PL179769B1 - Glass panel exhibiting antisolar properties for glazing windows and method of making same - Google Patents

Abstract

In the present invention, there is disclosed a glazing pane exhibiting advantageous properties as far as solar radiation screening is concerned, said pane comprising a vitreous substrate bearing an at least 400 nm thick, sprayed, pyrolytic tin-antimony oxide coating with a Sb/Sn molar ratio of 0.05 to 0.5. The coated substrate has a light transmission (TL) of less than 35 percent and selectivity (TL/TE) of at least 1.3. In the invention, there is also claimed the use of the above-described glazing pane as a vehicle roof window.

Description

The present invention relates to a glazing pane with solar control properties and a method of manufacturing such a pane.

Reflective, transparent, solar control glazing has become useful materials for architects to use on the exterior facades of buildings. Such panes make an aesthetic impression, reflecting the close surroundings, and because they are available in many colors, they create great design possibilities. Such glazing is also technically advantageous as it provides building occupants with protection from solar radiation through reflection and / or absorption, and by eliminating the glare effects of intense solar radiation and providing an effective shield against glare, increasing optical comfort and reducing eye fatigue.

From a technical point of view, it is desirable that too much of the total incident solar radiation does not pass through the glazing, so that the interior of the building does not overheat in sunny weather. The transmission of total incident solar radiation can be determined by the "solar factor". The term "solar coefficient" as used herein means the sum of the total energy directly transmitted and the energy that has been absorbed and re-radiated on the other side of the glazing as part of the total radiant energy incident on the coated glass.

Another important application of reflective, transparent, solar-controlling glazing is in vehicle glazing, especially in cars or railroad cars, where the goal is to protect passengers from solar radiation. In this case, the main energy factor taken into account is Total Direct Transmitted Energy (TE), since the energy that is internally absorbed and re-emitted is dissipated by vehicle motion. Thus, in the case of vehicle glazing, it is a prime objective that they have a low TE value.

The properties of the coated substrate as discussed herein are based on the standard definitions of the International Commission on Illumination-Commission Internationale de 1'Eclairage ("CIE").

The standard illuminants quoted here are: CIE Illuminant C and Illuminant A. Illuminant C represents average daylight with a color temperature of 6,700 ° K. Illuminant A is Planck radiator radiation at approximately 2856K.

"Light transmission coefficient" (TL) is the luminous flux transmitted through a substrate, expressed as a percentage of the incident flux.

"Light reflectance" (RL) is the luminous flux reflected from a substrate, expressed as a percentage of the incident flux.

The "selectivity" of coated glass for building glazing is the ratio of the light transmission factor to the solar factor (TL / FS).

The "purity" (p) of a substrate color refers to the excitation purity as measured by Illuminant C. It is specified on a linear scale where a specific white light source has a purity of zero and a pure color has a purity of 100%. The purity of the coated substrate is measured on the opposite side of the coating.

"Refractive Index" (n) is defined in CIE International Lighting Vocabulary, 1987, p. 138.

"Dominant wavelength" (Zd) means the peak wavelength in terms of transmission or reflection by a coated substrate.

"Emissivity" (ε) means the ratio of the energy emitted by a given surface at a given temperature to that of a perfect emitter (black body with emissivity 1.0) at the same temperature.

Many technologies for producing coatings on a glassy substrate are known, including pyrolysis. Pyrolysis generally has the advantage of producing a hard coating that eliminates the need for a protective layer. The pyrolytic coatings have good anti-corrosive properties and good abrasion resistance. This is assumed to be related in particular to the deposition process of the coating material on the hot substrate. In general, pyrolysis is cheaper than alternative vacuum sputtering processes.

179 769 and especially in terms of industrial investment. Deposition of the coatings by other techniques, such as vacuum spraying, for example, leads to products with very different properties, in particular lower abrasion resistance and random different refractive indices.

A great variety of glass coating materials have been proposed and with many different desired glazing properties. Tin oxide, SnOi, is commonly used, often in combination with other materials such as metal oxides.

GB 1,455,148 relates to a method of pyrolytically forming a coating on a substrate of one or more oxides, primarily by spraying metal or silicon compounds, to modify the light transmission and / or reflection from the substrate or to impart antistatic or electrical conductivity properties. Specific examples thereof include ZrO _2, SnOj, Sb2O3, T1O2, CO3O4, C CTY, S1O2, and mixtures thereof. Tin oxide (SnO2) is considered to be beneficial because of its hardness and antistatic or electrical conductivity. GB 2,078,213 relates to a sequential spraying method for pyrolytically forming a coating on a glassy substrate, in particular using tin oxide and indium oxide as the main components of the coating. When the precoating metal used is tin chloride, it is preferably admixed with a precursor selected from ammonium bifluoride and antimony chloride to increase the electrical conductivity of the coating.

It is also known that if the tin oxide coating is produced by pyrolysis of SnCU, the presence of a dopant such as antimony chloride SbCl ₅ mixed directly with tin chloride SnCU improves the absorption and reflection of some of the near infrared solar radiation.

The object of the present invention is a pyrolytically produced solar control glazing unit.

We have found that this and other useful purposes can be achieved by using chemical vapor deposition (CVD) in a pyrolytic coating involving tin and antimony oxides with a specific relationship to one another.

Thus, a first aspect of the present invention relates to a glazing unit consisting of a glass substrate supporting a tin / antimony oxide coating layer containing tin and antimony in an Sb / Sn molar ratio of 0.01-0.5, said layer the coatings are produced pyrolytically by chemical vapor deposition and the coated substrate thus has a solar factor FS of less than 70%.

Preferably, the substrate is in the form of a ribbon of a vitreous material such as glass or other rigid, transparent material. Considering that some of the incident solar radiation is absorbed by the glass, especially in an environment where it is exposed to strong and long-term solar radiation, which has the effect of heating the glass, this may in turn require that the glass be toughened beforehand. However, the durability of the coating allows the glazing to be mounted with the coated side outwards, thus reducing the heating effect.

Preferably, the substrate is made of colorless glass, although the invention also encompasses the use of colored glass as the substrate.

The Sb / Sn molar ratio in the coating layer is preferably at least 0.03, in particular at least 0.05, which provides a high level of absorption. On the other hand, said ratio is preferably less than 0.21 in order to obtain a high value of the light transmission coefficient (TL ·). The most preferred ratio is less than 0.15 because above this level the coating layer exhibits excess absorption combined with low selectivity.

The coated substrates of the present invention have a favorable light reflectance (RL) of less than 11%. Architects' low light reflection from building glass is highly appreciated by architects. This avoids the blinding glare of the glass in close proximity to the building.

It may be useful to prevent an interaction between the substrate glass and the tin / antimony oxide coating layer. For example, it was found that pyrolytically formed

The tin oxide coating of tin chloride on soda-lime glass, sodium chloride formed by the reaction of the glass with the pre-coating material or its reaction products, tends to penetrate the coating, leading to fogging of the coating.

Thus, preferably, an intermediate haze reducing layer is provided between the substrate and the tin / antimony oxide coating layer. The haze-reducing layer may be pyrolytically formed in an incomplete oxidation state by contacting the substrate in the subcoating chamber with the subcoating precoat in the presence of insufficient oxygen to fully oxidize the subcoating material. The expression "under-oxidized material" as used herein means an oxide with a lower valency of a multivalent element (for example, VO2 or TiO), as well as an oxide that contains oxygen "holes" in the structure: an example of the latter is SiO _x . where x is a number less than 2, which may have the general structure of S1O2, but has some "holes" that could be filled with oxygen in the dioxide.

Preferably, the haze-reducing coating layer consists of silicon oxide with a geometric thickness of about 100 nm. The presence of a silicon oxide subcoating on the soda-lime glass inhibits the migration of sodium ions from the glass, either by diffusion or otherwise into the tin / antimony oxide coating layer, during the formation of the outer coating or during subsequent high temperature heat treatment.

Alternatively, the subcoating may be an "antireflection" subcoating, such as an oxidized aluminum / vanadium layer as described in GB 2,248,243.

The glazing panes of the present invention have a solar factor of less than 70%, preferably less than 60% and in some cases less than 50%. If the glazing units according to the present invention are positioned with the coated surface towards the outside, i.e. towards the energy source, then they should preferably have a solar factor of less than 60%. In general, the orientation of the coated surface towards the light source improves the solar factor compared to the opposite. In those parts of the world where there is a lot of sunshine, it is necessary to use glass with a solar factor of less than 50% in buildings. In the case of vehicle roofs, an even lower solar factor may be desirable.

One of the methods of ensuring low solar factor is the commonly used colored glass, both in building and vehicle windows. When comparing the effectiveness of the coating layers, the different types of glass to which the coating is applied should be taken into account. Thus, in one example of the present invention, a coating on a clear glass gives a solar factor of 63%, while an identical coating on green glass produces a solar factor of 44.5%.

It is also desirable that the glazing also transmits a reasonable proportion of visible radiation to produce natural lighting inside a building or vehicle and to provide users with good visibility outside. Thus, it is desirable to increase the selectivity of the coating, i.e. to increase the ratio of the light transmission to the solar factor. In fact, it is preferable to achieve the maximum selectivity possible.

In general, it is preferred that the Light Transmission Index (TL) of the glazing of the present invention is 40-65%. However, a glazing with a light transmission factor of less than 40% can be used as a roof glass in vehicles.

Preferably, the tin / antimony oxide coating is 100-500 nm thick. Thick tin / antimony oxide layers, and especially those with a low Sb / Sn molar ratio, can provide a quick advantageous combination of a low solar factor with low emissivity. Another way to obtain this combination is to deposit, on the tin / antimony oxide layer of the present invention, a low emissivity tin oxide layer doped with, for example, fluorine. However, this is not convenient as it requires another layer to be deposited, which is time consuming and costly.

Essentially, another way to achieve the combination of low solar factor and low emissivity is to form a tin / antimony oxide layer in admixture with an agent such as fluorine. For example, GB patent specification 2200139

179 769 relates to a method of producing a pyrolytic tin oxide layer by spraying with a solution which, apart from the tin precursor, additionally contains compounds, as a result of which the resulting coating will contain fluorine and at least one of the elements: antimony, arsenic, vanadium, cobalt, zinc, cadmium, tungsten, tellurium and manganese.

Thus, for example, a coating can be formed from reagents containing tin, antimony and fluorine in a ratio of Sb / Sn = 0.028, F / Sn = 0.04. However, the presence of fluorine has been found to hinder the penetration of antimony into the coating more than it effectively reduces emissivity. For example, reagents containing antimony and tin in a ratio of Sb / Sn = 0.028 give a coating with a ratio of Sb / Sn = 0.057, while the same reagents with the addition of a fluorine-containing reagent in an amount such that the ratio F / Sn = 0.04. they give a coating with an Sb / Sn ratio of about 0.038.

The present invention offers the advantage that a Solar Coefficient (FS) of less than 60%, an emissivity of less than 0.4 (preferably less than 0.3) and a Light Transmission Coefficient (TL) of greater than 60% are simultaneously achieved. Thus, the coated product fulfills two important functions. In winter, it retains heat in the building due to its low emissivity. In summer, it prevents the penetration of solar heat into the building due to the low solar factor, which prevents the building from overheating. This is achieved in particular by using coatings with an Sb / Sn ratio between 0.01 and 0.12, in particular 0.03-0.07, and a thickness of 100-500 nm, for example 250-450 runes.

Preferably, the tin / antimony oxide layer is an outward facing layer and the glass pane has only one such tin / antimony oxide layer.

However, in order to achieve some desirable optical properties, one or more further layers may be applied, either by pyrolysis or by other coating methods. It should be noted, however, that the tin / antimony oxide layer produced by pyrolysis has sufficient mechanical durability and chemical resistance to be a suitable outward facing layer.

The panes according to the present invention may be installed individually or as sets. Although the coated side of the glass can be mounted as the inside of the glass so that the coating is not exposed to changing weather conditions which can shorten its life very quickly due to contamination, physical damage and / or oxidation, the coatings produced by pyrolysis can be exposed. to weathering due to its greater mechanical resistance than coatings produced by other methods. The coatings of the present invention can be used in glued glazing, for example when the surface is coated with the inner surface of the outer layer.

In accordance with a second embodiment of the present invention, there is provided a method of making a glazing pane having a tin / antimony oxide layer prepared by chemically depositing vapors from a mixture of reactants on a vitreous substrate, said mixture of reactants containing a source of tin and antimony having a Sb / mole ratio. Sn 0.01-0.5 and the coated substrate thus produced has a solar factor FS of less than 70%.

If it is desired to produce a pyrolytic coating on a flat glass pane, it is preferably done on freshly formed glass. It is economically viable to do so, since there is no need to reheat the glass for pyrolysis reactions, and the quality of the coating is then also advantageous since the glass surface is kept in its original state. Thus, preferably, said subcoating pre-material is applied to the upper surface of a hot glass substrate, which is a freshly formed flat glass.

Thus, the glazing panes of the present invention may be manufactured as follows. Each step of the pyrolytic coating formation can be carried out at a temperature of at least 400 ° C and ideally between 550 ° C - 750 ° C. The coatings can be produced on a glass sheet that runs in a tunnel kiln, or on a glass ribbon during its manufacture while it is still hot. The coatings can be produced inside the lehr, which is downstream of the glass ribbon forming device, or inside a float tank on the top surface of the glass ribbon, while the latter floats in a molten tin bath.

179 769

The coating layers are applied to the substrate by chemical vapor deposition (CVD). This is a particularly advantageous method as it ensures a regular layer thickness and composition. Such uniformity of the coating is particularly important when the product is to be used to cover a large area. CVD has a great advantage over the pyrolysis process using spraying of liquid reagents. In the spraying process, it is difficult to control both the gas phase process and achieve a good uniform film thickness. In addition, the pyrolysis of the spray liquid is substantially limited to the formation of oxide coatings such as SnO2 and TiClb. It is also difficult to produce multilayer coatings using liquid spraying, since each layer deposition causes the substrate to cool significantly. Moreover, chemical vapor deposition is more economical because of the raw materials leading to less waste.

The CVD film product is physically different from the spray film product. It should be noted that the spray coating shows traces of the spray droplets and the path of the spray gun, which is not the case with CVD.

To form each of the coatings, the substrate in the coating chamber is contacted with a gaseous medium containing a mixture of gaseous phase reactants. The coating chamber is fed with the gaseous stream of the reactant through one or more nozzles, the length of which must be at least the width of the surface to be coated.

Methods and devices for producing such a coating are described, for example, in French Patent No. 2,348,166 (BFG Glassgroup) or in French Patent Application No. 2,648,453 Al (Glaverbel). These methods and devices lead to particularly strong coatings with favorable optical properties.

Two successive nozzles are used to form tin / antimony oxide coatings. A mixture of reagents containing a source of tin and antimony feeds the first nozzle. When the mixture consists of chlorides, liquid at ambient temperature, it becomes vaporized in a stream of anhydrous carrier gas at elevated temperature. The vapor phase conversion is facilitated by the atomization of these reactants in the carrier gas. To generate the oxides, the chlorides are contacted with the steam supplied through a second nozzle. The water vapor is superheated and also injected into the gaseous carrier.

Preferably nitrogen is used as the carrier gas, which is substantially inert. Nitrogen is a sufficiently inert gas for this purpose and is otherwise inexpensive compared to noble gases.

S1O2 or SiO _x silicon oxide subcoats can be deposited from silane S1H4 and oxygen as described in GB 2234264 and GB 2247691.

If a glass substrate coated with a non-fully oxidized coating is exposed to an oxidizing atmosphere for a sufficiently long period of time, complete oxidation of the coating can be expected and thus its desired properties will be lost. Therefore, such a subcoating is covered with a tin / antimony oxide coating layer while it is not yet fully oxidized and the substrate is still hot, so as to keep the subcoating incomplete oxidation. The length of time a glass substrate freshly coated with the subcoating may be exposed to an oxidizing atmosphere such as air before being finally coated with the topcoat, without compromising the properties of the subcoating, will depend on the temperature of the glass during such exposure and on the type of subcoating.

Preferably, a reducing atmosphere is present around said subcoating chamber. Conditions are created to prevent atmospheric oxygen from entering the subcoating application chamber, which allows a better control of the oxidation conditions in that chamber.

The oxygen required for the subcoating reaction can be supplied in the form of pure oxygen, but this increases costs unnecessarily and according to the present invention, it is preferable to supply air to the chamber to supply oxygen therein.

It has been found that the Sb / Sn molar ratio which is desired in the reagent mixture does not always correspond to the ratio that is required in the tin / antimony coating layer.

179 769

Preferably, the tin source is selected from SnClU, monobutyric trichlorocin ("MBTC") and mixtures thereof. The antimony source is selected from SbCl ₅ , SbCl ₃ , organic antimony compounds, and mixtures thereof. Examples of suitable material sources are: Sb (OCH ₂ CH ₃ ) ₃ , Cl _; 7Sb (OCH ₂ CH ₃ ) i3, Cl ₂ SbOCHClCH ₃ , Cl ₂ SbOCH ₂ CHCH ₃ Cl and Cl ₂ SbOCH ₂ C (CH ₃ ) ₂ Cl.

In the following, the invention will be described in detail in the following non-limiting examples.

In the examples below, the Sb / Sn molar ratio in the coating layers was determined by X-ray analysis in which the respective elements were compared. This technique is not as precise as chemical determination, because the similarity of antimony and tin make them respond similarly to X-rays. The ratio of the measured amount of the observed signals of the respective elements gives an approximate molar ratio.

As can be seen from some examples, colored glass is used rather than clear. The properties of the respective types of colored glass are shown in Table 1 below. In all cases, the properties of the glass were measured on samples 4 mm thick, this being the thickness of the glass used in all examples except for Examples 17 and VII (for which the thickness is shown in Table 2). The symbols in the table headings have the meanings given above.

Regarding the calculation of the solar factor, it should be noted that for a light transmission factor (TL) of less than 60%, the effect of low emissivity is not negligible and should be taken into account, as the solar factor also decreases as emissivity decreases.

Table 1

Type of glass Green A Green B Grey Medium gray Dark gray λ ₀ transmission (nm) [Illuminant: C / A] 505.4 / 508.5 504.9 / 508.4 470.1 / 493.9 493.2 / 502.7 478.9 / 502.7 Purity (%) 2.9 / 3.4 2.1 / 2.5 1.5 / 0.8 5.6 / 5.1 2.6 / 1.8 TL (%) [Illuminant · C / A] 72.66 / 71.12 78.44 / 77.20 55.65 / 55.56 36.80 / 35.76 22.41 / 22.30 TE (%) (CIE) 44.0 53.2 56.9 25.9 31.11 FS (%) coated side (CIE) 56.8 62.9 66.3 43.4 47.3 TL / FE [Illuminant: C] 1.28 1.25 0.84 0.85 0.47

Example I

On colorless soda-lime glass moving at high speed? meters per minute along the float chamber, a subcoat is produced in a coating station located along the float chamber where the glass is at a temperature of about 700 ° C. Nitrogen, silane with a partial pressure of 0.25% and oxygen with a partial pressure of 0.5% (ratio 0.5) are introduced through the feed line. A 100 nm thick SiO ₂ coating is obtained.

The 6 mm thick subcoated substrate is then immediately coated by CVD pyrolysis using an apparatus consisting of two successive nozzles. A reagent containing a mixture of SnClU as the tin source and SbCfi as the antimony source is used. The Sb / Sn molar ratio in the mixture was about 0.2. The reagent mixture is vaporized under a stream of anhydrous nitrogen gas at a temperature of about 600 ° C and introduced into the first nozzle. The vapor phase conversion is facilitated by the atomization of these reactants in the carrier gas. The second nozzle is fed with superheated steam. The steam is superheated to about 600 ° C and is also injected into a carrier gas which is air heated to 600 ° C. The gas flow rate (gas

179 + 769 carrying reagent) in each nozzle is 1 ^m3 / cm width of substrate per hour at the process temperature.

The coating is achieved to a geometric thickness of the tin / antimony oxide coating on the subcoated substrate of 185 nm.

Example II-VII

In Examples 2 - 7 the procedure as in Example 1 was followed, changing parameters such as the mixture of reagents, the presence or absence of an oxide subcoating, the Sb / Sn ratio in the coating and in the reagent mixture, and the thickness of the glass substrate. For example, compared to Example 1, no subcoating was used in Example 2 and the tin / antimony oxide coating layer was 210 nm thick. The reagent mixtures were as follows:

Example II and III: mixtures the same as in Example I (but with a lower proportion of reactants in the carrier gas in Example III);

Example IV: MBTC and Ch ₇ Sb (OCH ₂ CH ₃ ) and ₃ ;

Example V: MBTC and Cl ₂ ŚbOCH ₂ CHCH ₃ Chl;

Example VI: MBTC and Cl ₂ SbOCH ₂ C (CH ₃ ) ₂ Cl;

Example VII: MBTC and SbCl ₃ .

Changes in the operating parameters for Examples 1-7 and the results obtained are shown in Table 2.

The glass panes for glazing in Examples ΠΙ - VII had a pleasant blue color: the dominant wavelength of the transmitted visible light is 470-490 nm in the forest.

In Example 6, a glazing was obtained which had a low FS solar factor and low emissivity.

In one variation of Example VI, the SiO ₂ subcoating was replaced with an antireflection SiO _x subcoating according to the procedure used in GB 2247691. In another embodiment, the SiO ₂ subcoating was replaced with an oxidized aluminum / vanadium layer according to the procedure used in GB 2248243. In variants, the glass did not have a purple appearance in reflection from the uncoated side.

Example VIII

Colored "Green A" float glass, advancing at 7 meters per minute along the float chamber, is subcoated in a coating station along the float chamber at a temperature of about 700 ° C.

Nitrogen, silane with a partial pressure of 0.2% and oxygen with a partial pressure of 0.5% (ratio 0.55) are fed through the feed line. A SiO _{x x} coating of approximately 1.8, with a refractive index of approximately 1.7, is obtained. The thickness of the obtained coating was 40 nm.

The 4 mm thick subcoated substrate is then coated by CVD pyrolysis. A reagent containing a mixture of MBTC as the tin source and ClijSb (OCH ₂ CH ₃ ) and _j3 as the antimony source is used. The Sb / Sn molar ratio of the mixture was approximately 0.195 (weight ratio 0.2). The reagent mixture is vaporized in a jet of dry air fed to the nozzle at a temperature of about 200 ° C. The conversion to the vapor phase is facilitated by trufluoroacetic acid. The F / Sn ratio in the reagent mixture of these examples was 0.04.

The changes in operating parameters and the results obtained are shown in Table 4 for Examples XV-XXII and in Table 5 for Examples XXIII-XXX. The silicon oxide SiO _x used in Examples 15 to XXX had an x value of approximately 1.8.

179 769

Table 2

1ΙΛ 110 ABOUT 70 0.18 0.20 low 55.0 13.7 59.6 0.92 479.3 and 10.3 1 577.0 33.1 0.79 1 / Ί ΙΛ 445 d iZ ABOUT 0.06 0.10 1 low ' 47.5 6.6 \ 47.2 1.01 483.0 8.0 490.0 6.0 0.25 > 105 SiO ₂ 70 0.15 _____ ’________ 1 0.20 low 61.6 Ζ.Ί1 62.2 0.99 481.0 8.7 557.6 35.2 θ ' ι / Ί IV 120 SiO ₂ 70 0.19 0.20 low 51.0 12.0 58.4 0.87 478.8 _ '___ 11.5 579.5 35.0 0.84 • Ti III 105 lack ABOUT 0.46 0.20 4.36-7.01 65.5 18.8 66.0 0.99 480.1 4.9 575.3 l'6l ABOUT AND WHAT 210 lack about 0.48 0.20 2.09 I 44.3 12.0 56.9 0.78 -560 3.9 494.5 θ ' Λ What - 185 SiO ₂ 100 0.48 0.20 And 0.07 45.7 ABOUT 55.3 0.83 587.5 3.4 472.3 36.9 > 0.7 What Example Thickness of tin / antimony subcoating (nm) Oxide subcoating Subcoat thickness (nm) Sb / Sn ratio in the shell Sb / Sn ratio in the reagents Haze (%) TL (%) RL (%) (coated side) FS (%) (coated side) (CIE) TL / FS λ _ΰ transmission (nm) Color Purity in Transmission (%) X _D reflected from the coated side (nm) Color purity (%) when reflected from the coated side Emissivity Glass thickness (nm)

179 769

Table 3

XIV 470 About this 40 0.09 0.07 36 [A] 7 [A] 27 43 5.4 [A] 493.4 [A] 5.4 [A] -576.0 [A] 1.5 [A] 0.35 colorless soda-lime XIII 320 CM ABOUT 40 0.09 0.07 OT 40/41 00 0 CT 39 1.02 / 1.05 501.0 / 491.6 7.2 / 8.6 -512.5 / 513.6 15.4 / 14.5 0.44 green A πχ 470 SiO ₂ 40 0.09 0.07 00 ^ 6/6 7/7 στ στ CT 0.31 / 0.31 494.2 / 480.0 7.0 / 11.8 -555.4 / 550.1 2.1 / 6.6 0.35 dark gray IX 470 SiO ₂ 40 0.09 0.07 grade 31/32 7/7 T © OO 36 0.86 / 0.89 497.2 / 487.2 7.6 / 10.8 -576.9 / 559.8 6.0 / 1.2 0.35 green B X 320 SiO ₂ 40 0.09 0.07 0 31/32 7/7 ABOUT 25 0.76 / 0.78 494.8 / 481.9 4.9 / 8.1 -511.8 / 512.2 17.2 / 16.3 0.44 Gray XI 120 S1O2 70 0.18 0.20 θ ' 39/20 11/11 OO 25 0.95 / 0.98 497.2 / 487.0 6.2 / 8.9 -572.5 / 566.9 2.2 / 2.9 0.85 green A ΙΙΙΛ 120 ri 0 ćZ 40 0l '0 0.07 0.36 53/55 9/10 OO 45 1.2 / 1.2 505.5 / 498.6 4.4 / 4.2 487.9 / 478.1 7.4 / 14.6 0.71 green A Example Thickness of tin / antimony subcoating (nm) Oxide subcoating Subcoat thickness (nm) Sb / Sn ratio in the shell Sb / Sn ratio in the reagents Haze (%) TL (%) [Illuminant A / Illuminant C] RL (%) (coated side) [Illuminant A / C] RL (%) (uncoated side) [Illuminant C] TE (%) (CIE) FS (%) (coated side) (CIE) TL / FS X _D transmission (nm) Color Purity in Transmission (%) λ ₀ reflected from the coated side (nm) Color purity (%) when reflected from the coated side Emissivity The color of the glass

179 769

Table 4

XXII 390 about (WITH 0.058 0.028 53.1 6.9 8.2 28.5 40.1 1.86 And 1.20 499.5 1 4.1 -550.3 7.0 0.27 green B XXI About Os and tZ 0.058 0.028 l 25.0 CM ^ 00 ^ ^! 13.7 1 ... - - 32.9 1.79 1 0.76 493.4 • / γ -495.0 0.27 medium gray XX O c \ π about HIM 0.058 0.028 and ___1 (No. 49.2 about ID 24.5 40.9 1.96 ABOUT 500.7 F. -492.8 F. 0.27 green A XIX o o m X About what 0.058 0.028 61.0 what cC 00 ^ 43.0 54.7 1.42 496.0 CM CM -495.2 ABOUT <r? 0.27 colorless XVIII about CM at cZ 0.053 0.028 0.65 28.2 CM ir? 15.8 34.4 0.82 494.0 00 ur? 482.9 18.0 0.29 medium gray XVII About CM ΓΛ X O cZ 0.053 0.028 0.65 60.1 00 00 33.1 47.2 CM 00 1.28 506.0 cT 484.0 15.8 0.29 green B XVI o cm m about <Z 0.053 0.028 0.65 55.7 CM 00 28.3 43.6 2.00 1.27 506.2 cn 484.2 16.2 0.29 green A XV About CM cc 1 S1O _X About MO 0.053 0.028 0.65 68.8 ¹ 1 σγ 00 Oy oo ¹ 50.8 60.3 1.35 ęi'i 524.0 υη θ ' 428.9 14.5 0.29 colorless Example Thickness of tin / antimony subcoating (nm) | Oxide subcoating Subcoat thickness (nm) Sb / Sn ratio in the shell Sb / Sn ratio in the reagents Haze (%) TL (%) [Illuminant C] RL (%) (coated side) RL (%) (uncoated side) TE (%) (CIE) FS (%) (coated side) (CIE) TL / TE TL / FS X _D transmission (nm) Color Purity in Transmission (%) λρ reflected from the coated side (nm) Color purity (%) when reflected from the coated side Emissivity The color of the glass

179 769

Table 5

XXX 410 SiO _x 90 (approx.) 0.037 0.028 1.2 56.4 8.3 6.9 30.6 45.4 1 1.81 1.24 543.7 507.0 0'l 0.23 green B XXIX ABOUT X o ίΛ ⁹⁰ (approx.) 0.037 0.028 (No. 26.9 7.2 4.8 14.6 33.6 j 1.73 0.76 502.7 3.6 491.8 Z'I 0.23 medium gray Xxviii 410 X O ΰ5 90 (approx.) 0.037 0.028 1 1.2 51.9 8.1 6.6 26.1 42.0 2.00 1.24 535.9 3.7 505.1 0.23 green A XXVII 410 O ćZ 90 (approx.) 0.037 0.028 64.2 8.8 7.7 47.2 57.7 1.36 1.10 SD o. O 3.5 549.3 3.3 0.23 colorless XXVI 290 X o 80 (approx.) 0.038 0.028 _____1 0.82 28.7 8.0 5.2 16.6 34.9 1.71 en 00 θ ' 498.5 3.3 507.2 11.3 0.28 medium gray Xxv 290 SiO _x 80 (approx.) 00 © © 0.028 0.82 61.0 _ ___ 9.2 00 * 34.7 48.3 1.74 1.27 549.4 2.7 508.9 9.6 0.28 green B Xxiv 290 X o t / 5 (z and [qAzjd) 08 0.038 0.028 0.82 56.7 .. 9.0 8.0 29.5 44.5 1.90 1.27 538.8 2.9 508.6 10.1 0.28 green A Xxiii 290 X o 80 (approx.) 0.038 0.028 0.82 70.2 10.0 9.5 54.3 63.0 οεΊ IIT 581.3 2.9 510.3 I '8 0.28 colorless Example Thickness of tin / antimony subcoating (nm) Oxide subcoating Subcoat thickness (nm) Sb / Sn ratio in the shell Sb / Sn ratio in the reagents Haze (%) TL (%) [IluminantC] RL (%) (coated side) RL (%) (coated side) TE (%) (C1E) FS (%) (coated side) (C1E) TL / TE TL / FS λ ₀ transmission (nm) Color Purity in Transmission (%) λ ₀ reflected from the coated side (nm) Color purity (%) when reflected from the coated side Emissivity The color of the glass

179 769

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Claims (18)

Patent claims A glazing pane, characterized in that it consists of a vitreous substrate supporting a tin / antimony oxide coating layer containing tin and antimony in a molar ratio of 0.01-0.5, said coating layer being produced by pyrolysis by chemical deposition vapor and the substrate thus coated has a solar factor (FS) of less than 70%. 2. Pane according to claim The method of claim 1, wherein the Sb / Sn molar ratio is at least 0.03. 3. Pane according to claim The method of claim 2, wherein the Sb / Sn molar ratio is at least 0.05. 4. Pane according to claim The method of claim 1, wherein the Sb / Sn molar ratio is less than 0.21. 5. Pane according to claim The method of claim 1 or 4, characterized in that the Sb / Sn molar ratio is 0.01-0.12. 6. Pane according to claim The method of claim 5, characterized in that the Sb / Sn molar ratio is 0.03-0.07. 7. Pane according to claim The method of claim 1, wherein the hazy reducing coating layer is intermediate between the substrate and the tin / antimony oxide coating layer. 8. Pane according to claim The anti-haze coating layer of claim 7, wherein the haze-reducing coating layer consists of silicon oxide. 9. Pane according to claim The method of claim 1, wherein its solar factor is less than 60%. 10. Pane according to claim The method of claim 9, characterized in that its solar factor is less than 50%. 11. Pane according to claim The method of claim 1, wherein the light transmission factor (TL) is 40% - 65%. 12. Pane according to claim The method of claim 1, wherein the thickness of the tin / antimony oxide coating is 100-500 nm. 13. Pane according to claim The process of claim 12, wherein the thickness of the tin / antimony oxide coating is 250-450 nm. 14. Pane according to claim The process of claim 1, wherein the tin / antimony oxide coating layer is an outward facing coating layer. 15. Pane according to claim. The method of claim 1, wherein it consists only of a tin / antimony oxide coating layer. 16. A method for producing a glazing pane, characterized in that a tin / antimony oxide layer is chemically deposited from a mixture of reactants on a glassy substrate, said reagent mixture consisting of a tin source and an antimony source, the molar ratio of antimony to tin in said mixture is 0.01-0.5, and the coated substrate thus produced has a solar factor (FS) of less than 70%. 17. The method according to p. The process of claim 16, wherein the tin source is selected from SnCL, monobutyltrichlorocin, and mixtures thereof. 18. The method according to p. The method of claim 16 or 17, wherein the antimony source is selected from antimony chlorides, organo-antimony compounds and mixtures thereof. 179 769