile of the layers 5пО:Э or 5пО0:5Б5

FoAvoY! 96 absorption of solar radiation by film (2:100-(95 T501I--95НАвой,1) - 300-2500nm

FoT8o! 90 transmission of solar radiation by the film - 300-2500nm ooIV5o1.1 9o reflection from the film on the glass surface - 300-2500nm ooIV501.2 9o reflection from the back surface of the glass - 300-2500nm oeTmiv 95 transmission! visible light film - 380-780nm 5.8. Surface resistance according to the 4-point test AIIevvi

Etiv. Sai. Emissivity calculated by surface resistance (-1-(1-0.00537 5.8.)7)

KTSV Coefficient? of thermal solar radiation through the center of a single glass plate "Ia Coefficient? of thermal solar radiation through the center of ISPZ

Tmiv-s 95 passes! of visible light through the center of a single glass plate - 380-780nm "IB 95 transmission! of visible light through the center of ISP - 380-780nm x,y calculated according to A5TM E308-96 with 9oVm color coordinates, Shitipapi S, 1931 Orzegmeg, interval 10nm

(Table 5, 5) - 380-770nm oo Vmiv 95 reflection of visible light from the film on the surface of the glass - 380-770nm (1) estimated by the function of the spectrum of sunlight (ABTM E891-87) using the data obtained on the Gatbraa R-E spectrometer 9 with an integrating sphere of 150 mm of spectral data (2) calculated according to the program M/ipdog 4.1, developed by Uipdomzhz 4 Juauiidni Stoir, I amtepse Veikeiieu

Maiyopai! And arogafgu (3) ISP insulated glass unit, which includes a coated (on the Me2 surface) sheet of glass with a thickness of 2.2 mm and a transparent sheet of glass with a thickness of 2.5 mm and a gap filled with argon with a thickness of 12.7 mm

Table C

Properties of the two-layer film 5pO:5p/5pO:E g/5B/a g/5B-R/a g/5B/s E/5B-B/a 9оЗЖСИз 300/240 300/240 300/240 300/240 ovo ооАеой, 2 of them: shin shih shi shih LISH 9vmva | -:/ 80 .Yu..BM/ | BzhyuzhKy 90 2 шЩщ | 85 | 90

KtoVs 7777177.058 2 Yur 060 | .-.Yuyuivv | 77057 24 0.310 0.297 0.302 0.303 0.297 0.313 0.299 0.307 0.295 0.308 0.297 0.304 0.308 0.315 0.310 0.314

FIG. 1

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Claims (40)

1. Glass with a coating that adjusts the parameters of solar radiation, with a preselected color of reflected light, in which the coating consists of at least two layers, which is characterized in that one of the layers is a layer that absorbs BIR radiation from the sun and that includes 5pO" and an alloying additive selected from the group consisting of stibium, tungsten, vanadium, ferrum, chromium, molybdenum, niobium, cobalt, nickel, and mixtures thereof, and the second of the layers is a low emissivity layer that includes ZpoO: and an alloying additive , selected from the group consisting of fluorine and phosphorus. 2. Glass according to claim 1, which differs in that the thickness of the layer that absorbs solar radiation is 80-300 nm, and the thickness of the layer with low emissivity is 200-450 nm. 3. Glass according to claim 1, which differs in that the thickness of the layer that absorbs solar radiation is 200-280 nm, and the thickness of the layer with low emissivity is 250-350 nm. 4. The glass according to claim 1, which differs in that the thickness of the layer that absorbs solar radiation is 220-260 nm with the concentration of the alloying additive in this layer of 2.5-790 by mass bpO", and the thickness of the layer with low emissivity is 280-320 nm at a concentration of fluorine dopant in this layer of 1-595 by mass 5poO", while the glass has a neutral-blue color of reflected light. 5. Glass according to claim 1, which is characterized by the fact that the layer that absorbs the radiation of the sun consists of 5pO"2 with the content of the dopant of stibium 3-695 by weight of 5pO" in this layer, and the layer with low emissivity consists of 5pO" with the content of the fluorine dopant additive 1-395 from the mass of 5pO: in this layer, the glass has a neutral blue color of reflected light. b. Glass according to claim 1, which differs in that the layer that absorbs solar radiation is located directly on the glass and the layer with low emissivity is located on top of the layer that absorbs solar radiation. 7. Glass according to claim 1, which differs in that the preselected color is red. 8. Glass according to claim 1, which differs in that the preselected color is yellow. 9. Glass according to claim 1, which differs in that the preselected color is green. 10. Glass according to claim 1, characterized in that the preselected color is blue. 11. Glass according to claim 1, characterized in that the preselected color is neutral blue. 12. Glass according to claim 1, characterized in that the layer that absorbs solar radiation and the layer with low emissivity are included in the unit film of 5pO»2, which contains at least two alloying additives, the first of which is selected from the group that consists of stibium, tungsten, vanadium, ferrum, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof, and the second alloying additive is selected from the group consisting of fluorine and phosphorus, and the first alloying additive is present in a greater concentration than the second, on one surface of the film and in a lower concentration than the second on the opposite surface of the film, and the part of the film adjacent to the first surface of the film functions as a layer that absorbs solar radiation, and the part of the film adjacent to the opposite surface of the film functions as layer with low emissivity. 13. Glass according to claim 1, which is characterized by the fact that the doping additive of the solar radiation-absorbing layer is stibium. 14. Glass according to claim 13, which is characterized in that the stibium dopant is derived from a precursor including stibium trichloride, pentachloride, triacetate, triethoxide, trifluoride, pentafluoride, or acetylacetonate of stibium. 15. Glass according to claim 1, which is characterized by the fact that the alloying additive of the layer with low emissivity is fluorine. 16. Glass according to claim 15, characterized in that the fluorine dopant is obtained from a precursor including trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, ethyl trifluoroacetate, ammonium fluoride, ammonium difluoride, or hydrofluoric acid. 17. Glass according to claim 1, which differs in that each of the layers is obtained by pyrolytic decomposition of the precursor state. 18. Glass according to claim 17, which is characterized in that the precursor stannium is selected from the group consisting of monobutylstannium trichloride, methylstannium trichloride, dimethylstannium dichloride, dibutylstannium diacetate or stanium tetrachloride. 19. Glass according to claim 1, which is characterized in that the layer that absorbs solar radiation includes at least two films that absorb solar radiation and have a total thickness of 80-320 nm. 20. Glass according to claim 19, which is characterized by the fact that the concentration of the alloying additive in the first of the solar radiation-absorbing films is different from the concentration of the alloying additive in the second of the solar radiation-absorbing films. 21. Glass according to claim 1, characterized in that the low emissivity layer includes at least two low emissivity films having a total thickness of 200-450 nm. 22. The glass according to claim 21, which differs in that the concentration of the dopant in the first of the films with low emissivity differs from the concentration of the dopant in the second of the films with low emissivity. 23. Glass according to claim 1, which is characterized by the fact that in the layer that absorbs solar radiation, it contains an alloying additive that modifies the color of the transmitted light. 24. Glass according to claim 23, which is characterized by the fact that the alloying additive that modifies the color of the transmitted light is fluorine or chlorine. 25. Glass according to claim 24, which is characterized by having a neutral blue color of reflected light and a blue color of transmitted light. 26. Glass according to claim 1, which differs in that the doping additive in the layer that absorbs solar radiation is chlorine. 27. The glass according to claim 1, which differs in that the BIR layer contains a doping additive of fluorine and has a color of reflected light that is different from the color of transmitted light. 28. Glass with a coating that adjusts the parameters of solar radiation, with a preselected color of reflected light, in which the coating consists of at least two layers, which is characterized in that the coating is made in the form of a film with 5pO", one of the layers of which is a layer that absorbs BIR radiation from the sun and the second is a low emissivity layer, wherein the film contains at least two dopants and has a difference in dopant concentration from one surface of the film to the opposite surface, the first dopant being selected from the group consisting of stibium, tungsten, vanadium, ferrum, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof, and the second alloying additive is selected from the group consisting of fluorine and phosphorus, the first alloying additive is at least 5095 of the alloying additives near the first surface of the film with 5pO" , forming a layer that absorbs solar radiation, and the second dopant is at least 5095 of the dopant near the second surface of the film with 5pO»2, about of the first layer, forming a layer with low emissivity. 29. The glass according to claim 28, characterized in that 7595 of the first dopant is located in a film zone with 5pO" that extends from the first surface to a depth of at least 80 nm, forming a layer that absorbs BIR radiation from the sun, and 7595 of the second dopant located in the film zone with 5pO", which extends from the second surface to a depth of at least 80 nm, forming a layer with low emissivity. 30. Glass with a coating that regulates the parameters of solar radiation, in which the coating consists of at least two layers, which is characterized by having a neutral blue color of reflected light, one of the layers is a layer that absorbs BIR radiation from the sun and includes 5po: 5 and an alloying additive selected from the group consisting of stibium, tungsten, vanadium, ferrum, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof, and the second of the layers is a low emissivity layer that includes 5po: and alloying an additive selected from the group consisting of fluorine and phosphorus. 31. Glass with a coating that regulates the parameters of solar radiation, in which the coating consists of at least two layers, which is characterized by having a color intensity index of reflected light of 12 or less, one of the layers is a layer that absorbs BIR radiation from the sun and includes bpO" and an alloying additive selected from the group consisting of stibium, tungsten, vanadium, ferrum, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof, and the second of the layers is a low emissivity layer that includes 5pO" and an alloying additive selected from the group consisting of fluorine and phosphorus. 32. Glass with a coating that regulates the parameters of solar radiation, in which the coating consists of at least two layers, which differs in that it has color coordinates S.I.E. for x - 0.285-0.310 and for y - 0.295-0.325 for reflected light, one of the layers is a layer that absorbs BIR radiation from the sun and includes 5pO»2 and an alloying additive selected from the group consisting of stibium, tungsten, vanadium , ferrum, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof, and the second of the layers is a layer with a low emissivity, which includes 5pO»2 and an alloying additive selected from the group consisting of fluorine and phosphorus. 33. Glass with a coating that regulates the parameters of solar radiation, in which the coating consists of at least two layers, which differs in that it has color coordinates according to S.I.E. 1931 for x - 0.285-0.325 and for y - 0.295-0.33 for reflected light, one of the layers is a layer that absorbs BIR radiation from the sun and includes ZpO2; and an alloying additive selected from the group consisting of stibium, tungsten, vanadium, ferrum, chromium, molybdenum, niobium, cobalt, nickel, and mixtures thereof, and the second of the layers is a low emissivity layer that includes 5poO:5 and alloying an additive selected from the group consisting of fluorine and phosphorus. 34. A method of manufacturing glass with a coating, which is characterized by the fact that it includes sequential treatment of the glass at its temperature above 400"C with a first gas carrier that includes an oxygen source, water, an organic precursor and an alloying additive precursor that contains a metal selected from a group consisting of stibium, tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium, and vanadium, and a second gas carrier that includes an oxygen source, water, an organic precursor, and a dopant precursor that contains fluorine or phosphorus, to create by pyrolysis a BIR layer comprising 5poO", which contains an alloying additive of stibium, tungsten, cobalt, nickel, chromium, ferrum, molybdenum, niobium or vanadium, and a low emissivity layer comprising 5poO", which contains doping additive of fluorine or phosphorus. 35. The method according to claim 34, which is characterized by the fact that the glass is brought into contact with the first gas carrier before contact with the second gas carrier. 36. The method according to claim 34, which is characterized by the fact that the first gas carrier also includes components of the second gas carrier to obtain a product in which the BIR layer contains an alloying additive of fluorine or phosphorus in addition to an alloying additive of stibium, tungsten, cobalt, nickel, chromium , ferrum, molybdenum, niobium or vanadium. 37. The method according to claim 34, which is characterized by the fact that the first gas carrier also includes a precursor of an alloying additive containing chlorine, fluorine or phosphorus. 38. The method according to claim 37, which is characterized by the fact that the precursor of the alloying additive containing chlorine, fluorine or phosphorus is trifluoroacetic acid, hydrogen chloride or phosphorus trichloride. 39. The method according to claim 34, which is further characterized in that the first gaseous carrier also includes a film modifier selected from the group consisting of chlorine, fluorine and phosphorus. 40. A coating that absorbs radiation in the near infrared region of the spectrum, in the form of a film, which is characterized by the fact that it includes a stannous oxide that contains a BiIR dopant selected from the group consisting of stibium, tungsten, cobalt, nickel chromium, ferrum, molybdenum, niobium and vanadium, and includes an alloying additive that modifies the color of light transmitted through the film and is present in an amount sufficient to modify the color of light transmitted through the film, which is selected from the group consisting of stibium, tungsten, cobalt, nickel, chromium .