FR2735123A1 - SOLAR PROTECTION WINDOWS AND METHOD FOR MANUFACTURING SUCH GLAZING - Google Patents

Abstract

The present invention relates to a solar protection glazing and its manufacturing process. The glazing comprises a vitreous material substrate carrying a tin oxide / antimony coating formed by vapor phase pyrolysis. The coating contains tin and antimony in an Sb / Sn molar ratio of 0.01 to 0.5. The coated substrate has a solar factor of less than 70%. Such glazing is used for buildings or vehicles.

Description

Sun protection glazing and method of manufacturing such glazing

  The present invention relates to a sun protection glazing and a

  method of manufacturing such a glazing.

  Transparent reflective glazing with solar protection properties is available to architects who designate them for the exterior facade of buildings. These windows reflecting the immediate environment have aesthetic qualities and, being available in several colors, constitute a source of aesthetic design. These windows also have technical advantages since they protect the occupants of a building against solar radiation by reflection and / or absorption and eliminate the effects of glare by intense sunlight, forming screen against glare, improving comfort visual

and reducing eye strain.

  From the technical point of view, it is desired that in sunshine conditions the glazing does not allow too much of the total incident solar radiation to pass in order to prevent the interior of a building from overheating. The transmission of 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 that is absorbed and re-

  radiated on the face opposite to the energy source, related to the radiation

  total energy reaching the coated glass.

  Another important application of transparent reflective solar protection glazing is in the field of vehicle glazing, especially for motor vehicles and railway cars, where their purpose is to protect the occupants of the vehicle against solar radiation. In this case the main energy factor to be considered is the total energy transmitted directly (TE), since the energy that is absorbed inside and re-radiated (AE) is dissipated by the movement of the vehicle. The main objective of the glazing of vehicles is therefore to possess a factor

TE low.

  The properties of the coated substrate described below are based on the

  standard definitions of the International Commission on Illumination ("CIE").

  The standard illuminants listed below are illuminant C and Illuminant A. Illuminant C represents an average daylight with a color temperature of 6700 K. Illuminant A represents the radiation of a Planck radiator at a temperature of about 2856 K. The "light transmittance" (TL) is the percentage of the flux

  incident light transmitted through a substrate.

  The "light reflection factor" (LR) is the percentage of the flux

  incident light reflected by a substrate.

  The "selectivity" of a coated substrate for building glazing is the ratio of light transmittance to solar factor (TIL / FS). The "purity" (p) of substrate color refers to purity. of excitation measured with Illuminant C. It is defined on a linear scale in which a defined source of white light has a purity of 0 and the pure color has a purity of 100%. The purity of a coated substrate is measured on the opposite side to the

coated side.

  The term "refractive index" (n) is defined in the Vocabulary

  International Institute of Illumination (CIE), 1987, page 138.

  The "dominant wavelength" (XD) is the wavelength peak in

  the range transmitted or reflected by the coated substrate.

  The "emittance" (ú) is the ratio of the energy emitted by a given surface at a given temperature to that of a perfect radiator (black body having a

  emissivity of 1.0) at the same temperature.

  Several techniques are known for forming coatings on a vitreous substrate, including pyrolysis. Pyrolysis generally presents

  the advantage of providing a hard coating that does not require a protective layer.

  The pyrolysis coatings have durable properties of resistance to abrasion and corrosion. This is thought to be due in particular to the fact that the process comprises the deposition of precursor on a substrate which is hot. Pyrolysis is also generally less expensive than other coating processes such as vacuum spraying, particularly in terms of investment in equipment. Coating deposition by other methods, for example by vacuum spraying, leads to products with very different properties, particularly less abrasion resistance and sometimes a different refractive index. A wide variety of coating materials have been proposed for glazing, to meet different desired properties. Tin oxide, SnO2, is widely used, often in combination with other materials such as other

metal oxides.

  British Patent 1,455,148 teaches a method of pyrolytically forming a coating of one or more oxide (s) on a substrate by sputtering

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  composed of a metal or silicon, so as to modify the light transmission and / or the light reflection of the substrate, or confer anti-static properties or electrical conductivity. Examples of specified oxides include ZrO 2, SnO 2, Sb 2 O 3, TiO 2, Co 3 O 4, Cr 2 O 3, SiO 2 and mixtures thereof. Tin oxide (SnO2) is considered advantageous because of its hardness and the ease with which it confers antistatic properties and electrical conductivity. British Patent 2,078,213 relates to a sequential spraying process for pyrolytically forming a coating on a vitreous support and relates primarily to oxide

  of tin or indium oxide as the main constituents of the coating.

  When its metal precursor is tin chloride, it is advantageously doped with a precursor chosen from ammonium bifluoride and chloride.

  of antimony to increase the electrical conductivity of the coating.

  It is also known that when a tin oxide coating is formed by pyrolysis of SnCl4, the presence of a dopant such as antimony chloride SbCl5, directly mixed with tin chloride SnCl4, improves the absorption and

  reflection of a part of the solar radiation of the near infrared.

  One of the objects of the present invention is to provide, using the

  pyrolysis, a glazing with solar protection properties.

  It has been discovered that this and other advantages can be achieved by the use of the CVD technique to apply a pyrolytic coating comprising tin and antimony oxides in

a specific report given.

  Therefore, according to its first aspect, the present invention relates to a glazing unit comprising a vitreous material substrate having a tin / antimony oxide coating, characterized in that the coating is formed by vapor phase pyrolysis and contains tin and antimony in a Sb / Sn molar ratio of between 0.01 and 0.5, and in that the substrate bearing the coating has a solar factor

(FS) less than 70%.

  The substrate is preferably in the form of a ribbon or sheet of vitreous material, such as glass or other transparent rigid material. Given the proportion of incident solar radiation that is absorbed by the glazing, particularly in environments where it is exposed to intense or long-lasting solar radiation, there is a heating of the glazing which may require that the substrate be subjected to a treatment reinforcement. However, the durability of the coating makes it possible to mount the glazing with its coated face facing outwards, which reduces

the warming effect.

  Preferably the substrate is made of clear glass, although the invention

  extends to the use of colored glass as a substrate.

  The Sb / Sn molar ratio in the coating layer is preferably at least 0.03, preferably at least 0.05. This helps to ensure a high level of absorption. On the other hand, said molar ratio is preferably less than 0.21 in order to obtain a high level of the light transmission factor (TL). Preferably, the ratio is less than 0.15, since beyond this level the

  coating has an excessively high level of absorption as well as poor selectivity.

  Coated substrates according to the invention offer the advantage of a light reflection factor (LR) of less than 11%. This low level of reflection is preferred by architects for building glazing. It avoids that the glazing causes

  dazzling in the vicinity of the building.

  It may be useful to avoid interaction between the substrate glass and the tin oxide / antimony coating layer. By way of example, it has been noted that during the pyrolytic deposition of a tin oxide coating from tin chloride on a soda-lime glass substrate, sodium chloride resulting from the reaction of the glass with the coating precursor or with the reaction products may become incorporated into the coating, and this leads to the appearance of haze in the coating. An intermediate coating layer for reducing the haze may advantageously be disposed between the substrate and the tin oxide / antimony coating layer. The void reducing layer may be formed by pyrolysis, in an incompletely oxidized state, by contacting the substrate, in a coating chamber, with an underlayer precursor in the presence of oxygen in a quantity.

  insufficient to completely oxidize the material of the sub-layer of the substrate.

  The term "incompletely oxidized material" is used herein to describe a true suboxide, i.e., an oxide of a multivalent element in a lower valence state (eg VO2 or TiO) and also to describe an oxidized material containing in its structure oxygen vacancies: an example of this latter material is SiOx or x is less than 2, which may have the general structure of SiO2 but has a

  proportion of gaps that would be filled by oxygen in the dioxide.

  Preferably the layer of a void reducing coating comprises a silicon oxide having a geometric thickness of about 100 nm. The presence of an underlayer of silicon oxide on soda-lime glass has the particular advantage of preventing the migration of sodium ions from the glass, by diffusion or in any other way, to the coating layer. tin oxide / antimony, whether during the formation of this top layer or during subsequent high temperature treatment.

  Alternatively, the underlayer may be an "anti-

  such as, for example, an oxidized alumina / vanadium layer such as

  described in patent application GB 2 248 243.

  The glazings according to the invention have a solar factor of less than 70%, preferably less than 60% and in some cases less than 50%. The preference of a solar factor of less than 60% appears when the windows according to the invention are arranged with their coated face facing outwards, that is to say toward the energy source. Generally this arrangement leads to an improved solar factor with respect to the arrangement of the glazing with the coated face opposite to the energy source. The need for a solar factor of less than 50% occurs in buildings located in parts of the world with strong sunlight. For vehicle roofs a solar factor

  even lower may be desirable.

  The use of colored glass is a way to obtain a low solar factor, and it is commonly used in both architectural glazing and automotive glazing. In comparing the effectiveness of the coating layers, it is therefore necessary to take into account the differences between the types of glass on which the respective coatings are deposited. Thus, an example of a coating according to the invention deposited on clear glass gives a solar factor of 63%, while

  equivalent coating deposited on green glass gives a solar factor of 44.5%.

  It is also desirable that the glazing also transmits a reasonable proportion of visible light in order to allow the natural illumination of the interior of a building or a vehicle and to allow its occupants to see

  outside. It is therefore desirable to increase the selectivity of the coating, i.e.

  say to increase the ratio of the transmission factor on the solar factor. In fact,

  selectivity is preferably as high as possible.

  In general, the light transmission factor (TL) of the glazing unit according to the invention is between 40 and 65%. Nevertheless, glazing having a light transmission factor of less than 40% can be used as a roof panel,

  for example a sunroof vehicle.

  Preferably, the tin / antimony oxide coating has a thickness of between 100 and 500 nm. Thick layers of tin / antimony oxide, particularly layers having a low Sb / Sn molar ratio, can provide the glazing with the advantageous combination of low solar factor (FS) and low emissivity. Another way of obtaining this combination is the deposition on the tin / antimony oxide layer according to the invention of a low-emissivity layer of doped tin oxide, for example tin oxide. doped with fluorine. This arrangement is nevertheless disadvantageous in that it requires the deposition of a layer

  extra, which is expensive in time and money.

  In principle, another way to obtain a low solar factor combined with a low emissivity is to form a tin oxide / antimony oxide coating layer containing a doping agent such as fluorine. For example, GB 2 200 139 teaches a process for forming a pyrolytic coating of tin oxide by spraying a solution which, in addition to the tin precursor, contains compounds which will give in the coating of fluorine and at least one of antimony, arsenic, vanadium, cobalt, zinc, cadmium, tungsten, tellurium

and manganese.

  Thus, for example, a coating could be formed from reagents containing tin, antimony and fluorine in the ratios Sb / Sn = 0.028, F / Sn = 0.04. It has been found, however, that the presence of fluorine has the distinct disadvantage of hindering the incorporation of antimony into the coating rather than effectively reducing emissivity. For example, the antimony and tin containing reagents in the Sb / Sn ratio = 0.028 give a coating having an Sb / Sn ratio of about 0.057, while the same reagents added a fluorine-containing reagent in a proportion such that F / Sn = 0.04 gives a coating having a Sb / Sn ratio

about 0.038.

  The invention has the advantage of simultaneously providing a solar factor (FS) of less than 60%, an emissivity of less than 0.4 (preferably less than 0.3) and a light transmittance (TL) of greater than 60%. . Therefore the coated product satisfies two important functions. In winter it keeps the heat in the building, due to its low emissivity. In summer it is opposed to the passage of solar heat in the building and thus avoids the overheating of the building, because of its low solar factor. This result is especially attained for coatings having a Sb / Sn ratio of between 0.01 and 0.12, particularly between 0.03 and 0.07, and

  a thickness of between 100 and 500 nm, for example between 250 and 450 nm.

  Preferably, the tin / antimony oxide coating constitutes an exposed layer and the glazing comprises a single layer of tin / antimony oxide coating. However, it is possible to arrange one or more other coating layers, whether by pyrolysis or by other methods, to obtain certain desired optical qualities. It should be noted, however, that the layer of tin / antimony oxide, when deposited by pyrolysis, has a durability

  mechanical and chemical resistance sufficient to form an exposed layer.

  Glazing according to the invention can be part of a single or multiple glazing. The coated surface of the glazing may be the internal surface of an outer glazing so that the coated surface is not exposed to climatic conditions which could in other cases reduce its life time by soiling,

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  physical degradation and / or oxidation, but coatings produced by pyrolysis generally have greater mechanical strength than coatings produced by other methods and can therefore be exposed to atmospheric conditions. The glazings according to the invention can also be used in laminated glass structures, for example in which the coated surface constitutes the internal surface of the

outer panel.

  The present invention, according to its second aspect, relates to a method of forming a glazing unit comprising pyrolytically depositing, on a substrate made of vitreous material, a tin / antimony oxide coating, characterized in that the deposition is carried out from a vapor phase reactive mixture comprising a source of tin and an antimony source, the tin / antimony molar ratio in the mixture being between 0.01 and 0.5 so that the substrate coated has a solar factor (FS)

less than 70%.

  When it is desired to manufacture flat glass coated with a pyrolytic layer, it is better to do it when the glass is freshly formed. This way of proceeding is advantageous from the economic point of view because it does not require the heating of the glass for the implementation of the pyrolysis reactions, and also allows a good quality of the coating, since it is formed on virgin glass . The coating precursor is therefore preferably placed in contact with a face

  superior of a hot glass substrate consisting of freshly formed flat glass.

  Glazing according to the invention can be manufactured in the following manner. Each pyrolytic deposition step can be carried out at a temperature of at least 400 C, ideally between 550 C and 750 C. The coatings can be formed on a glass sheet which moves in a tunnel oven or on a glass ribbon when of his training, while he is still hot. Coatings can be formed inside the gallery that follows the glass ribbon forming equipment or inside the float tank on the top surface of the glass ribbon while

  it floats on a bath of molten tin.

  The coating layers are applied to the substrate by chemical vapor deposition (CVD). This is a particularly advantageous method because it provides coatings of regular thickness and composition, such uniformity of the coating being particularly important when the product has to cover a large area. CVD provides many advantages over pyrolysis processes using the sprayed liquids as precursors. With spraying methods it is difficult to control the spraying process and to obtain a good uniformity of thickness of the coating. In addition, the pyrolysis of sprayed liquids is essentially limited to the manufacture of oxide coatings,

  such as SnO2 and TiO2. It is also difficult to manufacture multi-layer

  layers by means of sprayed liquids because each deposit of layers causes a significant cooling of the substrate. In addition, chemical vapor deposition is more economical in terms of raw materials, resulting in less waste. The product having a coating deposited by CVD is physically different from those having coatings obtained by spraying. A coating obtained by spraying retains in particular traces of spray droplets as well as traces of the path of the spray nozzle, which is not the case with CVD. To form each coating, the substrate is brought into contact, in a coating chamber, with a gaseous medium comprising the reactive mixture in the gas phase. The coating chamber is supplied with reactive gas by means of one or

  several nozzles, the length of which is at least equal to the width to be coated.

  Methods and devices for forming 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 A1 (Glaverbel). These methods and devices lead to the formation of particularly resistant coatings having

advantageous optical properties.

  To form the tin oxide / antimony coatings, two successive nozzles are used. The reaction mixture comprising sources of tin and antimony feeds the first nozzle. When this mixture comprises chlorides which are liquid at room temperature, it is vaporized in a stream of anhydrous carrier gas at elevated temperature. Spraying is facilitated by the atomization of these reagents in the carrier gas. In order to produce the oxides, the chlorides are brought into contact with water vapor conveyed to the second nozzle. The water vapor is overheated and is

  also injected into a stream of carrier gas.

  Advantageously, nitrogen is used as a substantially inert carrier gas. Nitrogen is sufficiently inert for the purposes pursued and it is

  inexpensive compared to noble gases.

  SiO2 or SiOx silicon oxide sublayers may be

  silane SiH4 and oxygen as described in the

  British Patent GB 2,234,264 and GB 2,247,691.

  If a glass substrate having an incompletely oxidized coating is exposed to an oxidizing atmosphere for a sufficient time, it can be expected that the coating will become completely oxidized resulting in the loss of the desired properties. Therefore, such an underlayer is surmounted by the tin oxide / antimony coating layer while it is still in an incompletely oxidized state and the substrate is still hot, so as to maintain the undercoat in

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  an incompletely oxidized state. The period during which the glass substrate carrying the freshly deposited undercoat can be exposed to an oxidizing atmosphere such as air and before the top layer is deposited, without deterioration of the properties of the undercoat, depends on the glass temperature during such exposure and the nature of the undercoat. Advantageously, the deposition chamber of the underlayer is surrounded by a reducing atmosphere. The adoption of this characteristic helps to prevent the entry of ambient oxygen into the deposit chamber of the underlayment and thus allows

  better control of the oxidation conditions in the deposition chamber of the sub-

layer.

  The oxygen required for deposition reactions of the underlayer can be provided in the pure oxygen state, but this unnecessarily increases the costs, and it is preferred that

  oxygen is introduced by supplying the deposition chamber with air.

  Note that the Sb / Sn molar ratio which is desirable in the reaction mixture does not always correspond to the ratio which is desirable in the reaction mixture.

  layer of tin / antimony coating.

  Preferably, the source of tin is selected from SnCl4, monobutyl trichloro tin ("fBTC") and mixtures thereof. The source of antimony may be selected from antimony chlorides SbCl3, SbCls, organo-antimony compounds and mixtures thereof. Examples of suitable raw materials are Sb (OCH2CH3) 3,

  Cl1.7Sb (OCH2CH3) 13, Cl2SbOCHCICH3, Cl2SbOCH2CHCH3Cl 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 molar ratio of the coatings is determined by an X-ray analysis technique in which the X-ray count of the respective elements is compared. This technique is not as accurate as if calibrated by chemical assay, but the similarity between antimony and tin means a similar response to X-rays. The ratio of observed counts for the respective elements thus gives a good

  approximation of their molar ratio.

  Colored glass is used rather than clear glass as indicated in some of the examples. The properties of the different types of colored glass are shown in Table 1 below. In all cases, the properties are measured on glass samples of 4 mm thickness, this being the thickness of the glass used in all the examples, with the exception of Examples 1 to 7 (for which the thicknesses are represented in Table 2). The initials in the headers of this

  table and the following tables (TL, TE, etc.) have the meanings described

above.

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  With regard to the calculation of the solar factor, it will be noted that for light transmission factors (TL) of less than 60% the effect of a low emissivity is not negligible and must be taken into account: when the emissivity decreases, he

The same goes for the solar fadctor.

Table 1

  Type of glass Green A Green B Gray Gray Gray ________________ Dark Medium XD Transmission 505.4 / 508.5 504.9 / 508.4 470.1 / 493.9 493, 2 / 502.7 478.9 / 502, 7 (nm) [Illuminant C / A] Purity (%) 2.9 / 3.4 2.1 / 2t5 1.5 / 0.8 5.6 / 5.1 2.6 / 1.8

  TL (%) 72.66 / 71.12 78.44 / 77.20 55.65 / 55.56 36.80 / 35.76 22, 41 / 22.30

[Illuminant: C / A] _ _

  TE (%) (CIE) 44.0 52.3 56.9 25.9 31.11

  FS (%) coated face 56.8 62.9 66.3 43.4 47.3

TI.TFS 1.28 1.25 0.84 0.85 0, 47

[Illuminant: CI]

EXAMPLE 1

  Soda-lime float glass moving at a speed of 7 m per minute along a float tank is coated with an undercoat in a coating chamber located at a location in the float tank where the glass is at a temperature of about 700 C. The supply line conveys nitrogen, silane is introduced under a partial pressure of 0.25% and oxygen under a partial pressure of 0.05% (ratio 0, 5). We obtain a coating of silicon oxide

  SiO2 having a thickness of 100 nm.

  The substrate provided with its underlayer, having a thickness of 6 mm, is then immediately coated by CVD pyrolysis by means of a coating device comprising two successive nozzles. A reagent comprising a

  mixture of SnC! 4 as a source of tin and SbCl $ as a source of antimony.

  The Sb / Sn molar ratio of the mixture is about 0.2. The reactive mixture is vaporized in a gaseous stream of anhydrous nitrogen at about 600 ° C, which feeds the first nozzle. The vaporization is favored by the atomization of these reagents in the carrier gas. Superheated steam is conveyed to the second nozzle. The steam is heated to about 600 ° C. and is also injected into a carrier gas, which is air heated to about 600 ° C. The gas flow (carrier gas + reagent) of each

  nozzle is lm3 / cm of substrate width per hour, at working temperature.

  The coating process continues until the geometric thickness of the tin / antimony oxide coating surmounts the coated substrate.

the underlayer is 185 nm.

EXAMPLES 2 TO 7

  In Examples 2 to 7, the procedure of Example 1 is followed but with variations of parameters such as the reaction mixture, the presence or absence of oxide underlayer, the Sb / Sn ratio in the coating. and in the reaction mixture and the thickness of the vitreous substrate. For example, in comparison with Example 1, no underlayer was applied in Example 2 and the tin / antimony oxide coating layer was 210 nm thick. The reaction mixtures are as follows: Example 2 and 3: the same as in Example 1 (but with a lower concentration of reactive mixtures in the carrier gas in Example 3); Example 4: MBTC and Cl1,7Sb (OCH2CH3) 1,3; Example 5: MBTC and C12SbOCH2CHCH3Cl; Example 6: MBTC and Cl2SbOCH2C (CH3) 2Cl;

Example 7: MBTC and SbCl3.

  The variations of the operating parameters of Examples 1 to 7 and the

  The results obtained are given in Table 2 below.

  The glazings according to Examples 3 to 7 have a blue color which is pleasant in transmission: the dominant wavelength in transmission in the visible spectrum is

between 470 and 490 nm.

  Example 6 provides glazing with a combination of low

  FS solar factor and low emissivity.

  In a variant of Example 6, the SiO 2 underlayer is replaced by an anti-reflective SiOx silicon oxide underlayer, according to the process of patent GB 2 247 691. In another variant, the SiO 2 underlayer is replaced by an oxidized aluminum / vanadium layer according to patent GB 2 248 243. In these variants

  the glazing does not have a purple appearance in reflection from the uncoated side.

EXAMPLE 8

  "Green A" colored float glass advancing at a speed of 7 m / min along a float tank is coated with an undercoat in a coating chamber disposed at a location along the float tank. the glass is at a temperature of about 700 C. The supply pipe conveys nitrogen; Silane is introduced under a partial pressure of 0.2% and oxygen at a partial pressure of 0.5% (ratio 0.55). An SiOx silicon oxide coating is obtained,

  with x approximately equal to 1.8, having a refractive index of about 1.7.

  The thickness of the coating is 40 nm.

  The substrate provided with the underlayer, having a thickness of 4 mm, is then coated by CVD pyrolysis. A reagent comprising a mixture of MBTC as a source of tin and Cl1.7Sb (OCH2CH3) 11.3 as the source of antimony is used. The Sb / Sn molar ratio of the mixture is approximately 0.195 (mass ratio

12; D2735123

  0.2). The reaction mixture is vaporized in a stream of anhydrous air at about 200 ° C, which feeds the nozzle. Spraying is facilitated by ratomization of these reagents in the

  carrier gas. Overheated steam at about 200C is then introduced.

  The coating process is continued until the geometric thickness of the tin / antimony oxide coating surmounts the substrate provided with the

underlayer is about 120 nm.

EXAMPLES 9 TO 14

  In Examples 9 to 14, the procedure of Example 8 is followed but with variations as shown in Table 3 in parameters such as the thickness of the underlayer, the Sb / Sn ratio in the coating and in the reaction mixture, the thickness of the tin oxide / antimony coating layer and the color of the

  glass. The results of Examples 8 to 14 are shown in Table 3.

  The windows according to Examples 9 to 14 have a blue color which is pleasant in transmission, the dominant wavelength in transmission in the visible spectrum being

  between 470 and 490 nm (Illuminant C).

  As a variant of example 9 in which the green glass A is replaced by medium gray glass, the resulting light transmission factor (TL) is 20%, the light reflection factor (RL) is 10% and the transmission factor energy

(TE) is 15%.

EXAMPLES 15 TO 30

  The process of Example 1 is followed in Examples 15 to 30 with variations in the reaction mixture, the color and thickness of the glassy substrate, the thickness of the oxide underlayer, and the ratio Sb / Sn in the reaction mixture and in the coating. For Examples 15 to 22 the reaction mixture is MBTC and Cl1,7Sb (OCH2CH3) 13 without trifluoroacetic acid, while for Examples 23 to 30 the reaction mixture is MBTC and CI1.7Sb (OCH2CH3) 13 with trifluoroacetic acid . The

  F / Sn ratio in the reaction mixture of these examples is 0.04.

  The variations in the procedures and the results obtained are given in Table 4 for Examples 15 to 22 and in Table 5 for Examples 23 to 30. The silicon oxide SiOx used in Examples 15 to 30 has a value of x

approximately equal to 1.8.

Table 2

  Example 1 2 3 4 5 6 7 Oxide Thickness 185 210 105 120 105 445 110 Tin / Antimony (nm) SiO2 oxide underlayer absent SiO2 SiO2 SiO2 SiO2 Thickness of sub-100 0 70 70 70 layer (nm) Sb / Sn ratio in the 0.48 0.48 0.46 0.19 0.15 0.06 0.18 coating Sb / Sn ratio in the 0.20 0.20 0.20 0.20 0,20 0,10 0,20 reagents Sail (%) 0.07 2.09 4.36 to 7.01 weak weak weak weak

  TL (%) 45.7 44.3 65.5 51.0 61.6 47.5 55.0

  LR (%) (coated side) 9.0 12.0 18.8 12.0 11.7 6.6 13.7 FS (%) (coated side) 55.3 56.9 66.0 58.4 62 , 2 47.2 59.6 (CIE)

  TU / FS 0.83 0.78 0.99 0.87 0.99 1.01 0.92

  BD in Transmission (n) 587.5 - 560 480.1 478.8 481.0 483.0 479.3 Color purity in 3.4 3.9 4.9 11.5 8.7 7.0 10.0 3 transmission (%) XD in reflection (472 face, 4994.5 575.3 579.5 577.6 490.0 577.0 coated) (nm) Color purity (%) at 36.9 7.0 19 , 1 35.0 35.2 6.0 33, 1 reflection (coated side) Emissivity> 0.7> 0.7> 0.7 0.84 0.71 0.25 0, 79 Glass thickness (mm) 6 6 6 5 5 5 5

Table 3

  Example 8 9 10 11 12 13 14 Oxide Thickness 120 120 320 470 470 320 470 Tin / antimony (nm) SiO2 SiO2 SiO2 SiO2 SiO SiO2 SiO2 oxide undercoat Thickness of the undercoat 40 70 40 40 40 40 40 (nm) Sb / Sn ratio in the 0.10 0.18 0.09 0.09 0.09 0.09 0.09 coating Sb / Sn ratio in the 0.07 0.20 0.07 0.07 0 , 07 0.07 0.07 reagents Voile (%) 0.36 0.1 1.0 1.8 1.8 1.0 1.8 TL (%) [Illuminant A / 53/55 39/20 31 / 32 31/32 9/9 40/41 36 [A] Illuminant C] RL (%) (coated side) 9/10 11/11 7/7 7/7 7/7 8/7 7 [A] [Illuminant A / C] RL (%) (uncoated side) 8 8 6 6 5 7 [Illuminant C]

TE (%) (CIE) 31 25 25 18 9 21 27

  FS (%) (coated side) 45 41 41 36 29 39 43 (CIE)

  TL / FS 1.2 / 1.2 0.95 / 0.98 0.76 / 0.78 0, 86 / 0.89 0.31 / 0.31 1.02 / 1.05 5.4 [A ]

  in transmission (nm) 505.4 / 498.6 497.2 / 487.0 494.8 / 481.9 497.2 / 487.2 494.2 / 480.0 501.0 / 491.6 493.4 [A] Color purity of 4.4 / 4, 6.2 / 8.9 4.9 / 8.1 7.6 / 10.8 7.0 / 11.8 7.2 / 8.6 , 4 [A] transmission (%) Xl in reflection (face 487.9 / 478.1 - 572.5 / 566.9 -511.8 / 512.2 -576.9 / 559.8 -555.4 / 550.1 -512.5 / 513.6 - 576.0 [A] coated) (nm) Purity of color (%) in 7.4 / 14.6 2.2 / 2, 9 17.2 / 16, 3 6.0 / 1.2 2.1 / 6.6 15.4 / 14.5 1.5 [A] reflection (coated side) _ Emissivity 0.71 0.85 0.44 0.35 0.35 0.44 0.35 Glass Color Green A Green A Gray Green B Dark Gray Green A Clear

Table 4

  Example 15 16 17 18 19 20 21 22 Oxide Thickness 320 320 320 320 390 390 390 390 Tin / Antimony (nm) SiOx SiOx SiOx SiOx SiOx SiOx SiOx SiOx oxide undercoat Thickness of the sub 60 60 60 60 80 80 80 80 layer (nm) (approximately) (approximately) (approximately) (approximately) (approximately) (approximately) (approximately) (approximately) Sb / Sn ratio in 0.053 0.053 0.053 0.058 0.058 0.058 0.058 0.058 coating Sb / Sn in 0.028 0.028 0.028 0.028 0.028 0.028 0.028 0.028 Reagents Voile (%) 0.65 0.65 0.65 0.65 1.2 1.2 1.2 1.2 TL (%) [Illuminant C] 68.8 55, 7 60.1 28.2 61.0 49.2 25.0 53.1 RL (%) (coated side) 8.9 8.2 8.4 7.2 9.0 8.0 7.2 6.9 RL (%) (uncoated side) 8.9 7.3 7.8 5.0 7.8 6.5 4.8 8.2

  TE (%) (CIE) 50.8 28.3 33.1 15.8 43.0 24.5 13.7 28.5

  MSDS (%) (coated side) 60.3 43.6 47.2 34.4 54.7 40.9 32.9 40.1 (CIE)

  TL / TE 1.35 2.00 1.82 1.75 1.42 1.96 1.79 1.86

  TL / FS 1.15 1.27 1.28 0.82 1.11 1.20 0.76 1.20

  p in transmission (nm) 524.0 506.2 506.0 494.0 496.0 500.7 493.4 499.5 Color purity in 0, 5 3.1 2.3 5.8 2.2 4 , 7 7.5 4.1 transmission (%) t XD in reflection (face 482.9 484.2 484.0 482.9 -495.2 -493.8 - 495.0 -550.3 coated) (nm) ) n Color purity (%) at 14.5 16.2 15.8 18.0 5.0 4.4 6.4 7.0 reflection (coated side) r_ _ Emissivity 0.29 0.29 0.29 0.29 0.27 0.27 0.27 0.27 Glass color Clear Green A Green B Medium gray Light Green A Medium gray Green B

Table 5

  Example 23 24 25 26 27 28 29 30 Thickness of oxide 290 290 290 290 410 410 410 410 tin / antimony (nôn) SiOx SiOx SiOx SiOx SiOx SiOx SiOx SiOx oxide undercoat Thickness of the sub 80 80 80 80 90 90 90 90 couchenm (approximately) (approximately) (approximately) (approximately) (approximately) (approximately) (approximately) (approximately) (approximately) Sb / Sn ratio in 0.038 0.038 0.038 0.038 0.037 0.037 0.037 0.037 coating _ Sb / ratio Sn in 0.028 0.028 0.028 0.028 0.028 0.028 0.028 0.028 reagents Voile (%) 0.82 0.82 0.82 0.82 1.2 1.2 1.2 1.2 TL (%) [Illuminant C] 70, 2 56.7 61.0 28.7 64.2 51.9 26.9 56.4 RL (%) (coated side) 10.0 9.0 9.2 8.0 8.8 8, 1 7, 2 8.3 RL (%) (uncoated side) 9.5 8.0 8.3 5.2 7.6 6.6 4.8 6.9

  TE (%) (CIE) 54.3 29.5 34.7 16.6 47.2 26.1 14.6 30.6

  MSDS (%) (coated face) (CIE) 63.0 44.5 48.3 34.9 57.7 42.0 33.6 45.4

  TL / TE 1.30 1.90 1.74 1.71 1.36 2.00 1.73 1.81

  TL / FS 1.11 1.27 1.27 0.83 1.10 1.24 0.76 1.24

  BD in transmission (nm) 581.3 538.8 549.4 498.5 568.6 535.9 502.7 543.7 Color purity in 2.9 2.9 2.7 3.3 3.5 3 3.6 3.5 transmission (%) ID in reflection fe (face 510.3 508.6 508.9 507.2 549.3 505.1 491.8 507.0 coated) (nm) Purity of color (%) in 8.1 10.1 9.6 11.3 3.3 1.1 1.2 1.0 reflection (coated side) Emissivity 0.28 0.28 0.28 0.28 0.23 0 , 23 0.23 0.23 Color of glass Clear Green A Green B Medium gray Light Green A Medium gray Green B

17 2735123

Claims (18)

CLAIMS CATIONS   1. Glazing comprising a vitreous material substrate having a tin oxide / antimony coating, characterized in that the coating is formed by pyrolysis in the vapor phase and contains tin and antimony in a molar ratio Sb / Sn is between 0.01 and 0.5 and in that the substrate carrying the coating has a solar factor (FS) of less than 70%. 2. Glazing according to claim 1, characterized in that the ratio Sb / Sn molar is at least 0.03.   3. Glazing according to claim 2, characterized in that the ratio Sb / Sn molar is at least 0.05.   4. Glazing according to one of claims 1 to 3, characterized in that the   Sb / Sn molar ratio is less than 0.21.   5. Glazing according to one of claims 1 or 4, characterized in that the   Sb / Sn molar ratio is between 0.01 and 0.12.   6. Glazing according to claim 5, characterized in that the ratio   Sb / Sn molar is between 0.03 and 0.07.   7. Glazing according to one of claims 1 to 6, characterized in that   intermediate layer reducing the haze is disposed between the substrate and the coating of tin oxide / antimony.   8. Glazing according to claim 7, characterized in that said layer   Veil reducing intermediate comprises silicon oxide.   9. Glazing according to one of claims 1 to 8, characterized in that the   solar factor is less than 60%.   10. Glazing according to claim 9, characterized in that the factor solar is less than 50%.   11. Glazing according to one of claims 1 to 10, characterized in that the   Light transmittance (TL) is between 40 and 65%.   12. Glazing according to one of claims 1 to 11, characterized in that   said tin / antimony oxide coating has a thickness of between 100 and 500 nm. 13. Glazing according to claim 12, characterized in that said   tin oxide / antimony coating has a thickness between 250 and 450 nm.   14. Glazing according to one of claims 1 to 13, characterized in that the   tin oxide / antimony coating constitutes an exposed layer.   15. Glazing according to one of claims 1 to 14, characterized in that   includes a single layer of tin oxide / antimony coating. 18 2735123   16. A method of forming a glazing unit comprising the pyrolytic deposition, on a substrate made of vitreous material, of a tin / antimony oxide coating, characterized in that the deposition is carried out using a reactive mixture of vapor phase comprising a source of tin and an antimony source, the molar ratio tin / antimony in the mixture being between 0.01 and 0.5 so that the substrate   coated has a solar factor (FS) less than 70%.   17. The method of claim 16, characterized in that said source   tin is selected from SnCl4, monobutyl trichloro tin and mixtures thereof.   18. Method according to one of claims 16 or 17, characterized in that   the source of antimony is chosen from antimony chlorides, the compounds   organo-antimony and their mixtures.