Oxide coating method

© Start of patent duration: 1975 12 15 Longest possible duration:

© Issued on: © Inventor:

1976 09 10

PLUMAT EMILE IN GILLY (BELGIUM), POSSET ROBERT IN MO NT / S / MÄBCHIENNE (BELGIUM).

© dependence:

OE 332022 © Pamphlets considered to delineate the prior art:

DT-OS1596722, DT-OS2029037, GB-PS1268753,

US PS2975076

No. 332022

The invention relates to a method for forming a metal oxide coating, such as a transparent or antistatic properties layer, on a substrate, for example, an at least partially glassy substrate.

It is known to prepare oxide coatings, for example cobalt oxide coatings, in such a way that a hydrated metal salt aqueous solution, for example an aqueous solution of CoCl₂6H₂O or FeCl₃6H₂O, is sprayed onto the surface of a substrate that is heated to a temperature sufficient to effect conversion of the metal salt in situ. The coating produced in this process is usually of poor quality, especially with regard to the uniformity of the thickness and the composition of such a coating. For example, when such an aqueous cobalt salt solution is applied, a granular deposit having an irregular thickness is obtained, and the coating usually adheres very poorly to the substrate. Coatings formed in this way can be easily removed in the form of dusts, u. zw. by simply gliding over a finger or by applying an adhesive tape on the cover and then pulling off the tape.

Other methods are also known whereby coatings are applied to a substrate for a particular purpose. Thus, German Offenlegungsschrift 2029037 describes the coating of glass articles, in particular glass fibers, with a solution of cationic compounds which react at elevated temperature with the network structure of the glass, whereby its mechanical strength is improved. According to German Offenlegungsschrift No. 1596722, an infrared-reflective film is deposited on a glass substrate

Based on gold or platinum based on gold or platinum-containing solutions containing additives such as alkoxides of metals, which are converted by heating in oxides with a higher index of refraction than glass. It is known from British Patent Specification No. 1, 268, 753 to apply a layer of colored iron oxide to hollow glass articles before the glass is passed through the annealing furnace. Finally, it is from US Pat. 2,975,076 discloses preparing cobalt oxide layers on glass starting from alcoholic solutions of cobalt acetate which are heated and sieved prior to application.

All of these methods of forming specific coatings make use of the solutions of metal compounds in hydrocarbon or alcohol solvents, which, given the high working temperatures that are possible, present considerable fire and / or explosion hazards and consequently expensive

Security measures is connected. It is therefore an object of the invention to be able to produce coatings with uniform properties in a series treatment in the rhythm of the treatment chain, wherein the coating in the hot atmosphere of the treatment station without fire or explosion hazard can be applied.

A further object of the invention is to provide a method, in the implementation of which metal oxide coatings of uniform thickness and composition can be easily produced on various substrates. In particular, the object of the present invention is to provide a process in which metal oxide coatings of high uniformity can be formed on the surfaces of at least partially glassy substrates so that this process is suitable for forming optical films on glassy bodies or objects For example, glazing panels, windshields, patterned glasses, and sunglass glasses. In addition, a method is to be provided, in the implementation of metal oxide coatings are produced which have antistatic or electrically conductive properties.

The method according to the invention for forming a metal oxide coating, such as a transparent or antistatic layer, on a substrate, for example a slightly glassy substrate, wherein a solution of at least one metal compound, such as acetates, halides and nitrates, is applied to the substrate and the compound or compounds in situ by the action of heat to form a coating of at least one metal oxide and optionally additionally a metal is converted or is characterized in that the metal salts are dissolved in an aprotic solvent having a dielectric constant of more than 15 and a dipole moment of more than 3D from the group dimethylformamide, dimethylacetamide, tetramethylurea, dimethylsulfoxide, acetonitrile, nitrobenzene, ethylene carbonate, tetramethylene sulfone or hexamethylphosphoramide and, if appropriate, acetone acetone is also added to the solution.

By the method according to the invention it is possible to form metal oxide coatings whose thickness and composition are substantially uniform. This is essential, for example, in the case of very thin, highly transparent coatings, as well as in the case of coatings, which must have a certain electrical resistance.

The method is therefore useful for making optical films on glassy bodies or objects to modify their translucency and / or light reflection, for example, to give these bodies or articles a colored appearance when viewed through

No. 332022 or reflected light. The process is also of great importance with regard to the production of antistatic or conductive films on substrates of a non-conductive material.

The uniformity of the coating, which is made possible according to the invention, is attributable not only to the choice of the particular metal salt, but also to the corresponding selection of the solvent5.

The metal salt solutions used for carrying out the invention can be prepared in a very inexpensive manner, so that a large-scale production of metal oxide coatings at a very low price is possible. These metal salt solutions may also be relatively concentrated. This is of particular advantage when the solution is to be applied to a substrate which moves relatively quickly with respect to the overdrawing station. Another important advantage is the safety with which such solvents can be used at very high temperatures. It is therefore possible to heat and evaporate the solvent very rapidly, achieving rapid conversion of the metal compound or compounds. This is also an important factor in the production of uniform density coatings.

With appropriate selection of the metal salts, various properties of the applied coating can be achieved. The applied solution may contain a single metal salt or a mixture of two or more metal salts. The process for producing coatings with certain optical or electrical properties is therefore very flexible. For example, it is possible to produce coatings of cobalt, iron and chromium oxide using a solution consisting of cobalt acetate, iron (HI) 20 chloride and chromium nitrate.

Preferably, the substrate is preheated to a temperature sufficient to provide the heat necessary to effect the transformation of the metal compound or compounds.

Preheating the substrate results in immediate evaporation of the solvent as well as conversion of the metal compound or compounds, ie, these effects occur as soon as the solution comes into contact with the substrate.

As already mentioned, a fast conversion promotes the uniformity of the coating.

In order to achieve the main objectives of the invention, a temperature between 300 and 700 ° C is generally complied with in the implementation of the overdrawing process. Preferably, the temperature is preferably selected prior to 30 such that it is sufficient to achieve the desired result while avoiding the risk of damage to the substrate. If glassy substrates are coated, it is recommended to work in a temperature range of 450 to 650 ° C. At a temperature within these limits very uniform coatings are obtained which adhere very well to glassy substrates. The adhesion is also affected by the temperature of the substrate at the time of application of the overdraft solution.

The metal salt solution is preferably applied in the form of droplets. The desired results are achieved very simply in such a way that the solution is applied in such a form. For example, a spray gun of the funnel mix type, which is supplied with compressed air and saline solution separately, with the air and brine at the same pressure 40 above atmospheric pressure, may be used. The salt solution itself may be at ambient or at a higher temperature, provided that there is no undesirable premature evaporation of the solvent and no decomposition and oxidation of the metal compound or compounds, with the further proviso that the substrate is not subject to adverse thermal shocks.

As already mentioned, the results achievable by the method according to the invention are partly due to the selection of an aprotic solvent with a dielectric constant of more than 15 and a dipole moment of more than 3D. Examples of aprotic solvents having such properties include dimethylformamide, dimethylacetamide, tetramethylurea, dimethylsulfoxide, acetonitrile, nitrobenzene, ethylene carbonate, tetramethylenesulfone and hexamethylphosphoramide.

Dimethylformamide is particularly preferred. This solvent is particularly suitable for most of the metal salts in question so that these compounds can be applied in relatively high concentrations, meaning that the rate of application of the solution to a given zone of the surface of a substrate to produce a coating of a given thickness is relatively can be low. Dimethylformamide can also be used to apply coatings to substrates at very high temperatures without the risk of fire or explosion hazard.

According to preferred embodiments of the invention, the solution applied to the substrate consists of one or more acetates, halides or nitrates of a metal or of metals selected from the following group: Mg, Zr, V, Cr, W, Mn, Fe , Co, Ni, Cu, Zn, Cd, In, Sn, Pb, Bi, Th and Si.

Nr.332022

It is advantageous to use in admixture with one or more of the salts mentioned one or more acetates, halides or nitrates of a metal or of metals selected from the following group: Au, Ti, Ce, Mo, Sb, Al, As and Rh.

It should be noted that the coating formed on the substrate is not necessarily formed from a metal oxide or metal oxides, but rather, the coating may also contain an element such as gold in a metallic state. In general, all of the salts mentioned above may be used in admixture with the selected solvent or solvents, without taking special precautions, with the exception of per se known precautions aimed at undesirable redox or hydrolysis reactions in the solution to avoid.

When such solutions are used, it is possible to produce very thin and high quality metal oxide coatings which modify the light reflectance and transmissivity of the substrate to yield metal coatings that are absolutely solid on ceramic substrates as well as on glass, and especially glassy substrates, for example vitrocrystalline or vitroceramic substrates, where these materials are mainly such materials, that require an optical coating. It is also possible to form thin metal oxide coatings with a certain electrical resistance which meets certain requirements. In this latter case, the coatings are preferably applied to non-conductive substrates, for example glasses, ceramic materials and vitro-crystalline or vitroceramic materials.

Advantageously, acetylacetone is present in the applied saline solution. The presence of acetylacetone is generally particularly advantageous when a solution of one or more halides or nitrates is applied. The acetylacetone enables optimal film formation and allows better pyrolysis of the metal compounds.

For example, it is possible to obtain coatings of improved optical quality such that acetylacetone is added to solutions containing vanadium chloride, chromium nitrate, iron or nickel nitrate or kidium nitrate.

In some cases, the presence of acetylacetone ensures greater safety in the production of the film-forming solution. For example, is it necessary to use a solution of anhydrous SnGl₄ in dimethylformamide, it is preferable to first mix the tin (TV) chloride with acetylacetone and pour the resulting liquid into the selected solvent to prevent the latter from igniting.

It has been found that when acetylacetone is used it is preferable to maintain proportions such that the amount of acetylacetone used is of the order of n times the number of moles of metal employed, where n is the valency or the sum of the equivalents of the metal cation (s).

As already mentioned, the invention has proven to be particularly important for the production of metal oxide coatings on glassy or partially glassy substrates, for example on substrates of vitro-crystalline or vitroceramic materials. This is because the process allows the formation of thin metal oxide coatings which are very uniform in both thickness and density. These are properties which are particularly sought in the case of optical, antistatic or conductive films which serve to modify the optical and / or dielectric properties of bodies or articles on which the coatings are applied.

Glassy or partially vitreous bodies or articles of any shape may be coated by the method of the present invention to impart predetermined hue and tint, as well as particular light-reflecting properties, or to provide them with certain antistatic or conductive properties. The method is particularly useful for forming coatings on wholly glassy transparent bodies and articles, such as windshields or glazing panels, because the method allows for the formation of metal oxide coatings which impart different tints to the subject or body, if used in both applications viewed through both transmitted and reflected light. The method has been found to be suitable not only for producing a metal oxide coating directly on a glass or on a surface of a partially glassy material, but also for producing such a metal oxide coating on an already formed coating film adhered to the glassy substrate, in particular on a 55 already present Metalloxydüberzugsfilm, for example on a film of titanium oxide or copper oxide.

The metal hydroxide coating thickness selected in each case depends on the function of the coating which it is intended to exert. For example, it can vary between a few hundred and a few thousand Å. A coating of a given thickness may be formed, if necessary, or optionally of two or more successive layers. The thickness of a coating is best

No. 332022, but it is also possible to dissolve the coating, to analytically determine the weight of the coating per unit area and to calculate the thickness thereof, taking into account the known density of the oxide and its degree of compaction as a thin film.

The method can be carried out particularly economically for producing a coating film on flat glass in such a way that the solution is sprayed onto an endless glass ribbon during its production, for example in an overdrawing station located in the drawing chamber of a glass drawing machine or in a cooling tunnel. The solution is preferably applied when the glass is at a temperature within 300 to 700 ° C, and preferably between 450 and 650 ° C, as already indicated above. It is convenient to direct the spray of coating solution perpendicular to the glass ribbon and to reciprocate the device transversely of the direction of travel of the ribbon with respect to the coating station. The method may also be advantageously carried out so that the solution is sprayed onto patterned glass during its production in the form of an endless belt. Such a glass moves at a relatively higher speed than flat glass, but this does not pose any difficulty, since the prepared solution can be concentrated to such an extent that the coating can be produced within the time limits imposed by the method of manufacture of the glass be staked out.

When a mixture of two or more salts is used, the proportions of the various salts can be adjusted to control the properties of the coating, for example to control the color of the coating by transmitted and / or reflected light, or its electrical resistance to regulate.

It is often convenient to use the metal acetates, halides or nitrates in fully crystalline form. For example, one or more hydrated acetates may be used, for example, dibasic cobalt acetate which crystallizes with 4 molecules of water, or anhydrous acetates such as zinc acetate, unless an interfering precipitate causes waste losses of the coating material.

To produce films with selected colorations in transmitted and reflected light, it is possible to blend mixtures of a variety of acetates, halides, or nitrates dissolved in one or more aprotic solvents having a dielectric constant greater than 15 and a dipole moment greater than 3D , to use. For example, blends of salts of cobalt, iron and chromium may be used to produce coatings which have a bronze color when viewed in transmitted light and which also have good resistance to external conditions, e.g. also in the presence of an acid.

A particularly advantageous application of the method according to the invention is the coating of a heat-radiation-impermeable glass with a highly reflective coating, without thereby the Ener35 gieabsorption is significantly increased.

The light and energy transmission of a coating of a given thickness can be increased without appreciable change in light or energy reflection when appropriately selected metal compounds are used, for example one or more acetates, nitrates or halides of one or more metals of the following group: aluminum, Zinc, thorium, ger, tin and magnesium. 40 In general, the presence of water in a relatively high amount is acceptable in the film-forming solution, but preferably this amount should not exceed 10% by volume. If the amount of water is too large, then the resulting coating can have very small dark spots, often referred to as pittings. It should be noted, however, that the extent to which such defects are visually, if any, perceptible in practice will depend on a variety of other factors, particularly the composition and geometry of the coated surface and the thickness of the coating. These defects are less noticeable on patterned glass, on which the subject is very compact, or on reinforced glass (glass, in which a wire mesh is incorporated). The same applies to profiled glass, for example in the form of a U, and certain vitro-crystalline materials, u. in each case in comparison to flat glass with flat surfaces.

Even if the coating is applied to flat glass, such defects become less apparent as the thickness of the coating increases. On the other hand, as the thickness of the coating increases, its transmittance is reduced, in cases where this factor is important, the optimum thickness of the coating is a compromise between the lack of defects and the degree of transparency.

For example, a cobalt coating applied to a flat glass surface and having an optical thickness of 500 Å has a light transmittance of 47%. Failure to comply with the described favorable conditions to produce a defect-free coating, dam such defects occur easily and are visible to the naked eye. If the same solution is applied to form a coating of oxide having an optical thickness of 900 Å, the defects are difficult to see if

No. 332022 they are not completely invisible at all, but the light transmission is only 26%.

The hardness of the coatings produced according to the invention using the preferred formulations is generally high. Most of the glazings used in this manner are used as single glazings, with the covered surface being able to be exposed to environmental conditions, since such coatings are sufficiently resistant to mechanical damage under normal conditions of use. However, if a protective coating is required, for example a coating of SnO, ZrO or TiO, then this can, for example, a colored coating

Ct 6 <5 are applied.

In order to test the hardness and adhesion of the coatings produced according to the invention, it is possible to use a reciprocating friction element having a surface of 1 cm² to be used, which consists of rubber in which corundum Teilehen have been added with a diameter of 75 to 125 μ. The friction element is inserted in a balanced tube (weight of the assembly 100 g), which slides vertically in a contactor. Constant contact is thus ensured between the friction element and the sample. The friction element is reciprocated by a crank system. The movement amplitude is 3 cm, the frequency is set to a forward and backward movement / sec. After some time, the abrasion results from scratches that are very close to each other, with non-destructive coating between these scratches.

In conducting various tests using glasses coated with oxide coatings, for example ZrO₂, SnO₂, SnO₂ and Sb₂O₃, TiO₂, Co₃O₄, Cr₂O₃, Y₂O₃, Tho₂.,

CeO₂, SiO₂ or a mixture of these oxides, it was found that after 5 minutes 5% of the surface exposed to friction was scratched. It takes at least 1 h to scratch 95% of the surface.

According to certain embodiments of the invention, a layer containing tin oxide is formed on a substrate. Such a coating is particularly advantageous because tin oxide imparts a considerable hardness to the coating.

For example, it is possible to apply coatings on a glass substrate consisting essentially of iron oxide containing a small amount of tin oxide, for example 90% Fe₂O₃ and 10% SnO₂, These coatings are colored and can be used for a single glazing. This is not possible if a colored coating is used, which consists only of iron oxide. A coating of this type can be prepared in a simple manner by spraying a solution of iron (HI) chloride on glass, wherein the iron (HI) chloride solution acetylacetone and anhydrous SnCl₂ have been added in dimethylformamide.

The presence of tin oxide in a coating which also contains one or more colored oxides makes it possible to control and dilute the coloration when viewed in transmitted and reflected light.

The presence of tin oxide is also very advantageous when coatings are prepared which have antistatic or electrically conductive properties.

To produce such coatings solutions are used which preferably contain one or more tin chlorides, which may optionally be anhydrous Kinnen, for example SnCl₂, SnCl₂.2H₂O, SnCl₄5H₂O or SnClj.

To produce coatings with a certain required electrical resistance, the thickness and the Zn pa.-mm pn of these coatings are controlled. For example, to make an antistatic coating on a glassy material substrate, it is preferable to use a coating containing tin oxide and having a thickness of between 200 and 800 Å.

To obtain a resistance equivalent to an antistatic or conductive coating, it is possible to use coatings containing small amounts of antimony in addition to tin oxide. In order to obtain a conductive coating, it is preferable to use a saline solution for preparing the coating containing a tin (H) salt as a main component.

The following examples illustrate the invention without these examples being intended to limit the invention. Example 8 makes reference to the figure which shows the result that a specific embodiment of the invention is achieved. The figure is a graph showing two curves. The curve -I- gives the light transmittance of an oxide film of SnO₂ and Sb₂O₃ in varying proportions, while curve -2- represents the electrical resistance of the film to the amount of antimony salt present in the film-forming solution.

Example 1: A film-forming solution is prepared by reacting 199 g of divalent 55 cobalt acetate crystallized with 4 molecules of water and 73 g of anhydrous zinc acetate in 11

Solvent be dissolved. The selected solvent consists of dimethylformamide.

The solution prepared in this way contains, based on oxides, 65% by weight of CoO and 35% by weight of ZnO.

This solution, whose temperature is kept at 70 ° G, is then applied to a glass ribbon during its course

No. 332022 continuous preparation by means of a drawing process sprayed. In carrying out this method, the glass ribbon runs upwardly through a cooling tunnel. The spraying is carried out at a point at which the glass ribbon has a temperature of 590 ° C.

An internal mixing spray gun is used, which with the solution as well as with compressed air under a pressure of 3.5 kg / cm² is supplied above atmospheric pressure.

The distance between the gun opening and the glass plate is 25 em. The gun is continuously reciprocated transverse to the advancing direction of the belt, with the forward speed being 1.5 m / min. The reciprocating movement of the pistol takes place with a forward and backward movement period of 6 sec (glass band width: 3 m).

From the gun, 12.7 1 solution / h are delivered, giving a solution flow rate of 47 cm³/ m² Glass band corresponds. The solution is sprayed to form a film having a thickness of 650 Å.

After cooling the glass, an optical film having a green color in transmitted light which is highly reflective is obtained. The characteristic properties of the product obtained are as follows:

Translucency: 70.5%

Light reflection on the coating side: 14, 8%

Light reflection on the glass side: 16%

Energy permeability: 69.7%

Energy reflection on the coating side: 13.7%

Energy reflection on the glass side: 13, 9%

Energy absorption on the coating side: 16, 6%

Energy absorption on the glass side: 16.4%

The film has a uniform thickness and is free of pittings, ie small holes.

A similar result is obtained when the dimethylformamide is replaced by another solvent such as dimethylacetamide, tetramethylurea, dimethylsulfoxide, acetonitrile, nitrobenzene, ethylene carbonate, tetramethylenesulfone or hexamethylphosphoramide.

Example 2: 79 g of chromium nitrate [Cr (NO_G)₃, 9H₂O] are dissolved in 0.8 l of dimethylformamide.58.5 cm³Acetylacetone are then added. The mixture is heated to a temperature of 50 ° C over a period of 15 to 20 minutes. The heating is then stopped, followed by cooling the solution

52.8 g of iron (Hi) chloride (FeCl₃6H₂O) and 58.5 cm³ Acetylacetone be added.

169 g of a divalent cobalt acetate [Co (CH_GCOO)₂.4H₂O] and 23 cm³ Acetylacetone plus 34.9 cm³H₂O₂ are then added to the resulting solution. The hydrogen peroxide serves to convert the divalent cobalt into trivalent cobalt. The solution is stirred under cooling for a period of from about 15 minutes to 15 minutes. Dimethylformamide is added in such an amount to bring the solution to a volume of 11. The resulting solution has a total oxide concentration of 85.1 g / 1 solution, with the individual components being distributed as follows (weight percentage):

64.1% Co₂O₃18.4% Fe₂O₃

17.5% Cr₂O₃

This solution is then sprayed on a glass ribbon having a thickness of 4 mm, which has been prepared in the same manner as in Example 1. The temperature of the glass during spraying is 600 ° C.

The device used for spraying corresponds to the device described in Example 1.

The output from the gun is 13.8 1 solution / h.

The applied coating has a uniform thickness of 800 Å and has a bronze color when viewed in transmitted light.

The oxide composition in the coating is, by weight, as follows:

12% Fe₂O₃

18% Cr₂O₃

70% co₃0₄

The light transmission is 47.1%.

The energy permeability is determined to 51.3%.

No. 332022

If the thickness of the coating is increased to 1200 Å, then a more yellowish tint is achieved, u. tw.

when viewed in transmitted light.

In this case, the light transmittance is 36.7%, while the energy transmission is found to be 42.6%.

The resulting coating has sufficient hardness for use in a single glazing unit and excellent resistance to external conditions, including acids.

The same procedure is repeated using a patterned glass which is at a temperature of 640 ° C during its manufacture. An oxide coating having a thickness of 540 Å 10 is deposited on this glass using the apparatus described above. The amount of solution dispensed is 16.11 / h and the glass movement speed is 3.15 m / min (bandwidth: 2 m).

Example 3: 113.5 g of zirconium chloride (ZrCl₄) are dissolved in 0.8 l of dimethylformamide. The solution is then brought to a volume of 11 and has a concentration which is 60 g ZrO_G / 1 is equivalent to the solution. This solution has a yellowish tinge and is cloudy.

This solution is then sprayed onto a glass plate having a temperature of 600 ° C. The resulting coating has a gray tint and has a number of small bright spots.

The same test is repeated except that acetylacetone is added to the starting solution. The amount of acetylacetone is 4 mol / 1 mol of ZrCl_{4 <} The amount of acetylacetone added is 195 cm³, After heating to 50 ° G for a period of about 15 minutes, the solution becomes completely clear.

When this solution is sprayed on a glass plate, the resulting film is absolutely uniform and gray when viewed in transmitted and reflected light.

The properties of the product obtained are as follows:

<td></td><td>Light transmission:</td><td>73, 8%</td>

<td>25</td><td>Energy transmission:</td><td>74%</td>

<td></td><td>Light reflection on the coating side:</td><td>22, 8%</td>

<td></td><td>Energy reflection on the coating side: The resulting coating is very hard.</td><td>18, 2%</td>

Example 4: A number of film-forming solutions are prepared by dissolving the metal salt corresponding to the desired oxide in a suitable solvent. The solutions, summarized in the following table, are sprayed onto a 4 mm thick glass plate which has been heated to a temperature of 600 ° C. The properties of the obtained

Products are shown in the table:

No. 332022

<td rowspan="2">Properties of the movie as well</td><td colspan="2" rowspan="2">of the product obtained</td><td rowspan="2">Translucency 79, 3%</td><td rowspan="2">ATS fr · £ $ • SP 'cq CQ : ti Frt 3 R • s Φ 'S) R Φ ti</td><td rowspan="2">Yellow when viewed in transmitted.</td><td colspan="4">Φ £ φ .a O s</td><td rowspan="2">(The film is on the inner surface of the</td><td rowspan="2">applied to outer glass)</td><td colspan="6">φ *8th R 1</td><td rowspan="2">Gray-brownish tint in the passage</td><td rowspan="2">light</td><td rowspan="2">Translucency 67, 7%</td><td rowspan="2">Energy permeability 71, 3%</td><td rowspan="2">The effect of the presence of Rh₂ O₃ is on limited the dimensions of the Au particles.</td><td rowspan="2">Film with blue tint in transmitted light.</td><td rowspan="2">After assembly, a duplicate</td><td rowspan="2">glass unit, the following values ​​are determined:</td><td rowspan="2">fiR rd fr · © £ CQ 3 • rt ffl</td><td rowspan="2">ATS &lt;N rd 3 's R a</td><td rowspan="2">ATS © 00 cq 1 £ 0 CQ -§ • rt bO H Φ a ffl</td><td rowspan="2">Ö3 cq © © £ • ä bß • rt CQ :8th rrt § Φ 'S) R Φ fl w</td><td rowspan="2">ATS © τμ rd 3 *8th R 5 bß R Φ ti</td>

<td>Light after an assembly:</td><td>glazing unit:</td><td>Translucency 57, 6%</td><td>Energy permeability 59, 5%</td><td>Translucency 79, 3%</td><td>Energy audacity 77.4%</td><td>Gray coloring in passed through</td><td>danced light</td><td>ATS fr · © £ • SP CQ CQ : ti 1 • rt ffl</td><td>Energy permeability 70%</td>

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No. 332022

Example 5: Tin oxide coatings are prepared by spraying solutions of stannous chloride in dimethylformamide.

Three solutions are prepared by dissolving the following components in dimethylformamide:

SnCl₂, SnCl₂ , 2H₂O and SnCl₄ , 5H₂O.

A fourth solution is prepared by first adding SnCl₄ in acetylacetone to produce a very viscous red liquid which is then dissolved in dimethylformamide.

These four solutions have an identical tin content and are sprayed on a glass plate with a temperature of 85 ° C. The coatings obtained from the four solutions are optically identical. Their color is green in all four cases in reflected light.

Example 6: A film-forming solution is prepared by dissolving 400 g of tin (H) chloride (SnCl₂.2H₂O) and a small amount of antimony chloride, u. between 7.5 g of SbCl₃prepared in 11 dimethylformamide.

This solution is sprayed at a flow rate of 15.8 l / h onto the smooth surface of a printed glass ribbon moving at a speed of 3.5 m / min., U. above the cooling tunnel at a point where the temperature of the glass is in the order of 680 ° C. 15 The total width of the band is 1.57 m. The pistol is moved back and forth over a distance of 1.27 m. The number of sweep cycles is 25 / min.

A coating with a uniform purple tint is obtained over a width of 1.10 m. The thickness of the coating is 2700 Å. The electrical resistance of the coating is determined to be 60 Ω / □ (ohms per square area). A glass piece measuring 30 × 30 cm is cut out of this tape20 and subjected to heat curing. Then silver paint electrodes are applied. When applying a voltage of 220 V, the temperature is a few millimeters above the glass 92 ° C. If a coating with a smaller thickness, for example 200 to 800 Å, applied, then the same starting solution gives an antistatic coating, which is no longer electrically conductive.

It is also possible to prepare antistatic coatings by spraying a film-forming solution containing 70 to 90% by weight SnCl onto the glass₄ and 30 to 10% by weight SnCl₂ contains.

Example 7: Tin (IV) chloride (SnCl₄) is dissolved in acetylacetone, whereupon the resulting liquid is dissolved in dimethylformamide. Then.iron (IH) chloride (FeCl₃6H₂O) was added.

Various solutions containing various amounts of tin (IV) salt and iron (DI) salt are sprayed onto a glass which is heated to 550 ° C.

The Qxydkonzentration is always 60 gA. The film thickness is on the order of 500 Å.

The following table shows the characteristic properties of the films obtained using the indicated solutions:

<td>Percentage in</td><td>f SnO₂</td><td>0</td><td>10</td><td>20</td><td>30</td><td>40</td><td>100</td>

<td>the solution</td><td>L Fe₂O₃</td><td>100</td><td>90</td><td>80</td><td>70</td><td>60</td><td>0</td>

<td>Percentage in</td><td>f SnO₂</td><td>0</td><td>25</td><td>41</td><td>64</td><td>79</td><td>100</td>

<td>the movie</td><td>t ^Fe2 ° 3</td><td>100</td><td>75</td><td>59</td><td>36</td><td>21</td><td>0</td>

<td>Translucency (%)</td><td></td><td>50.3</td><td>55.2</td><td>60.1</td><td>65.6</td><td>71.1</td><td>76.8</td>

<td>coloring</td><td></td><td>pronounced yellow / Bernhard stone colors</td><td>Amber- color / gray</td><td>Amber- to dye</td><td>yellowish Gray</td><td>Gray</td><td>bright- Gray</td>

Example 8: 75.5 g of anhydrous SnCl₂ and 15 g of SbCl₃ are dissolved in 11 dimethylformamide.

The solution is sprayed onto a glass plate to form a coating having a thickness of the order of 2000 Å.

The coating has a very intense blue color when viewed in transmitted light. The light transmission is on the order of 21%.

Light reflection: 5%.

By adjusting the SbCl concentration, it is possible to change the intensity of the blue color as well as the resistance of the coating. This is apparent from Fig. 1, wherein the curve -1- the light transmission of the film against the SbCl₃Amount in the film-forming solution, while the curve -2- the resistance of the film against the present in the solution SbCl₃Quantity shows.

Curves -1 and 2- are plotted based on the following values: the light transmittance (TL) of the film having a thickness of 700 Å (as a percentage) is plotted on the left ordinate, while the electrical resistance in Ω / c is plotted on a logarithmic scale recorded on the right ordinate.

The abscissa indicates the number of grams of SbCl₃ again, which 1 1 solution has been added, the

75, 5 g of anhydrous SnCl₂ contains.

No. 332022

Example 9: 127 g indium chloride (InCl₃.4H₂O) are dissolved in 1 1 of dimethylformamide. 1.58 g

SnCl₂ are added (with 2% of metallic Sn present in the metallic In content).

The solution is sprayed onto a glass heated to a temperature of 500 ° C to form a coating having a thickness of the order of 1200 Å.

A coating of this kind has a blue color in reflected light and looks slightly yellowish in transmitted light.

Translucency: 87.2%

Energy permeability: 79.5%

Electrical resistance: 70 Ω / Π '

A coating of this kind can be used as glazing for heating purposes. It was found that the addition of a small amount of acetylacetone to the film-forming solution (ie 1/3 mole of acefylacetone per 1 mole of hxCl₃.4H₂O) improves the optical quality of the film, while it is possible to obtain films whose electrical resistance is 25 Ω / □ or even less.

Example 10: A spray solution is prepared in such a manner that silicon chloride (SiCl₄) to which acetylacetone has been added is diluted in dimethylformamide.

The solution is sprayed onto a glass plate that has been heated to 500 ° C. This is a very thin film of SiO₂ formed with a thickness of the order of 150 Å.

An indium oxide coating identical to the coating described in Example 9 is then applied to the thus coated glass.

The optical as well as the electrical properties of the coating are similar to the corresponding properties determined according to Example 9, the quality and the uniformity of the coating being particularly high.

The solvents having a dielectric constant of more than 15 used according to the invention may be referred to as dipolar aprotic solvents (see AJ Parker The Effects of Solvation on the Properties of Anions in Dipolar Aprotic Solvents, Quarterly Reviews, Vol.16 [1962], p.163 ).