Glazing pane for screening solar radiation and process for producing thereof

SWEDEN («) PATENTS (13) C2 (11) 514 055 (19) SE (51)

International class ⁷C03C 17/245, 17/34

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PATENT AND REGISTRATION (45) (41) (22) (24) (62) (86) (86) (83)

Patent filed Application widely available The patent application was submitted on expiration date

National application number International filing date Filing date for European patent application Deposit of microorganism

2000-12-18

1996-12-10

1996-06-07

1996-06-07 (21) Patent Application Number g602269 ~ 4

Application received as:

Swedish patent application completed international patent application with number □ converted European patent application with number (30)

1995-06-09 GB 9511691

1995-07-12 GB 9514190 (73) (72) (74) (54) (56) (57)

PATENTHÄVÄRE Glaverbel, Brussels BE

INVENTORS Robert Terneu, Thimeon BE, Philippe Legrand, Michel Hannotiau, Pietrain BE, Alain Schutz,

OMBUD Älbihns Patentbyrå Stockholm AB

NAME Glass panel with sun-filtering properties for making it

CALLED PUBLICATIONS:

SE B 410 180 (C03C 17/25)

SUMMARY:

Soignies BE, Gosselies BE and procedure

The invention relates to a glazing panel comprising a vitreous substrate supporting a pyrolytically shaped tin / antimony oxide coating layer containing tin and antimony in a Sb / Sn mole ratio of 0.01 to 0.5. The coated substrate exhibits a solar factor of less than 70%. The panel is prepared by chemical vapor deposition from a reaction mixture comprising a tin source and an antimony source.

The numbers in brackets indicate international identification code, INID code. Letters in clamps indicate international document code.

514 055

The present invention relates to a glazing panel exhibiting sun-filtering properties and to a process for producing such a panel.

Reflective transparent sun-filtered glazing panels have become a useful material for architects for use as the exterior facade of buildings. Such panels exhibit aesthetic properties in and because they reflect the immediate environment and because they are available in a variety of colors allow for special designs. Such panels also show technical advantages by providing the building's inhabitants with protection from solar radiation through reflection and / or absorption and by eliminating the dazzling effects of intense sunlight, thereby providing an effective shielding against glare, improved visual comfort and reducing eye fatigue.

From a technical point of view, it is desirable that the glazing panel should not allow an excessive amount of incident solar radiation to pass so that the building will not overheat in sunny weather. The transmission of the total incident solar radiation can be expressed in terms of "solar factor". As used herein, the term "solar factor" refers to the sum of the total energy directly transmitted and the energy absorbed and radiated on the side facing away from the energy source, as a proportion of the total radiant energy incident on the coated glass.

Another important application for reflective transparent solar control glazing panels is found in vehicle windows, especially in cars or rail cars, where the purpose is to protect vehicle road users from solar radiation. In this case, the main energy factor to be taken into account is the total energy directly transmitted (TE) since the energy absorbed internally and radiated (AE) is dissipated.

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through the movement of the vehicle. Thus, the main purpose of vehicle panels is to have a low TE factor.

The properties of the coated substrate described below are based on standard definitions from the International Commission on Illumination - Commission

International de I'Eclairage ("CIE").

The standard light sources cited below consist of CIE light source C and light source A. Light source C represents average daylight with a color temperature of 6700g ° K. Light source A represents the radiation from a Planck radiator at a temperature of about 2856 ° K.

The "light transmittance" (TL) is the luminous flux that passes through a substrate as a percentage of the incident luminous flux.

The "light reflectance" (RL) refers to the luminous flux reflected from a substrate as a percentage of the incident luminous flux.

The "selectivity" of a coated substrate for use as a glazing panel for construction is the ratio of light transmittance to solar factor (TL / FS).

The "purity" (p) of the substrate's color refers to excitation purifications measured by light source C. It is specified according to a linear scale on which a defined white light source has the purity zero and the pure color exhibits a purity of 100%. The purity of the coated substrate is measured from the side opposite to the coated side.

The term "change performance index" (s) is defined in the CIE International Lighting Vocabulary, 1987, p. 138th

The "dominant wavelength" (λρ&gt;) is the wavelength peak in the region transmitted or reflected by the coated substrate.

514 055 "Emissivity" (ε) is the ratio of energy emitted from a given surface at a given temperature to that of a perfect radiator (black body with emissivity of 1.0) at the same temperature.

A number of different techniques are known for forming coatings on glass substrates including pyrolysis. Pyrolysis usually has the advantage of providing cured coatings, which eliminates the need for a protective layer. The coatings formed by pyrolysis exhibit durable abrasion and corrosion resistant properties. This is believed to be due in particular to the fact that the process involves depositing a coating material onto a substrate which is hot. Pyrolysis is also generally cheaper than alternative coating methods such as sputtering, especially in terms of factory investment. The deposition of coatings by other methods, for example by sputtering, gives products with very different properties, in particular a lower resistance to abrasion and, among other things, a different index of refraction.

A large amount of coating material was proposed for glazing panels and for various desired properties of the glass material. Tin oxide, SnO2, has come into wide use, often in combination with other materials such as other metal oxides.

British patent GB 1 455 148 discloses a process for pyrolytic forming a coating consisting of one or more oxides on a substrate, primarily by spraying the compounds of a metal or silicon, thereby modifying the light transmission and or light reflection of the substrate or to provide antistatic or electrically conductive properties. Examples of specified oxides include Z1O2, SnC&gt; 2, Sb2C&gt; 3, T1O2, CO3O4, C12O3, S1O2 and mixtures thereof. Tin oxide (SnC&gt; 2) is considered to be advantageous because its hardness and its ability to exhibit antistatic or electrically conductive properties. GB patent 2,078,213 relates to a sequential spraying method for pyrolytically forming a coating on a vitreous substrate and in particular deals with tin oxide or indium oxide as the main coating constituents. When the metal coating precursor is made of tin chloride, dop is doped

514 Preferably with a precursor selected from ammonium bifluoride and antimony chloride to increase the electrical conductivity of the coating.

It is also known that when a tin oxide coating is formed by pyrolysis of SnCl 3, the presence of a dopant such as antimony chloride SbCl 2, directly mixed with the tin chloride SnCl 2

It is an object of the present invention to provide pyrolytically shaped glazing panels which exhibit sun-filtering properties.

We have discovered that this and other useful purposes can be achieved by using chemical vapor deposition (CVD) to apply a pyrolytic coating comprising tin and antimony oxides in a specific relative ratio.

Thus, according to a first aspect of the present invention, a glazing panel comprising a vitreous substrate supporting a tin layer of tin oxide containing tin and antimony in an Sb / Sn mole ratio of 0.01 to 0.5, wherein said layer is pyrolytically formed by chemical vapor deposition, wherein through the substrate so coated exhibits a solar factor FS of less than 70%.

The substrate is preferably in the form of bands of vitreous material, such as glass or some other transparent material. Given the proportion of incident solar radiation absorbed by the glazing panel, especially in environments where the panel is exposed to strong or prolonged solar radiation, there is a warming effect on the glazing panel which may then require the glass substrate to be subjected to a curing process. However, the durability of the coating allows the glazing panel to be mounted with the coated surface at the outermost, thereby reducing the heating frequency.

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Preferably, the substrate is a clear glass, although the invention also covers the use of colored glass as a substrate.

The Sb / Sn molar ratio in the coating genus is preferably at least 0.03, most preferably at least 0.05. This helps to ensure a high absorption level. On the other hand, said ratio is preferably less than 0.21 in view of achieving a high light transmittance level (TL). Most preferably, the ratio is lower than 0.15 since above this level the coating layer exhibits an unnecessarily high absorption level coupled with a poor selectivity.

Coated substrates according to the invention offer the advantage of a light reflectance (RL) less than 11%. This low level of reflection of a glazing panel intended for buildings is favored by architects. This prevents the panels from creating a dazzling glow near the building.

It may be useful to prevent interaction between the substrate glass and the tin / antimony oxide coating layer. For example, it has been found that in the pyrolytic formation of a tin oxide coating from tin chloride on a soda glass substrate, sodium chloride exhibits a tendency to be incorporated into the coating as a result of reaction of the glass with the coating precursor material or its reaction products and this leads to light diffusion in the bead diffusion.

Thus, an intermediate light diffusion-reducing coating layer is preferably placed between the substrate and the tin / antimony oxide coating layer. The light-efficiency reducing layer can be formed pyrolytically in a not fully oxidized state by contacting the substrate with an intermediate coating precursor in a chamber for coating with an intermediate coating in the presence of oxygen in insufficient amount to fully oxidize the intermediate coating material on the substrate. The term "not fully oxidized material" is used herein to denote a true suboxide, i.e., an oxide with lower valence number of a multivalent element (e.g., VO2 or TiO) and also to denote an oxide material containing oxygen holes in the structure: an example of the later mate514 055

The g rial is SiO_x where x is less than 2, which can generally exhibit the general structure of S102 but has a proportion of holes which would be filled with oxygen in the dioxide.

We prefer that the light diffusion reducing coating layer comprises a silicon oxide having a geometric thickness of about 100 nm. The presence of a silica with an intermediate coating on the soda glass has the special advantage of preventing the migration of sodium ions from the glass by diffusion or otherwise into the tin / antimony oxide coating layer during the formation of the upper layer or during a subsequent high temperature treatment.

Alternatively, the intermediate coating may consist of an "anti-reflection" intermediate coating such as, for example, an oxidized aluminum / vanadium layer described in GB patent 2,248,243.

The glazing panels of the invention exhibit solar factors of less than 70%, preferably less than 60%, and in some cases less than 50% are preferred. The preference for a solar factor of less than 60% arises when panels according to the invention are placed with the coated side facing the exterior, ie with the coating against the energy source. Generally, this placement results in an improved solar factor compared to the placement of the panel with the coated side on the side calculated from the energy source. The need for a solar factor of less than 50% arises in buildings in parts of the world with high levels of solar energy. For vehicle solar roofs, an even lower solar factor may be desirable.

The use of stained glass is a way of providing a lower solar factor and is often used in both building glass and vehicle glass. When comparing the effect of the coating layers, it is therefore necessary to take into account any differences between the types of glass on which, respectively. coating deposited. Thus, an example of a coating according to the invention on a clear glass gave a solar factor of 63%, while an equivalent coating on a green-colored glass gave a solar factor of 44.5%.

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It is also desirable for the glazing panel to transmit a reasonable proportion of visible light to allow natural illumination in the interior of the building or vehicle and to provide that the persons inside the building or car may look. Thus, it is desirable to increase the selectivity of the coating, i.e., increase the ratio of transmittance to solar factor. In fact, it is desirable that the selectivity be as high as possible.

Generally, it is preferred that the light transmittance (TL) of the panel of the invention exhibit a value between 40 and 65%. Nevertheless, a panel exhibiting a light transmittance below 40% can be used as an upwardly directed glazing panel, for example as a sunroof in a vehicle.

Preferably, the tin / antimony oxide coating has a thickness of from 100 to 500 nm. Thick layers of tin / antimony oxide, especially layers having a low Sb / Sn mole ratio, can provide a glazing panel with the advantageous combination of low solar factor (FS) and low emissivity. Another way of obtaining this combination is to deposit on the tin / antimony oxide layer according to the invention a low emissivity layer consisting of doped tin oxide, for example tin oxide doped with fluorine. However, this is disadvantageous in the sense that it necessitates the deposition of an additive layer which takes time and is expensive.

In principle, another way of providing a combination of low solar factor and low emissivity would be to form a tin / antimony oxide layer containing a dopant such as fluorine. 11 For example, GB Patent 2,200,139 discloses a process for forming a pyrolytic tin oxide coating by spraying a solution which, in addition to the tin precursor, contains compounds which will result in the coating containing fluorine and at least one of antimony, arsenic, vanadium, cobalt, zinc, cadmium, molybdenum, tellurium and manganese.

Thus, for example, one could form a coating of reactants containing tin, antimony and fluorine in the ratios Sb / Sn = 0.028, F / Sn = 0.04. However, we have discovered that the presence of fluoride may have the apparent disadvantage of preventing

the use of antimony in the coating rather than effectively reducing the emissivity.

For example, reactants containing antimony and tin in the ratio Sh / Sn = 0.028 gave a coating with an Sb / Sn ratio of about 0.057, while the same reactants plus a fluorine-containing reactant in an amount such that F / Sn = 0.04 gave a coating with an Sb / Sn ratio of about 0.038.

The invention thus provides the advantage of either giving a solar factor (FS) below 60%, an emissivity of less than 0.4 (preferably less than 0.3) and a light transmittance (TL) of more than 60%. Thus, the coated product fulfills two important functions. During winter, it retains heat in the building due to its low emissivity. In the summer, it resists the passage of solar heat into the building, thereby avoiding overheating in the building, thanks to its low solar factor. This is particularly achieved for coatings having an Sb / Sn ratio of 0.01 to 0.12, preferably 0.03-0.07, and a thickness between 100 and 500 nm, for example between 250 and

450 nm.

Preferably, the tin / antimony oxide coating layer is an exposed coating layer and the glazing panel comprises only one such tin / antimony oxide coating layer.

However, it is possible to provide one or more additional coating layers, either by pyrolysis or by other coating methods, to achieve a particularly desired optical quality. However, it should be noted that the tin / antimony oxide layer when applied by pyrolysis has sufficient mechanical durability and chemical resistance to suitably function as the exposed layer.

Panels according to the invention can be installed in single or multiple glazing units. While the coated surface of the panel may constitute the inside of the outer glazing panel so that the coated surface is not exposed to weather conditions, which would otherwise reduce its service life more quickly through soiling, physical damage and / or oxidation, coatings produced by pyrolysis generally exhibit greater mechanical resistance. than coatings produced by other methods and they can therefore be exposed to the atmosphere ex514,055. The panels of the invention can advantageously be used in laminated glass structures, for example, where the coated surface is the inner surface of the outer laminate.

According to a second aspect of the invention, there is provided a process for forming a glass panel comprising the chemical vapor deposition (CVD) of a tin / antimony oxide layer from a reaction mixture on a vitreous substrate, said reaction mixture comprising a tin source and an antimony source, wherein the Sb / Sn in said mixture is from 0.01 to 0.5, the substrate so coated having a solar factor FS of less than 70%.

Since it is desirable to produce pyrolytically coated flat glass, it is best to do so when the glass has recently been formed. Doing so has economic benefits as it is not necessary to reheat the glass for the pyrolytic reaction to occur and it is also of benefit to the quality of the coating as it ensures that the surface of the glass is in its original condition. Thus, it is preferred that said intermediate coating precursor material be contacted with an outer surface of a hot glass substrate consisting of a newly formed flat glass.

Thus, the glazing panels of the invention can be prepared as described below. Any pyrolytic coating method can be carried out at a temperature of at least 400 ° C, ideally from 550 to 750 ° C. The coatings can be formed on a sheet of glass that is moved in a tunnel oven or on a glass strip during formation, while it is still hot. Coatings can be formed inside the cooling duct placed after the glass band forming device or inside the transfer tank on the upper surface of the glass band as the latter floats on a bath of molten tin.

Coating layers are applied to the substrate by CVD technique. This is a particularly useful method because it provides for the possibility of coatings of ordinary thickness and composition, where such uniformity of the coating is particularly important when the product is to cover a large surface. CVD offers many advantages over

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ΙΟ pyrolysis methods using sprayed liquids as the reacting material. With such spraying methods, it is difficult both to control the evaporation process and to obtain a good uniformity of the coating thickness. In addition, pyrolysis of sprayed liquids is substantially limited to the production of oxide coatings, such as

SnC&gt; 2 and Ί1Ο2 · It is also difficult to prepare multilayer coatings using sprayed liquids since each coating deposit produces a significant cooling of the substrate. Furthermore, CVD is more economical in terms of raw material, and leads to reduced waste.

The product with CVD coatings is physically different from the coatings obtained by spraying. It should be noted that a coating applied by spray retains traces of the sprayed droplets and the spray gun's path, which is not the case with CVD.

To form each coating, the substrate is contacted in a coating chamber with a gaseous medium comprising the gaseous phase reaction mixture. The coating chamber is fed with the reaction gases through one or more nozzles whose length is at least equal to the width of what is to be coated.

Methods and devices for forming such coatings have been described, for example, in French Patent 2,348,166 (BFG Glassgroup) or in French patent application no. 2 648 453 Al (Glaverbel). These methods and devices lead to the formation of particularly strong coatings with advantageous optical properties.

To form the tin / antimony oxide coatings, two successive nozzles are used. The reaction mixture comprising a source of tin and antimony is fed into the first nozzle. When this mixture comprises chlorides which are liquid at ambient temperature, it is evaporated in a stream of anhydrous carrier gas at an elevated temperature. To produce the oxides, the chlorides are contacted with water vapor which is passed to the second nozzle. The steam is overheated and is also injected into a carrier gas.

514 055 ΤΙ

Advantageously, nitrogen is used as the substantially inert gas carrier. Nitrogen is sufficiently inert for the purposes present and it is relatively inexpensive compared to the noble gases.

Interlayer silica oxide S1O2 or SiO_x may be deposited from silane S1H4 and oxygen in accordance with the disclosure of British Patent Applications GB 2,234,264 and GB 2,247,691.

If a glass substrate carrying a non-fully oxidized coating is exposed to an oxidizing atmosphere for a sufficient period of time, it can be expected that the coating has a tendency to fully oxidize so that its desired properties are lost. Therefore, such an intermediate coating is coated with the tin / antimony oxide coating while it is still in a not fully oxidized state and while the substrate is still hot to thereby retain such intermediate coating in its not fully oxidized state. The time during which newly coated glass substrate can be exposed to an oxidizing atmosphere such as air and, further, before the coating is provided with an upper coating without damaging the properties of the coating, will depend on the temperature of the glass during such exposure and on the type of coating.

Preferably, the chamber for said intermediate coating is surrounded by reducing atmosphere. Using this feature helps prevent the ambient oxygen from entering the interlayer chamber and thus permits better control of the oxidizing conditions in the interlayer chamber.

The oxygen required for the intermediate coating reactions can be supplied in the form of pure oxygen, but this unnecessarily increases the costs and it is therefore preferred to supply air to the intermediate coating chamber to introduce oxygen there.

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It is noted that the Sb / Sn mole ratio desirable in the reaction mixture does not always correspond to the desirable ratio for the tin / antimony coating layer.

Preferably, the tin source is selected from SnCl4, monobutyl trichlorotin ("MBTC") and mixtures thereof. The antimony source can be selected from SbCl5, SbCl₃, organic antimony compounds and mixtures thereof. Examples of suitable source materials are Sb (AND₂CH₃)₃, Cli_J7Sb (OCH₂CH₃)in_&gt;3, Cl₂SbOCHClCH₃,

Cl₂ShOCH₂CHCH₃Cl and Cl₂SbOCH₂C (CH₃)₂Cl.

The invention will now be described in more detail with reference to the following non-limiting examples.

In the examples, the Sb / Sn mole ratio in the whole-layering layers was determined by X-ray analysis technique in which the number of X-ray pulses from and to the element was compared. Although this technique is not quite as accurate as a calibration by chemical dosing, the similarity between antimony and tin means that they react in a similar way to X-rays. The ratio of the measured number of impulses observed for the resp. elements thus give a close approximation to their molar ratio.

Colored rather than clear glass was used as indicated in some of the examples. The properties of the resp. The types of stained glass are shown in Table 1 below. In all cases, the properties were measured on glass samples having a thickness of 4 mm, this being the thickness of all glass used in all Examples except Examples 1-7 (for which the thickness is shown in Table 2). The abbreviations in this and the other following tables (TL, TE etc) have the above meanings.

With regard to the calculations of the solar factor, it should be noted that for light transmittance (TL) below 60%, the effect of low emissivity is not negligible and should be taken into account: when the emissivity is reduced, the same applies to the solar factor.

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I3

Table 1

<td></td><td></td><td></td><td>S Κί - i</td><td></td><td>⁵; s ssss-iss ·</td>

<td>XD at transmission (nm) [Light source: C / A]</td><td> 505,4/508,5</td><td> 504,9/508,4</td><td> 470,1/493,9</td><td> 493,2/502,7</td><td> 478,9/502,7</td>

<td>Purity (%)</td><td> 2,9/3,4</td><td> 2,1/2,5</td><td> 1,5/0,8</td><td> 5,6/5,1</td><td> 2,6/1,8</td>

<td>TL (%) [Light source: C / A]</td><td> 72,66/71,12</td><td> 78,44/77,20</td><td> 55,65/55,56</td><td> 36,80/35,76</td><td> 22,41/22,30</td>

<td>TE (%) (CIE)</td><td> 44,0</td><td> 52,3</td><td> 56,9</td><td> 25,9</td><td> 31,11</td>

<td>FS (%) Coated Page (CIE)</td><td> 56,8</td><td> 62,9</td><td> 66,3</td><td> 43,4</td><td> 47,3</td>

<td>TL / FS [Light source: C]</td><td> 1,28</td><td> 1,25</td><td> 0,84</td><td> 0,85</td><td> 0,47</td>

Example 1

Clear sodium float glass moving forward at a speed of 7 m / min along a float chamber was provided with an intermediate coating on a full-laying station located at a position along the float chamber where the glass had a temperature of about 700 ° C. The supply line was fed with nitrogen gas, the silane introduced into it at a partial pressure of 0.25% and oxygen introduced at a partial pressure of 0.5% (ratio 0.5). A coating of silica S102 with a thickness of 100 nm was obtained.

The intermediate coated substrate exhibited a thickness of 6 mm and then immediately coated by CVD pyrolysis using a coating device comprising two consecutive nozzles. A reaction mixture comprising a mixture of SnCl4 as a tin source and SbCl5 as an antimony source was used. The Sb / Sn ratio in the mixture was about 0.2. The reaction mixture was evaporated in a stream of anhydrous nitrogen gas at about 600 ° C and fed

514 055 / V at the first nozzle. Evaporation is accomplished by atomizing these reagents in the host gas. superheated water vapor was passed to the second nozzle. The water vapor was heated to about 600 ° C and also injected into a barley gas which was air heated to about 600 ° C. The flow rate of the gas (carrier gas plus reagent) in each nozzle was 1 m 2 / cm wide of substrate per hour at the operating temperature.

The coating process was continued until the geometric thickness of the tin / antimony oxide coating applied to the intermediate substrate was 185 nm.

Examples 2-7

In Examples 2-7, the procedure of Example 1 was followed but with variations of such parameters as the reaction mixing, the presence or absence of intermediate oxide, the ratio of Sh / Sn in the coating and in the reaction mixing and the thickness of the glass substrate. For example, compared to Example 1, in Example 2, no intermediate coating was applied and the tin / antimony oxide coating layer had a thickness of 210 nm. The reaction mixtures are given below:

Examples 2 and 3: the same as in Example 1 (but with a lower concentration of the reaction mixture in the gas of Example 3);

Example 4: MBTC and Cl177Sb (AND₂CH3) in_?3;

Example 5: MBTC and Cl2SbOCH₂CHCH3Cl;

Example 6: MBTC and Cl2ShOCH₂C (CH 3) 2 Cl;

Example 7: MBTC and ShCl3

The variations in the operating parameters of Examples 1-7 and the results obtained are given in the accompanying Table 2.

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I5

The glazing panels of Examples 3-7 exhibited a nice blue color when illuminated: the dominant wavelength of the transmission within the visible wavelength range was in the range of 470-490 nm.

Example 6 gave a glazing panel with the combination a low solar factor FS and low emissivity.

In a variant of Example 6, the intermediate coating of S1O2 was replaced by an anti-reflective intermediate coating of silica SiO_x according to the process of the British patent

GB 2,247,691.1 In a further variant, the S1O2 intermediate coating was replaced by an oxidized ahiminium / vanadium layer according to the British patent.

248 243.1 of these variants, the glazing panels did not exhibit a purple tone upon reflection from the uncoated side.

Example 8

Colored float glass "green A" which moves at a speed of 7 m / min along a float chamber is coated with an intermediate coating at a coating station located at a position along the float chamber where the glass temperature was about 700 ° C. The feed line was fed with nitrogen gas, the silane was introduced at a partial pressure of 0.2% and oxygen was introduced at a partial pressure of 0.5% (ratio 0.55). A coating of silica SiO_x with x approximately equal to 1.8 was obtained with a refractive index of about 1.7. The coating thickness was 40 nm.

The interlayered substrate exhibited a thickness of 4 mm and then coated by CVD pyrolysis. A reaction mixture comprising a mixture of MBTC as a source of tin and Cli 7Sb (OCH2CH3) in 3 as an antimony source was used. The Sb / Sn mole ratio in the mixture was about 0.195 (mass ratio 0.2). The reaction mixture was evaporated in a stream of anhydrous air at about 200 ° C, fed to the nozzle. Evaporation is achieved by atomizing them in the reaction, and substances in the carrier gas are included. superheated water vapor was then introduced, heated to about 200 ° C.

The coating process was continued until the geometric thickness of the tin / antimony oxide coating applied to the intermediate coating was 120 nm.

Examples 9-14

In Examples 9-14, the procedure of Example 8 was followed but with variations shown in accompanying Table 2 of such parameters as the thickness of the intermediate coating, the Sb / Sn ratio in the coating and in the reaction mixture, the thickness of the tin / antimony oxide coating layer and the color of the glass. The results of Examples 8-14 are shown in Table 3.

The glazing panels of Examples 9-14 exhibited a nice blue color in illumination, the dominant wavelength of the transmission in the visible spectrum being in the range 470-490 nm (light source C).

In various variants of Example 9 in which the glass A was replaced by medium gray glass, the resulting light transmittance (TL) was 20%, the light reflectance (RL) 10% and the energy transmission (TE) 15%.

Examples 15-30

The procedure of Example 1 was followed for further Examples 15-30 with variations in the mixture of constituent reactants, color and thickness of the glass substrate, the thickness of the intermediate coating and the Sb / Sn ratio in the reaction mixture and in the coating. In Examples 15-22, the starting reaction mixture was MBTC and Cli 7Sb (OCH2CH3) in 3 without trifluoroacetic acid, while in Examples 23-30 the reaction mixture was MBTC and Cli 7Sb (OCH2CH3) in 3 with trifluoroacetic acid. The ratio of F / Sn in the reaction mixture for these examples was 0.04.

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The variations of operating parameters and the results obtained are shown in accompanying Ta bell 4 for Examples 15-22 and in the accompanying Table 5 for Examples 23-30. Silica SiO_x used in Examples 15-30 has a value of x approximately equal to 1.8.

Table 2

514 055 /8

<td>ί</td><td>© F * 4</td><td>&lt;s O • fM «Λ</td><td> 70</td><td> 0,18</td><td> 0,20</td><td></td><td> 55,0</td><td>F one f * H</td><td> 59,6</td><td> 0,92</td><td> 479,3</td><td>rs F O</td><td> 577,0</td><td>F one one</td><td> 0,79</td><td>vs</td>

<td> &gt;&lt;&gt;&amp;*+$</td><td> 445</td><td>&lt;S O • FM TZA</td><td> 70</td><td> 0,06</td><td>O F O</td><td>JP OCO</td><td>r tt</td><td>sO F SD</td><td> 47,2</td><td>O F f «M</td><td> 483,0</td><td> 8,0</td><td> 490,0</td><td> 6,0</td><td>VS 4 Fl O</td><td>vs</td>

<td>i \ ~ &lt; ^s&amp; Ύώ &amp;</td><td>VS O</td><td>ts O • FM CO</td><td>O Γ-</td><td>f » O</td><td> 0,20</td><td>jc</td><td> 61,6</td><td>F W · ^ fH</td><td> 62,2</td><td> 0,99</td><td> 481,0</td><td>γ- F 00</td><td>sO w Γ ' «η</td><td> 35,2</td><td>F r ~ O'</td><td>vs</td>

<td>·· $ «« S • Ζ.'ζΐ, 'Κ s J</td><td>O ts</td><td rowspan="2">&lt;s O in / 5</td><td rowspan="2"> 70</td><td rowspan="2">Olympics f M f O</td><td rowspan="2"> 0,20</td><td rowspan="2">low</td><td rowspan="2"> 51,0</td><td rowspan="2">O F &lt;s</td><td rowspan="2"> 58,4</td><td rowspan="2"> 0,87</td><td rowspan="2"> 478,8</td><td rowspan="2">«η F fH</td><td rowspan="2"> 579,5</td><td rowspan="2"> 35,0</td><td rowspan="2"> , 0,84</td><td rowspan="2">vs</td>

<td>K &amp; 3S &amp;</td><td></td>

<td>-XsZ-&gt; X &amp; A&gt; &lt; Si IB ^; W '</td><td> 105</td><td>No</td><td>O</td><td> 0,46</td><td> 0,20</td><td> 4,36-7,01</td><td>vs F VS sO</td><td>00 F 00 FM</td><td> 66,0</td><td> 0,99</td><td> 480,1</td><td>Os F acting</td><td> 575,3</td><td>F "4 Os</td><td> &gt;0,7</td><td>O</td>

<td> 1</td><td>O ts</td><td>No</td><td>O</td><td> 0,48</td><td> 0,20</td><td> 2,09</td><td> 44,3</td><td>O F Γ9 fH</td><td> 56,9</td><td>00 Γ F O</td><td> -560</td><td>Os F &lt;n</td><td> 494,5</td><td>O F r</td><td>Fi O Λ</td><td>SE</td>

<td>g</td><td>V ~&gt; 00</td><td rowspan="2">(S O «Λ</td><td rowspan="2">O O FM</td><td rowspan="2">00 F O</td><td rowspan="2"> 0,20</td><td rowspan="2"> 0,07</td><td rowspan="2">r F VS 'Φ</td><td rowspan="2">O os'</td><td rowspan="2"> 55,3</td><td rowspan="2"> 0,83</td><td rowspan="2"> 587,5</td><td rowspan="2">F ns</td><td rowspan="2"> 472,3</td><td rowspan="2"> 36,9</td><td rowspan="2">F O A</td><td rowspan="2">SE</td>

<td></td><td></td>

<td>6 ibll • On-aw? S $ NSM { | / Ϊ́: ΐ: «&lt;- Sw B , νή&gt; ^ \ ^ss% xT s, i 3¾¾¾ «« «&lt;· &gt; «: &lt;-Of&gt; X ·</td><td>Tin / antimony oxide thickness (nm)</td><td>Between Coating Oxide</td><td>z ^ « U «ä 1) 3 O O Ό WE § op = f T3 1 * 33 3</td><td>Sb / Sn ratio in the coating</td><td>Sb / Sn ratio among constituent reactants</td><td>Diffusion (%)</td><td>TL (%)</td><td>'É? T3 • fM CA. Ό 00 jf 3 es o</td><td>FS (%) (coated side) (CIE)</td><td>TL / FS</td><td>λρ at transmission (nm)</td><td>Color purity on transmission (%)</td><td>λθ on reflection from the coated side (nm)</td><td>Color purity (%) on reflection from the coated side</td><td>emissivity</td><td>Glass thickness (mm)</td>

ί4

514, 0SR

Table 3

<td rowspan="2"></td><td> 470</td><td>CM O (Λ</td><td> 40</td><td> 0,09</td><td> 0,07</td><td>00 Λ</td><td>36 [A]</td><td>g l&gt;</td><td></td><td>-1 r CM</td><td>μ- &lt; cn «t</td><td>• n</td><td>493.4 [A]</td><td>2 M · Λ «η</td><td>-576.0 [A]</td><td>1.5 [A]</td><td>«η cn e. O</td><td>Clear soda lime glass</td>

<td> 320</td><td>O • WM GO</td><td> 40</td><td> 0,09</td><td> 0,07</td><td>O</td><td> 40/41</td><td> .8/7</td><td></td><td>CM</td><td> 39</td><td> 1,02/1,05</td><td> 501,0/491,6</td><td> 7,2/8,6</td><td> -512,5/513,6</td><td> 15,4/14,5</td><td> 0,44</td><td>Green A</td>

<td></td><td> 470</td><td>CM O Tzi</td><td> 40</td><td> 0,09</td><td> 0,07</td><td>00 r&gt;</td><td> 9/9</td><td>t</td><td>Ό</td><td>ol</td><td> 29</td><td>cn r. O one &lt;1 O</td><td> 494,2/480,0</td><td>00 e »</td><td> -555,4/660,1</td><td> 2,1/6,6</td><td>«Λ cn r » O</td><td>Dark Gray</td>

<td></td><td> 470</td><td>O' GO</td><td> 40</td><td> 0,09</td><td> 0,07</td><td> 00</td><td> 31/32</td><td> 7/7</td><td>LO</td><td> 00</td><td> 36</td><td> 0,86/0,89</td><td> 497,2/487,2</td><td> | 7,6/10,8</td><td> -576,9/559,8</td><td> 6,0/1,2</td><td>v&gt; cn O</td><td>Green B</td>

<td></td><td> 320</td><td>CM O • vM CO</td><td> 40</td><td> 0,09</td><td> 0,07</td><td>O ^ 1</td><td> 31/32</td><td> 7/7</td><td>LO</td><td> 25</td><td>Tj</td><td> 0,76/0,78</td><td> 494,8/481,9</td><td> 4,9/8,1</td><td> -511,8/512,2</td><td> 17,2/16,3</td><td>• 'S' &lt;o</td><td>Gray</td>

<td> £3&amp;</td><td>ο CM</td><td>CM O CO</td><td> 70</td><td>00 Μ * » ο</td><td> 0,20</td><td>O</td><td> 39/20</td><td> 11/11</td><td> 00</td><td> 25</td><td> 1—</td><td> 0,95/0,98</td><td> 497,2/487,0</td><td>j 6.2 / 8.9</td><td> -572,5/566,9</td><td> 2,2/2,9</td><td>«η 00 ο</td><td>Green A</td>

<td></td><td>O CM 1-M</td><td>CM O co</td><td> 40</td><td> 0,10</td><td> 0,07</td><td>LO cn O</td><td> 53/55</td><td> 9/10</td><td> 00</td><td>cn</td><td> 45</td><td> 1,2/1,2</td><td> 505,5/498,6</td><td> 4,4/4,2</td><td> 487,9/478,1</td><td> 7,4/14,6</td><td>c e » O</td><td>Green A</td>

<td></td><td>Tin / antimony oxide thickness (nm)</td><td>Between Coating Oxide</td><td>The thickness of the coating (nm)</td><td>Sb / Sn ratio in the coating</td><td>Sb / Sn ratio among constituent reactants</td><td>Diffusion (%)</td><td>TL (%) [light source C]</td><td>1 RL (%) (coated side) [light source A / C]</td><td>RL (%) (unpainted page) [light source C]</td><td>TE (%) (CIE)</td><td>FS (%) (coated side) (CIE)</td><td>TL / FS</td><td>λο at transmission (nm)</td><td>Color purity on transmission (%)</td><td>λρ on reflection from the coated side (nm)</td><td>Color purity (%) on reflection from the coated side</td><td>emissivity</td><td>The color of the glass</td>

514 055 £0

Table 4

<td>| Egl © Mn</td><td>X O 5Λ</td><td>^zx ' O 00</td><td> 0,058</td><td> 0,028</td><td>CM ice</td><td>♦ s m &lt;n</td><td>Os ice sO</td><td>CM ice 00</td><td>vs ice 00 CM</td><td>iX ice O X</td><td>SE οο iS RX</td><td>© CM ice</td><td> 499,5</td><td>wH ice TT</td><td> -550,3</td><td>© ice</td><td>CM ice ©</td><td>Green B</td><td></td>

<td>| 06 £ l</td><td>X O take</td><td>'x O O 00</td><td>00 vn O ice O</td><td>oo CM O Λ O</td><td>CM</td><td>O ice vs CM</td><td>CM e.</td><td>00 ice X</td><td>t ~ fs cn WX</td><td>Os ice CM cn</td><td>Os C ice WX</td><td>SE C ice ©</td><td>X ice cn © X</td><td>vs R &lt;</td><td>© ice vs Olympics X</td><td>X ice SE</td><td>Γ- CM ice ©</td><td>δ</td><td></td>

<td>HB ·. K * in</td><td>X O CZ3</td><td>'X' O O 00</td><td>00 VS O ice O</td><td>00 CM O ice O</td><td>CM ice</td><td>CM ice Os X</td><td>O ice 00</td><td>vs ice sO</td><td>VS ice X CM</td><td>os &lt;s O X</td><td>sO Os * rX</td><td>© CM ice</td><td>t ice © © vs</td><td>t ice "X ·</td><td>00 ice cn © X ·</td><td>X ice X</td><td>· r CM ice ©</td><td> &lt; 1</td><td></td>

<td>m © HI © Mn</td><td>X O • wx 03</td><td>'x O p-z O 00</td><td>00 vs O ice O</td><td>oo CM O O'</td><td>CM * 1</td><td>O ice SE</td><td>O ice Os</td><td>00 c * '</td><td>O ice cn X</td><td>ice x «η</td><td>CM X ice + x</td><td>iX , X «p , X</td><td>© ice sO Olympics X</td><td>CM ice CM</td><td>CM ice VS Olympics 1</td><td>© ice vs</td><td>c- ~ CM ice ©</td><td> «3 2</td><td></td>

<td>s WEA fo ^ FSI · 'HH</td><td>X O • ^ x 03</td><td>O SE</td><td>cn v » O ice O</td><td>00 CM O ice O</td><td>vs O rs O</td><td>CM OO CM</td><td>CM C '·'</td><td>© _ v?</td><td>00 ice «η + x</td><td>X ice X cn</td><td>vs Γ ice RX</td><td>CM 00 ice ©</td><td>© ^ x Os X</td><td>00 ice vs</td><td>© ice CM 00 X ·</td><td>© ice 00 + x</td><td>© CM ice ©</td><td>1 δ - ts 1¾</td><td></td>

<td>Mo</td><td>X O 03</td><td>'X' O O SE</td><td>m vs O ice O</td><td>oo CM O ice O</td><td>vs SE ©</td><td>ice O sO</td><td>X • p 00</td><td>00 ice C</td><td>R ** X ice cn cn</td><td>CM rs r X</td><td>CM oo R-H</td><td>00 CM fS</td><td>© ice sO © vs</td><td>cn ice CM</td><td>© • p X 00 X ·</td><td>oo ice vs</td><td>© CM ice ©</td><td>A 1</td><td></td>

<td>l</td><td>X O 5Λ</td><td>'X' O SE</td><td>cn vs O O</td><td>oo CM O iS O</td><td>«η SE ice O</td><td>Γ ice • n wn</td><td>CM ice 00</td><td>cn f&gt;</td><td>m ice 00 CM</td><td>SE • p cn rf</td><td>O © ice CM</td><td>t ~ CM ice + x</td><td>CM sO © vs</td><td>RX ice cn</td><td>CM ♦ s X 00 X</td><td>CM ice SE</td><td>© CM ice ©</td><td> &lt; 1</td><td></td>

<td>jh</td><td>X O • ** x 03</td><td>c? O s' O sO</td><td>cn «η O ice O</td><td>oo CM O ice O</td><td>vs SE O'</td><td>00 ice 00 sO</td><td>Os • p 00</td><td>Os ice 00</td><td>00 r » O «η</td><td>cn ice δ</td><td>vs cn ice</td><td>vs ▼ »x in &lt; rX</td><td>© ice X CM VS</td><td>vs ©</td><td>© ice CM 00 X</td><td>vs ice X</td><td>© CM ice ©</td><td>o 2</td><td></td>

<td> |</td><td>Ό • g tO op o0 sx * 53 1 * 3 s</td><td>z m p © 32 O O Ό C0 C &lt;u M * 53 1 * 53 s</td><td>«3 O £ * 53 ^ 3 • rH O 1 rH SS S &lt;2 c 03 03</td><td>* § 1 .Si Ό 5 3 * § § S il &lt;2 e έ · 8 os xä • 5 © 03 C</td><td>«3 O • wX CO s ♦ wX Q</td><td>O JS 33 32 C0 O 5 O\ u hrs</td><td>'X' Ό 3 Ό δ³3 X p-z £</td><td>s • xx ΚΛ Ό g³»4 ω X O 0^s</td><td>A u g s</td><td>S ο ί CO g * 53 . © 03 Ρη</td><td>ω s</td><td>03 § hrs</td><td>c © • * x S3 1 Ό · £ 5</td><td>g § • wx CO CO Ί IN Ό · £ 1 IN tu.</td><td>CÖ TJ J * 53 δ Ό 1 § O Ό • s δ Q * S * &lt;«Β</td><td>1 1 © A 2 · £ δ X to X p Ö * 53 : 3 δ fe TJ</td><td>2 Έ co co ii</td><td>in CO Ouch CO o Q</td><td></td>

514 055

2-|

Table 5

<td>«« · · » K / yX £</td><td>O</td><td>O ϊλ</td><td>90 (ca)</td><td> 0,037</td><td> 0,028</td><td>CM fairy</td><td> 56,4</td><td>co fairy 00</td><td>Os fairy sO</td><td> 30,6</td><td> 45,4</td><td>00 fairy</td><td>xt CM fairy</td><td> 543,7</td><td>• n fairy ro</td><td> 507,0</td><td> 1,0</td><td> 0,23</td><td>Green B</td>

<td colspan="2">P4W</td><td>X O iZ</td><td>90 (ca)</td><td> 0,037</td><td> 0,028</td><td>CM fairy</td><td> 26,9</td><td>CM fairy r</td><td>00 fairy</td><td>SE fairy τ | "</td><td> 33,6</td><td>ro fairy</td><td>SE t O'</td><td> 502,7</td><td> 3,6</td><td> 491,8</td><td>CM fairy</td><td> 0,23</td><td>Between- gray</td>

<td colspan="2">lli o ESfiEa |||| Ι ^ ·</td><td>X O • wX CO</td><td>90 (ca)</td><td> 0,037</td><td> 0,028</td><td>cm fairy f "4</td><td>Olympics fairy → 4 »n</td><td>fairy 00</td><td>SE fairy sO</td><td>fairy SE CM</td><td> 42,0</td><td> 2,00</td><td>CM fairy</td><td> 535,9</td><td>ro</td><td> 505,1</td><td>fairy</td><td> 0,23</td><td>Green A</td>

<td colspan="2">111 o mi'i ·</td><td>X O • fM ΐΛ</td><td>90 (ca)</td><td> 0,037</td><td> 0,028</td><td>CM fairy</td><td> 64,2</td><td>00 fairy 00</td><td>r fairy Γ</td><td> 47,2</td><td> 57,7</td><td>SE ro fairy</td><td>O</td><td> 1 568,6</td><td>fairy co</td><td> 549,3</td><td>co fairy co</td><td> 0,23</td><td>Clear</td>

<td>hrs Å</td><td> 290</td><td>X O • fm CO</td><td>80 (ca)</td><td> 0,038</td><td> 0,028</td><td> 0,82</td><td> 28,7</td><td>O fairy 00</td><td>CM fairy V »</td><td>SE fairy sO Ή</td><td> 34,9</td><td></td><td>co oo fairy O</td><td> 498,5</td><td> 3,3</td><td> 507,2</td><td>one fairy F 'X</td><td> 0,28</td><td>Between- gfo_</td>

<td>&lt;4SA (in</td><td> 290</td><td>X O • ^ 4 CO</td><td>80 (ca)</td><td> 0,038</td><td> 0,028</td><td> 0,82</td><td>O fairy Fe ** 4 SE</td><td>CM fairy Olympics</td><td> 8,3</td><td> 34,7</td><td> 48,3</td><td>F H</td><td>Γ CM fairy</td><td> 549,4</td><td>~ C CM</td><td> 508,9</td><td>sO fairy Os</td><td> 0,28</td><td>Green B</td>

<td>&gt; 't' 5 £ «M« w</td><td> 290</td><td>X O • F * ( CO</td><td>80 (ca)</td><td> 0,038</td><td> 0,028</td><td> 0,82</td><td> 56,7</td><td>O Os</td><td> 8,0</td><td> 29,5</td><td> 44,5</td><td>O Olympics fairy</td><td>Γ CM fairy → 4</td><td> 538,8</td><td>O\ cf</td><td> 508,6</td><td>fairy O</td><td> 0,28</td><td>Green A</td>

<td>? g ^ SXsÄt</td><td> 290</td><td>X O CO</td><td>80 (ca)</td><td> 0,038</td><td> 0,028</td><td> 0,82</td><td> 70,2</td><td>O fairy O</td><td>«η fairy Os</td><td> 54,3</td><td>O fairy co SE</td><td>O co fairy</td><td>"" 4 fairy FEH</td><td> 581,3</td><td>Os fairy CM</td><td> 510,3</td><td>fairy OO</td><td> 0,28</td><td>Clear</td>

<td>KpWZj * z * A? . ·&gt; &gt; 8 w Å ιΐί ™; iSSSii »£ §; $$ B 1111 m A</td><td>Tin / antimony oxide thickness (nm)</td><td>Between Coating Oxide</td><td>'5' • 8 3 O τ? ca § 4 · 4 "in 1 'O</td><td>Sb / Sn ratio in the coating</td><td>Sb / Sn ratio among constituent reactants</td><td>Diffusion (%)</td><td>TL (%) [light source C]</td><td>RL (%) (coated side)</td><td>RL (%) (unpainted page)</td><td>TE (%) (CIE)</td><td>FS (%) (coated side) (CIE)</td><td>TL / TE</td><td>CO o</td><td>λβ at transmission (nm)</td><td>Color purity on transmission (%)</td><td>λρ on reflection from the coated side (nm)</td><td>Color purity (%) on reflection from the coated side</td><td>emissivity</td><td>The color of the glass</td>

514 055

22j