A method of obtaining a coating of tin oxide on glass

 

(57) Abstract:

The invention relates to a method for producing doped with fluorine coating of tin oxide on the glass done by preparing a homogeneous mixture of gaseous reagents, including ORGANOTIN compound, HF, water and oxygen, and feeding the mixture of reactants to the surface of a hot glass ribbon, where these compounds interact with the formation of doped fluorine coating of tin oxide. Doped with fluorine coating of tin oxide, applied in accordance with the invention, are characterized by low specific surface resistance of the layer and a higher homogeneity of the specific surface resistance of the layer on the surface of the coated glass. 3 C. and 16 h.p. f-crystals.

The present invention relates to a method for producing glass olowookere coating, in particular to a method for olowookere coating doped with fluorine, on a hot glass substrate by chemical vapor deposition.

BACKGROUND OF THE INVENTION

Glass coating, typically made of a continuous coating on the glass substrate during the process it is nnu from the melt tin, equipped with appropriate fencing, and after sufficient cooling of the glass it comes to removing rollers that are installed flush with the tub, and finally cooling the glass as the forward movement on the rolls first in Lera, and then outdoors. To prevent oxidation at the site of the float bath during this process, when the glass is in contact with a bath of molten tin support non-oxidizing atmosphere. In Lera support air atmosphere. Chemical vapor deposition (HOP) various coatings can be effectively implemented in the bath or Lera or even in the transition zone between the contact surface of the hot glass vapors of chemicals, including chemicals that pyrolytic decompose with the formation of a coating of metal oxide. It is obvious that the evaporation temperature of such chemicals should be below the temperature of thermal decomposition. There are several compounds of tin, which when making HOP-method is able to evaporate to form on the glass olowookere coverage.

Target performance characteristics olowookere coatings on glass, for example, t is t light transmittance, high ability to reflect infrared rays and so on, improve the introduction of olowookere floor dopant. Up to the present time as dopants in the art to use multiple materials, but the most effective for tin oxide is elemental fluorine. Fluorine can be introduced into the deposition reaction in the form of ORGANOTIN fluoride or in separate fluorine-containing compound that reacts together with the compound of the tin.

Regarding the physical condition can be noted, the processes of carrying coatings on glass reagents usually used in the form of liquids, solids, evaporated liquids or solids, liquid or solid substances dispersed in the gaseous mixture as the carrier or vaporized liquids or solids dispersed in the gaseous mixture as the carrier. In the process of chemical deposition from the vapor phase is usually used evaporated liquid or solid substance which, as a rule, is dispersed in a gaseous mixture as the carrier.

The coating of tin oxide doped with fluorine, chemical vapor deposition is used as organizovannogo fluorine olowookere coating on a hot glass substrate by contacting with the glass in the form of vaporized reagents tin tetrachloride is used, fluoride-hydrogen acid (HF), air and water. Similarly, in U.S. patent 4387134 States that the surface resistivity layer doped with fluorine oxide films in 1-10 Ohms/square can be achieved using a combination of evaporated water, methanol, HF, chloride tetravalent tin and gaseous H2/N2.

Other commonly used preferred methods of application doped olowookere coatings on glass include evaporation of a mixture of organic compounds of tin and fluorine-containing compounds, then these vaporized reagents directed to the surface of the hot glass substrate. This method is described in U.S. patent 4293594, and it is additionally assumed to apply oxygen-containing gaseous medium.

In U.S. patent 4590096 described a similar method of chemical deposition from the vapor phase to obtaining doped with fluorine olowookere coatings using a mixture of ORGANOTIN compounds, organic fluorine dopant, air and water vapor. This patent States that when implementing this method, the gas stream contains a sufficient number of DIMMs 6-100%.

In U.S. patent 4325987 described HOP-the way in which the glass surface is directed gaseous mixture of tin tetrachloride and water vapour in the composition of the gaseous medium containing at least 30% of hydrogen. On this glass surface can also send a separate gaseous mixture of HF and water vapor. Although, as described in this publication, the preferred compound of tin is tin tetrachloride is used, and this compound is the only compound of tin, for which the presented examples, mention the possibility of using volatile compounds tin type Sn(Alk)4where Alk denotes a lower alkyl radical, and dibutyltindilaurate. Because there is no any information about how to implement the method according to the invention using the ORGANOTIN compounds, this method cannot be considered as a significant improvement in the art.

Regarding the present invention, it should be noted that the above literature sources were collected and studied only as a guide. One should not conclude that the information about so many different methods could be collected when accurately is to improve the known to the present time, methods of application to the surface of the hot glass substrate doped with fluorine olowookere coating process HOP and therefore, to improve low specific surface resistance of the layer and uniformity of this specific surface resistance of the layer of glass coating. Another objective of the present invention is to develop a method of applying to the surface of the hot glass substrate doped with fluorine olowookere coverage at a lower cost than in the implementation of the previously known methods.

SUMMARY OF THE INVENTION

According to the present invention proposes a method of chemical deposition from the vapor phase to be applied on the surface of the hot glass substrate doped with fluorine olowookere coverage. Unexpectedly, it was found that the target characteristics of doped fluorine olowookere coatings on the glass can be improved by using a method comprising a) obtaining a hot glass substrate, on which surface you want to apply doped fluoride olowookere floor; b) preparing a homogeneous mixture of the vaporized reagents containing ORGANOTIN compound, hydrogen fluoride, oxygen and water, and C) the supply of vaporized mixture of reagents to the surface of a hot glass substrate, where the second substrate doped with fluorine olowookere coverage.

In a preferred embodiment, prior to deposition of doped fluorine tin oxide on the surface of the glass substrate is applied nitritification barrier, preferably a layer of silicon dioxide. The method according to the present invention is particularly effective in the manufacture of glass, equipped with alloyed with fluorine olowookere coating that can be applied for the manufacture of energy efficient Windows in buildings, aircraft and cars, as well as various optical and electronic devices.

A DETAILED DESCRIPTION OF THE PREFERRED OPTION

Olowookere coatings doped with fluorine, can be applied to the surface of the hot glass substrate according to methods that are well known in the art as a method of chemical deposition from vapor phase (HOP). In accordance with this method the reagents are mixed so as to form a homogeneous flow of the vaporized reactants, which serves to the surface of a hot glass substrate and in which the reaction takes place by deposition on the surface of the hot glass substrate doped with fluorine olowookere coverage. In an oxidizing atmosphere, which must exist near the surface of hot glass, about the closure.

This process is usually carried out in the manufacture of float glass, and he is in the float bath, Lera or in the transition zone between the bathroom and lerom when the glass is still in a hot condition. A glass substrate is usually treated at a temperature in the range of from about 750 to about 1500oF. These temperatures are typical for glass at different stages when it is produced in the float process.

Glass substrates suitable for use in the method according to the present invention include any conventional glass substrates, which are known in the art of manufacturing glass products with coatings. A typical glass substrate used in the manufacture of glass for cars and sheet glass, usually referred to as sodium-calcium-silicate glass. Other acceptable glass in General can be an alkali calcium silicate glass, borosilicate glass, aluminosilicate glass, bioluminescence glass, phosphate glass, quartz glass, etc. and combinations thereof. Preferably sodium calcium silicate glass.

The flow of reagents to HOP according to the present invention includes an ORGANOTIN compound for the a or close to it. Acceptable ORGANOTIN compounds, which can be used for implementing the method according to the invention, include, but are not limited to, dimethylglutaric, diethylaluminium, dibutylaminoethanol, tetramethylurea, mediaoutrage, triethylborane, trimethylolpropane, atenololatenolol, propylresorcinol, isopropylacrylamide, second-butyronitrile, tert-butyronitrile, familyoperated, carbethoxytetramic, etc. and combinations thereof. In General, these compounds are well known in the field of machinery HOP, and technically available as precursors intended for application olowookere coating on a hot glass. Preferred ORGANOTIN compound is dimethylglutaric. To obtain a gaseous stream containing ORGANOTIN compound reagent is evaporated ORGANOTIN compound and optionally a gaseous medium, an oxidant, a stabilizer, a hydrocarbon, inert gas, etc. Used in this description, the term "gaseous stream containing ORGANOTIN compound reagents typically includes evaporated ORGANOTIN compound, an oxidizer and ine the WMD of the methods which is well known in the art, such as evaporation dispersed or fluidized ORGANOTIN powders or evaporation ORGANOTIN particles in the fluidized bed by the stream of hot gaseous media, or the injection box solubilizing ORGANOTIN compounds in the stream of hot gaseous medium, or bubbling of gaseous media through the liquid ORGANOTIN compound. These methods are described in more detail in U.S. patent 3852098, 2780553, 4351861, 4571350, 3970037, 4212663 and 4261722, which are not fully included in the present description as a reference. The preferred method of obtaining flow of reagents containing vaporized ORGANOTIN compound, is the evaporation of this compound in a film evaporator in the presence of mixing gas, as described, for example, in U.S. patent 5090985, which is fully included in the present description by reference. As noted above, this gaseous stream, which includes mainly inert gaseous media, such as helium, nitrogen, argon, or mixtures thereof, optionally may contain oxidizing agents, such as water or oxygen. The preferred gaseous notok reagents containing vaporized ORGANOTIN compound, usually heated to a temperature of from about 250 to about 450oF, and then sent to the reaction zone on the surface of the hot glass substrate.

Gaseous hydrogen fluoride or fluoride-hydrogen acid (abbreviation "HF" is used in this description to refer to either gaseous hydrogen fluoride or fluoride-hydrogen acid) is mixed with the vaporized by ORGANOTIN compounds. You get a separate stream containing HF reagents, which includes mainly HF and a carrier, preferably water vapor. Adding water containing HF flow of reagents reduces the emissivity coated glass, while increasing the growth rate of the layer of deposited tin oxide doped with fluorine. Containing HF flow of reagents may optionally include conventional additives, such as helium, nitrogen or argon, and mixtures thereof, and oxidizing agents such as oxygen.

Containing HF flow of reactants combine with containing ORGANOTIN reagent stream at a point located before the release of the reagents to the surface of a hot glass substrate, on which put the covered connection using one of the methods described above in the section related to the evaporation of ORGANOTIN compounds, or HF in the form of gas. HF containing stream is vaporized reactants can be combined with the flow of reagents containing vaporized ORGANOTIN compound, by mixing these two gaseous streams before applying to the surface of a hot glass substrate. According to another variant containing HF flow of reagents in the form of liquid or solution it is possible to inject into the hot stream of reagents containing vaporized ORGANOTIN compound, thereby vaporizing fluoride solution or liquid compound. After combining the vaporized reagents, including ORGANOTIN compound, HF, water and oxygen, is directed to the surface of the hot glass, so that they interact with the deposition on this surface coating of tin oxide doped with fluorine.

In a preferred embodiment, the stream with the ORGANOTIN reagent is produced by evaporation of dimethylammoniumchloride in the presence of an inert gaseous medium such as nitrogen, helium or a mixture thereof, in the evaporator, such as described above. Next, the resulting gaseous stream is combined with gaseous oxygen. Odgovara combined with the gaseous stream with an ORGANOTIN reagent, resulting in a uniform stream of gaseous reagents. This uniform flow of gaseous reactants fed to the surface of the hot glass substrate so that the surface is deposited doped with fluorine olowookere coverage. This uniform flow of gaseous reactants can be fed to the glass surface using any acceptable device for coating. One of predpochtitelno device for coating described in U.S. patent 4504526, which fully included in the present description by reference.

In a preferred embodiment, a homogeneous gaseous mixture of the reactants, which serves to the surface of a hot glass substrate in accordance with the invention, includes (in mol.%) from about 10 to about 60% oxygen, from about 2 to about 50% water and from about 0.2 to about 2% HF, most preferably from about 30 to about 50% oxygen, from about 15 to about 35% water and from about 0.5 to about 1.5% HF. This homogeneous gaseous mixture of the reactants also include ORGANOTIN compound, the target concentration of which depends on the required thickness olowookere cover and linear skies connection served in the composition of the gaseous mixture of the reactants in the quantity sufficient for the coating of the required thickness when the target linear speed of the substrate. To conduct typical processes on an industrial scale such gaseous mixture of the reactants typically includes from about 0.01 to about 8% of the ORGANOTIN compounds.

It was found that when applying doped with fluorine olowookere coating in accordance with the present invention in a preferred embodiment, it is necessary to put a layer of material that acts as nitritification barrier between the glass substrate and alloyed with fluorine olowookere coating. Provided with a coating of glass products have been found, low emissivity, low specific surface resistance of the layer and lower the opacity, when doped with fluorine olowookere coating obtained in accordance with the invention, is applied not directly to the raw glass, and glass, provided with intermediate nitritification layer. In the preferred embodiment, this nitritification layer derived from silicon dioxide. This layer of silicon dioxide is preferably applied with a conventional method HOP.

It should be noted that for successful integration and delivery of the vaporized reagents in accordance with the present invention, the process conditions of the critical value have no. The above process conditions described mainly on the example of those parameters that are common to the implementation of the method according to the present invention. Sometimes, however, the above-described process conditions may be not exactly acceptable for each of the compounds covered by the present framework. Such compounds can usually be easily determined by the expert in this is x modifications well-known experts in the art, for example by raising or lowering the temperature, the variation of the ratios combine ORGANOTIN compounds and HF as reagents, the usual modifications of the conditions of the evaporation process, etc., or for the implementation of the method according to the invention it is possible to create other technological conditions, which otherwise is usually acceptable.

It should also be noted that the method according to the invention can be performed repeatedly as many times as needed for a given substrate, with the aim to obtain a coating consisting of several successively deposited layers, and for each of these layers is not necessary to use materials of the same composition. Obviously, when these costs threads reagents thickness of the coating layer depends on the speed of movement of the substrate. In such conditions, if necessary, the number of reaction sites can be increased by placing two or more devices for coating. In this way subsequent layers applied on top of previous layers before the time comes for their cooling, resulting in a particularly uniform uniform coating.

Below the invention is illustrated on the line is for illustrative purpose and that in practice the invention may be implemented or otherwise, while staying within its volume.

COMPARATIVE EXAMPLE

Dimethylglutaric melted and then evaporated in film evaporator of the type described in U.S. patent 5090985. At the same time in this film evaporator as the gaseous medium is injected helium. Film evaporator equipped with a steam jacket, maintaining temperature of approximately 350oF. the Resulting gaseous mixture of DME and helium, leaving a thin film evaporator, direct main line supply of reagents. In this main line in the gas flow DIR/Not injected gaseous oxygen. The resulting gas stream is constantly moving on the main line supply of reagents.

Simultaneously, the second film evaporator, the temperature of which is maintained at a level of approximately 400oF, direct triperoxonane acid (TFA) and water. The resulting gaseous mixture of TFA and water leaving this second film evaporator, serves on the power line, which is connected to the main supply line predecessor, bringing a gas mixture of TFA/water with gas flow DIR/Not/O2thanks to what these streams are thoroughly mixed with the formation of a homogeneous flow of evaporated felyae, 0,97% TFA and 2.5-3 percent of DHS, and the total consumption of this final gaseous mixture is about 384 liters (standard conditions)/min per meter width of the finished glass product is coated.

Using the device for coating according to the U.S. patent 4504526 the flow of the vaporized reagents immediately served to the surface of the ribbon of glass, which by known techniques HOP pre-first put a thin layer of tin oxide and a second thin layer of silicon dioxide. The ribbon of glass moves with a linear velocity of approximately 466 inches/min and its temperature ranges from about 1100 to 1200oF. On the surface of the hot glass reagents contained in the stream, interact with the formation of coatings of doped fluorine tin oxide over the layer of silicon dioxide and tin oxide. Thickness of the resulting layer of tin oxide doped with fluorine, approximately

The width of the finished glass product is coated every 2 inches to determine the specific surface resistance of the layer. This is the surface resistivity of the layer is 13.3-18,0 Ohms/square, with an average specific surface resistance of the layer 14.4 Ohms/square.

EXAMPLE

Dimethylaluminum in this film evaporator as the gaseous medium is injected helium. Film evaporator equipped with a steam jacket, maintaining temperature of approximately 350oF. the Resulting gaseous mixture of DME and helium, leaving a thin film evaporator, direct main line supply of reagents. In the main supply line of the reactants in the gas flow DIR/Not injected gaseous oxygen. The resulting gas stream is constantly moving on the main line supply of reagents.

Simultaneously, the second film evaporator, the temperature of which is maintained at a level of approximately 400oF, send an aqueous solution of HF. In this second film evaporator introduce additional amount of water. The resulting gaseous mixture of HF and water leaving the second film evaporator, serves on the power line, which is connected to the main supply line predecessor, bringing a gas mixture of HF/water with gas flow DIR/Not/ABOUT2thanks to what these streams are thoroughly mixed with the formation of a homogeneous flow of the vaporized reactants. The final gaseous mixture comprises approximately (in mol.%) 42.9% oxygen, 24.6% of water, 29.3% of helium, 0,70% HF and 2.5% DIR, and the total consumption of this final gaseous mixture is about 395 l (standard Yesenia coating according to the U.S. patent 4504526 the flow of the vaporized reagents immediately served to the surface of the glass ribbon, which by the known technique HOP pre-first put a thin layer of tin oxide and a second thin layer of silicon dioxide. The ribbon of glass moves with a linear velocity of approximately 466 inches/min and its temperature ranges from about 1100 to 1200oF. On the surface of the hot glass reagents contained in the stream, interact with the formation of coatings of doped fluorine tin oxide over the layer of silicon dioxide and tin oxide. Thickness of the resulting layer of tin oxide doped with fluorine, approximately .

The width of the finished glass product is coated every 2 inches to determine the specific surface resistance of the layer. This is the surface resistivity of the layer is at 13.0-15.9 Ohms/square, with an average specific surface resistance of the layer of 14.0 Ohms/square.

1. The method of chemical vapour deposition coating of tin oxide doped with fluorine, the surface of the hot glass substrate, comprising the stage of: A) obtaining hot glass substrate, on which surface precipitated doped with fluorine coating of tin oxide, (B) preparing a homogeneous mixture of gaseous reactants containing ooVoo the tee hot glass substrate, and in this homogeneous mixture of gaseous reactants reaction takes place by deposition on the surface of the hot glass substrate doped with fluorine coating of tin oxide.

2. The method according to p. 1, where the glass is selected from the group including sodium-calcium-silicate glass, alkali-calcic silicate glass, borosilicate glass, aluminosilicate glass, phosphate glass, quartz glass, and combinations thereof.

3. The method according to p. 1, where the glass is a sodium-calcium-silicate glass.

4. The method according to p. 1 wherein the ORGANOTIN compound selected from the group including dimethylglutaric, diethylaluminium, dibutylaminoethanol, tetramethylurea, mediaoutrage, triethylborane, trimethylolpropane, atenololatenolol, propylresorcinol, isopropylacrylamide, second-butyronitrile, tert-butyronitrile, familyoperated, carbethoxytetramic and combinations thereof.

5. The method according to p. 1 wherein the ORGANOTIN compound is dimethylglutaric.

6. The method according to p. 1, where the glass substrate obtained at a temperature of approximately 750-1500oF.

7. The method according to p. 1, where homogeneous causa helium, nitrogen, argon and the oxide of trivalent nitrogen.

8. The method according to p. 1, additionally comprising the first stage of deposition directly on the surface of the hot glass substrate a layer of material that acts as nitritification barrier, and then a second deposition directly on the specified layer patricipating barrier doped with fluorine coating of tin oxide.

9. The method according to p. 8, where before deposition of doped fluorine coating of tin oxide on the surface of the hot glass substrate precipitated layer of silicon dioxide.

10. The method according to p. 9, where the layer of silicon dioxide is precipitated on the surface of the hot glass substrate by the method of chemical deposition from the vapor phase.

11. The method according to p. 9, where before deposition of the layer of silicon dioxide on the surface of the hot glass substrate precipitated layer of tin oxide.

12. The method according to p. 1, where the mixture of gaseous reactants includes about 0.2 to 2 mol.% fluoride hydrogen.

13. The method according to p. 12, where the mixture of gaseous reactants includes about 0.5 to 1.5 mol.% fluoride hydrogen.

14. The method according to p. 1, where the mixture of gaseous reactants includes approximately 2-50 mol.% water.

15. The method according to p. 14, where the mixture hentov includes approximately 10-60 mol.% the oxygen.

17. The method according to p. 16, where the mixture of gaseous reactants includes about 30-50 mol.% the oxygen.

18. The method of chemical vapour deposition coating of tin oxide doped with fluorine, the surface of the hot glass substrate, comprising the stage of: A) obtaining hot glass substrate at a temperature of approximately 750-1500oF, on the surface of which is precipitated doped with fluorine coating of tin oxide; B) preparing a homogeneous mixture of gaseous reagents containing ORGANOTIN compound, about 0.2 to 2 mol.% of hydrogen fluoride, about 2 to 50 mol.% water and about 10 to 60 mol.% oxygen; and B) feeding the mixture of gaseous reactants to the surface of a hot glass substrate, and in this homogeneous mixture of gaseous reactants reaction takes place by deposition on the surface of the hot glass substrate doped with fluorine coating of tin oxide.

19. The method of chemical vapour deposition coating of tin oxide doped with fluorine, the surface of the hot glass substrate, comprising the stage of: A) obtaining hot glass substrate at a temperature of approximately 750-1500oF, on the surface of which is precipitated doped with fluorine coating of oxide ol the art of gaseous reagents, containing ORGANOTIN compound, about 0.2 to 2 mol.% of hydrogen fluoride, about 2 to 50 mol.% water and about 10 to 60 mol.% oxygen, and (B) feeding a mixture of gaseous reactants to the surface of a hot glass substrate, and in this homogeneous mixture of gaseous reactants reaction takes place by deposition on the layer of silicon dioxide on the surface of the hot glass substrate doped with fluorine coating of tin oxide.

 

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